EP1147254A1 - Process and product for the treatment of textile fabrics - Google Patents

Process and product for the treatment of textile fabrics

Info

Publication number
EP1147254A1
EP1147254A1 EP00972835A EP00972835A EP1147254A1 EP 1147254 A1 EP1147254 A1 EP 1147254A1 EP 00972835 A EP00972835 A EP 00972835A EP 00972835 A EP00972835 A EP 00972835A EP 1147254 A1 EP1147254 A1 EP 1147254A1
Authority
EP
European Patent Office
Prior art keywords
optionally
bleach
water
product
aqueous liquor
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.)
Granted
Application number
EP00972835A
Other languages
German (de)
French (fr)
Other versions
EP1147254B1 (en
Inventor
Machiel Unilever Research Vlaardingen GOEDHART
Jean-Paul Unilever Rch. Port Sunlight JANSSENS
Karin Unilever Research Vlaardingen VRIESWIJK
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Unilever PLC
Unilever NV
Original Assignee
Unilever PLC
Unilever NV
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Publication of EP1147254A1 publication Critical patent/EP1147254A1/en
Application granted granted Critical
Publication of EP1147254B1 publication Critical patent/EP1147254B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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 and product suitable for removing stains from textile fabrics,
  • the process is especially suitable 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.
  • the present invention provides a process for removal of stains from textile fabrics, which process comprises the steps of:
  • the invention further provides a product for the treatment of textile fabrics to remove stains, comprising two separately packaged particulate compositions, wherein:
  • the first particulate composition (i) has a pH (of a 1% solution in demineralised water at 25°C) of from 2 to 5 , preferably from 3.5 to 4.5, and comprises:
  • a preferred process according to the invention comprises the steps of :
  • a preferred product according to the invention comprises two separately packaged particulate compositions, wherein:
  • the first particulate composition (i) has a pH (of a 1% solution in demineralised water at 25°C) of from 2 to 5, preferably from 3.5 to 4.5, and comprises:
  • the first aspect 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 suitable for carrying out by hand, using simple utensils such as buckets or bowls as are usually used in laundering fabrics by hand. However, the process may also be carried out by machine.
  • the second aspect of the invention is a product comprising two separately packaged particulate products which may be used to prepare the two aqueous liquors used in the process of the invention.
  • 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 pH 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 may also advantageously contain 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 0 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
  • 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.
  • 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.
  • the second aqueous liquor may be generated purely by dissolving bleach in water; at the other extreme, the seocnd 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 is used to prepare the first aqueous liquor, This suitably contains:
  • the balance if any may be constituted by an inert filler such as sodium sulphate.
  • the first particulate composition preferably contains from 0.5 to 10 wt% of potassium iodate, magnesium monoperoxyphthalate or potassium benzenecarboperoxoate .
  • Potassium iodate is especially preferred and is effective in an amounts of from 0.5 wt%, preferably from 0.5 to 2 wt%.
  • the first particulate composition preferably contains from 0.5 to 10 wt%, preferably from 0.5 to 6 wt% and more preferably from 0.5 to 4 wt%, of alkali metal dichlorocyanurate .
  • the first particulate composition has a pH (of a 1% solution in demineralised water at 20°C) within the range of from 2.0 to 5.0, preferably within the range of from 3.5 to 4.5, and desirably about 4.0.
  • a surfactant system is preferably present.
  • this comprises one of more anionic and/or nonionic surfactants.
  • compositions may, for example, contain the following ingredients in the following concentration ranges (suitable and preferred, wt%) :
  • Anionic surfactant (LAS or AOS) 0-25 3-25
  • Nonionic surfactant eg C i2 7EO 0-5 0-5
  • the first particulate composition may suitably be used at a dosage of from 2 to 20 g, preferably from 5 to 10 g, per 250 g fabrics to prepare the first aqueous liquor.
  • a second particulate composition is used to prepare the second aqueous liquor.
  • This product comprises:
  • the second particulate composition may suitably be used at a dosage of from 2 to 20 g, preferably from 5 to 10 g, per 250 g of fabrics.
  • compositions may, for example, contain the following ingredients in the following concentration ranges (suitable and preferred, weight %) :
  • Anionic surfactant (LAS or AOS) 10 -30 20 -25
  • Nonionic surfactant eg C ⁇ 2 7E0
  • Sequestrant eg Dequest 2047
  • Fluorescer eg Tinopal CBS-X 0.1-1 0.2-0.5
  • Protease granules 0-5 1-3 Cellulase granules 0.5 1.3
  • Perfume 0.05-1. .0 0.1-0.5
  • the two particulate compositions are separately packaged. According to a preferred embodiment of the invention, they are packaged in unit dose form so that a single dose of each composition may be used per treatment. Especially preferred are sachets. Opening sachets of paper or nonwoven fabric are preferred. Sachets suitable for containing detergent powders and similar materials are widely disclosed in the prior art.
  • the sachets containing the two particulate compositions are visually distinct, for example, colour coded.
  • the sachets may then be packed together in common outer packaging, for example, a bag or carton, possibly grouped in pairs, while remaining readily distinguishable.
  • a first particulate composition 1 (i) having a 1 wt% solution pH of 4.0 had the following formulation:
  • a second particulate composition l(ii) had the following formulation:
  • a first particulate composition 2 (i) having a 1 wt% solution pH of 4.0 had the following formulation:
  • a second particulate composition 2 (ii) had the following formulation:
  • a first particulate composition 3 (i) having a 1 wt% solution pH of 4.0 had the following formulation:
  • a second particulate composition 3 (ii) had the following formulation:
  • a first particulate composition 4 (i) had the following formulation:
  • composition 4 (i) 7.5 g doses of Composition 4 (i) were packaged in sachets of nonwoven fabric.
  • the 1% solution pH of Composition 1 (i) was 2.4-2.5.
  • a second particulate composition 4 (ii) had the following formulation:
  • 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/1 solution of composition 1(a), then soaked for 30 minutes in a 5.0 g/1 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/1 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.

Landscapes

  • 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

PROCESS AND PRODUCT FOR THE TREATMENT OF
TEXTILE FABRICS
Technical field
The present invention is concerned with a process and product suitable for removing stains from textile fabrics, The process is especially suitable 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.
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) optionally 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.
The invention further provides a product for the treatment of textile fabrics to remove stains, comprising two separately packaged particulate compositions, wherein:
the first particulate composition (i) has a pH (of a 1% solution in demineralised water at 25°C) of from 2 to 5 , preferably from 3.5 to 4.5, and comprises:
(i) (a) a water-soluble solid acid, optionally in admixture with a water-soluble salt thereof,
(i) (b) optionally from 0 to 30 wt% of a surfactant; (i) (c) optionally from 0 to 10 wt% of a bleach stable and effective at a pH of from 2 to 5 ,
and the second particulate composition (ii) comprises
(ii) (a) from 1 to 100 wt% of a bleach,
(ii) (b) optionally from 0 to 30 wt% of a surfactant,
(ii) (c) optionally from 0 to 99 wt% of an alkaline buffering agent. Preferred embodiments of the invention
A preferred process according to the invention 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) optionally 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. A preferred product according to the invention comprises two separately packaged particulate compositions, wherein:
the first particulate composition (i) has a pH (of a 1% solution in demineralised water at 25°C) of from 2 to 5, preferably from 3.5 to 4.5, and comprises:
(i) (a) from 50 to 100 wt% of a water-soluble solid acid, optionally in admixture with a water-soluble salt thereof,
(i) (b) optionally from 0 to 30 wt% of a surfactant; (i) (c) optionally from 0 to 10 wt% of an oxidising agent capable of masking and/or neutralising sulphurous odours , (i) (d) optionally from 0 to 10 wt% of a bleach stable and effective at a pH of from 2 to 5, which is not the oxidising agent (i) (c) ,
and the second particulate composition (ii) comprises
(ii) (a) from 1 to 100 wt% of a bleach,
(ii) (b) optionally from 0 to 30 wt% of a surfactant,
(ii) (c) optionally from 0 to 99 wt% of an alkaline buffering agent, (ii) (d) optionally from 0 to 50 wt% of one or more builder and/or filler salts, (ii) (e) optionally from 0 to 5 wt% of a sequestrant bleach stabiliser, (ii) (f) optionally from 0 to 5 wt% of a fluorescer, (ii) (g) optionally an effective amount of one or more detergent enzymes,
and other minor ingredients to 100 wt%. Detailed description of the invention
The first aspect of 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 suitable for carrying out by hand, using simple utensils such as buckets or bowls as are usually used in laundering fabrics by hand. However, the process may also be carried out by machine.
The second aspect of the invention is a product comprising two separately packaged particulate products which may be used to prepare the two aqueous liquors used in the process of the invention.
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 pH 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:
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 may also advantageously contain 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-C0 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 seocnd 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.
The product of the invention
In the product of the invention, a first particulate composition is used to prepare the first aqueous liquor, This suitably contains:
(i) (a) from 50 to 100 wt% (in total) of a solid water- soluble acid optionally in admixture with a salt thereof,
(i) (b) optionally from 0 to 30 wt% (eg 1 to 30 wt%) of one or more surfactants;
(i) (c) optionally from 0 to 10 wt% (eg 0.5 to 10%) of an oxidising agent capable of masking and/or neutralising sulphurous odours ,
(i) (d) optionally from 0 to 10 wt% (eg 0.5 to 10 wt%) of a bleach stable and effective at a pH below 5.0, which is not the oxidising agent (i) (c) ,
and optionally other minor ingredients.
The balance if any may be constituted by an inert filler such as sodium sulphate.
As oxidising agent (i) (c) , the first particulate composition preferably contains from 0.5 to 10 wt% of potassium iodate, magnesium monoperoxyphthalate or potassium benzenecarboperoxoate . Potassium iodate is especially preferred and is effective in an amounts of from 0.5 wt%, preferably from 0.5 to 2 wt%.
As a bleach stable and effective at a pH below 5.0 (i) (d) , the first particulate composition preferably contains from 0.5 to 10 wt%, preferably from 0.5 to 6 wt% and more preferably from 0.5 to 4 wt%, of alkali metal dichlorocyanurate . The first particulate composition has a pH (of a 1% solution in demineralised water at 20°C) within the range of from 2.0 to 5.0, preferably within the range of from 3.5 to 4.5, and desirably about 4.0.
As previously indicated, a surfactant system is preferably present. Preferably this comprises one of more anionic and/or nonionic surfactants.
Preferred compositions may, for example, contain the following ingredients in the following concentration ranges (suitable and preferred, wt%) :
Citric acid 35-95 40-55 Sodium citrate 0-50 30-45
Anionic surfactant (LAS or AOS) 0-25 3-25
Nonionic surfactant (eg Ci2 7EO) 0-5 0-5
Potassium iodate 0-2 0.5-1.5
NaDCCA 0-6 0.5-3 Perfume 0.05-1.0 0.1-0.5
The first particulate composition may suitably be used at a dosage of from 2 to 20 g, preferably from 5 to 10 g, per 250 g fabrics to prepare the first aqueous liquor.
A second particulate composition is used to prepare the second aqueous liquor. This product comprises:
(ii) (a) from 1 to 100 wt% (preferably from 1 to 20 wt%) of the bleach;
(ii) (b) optionally from 0 to 30 wt% (preferably from 1 to 30 wt%) of surfactant, preferably anionic and/or nonionic surfactant; (ii) (c) optionally from 0 to 99 wt% (preferably from 1 to 99 wt%) of an alkaline buffering agent,
(ii) (d) optionally from 0 to 50 wt% (preferably from 1 to 50 wt%) of one or more builder and/or filler salts,
(ii) (e) optionally from 0.1 to 5 wt% of a sequestrant bleach stabiliser,
(ii) (f) optionally from 0.01 to 5 wt% of a fluorescer,
(ii) (g) optionally an effective amount of one or more detergent enzymes,
and minor ingredients to 100 wt%.
The second particulate composition may suitably be used at a dosage of from 2 to 20 g, preferably from 5 to 10 g, per 250 g of fabrics.
Preferred ingredients (ii) (a) - (ii) (g) are discussed above.
Preferred compositions may, for example, contain the following ingredients in the following concentration ranges (suitable and preferred, weight %) :
NaDCCA or PAP 1 - 10 2 - 6
Sodium carbonate (soda ash) 5 - 90 5- 10 Sodium bicarbonate 0 -60 5 - 10
Sodium tripolyphosphate 5 -30 10 -20 Sodium sulphate 0 -30 10 -25
Anionic surfactant (LAS or AOS) 10 -30 20 -25 Nonionic surfactant (eg Cι2 7E0) 0 - 5 0 Sequestrant (eg Dequest 2047) 0-5 0.1-2 Fluorescer, eg Tinopal CBS-X 0.1-1 0.2-0.5 Protease granules 0-5 1-3 Cellulase granules 0.5 1.3 Perfume 0.05-1. .0 0.1-0.5
Packaging and presentation
In the product of the invention, the two particulate compositions are separately packaged. According to a preferred embodiment of the invention, they are packaged in unit dose form so that a single dose of each composition may be used per treatment. Especially preferred are sachets. Opening sachets of paper or nonwoven fabric are preferred. Sachets suitable for containing detergent powders and similar materials are widely disclosed in the prior art.
Preferably, the sachets containing the two particulate compositions are visually distinct, for example, colour coded. The sachets may then be packed together in common outer packaging, for example, a bag or carton, possibly grouped in pairs, while remaining readily distinguishable.
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 of the invention
A first particulate composition 1 (i) having a 1 wt% solution pH of 4.0 had the following formulation:
A second particulate composition l(ii) had the following formulation:
7.5 g doses of Compositions l(i) and 1 (ii) were packaged in sachets of nonwoven fabric. EXAMPLE 2: product of the invention
A first particulate composition 2 (i) having a 1 wt% solution pH of 4.0 had the following formulation:
A second particulate composition 2 (ii) had the following formulation:
7.5 g doses of Compositions 2 (i) and 2 (ii) were packaged in sachets of nonwoven fabric. EXAMPLE 3 : product of the invention
A first particulate composition 3 (i) having a 1 wt% solution pH of 4.0 had the following formulation:
A second particulate composition 3 (ii) had the following formulation:
7.5 g doses of Compositions 3 (i) and 3 (ii) were packaged in sachets of nonwoven fabric. EXAMPLE 4 : product of the invention
A first particulate composition 4 (i) had the following formulation:
7.5 g doses of Composition 4 (i) were packaged in sachets of nonwoven fabric. The 1% solution pH of Composition 1 (i) was 2.4-2.5.
A second particulate composition 4 (ii) had the following formulation:
7.5 g doses of Composition 4 (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/1 solution of composition 1(a), then soaked for 30 minutes in a 5.0 g/1 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/1 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.

Claims

1 A process for the removal of stains from textile fabrics, characterised by 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) optionally 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.
2 A process as claimed in claim 1, characterised in that the first aqueous liquor comprises: (i) (a) a water-soluble solid acid, optionally in admixture with a water-soluble salt thereof, (i) (b) optionally 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 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/1, preferably at least 3 g/1. 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/1, preferably at least 0.2 g/1.
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.
11 A process as claimed in any preceding claim, carried out by hand.
12 A product for the treatment of textile fabrics to remove stains, comprising two separately packaged particulate compositions, characterised in that:
the first particulate composition (i) has a pH (of a 1% solution in demineralised water at 25°C) of from 2 to 5, preferably from 3.5 to 4.5, and comprises:
(i) (a) a water-soluble solid acid, optionally in admixture with a water-soluble salt thereof,
(i) (b) optionally from 0 to 30 wt% of a surfactant; (i) (d) optionally from 0 to 10 wt% of a bleach stable and effective at a pH of from 2 to 5 ,
and the second particulate composition (ii) comprises
(ii) (a) from 1 to 100 wt% of a bleach,
(ii) (b) optionally from 0 to 30 wt% of a surfactant,
(ii) (c) optionally from 0 to 99 wt% of an alkaline buffering agent.
13 A product as claimed in claim 12, characterised in that the first particulate composition comprises:
(i) (a) from 50 to 100 wt% of a water-soluble solid acid, optionally in admixture with a water-soluble salt thereof,
(i) (b) optionally from 0 to 30 wt% of a surfactant; (i) (c) optionally from 0 to 10 wt% of an oxidising agent capable of masking and/or neutralising sulphurous odours,
(i) (d) optionally from 0 to 10 wt% of a bleach stable and effective at a pH of from 2 to 5, which is not the oxidising agent (i) (c) ,
and the second particulate composition (ii) comprises
(ii) (a) from 1 to 100 wt% of a bleach, (ii) (b) optionally from 0 to 30 wt% of a surfactant, (ii) (c) optionally from 0 to 99 wt% of an alkaline buffering agent,
(ii) (d) optionally from 0 to 50 wt% of one or more builder and/or filler salts, (ii) (e) optionally from 0 to 5 wt% of a sequestrant bleach stabiliser, (ii) (f) optionally from 0 to 5 wt% of a fluorescer,
(ii) (g) optionally an effective amount of one or more detergent enzymes,
and other minor ingredients to 100 wt%. 14 A product as claimed in claim 12 or claim 13, characterised in that the first particulate composition comprises from 0.5 to 10 wt% of an oxidising agent capable of masking and/or neutralising sulphurous odours, preferably an alkali metal iodate.
15 A product as claimed in any one of claims 12 to 14, characterised in that the first particulate composition comprises from 0.5 to 10 wt% of a bleach (i) (d) stable and effective at a pH below 5.0 which is not the oxidising agent (i) (c) , preferably from 0.5 to 6 wt% of an alkali metal dichlorocyanurate .
16 A product as claimed in any one of claims 12 to 15, 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.
17 A product as claimed in any one of claims 12 to 16, characterised in that the second particulate composition comprises as the bleach (ii) (a) from 1 to 20 wt% of alkali metal dichlorocyanurate or N,N' -phthaloylaminoperoxycaproic acid. 18 A product as claimed in any one of claims 12 to 17, characterised in that the first and second particulate compositions are packaged in unit dose form.
19 A product as claimed in claim 18, characterised in that the first and second particulate compositions are packaged in sachets.
20 A product as claimed in claim 19, characterised in that the first and second particulate compositions are packaged in visually distinct sachets within common outer packaging.
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
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 true EP1147254A1 (en) 2001-10-24
EP1147254B1 EP1147254B1 (en) 2006-06-21

Family

ID=10865276

Family Applications (1)

Application Number Title Priority Date Filing Date
EP00972835A Expired - Lifetime EP1147254B1 (en) 1999-11-26 2000-10-19 Process and product for the treatment of textile fabrics

Country Status (8)

Country Link
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
WO2005100529A1 (en) * 2004-04-05 2005-10-27 The Procter & Gamble Company Liquid bleaching compositions
EP1593733A1 (en) * 2004-04-05 2005-11-09 The Procter & Gamble Company Liquid bleaching compositions
CA2885774C (en) * 2012-10-04 2019-04-02 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
EP0143476B1 (en) * 1983-10-03 1987-09-09 Akzo N.V. 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

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0138626A1 *

Also Published As

Publication number Publication date
BR0007725A (en) 2001-10-30
DE60028930D1 (en) 2006-08-03
WO2001038626A1 (en) 2001-05-31
EP1147254B1 (en) 2006-06-21
ZA200105008B (en) 2002-06-19
AU1142801A (en) 2001-06-04
GB9928079D0 (en) 2000-01-26
ATE331065T1 (en) 2006-07-15

Similar Documents

Publication Publication Date Title
CA1241156A (en) Bleaching compositions
US4028263A (en) Bleaching and brightening detergent composition
CA1302200C (en) Detergent bleach composition and method of cleaning fabrics
JPH10505365A (en) Peroxygen bleaching composition
US4146496A (en) Peroxy bleach system suitable for colored laundry
US4120650A (en) Laundering process for dual bleaching stained fabrics
US4055505A (en) Activated percompound bleaching compositions
EP1809730A1 (en) Liquid detergent composition
EP1240378B1 (en) Method of treating a textile
US4699623A (en) Process of bleaching laundry
AU674672B2 (en) Peroxygen bleach composition
JPH02196900A (en) Heavy,granular,synthetic,organic nonionic detergent composition
WO2020074302A1 (en) Cleaning composition comprising foam boosting silicone
CA1207956A (en) Peroxyacid bleaching and laundering composition
CA2232595C (en) Hypochlorite bleaching composition having enhanced fabric whitening benefits
EP1147254A1 (en) Process and product for the treatment of textile fabrics
KR100392571B1 (en) Bleach Product
WO1999061572A1 (en) Process and product for the treatment of textile fabrics
US5336447A (en) Process and composition for treating fabrics
WO1994024250A1 (en) Composition and process for inhibiting dye transfer
CA1090505A (en) Bleaching compositions
US20050065054A1 (en) Detergent formulations containing alkaline peroxide salts and organic acids
CA1115619A (en) Detergent compositions
JPH0288699A (en) Liquid bleaching agent for treatment before washing
US20030096721A1 (en) Complex for catalytically bleaching a substrate

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20010608

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

AX Request for extension of the european patent

Free format text: AL;LT;LV;MK;RO;SI

17Q First examination report despatched

Effective date: 20040206

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20060621

Ref country code: BE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060621

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060621

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060621

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060621

Ref country code: LI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060621

Ref country code: CH

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060621

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REF Corresponds to:

Ref document number: 60028930

Country of ref document: DE

Date of ref document: 20060803

Kind code of ref document: P

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060921

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060921

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060922

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20061002

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20061019

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20061031

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20061121

NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

EN Fr: translation not filed
26N No opposition filed

Effective date: 20070322

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20070309

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060922

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20061019

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060621

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060621

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20161020

Year of fee payment: 17

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20171019

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20171019