EP0337274B1 - Compositions détergentes pour tissus - Google Patents

Compositions détergentes pour tissus Download PDF

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Publication number
EP0337274B1
EP0337274B1 EP89105946A EP89105946A EP0337274B1 EP 0337274 B1 EP0337274 B1 EP 0337274B1 EP 89105946 A EP89105946 A EP 89105946A EP 89105946 A EP89105946 A EP 89105946A EP 0337274 B1 EP0337274 B1 EP 0337274B1
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EP
European Patent Office
Prior art keywords
sodium
precursor
fabric
bleach
composition
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
EP89105946A
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German (de)
English (en)
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EP0337274A3 (en
EP0337274A2 (fr
Inventor
David William Roberts
Peter Stanford Sims
David William Thornthwaite
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
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Unilever PLC
Unilever NV
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Publication date
Priority claimed from GB888808836A external-priority patent/GB8808836D0/en
Priority claimed from GB888809729A external-priority patent/GB8809729D0/en
Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Publication of EP0337274A2 publication Critical patent/EP0337274A2/fr
Publication of EP0337274A3 publication Critical patent/EP0337274A3/en
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Publication of EP0337274B1 publication Critical patent/EP0337274B1/fr
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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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • C11D3/3915—Sulfur-containing compounds
    • 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
    • C11D17/0004—Non aqueous liquid compositions comprising insoluble particles

Definitions

  • This invention relates to fabric-washing compositions. More particularly it relates to an improved low temperature bleaching fabric-washing composition comprising a peroxide compound, a peroxyacid bleach precursor and enzymes.
  • active oxygen-releasing peroxide compounds are effective bleaching agents. These compounds are frequently incorporated in detergent compositions for stain and soil removal. They have, however, an important limitation: the activity is extremely temperature-dependent. Thus, active oxygen-releasing bleaches are essentially only practical when the bleaching solution is heated above 60°C. At a bleach solution temperature of about 60°C, extremely high amounts of the active oxygen-releasing compounds must be added to achieve any bleaching effect. This is both economically and practically disadvantageous. As the bleach solution temperature is lowered below 60°C, peroxide compounds, e.g. sodium perborate, are rendered ineffective, regardless of the level of peroxide compound added to the system.
  • peroxide compounds e.g. sodium perborate
  • peroxide compounds are commonly used as a detergent adjuvant in textile wash processes that utilize an automatic household washing machine operating at wash water temperatures of below 60°C. Such wash temperatures are utilized because of textile care and energy considerations. Consequently, a constant need has developed of substances which render peroxide compound bleaches more effective at bleach solution temperatures below 60°C. These substances are generally referred to in the art as bleach precursors, promoters or activators.
  • the precursor is a reactive compound of the N-acyl or O-acyl type such as a carboxylic acid ester that in alkaline solution containing a source of hydrogen peroxide, e.g. a persalt, such as sodium perborate, will generate the corresponding peroxyacid, which is more reactive than peroxide compounds alone.
  • a source of hydrogen peroxide e.g. a persalt, such as sodium perborate
  • the reaction involves nucleophilic substitution on to the precursor molecule by perhydroxide anions (HOO ⁇ ) and is facilitated by precursors having good leaving groups. Often this reaction is referred to as perhydrolysis.
  • perhydrolysis Numerous substances have been proposed in the art as effective bleach precursors, promoters or activators, such as disclosed in a series of articles by Allan H.
  • the precursor is also a hydrolysable material which can react with moisture and alkaline components of the detergent compositions during storage, forming non-reactive products.
  • This reaction referred to as hydrolysis, causes loss of precursor during storage when incorporated in detergent compositions, the extent of which is highly dependent upon the ease at which the precursor undergoes the hydrolysis reaction.
  • TAED N,N,N',N'-tetraacetylethylene diamine
  • TAED One drawback of TAED, however, is the sluggishness of the peroxyacid release from the reaction with the peroxide compound liberating hydrogen peroxide, such as sodium perborate, sodium percarbonate, sodium persilicate, urea peroxide and the like, resulting in a non-optimal bleaching effect.
  • TAED can thus be classed as a slow-acting precursor, which can be incorporated in enzymatic alkaline detergent compositions without undue stability problems.
  • TAED has a solubility in water, i.e. somewhere in the region of 1%, which is another reason for the non-optimal bleaching performance of TAED/H2O2 systems.
  • TAED/peroxide compound systems With the trend towards still lower fabric-washing temperatures, to e.g. 40°C and below, there is an incentive to improve on the bleaching performance of TAED/peroxide compound systems.
  • One option is to replace TAED by a more reactive precursor, such as for example sodium p-acetoxybenzene sulphonate as disclosed in GB patent 846,798.
  • EP-A-0098129 is concerned with forming aliphatic peroxy acids in wash solution by reaction of certain types of peroxyacid precursors with alkaline hydrogen peroxide.
  • the precursor is added in the form of a detergent additive product comprising the precursor in combination with a non-particulate flexible substrate.
  • EP-A-0241137 is concerned with forming a storage-stable liquid laundry bleach formulation containing peracid precursors.
  • a disadvantage of such more reactive precursors is that they tend to (per)hydrolyse more readily than tetraacetylethylene diamine (TAED), and hence suffer from a more severe decomposition problem during storage.
  • TAED tetraacetylethylene diamine
  • Another disadvantage of more reactive precursors is that they tend to more readily attack enzymes, especially proteolytic enzymes, which as a class is an essential ingredient in the majority of current household fabric-washing compositions.
  • the invention therefore provides an improved alkaline fabric-washing composition
  • a surface-active material comprising a surface-active material, detergency builders, a peroxide compound bleach, a peroxyacid bleach precursor and a proteolytic enzyme, characterized in that said peroxyacid bleach precursor is a carboxylic acid ester of the following specific structural formulae: wherein R is an unsubstituted alkyl group containing 1 to 4 carbon atoms or a phenyl group; and M is hydrogen, alkali metal, alkaline earth metal, ammonium or alkyl or hydroxyalkyl substituted ammonium cation.
  • the alkaline fabric-washing compositions of the invention comprising the peroxyacid bleach precursor described herein will have a 2-5 g/l solution pH of 8.5-10.5.
  • the compounds of the invention are much more reactive than TAED and are surprisingly stable upon storage both alone and when mixed with additional components in alkaline fabric-washing detergent compositions.
  • Hydrogen peroxide sources are well known in the art. They include the alkali metal peroxides, organic peroxide bleaching compounds such as urea peroxide, and inorganic persalt bleaching compounds, such as the alkali metal perborates, percarbonates, perphosphates and persulphates. Mixtures of two or more such compounds may also be suitable. Particularly preferred are sodium perborate tetrahydrate and, especially, sodium perborate monohydrate. Sodium perborate monohydrate is preferred because it has excellent storage stability while also dissolving very quickly in aqueous bleaching solutions. Rapid dissolution is believed to permit formation of higher levels of percarboxylic acid which would enhance surface bleaching performance.
  • the molar ratio of hydrogen peroxide (or a peroxide compound generating the equivalent amount of H2O2) to precursor will range from 0.5:1 to about 20:1, preferably 1:1 to 15:1, most preferably from 2:1 to 10:1.
  • a detergent formulation of the invention containing a bleach system consisting of an active oxygen-releasing material and the specific carboxylic acid ester as herein defined will, in addition to surface-active materials, detergency builders and enzymes, usually also contain other known ingredients of such formulations.
  • the peroxyacid bleach precursor may be present at a level ranging from about 0.1% to 20% by weight, preferably from 0.5% to 10% by weight, particularly from 1% to 7.5% by weight, together with a peroxide bleaching compound, e.g. sodium perborate mono- or tetrahydrate, the amount of which is usually within the range of from about 2% to 40%, preferably from about 4% to 30%, particularly from about 10% to 25% by weight.
  • a peroxide bleaching compound e.g. sodium perborate mono- or tetrahydrate
  • the surface-active material may be naturally derived, such as soap, or a synthetic material selected from anionic, nonionic, amphoteric, zwitterionic, cationic actives and mixtures thereof. Many suitable actives are commercially available and are fully described in literature, for example in "Surface Active Agents and Detergents", Volumes I and II, by Schwartz, Perry and Berch.
  • the total level of the surface-active material may range up to 50% by weight, preferably being from about 1% to 40% by weight of the composition, most preferably 4% to 25%.
  • Synthetic anionic surface actives are usually water-soluble alkali metal salts of organic sulphates and sulphonates having alkyl radicals containing from 8 to 22 carbon atoms, the term alkyl being used to include the alkyl portion of higher aryl radicals.
  • suitable synthetic anionic detergent compounds are sodium and ammonium alkyl sulphates, especially those obtained by sulphating higher (C8-C18) alcohols produced, for example, from tallow or coconut oil; sodium and ammonium alkyl (C9-C20) benzene sulphonates, particularly sodium linear secondary alkyl (C10-C15) benzene sulphonates; sodium alkyl glyceryl ether sulphates, especially those esters of the higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum; sodium coconut oil fatty acid monoglyceride sulphates and sulphonates; sodium and ammonium salts of sulphuric acid esters of higher (C9-C18) fatty alcohol alkylene oxide, particularly ethylene oxide, reaction products; the reaction products of fatty acids such as coconut fatty acids esterified with isethionic acid and neutralized with sodium hydroxide; sodium and ammonium salts of fatty acid amides of
  • nonionic surface-active compounds which may be used, preferably together with the anionic surface-active compounds, include in particular the reaction products of alkylene oxides, usually ethylene oxide, with alkyl (C6-C22) phenols, generally 5-25 EO, i.e. 5-25 units of ethylene oxide per molecule; the condensation products of aliphatic (C8-C18) primary or secondary linear or branched alcohols with ethylene oxide, generally 6-30 EO, and products made by condensation of ethylene oxide with the reaction products of propylene oxide and ethylene diamine.
  • alkylene oxides usually ethylene oxide
  • alkyl (C6-C22) phenols generally 5-25 EO, i.e. 5-25 units of ethylene oxide per molecule
  • condensation products of aliphatic (C8-C18) primary or secondary linear or branched alcohols with ethylene oxide generally 6-30 EO
  • nonionic surface actives include alkyl polyglycosides, long chain tertiary amine oxides, long chain
  • Amounts of amphoteric or zwitterionic surface-active compounds can also be used in the compositions of the invention, but this is not normally desired owing to their relatively high cost. If any amphoteric or zwitterionic detergent compounds are used, it is generally in small amounts in compositions based on the much more commonly used synthetic anionic and nonionic actives.
  • soaps may also be incorporated in the compositions of the invention, preferably at a level of less than 25% by weight. They are particularly useful at low levels in binary (soap/anionic) or ternary mixtures together with nonionic or mixed synthetic anionic and nonionic compound.
  • Soaps which are used are preferably the sodium, or, less desirably, potassium salts of saturated or unsaturated C10-C24 fatty acids or mixtures thereof.
  • the amount of such soaps can be varied between 0.5% and 25% by weight, with lower amounts of 0.5% to 5% being generally sufficient for lather control. Amounts of soap between 2% and 20%, especially between 5% and 10%, are used to give a beneficial effect on detergency. This is particularly valuable in compositions used in hard water when the soap acts as a supplementary builder.
  • the detergent compositions of the invention also contain a detergency builder.
  • Builder materials may be selected from 1) calcium sequestrant materials, 2) precipitating materials, 3) calcium ion-exchange materials and 4) mixtures thereof.
  • Examples of calcium sequestrant builder materials include alkali metal polyphosphates, such as sodium tripolyphosphate; nitrilotriacetic acid and its water-soluble salts; the alkali metal salts of carboxymethyloxy succinic acid, ethylene diamine tetraacetic acid, oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids, citric acid; and polyacetal carboxylates as disclosed in US patents 4,144,226 and 4,146,495.
  • alkali metal polyphosphates such as sodium tripolyphosphate
  • the alkali metal salts of carboxymethyloxy succinic acid, ethylene diamine tetraacetic acid, oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids, citric acid and polyacetal carboxylates as disclosed in US patents 4,144,226 and 4,146,495.
  • precipitating builder materials examples include sodium orthophosphate, sodium carbonate and long chain fatty acid soaps.
  • Examples of calcium ion-exchange builder materials include the various types of water-insoluble crystalline or amorphous aluminosilicates, of which zeolites are the best known representatives.
  • compositions of the invention may contain any one of the organic or inorganic builder materials, such as sodium or potassium tripolyphosphate, sodium or potassium pyrophosphate, sodium or potassium orthophosphate, sodium carbonate or sodium carbonate/calcite mixtures, the sodium salt of nitrilotriacetic acid, sodium citrate, carboxymethyl malonate, carboxymethyloxy succinate and the water-insoluble crystalline or amorphous aluminosilicate builder materials, or mixtures thereof.
  • the organic or inorganic builder materials such as sodium or potassium tripolyphosphate, sodium or potassium pyrophosphate, sodium or potassium orthophosphate, sodium carbonate or sodium carbonate/calcite mixtures, the sodium salt of nitrilotriacetic acid, sodium citrate, carboxymethyl malonate, carboxymethyloxy succinate and the water-insoluble crystalline or amorphous aluminosilicate builder materials, or mixtures thereof.
  • These builder materials may be present at a level of, for example, from 5% to 80% by weight, preferably from 10% to 60% by weight.
  • proteolytic enzymes which are suitable for use in the present invention are normally solid, catalytically active protein materials which degrade or alter protein types of stains when present as in fabric stains in a hydrolysis reaction. They may be of any suitable origin, such as vegetable, animal, bacterial or yeast origin.
  • proteolytic enzymes or proteases of various qualities and origins and having activity in various pH ranges of from 4-12 are available and can be used in the composition of the present invention.
  • suitable proteolytic enzymes are the subtilisins which are obtained from particular strains of B . subtilis and B . licheniformis , such as the commercially available subtilisins Maxatase®, as supplied by Gist-Brocades N.V., Delft, Holland, and Alcalase®, as supplied by Novo Industri A/S, Copenhagen, Denmark.
  • protease obtained from a strain of Bacillus having maximum activity throughout the pH range of 8-12, being commercially available e.g. from Novo Industri A/S under the registered trade names Esperase® and Savinase®.
  • Esperase® obtained from Novo Industri A/S under the registered trade names Esperase® and Savinase®.
  • the preparation of these and analogous enzymes is described in British Patent Specification N° 1,243,784.
  • proteases are pepsin, trypsin, chymotrypsin, collagenase, keratinase, elastase, papain, bromelin, carboxypeptidases A and B, aminopeptidase and aspergillopeptidases A and B.
  • the amount of proteolytic enzymes normally used in the composition of the invention may range from 0.001% to 10% by weight, preferably from 0.01% to 5% by weight, depending upon their activity. They are generally incorporated in the form of granules, prills or "marumes" in an amount such that the final washing product has proteolytic activity of from about 2-20 Anson units per kilogram of final product.
  • the detergent compositions of the invention can contain any of the conventional additives in the amounts in which such materials are normally employed in fabric-washing detergent compositions.
  • these additives include lather boosters, such as alkanolamides, particularly the monoethanol amides derived from palmkernel fatty acids and coconut fatty acids; lather depressants, such as alkyl phosphates and silicones; anti-redeposition agents, such as sodium carboxymethyl cellulose and alkyl or substituted alkyl cellulose ethers; peroxide stabilizers, such as ethylene diemine tetraacetic acid, ethylene diamine tetra (methylene phosphonic acid) and diethylene triaminepenta (methylene phosphonic acid); fabric-softening agents including clays, inorganic salts, such as sodium sulphate, and, usually present in very small amounts, fluorescent agents, perfumes, other enzymes, such as cellulases, lipases and amylases, germicides and colorants.
  • polymeric materials such as polyacrylic acid, polyethylene glycol and the copolymers (meth)acrylic acid and maleic acid, which may also be incorporated to function as auxiliary builders together with any of the principal detergency builders such as the polyphosphates, aluminosilicates and the like.
  • the bleach precursors will advantageously be presented in the form of particulate bodies comprising said bleach precursor and a binder or agglomerating agent.
  • Many and diverse methods of preparing such precursor particulates have been described in various patent literature documents, such as e.g. in Canadian Patent N° 1,102,966; GB Patent N°1,561,333; US Patent N° 4,087,369; EP-A-0,240,057; EP-A-0,241,962; EP-A-0,101,634 and EP-A-0,062,523. Each of these methods may be selected and applied to the bleach precursor of the invention.
  • Particulates incorporating the precursors of the present invention are normally added to the spray-dried portion of the detergent composition with the other dry-mix ingredients, such as enzymes, inorganic peroxygen bleaches and suds depressants.
  • the detergent composition to which the precursor particulates are added may itself be made in a variety of ways, such as dry-mixing, agglomeration extrusion, flaking, etc., such ways being well known to those skilled in the art and not forming part of the present invention.
  • the peroxyacid precursors herein described are particularly suitable for incorporation in so-called non-aqueous liquid laundry detergent compositions containing an enzyme together with a peroxide bleaching compound, e.g. sodium perborate, to impart an effective cleaning and stain-removing capacity to the products on fabrics and textiles.
  • a peroxide bleaching compound e.g. sodium perborate
  • Non-aqueous liquid detergent compositions including paste-like and gelatinous detergent compositions in which the precursor compounds can be incorporated are known from the art and various formulations have been proposed, e.g. in US Patents 2,864,770; 2,940,938; 4,772,412; 3,368,977; GB-A-1,205,711; 1,270,040; 1,292,352; 1,370,377; 2,194,536; DE-A-2,233,771; and EP-A-0,028,849.
  • compositions which normally comprise a nonaqueous liquid medium with or without a solid phase dispersed therein.
  • the non-aqueous liquid medium may be a liquid surfactant, preferably a liquid nonionic surfactant; a non-polar liquid medium, e.g. liquid paraffin; a polar solvent, e.g. polyols, such as glycerol, sorbitol, ethylene glycol, optionally combined with low-molecular monohydric alcohols, e.g. ethanol or isopropanol; or mixtures thereof.
  • the solid phase can be builders, alkalis, abrasives, polymers, clays, other solid ionic surfactants, bleaches, enzymes, fluorescent agents and other usual solid detergent ingredients.
  • the following granular detergent composition was prepared by spray-drying an aqueous slurry: Composition Parts by weight sodium alkyl benzene sulphonate 6.0 C14-15 alcohol / 7 ethylene oxide 7.0 sodium soap 1.6 zeolite 24.0 alkaline silicate 0.5 polyacrylate 4.0 sodium carbonate 8.0 sodium carboxymethyl cellulose 0.5 ethylene diamine tetraacetate 0.2 fluorescer 0.2 salts 0.7
  • compositions of the invention containing the precursors 1) S-4-BOB and 2) S-3-BOB are superior to TAED in removing tea stains from fabrics at 40°C.
  • Samples of the finished powder formulations of Example II containing perborate, enzyme and unprotected precursors were stored in open phials at 25°C and 81% R.H. for seven days.
  • Enzyme activities were determined in the stored samples after seven days and compared with the freshly made samples.
  • the results presented in Table III as percentage loss of enzyme activity were the average of duplicate storage tests: Table III Precursor % loss of enzyme activity S-4-BOB 20 S-3-BOB 14 TAED 33

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
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  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
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Claims (4)

  1. Composition basique détergente de tissu comprenant une matière tensio-active, des adjuvants de détergence, un composé de blanchiment peroxyde, un précurseur de blanchiment de peroxyacide et un enzyme protéolytique, caractérisée en ce que ledit précurseur de blanchiment de peroxyacide est un ester d'acide carboxylique de structure spécifique suivante
    Figure imgb0004
     dans lesquelles R est un groupe alkyle non substitué contenant 1 à 4 atomes de carbone ou un groupe phényle; et M est un atome d'hydrogène, un métal alcalin, un métal alcalino-terreux, un cation ammonium ou un cation d'ammonium substitué par un groupe alkyle ou hydroxyalkyle.
  2. Composition selon la revendication 1, dans laquelle R est un groupe phényle.
  3. Composition selon la revendication 1, caractérisée en ce que sa solution à raison de 2 à 5 g a un pH de 8,5 à 10,5.
  4. Composition selon l'une quelconque des revendications 1 à 3, caractérisée en ce que la composition est une composition détergente liquide non aqueuse.
EP89105946A 1988-04-14 1989-04-05 Compositions détergentes pour tissus Expired - Lifetime EP0337274B1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
GB8808836 1988-04-14
GB888808836A GB8808836D0 (en) 1988-04-14 1988-04-14 Fabric washing compositions
GB8809729 1988-04-25
GB888809729A GB8809729D0 (en) 1988-04-25 1988-04-25 Bleach precursors & their use in bleaching &/detergent compositions

Publications (3)

Publication Number Publication Date
EP0337274A2 EP0337274A2 (fr) 1989-10-18
EP0337274A3 EP0337274A3 (en) 1990-08-29
EP0337274B1 true EP0337274B1 (fr) 1994-11-30

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EP89105946A Expired - Lifetime EP0337274B1 (fr) 1988-04-14 1989-04-05 Compositions détergentes pour tissus

Country Status (7)

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EP (1) EP0337274B1 (fr)
JP (1) JPH01306498A (fr)
AU (1) AU614350B2 (fr)
BR (1) BR8901766A (fr)
DE (1) DE68919506D1 (fr)
NO (1) NO172593C (fr)
TR (1) TR23958A (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8815841D0 (en) * 1988-07-04 1988-08-10 Unilever Plc Bleaching detergent compositions
AU3672989A (en) * 1988-09-06 1990-03-15 Clorox Company, The Proteolytic perhydrolysis system and method
US5078907A (en) * 1989-11-01 1992-01-07 Lever Brothers Company, Division Of Conopco, Inc. Unsymmetrical dicarboxylic esters as bleach precursors
US5183473A (en) * 1991-04-26 1993-02-02 Monsanto Company Enzyme activated peroxydisulfate bleach composition
DE4402053A1 (de) * 1994-01-25 1995-07-27 Henkel Kgaa Gerüststoff für Wasch- oder Reinigungsmittel
JPH07316591A (ja) * 1994-03-31 1995-12-05 Lion Corp 漂白性組成物
WO1998000510A2 (fr) 1996-06-28 1998-01-08 The Procter & Gamble Company Composition detergente liquide non aqueuse contenant des precurseurs de blanchiment

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB836988A (en) * 1955-07-27 1960-06-09 Unilever Ltd Improvements in or relating to bleaching and detergent compositions
EP0120591A1 (fr) * 1983-02-23 1984-10-03 The Procter & Gamble Company Ingrédients de détergents et leur utilisation dans des compositions de nettoyage et des procédés de lavage

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5922999A (ja) * 1982-06-30 1984-02-06 ザ・プロクタ−・エンド・ギヤンブル・カンパニ− 漂白組成物
GR79230B (fr) * 1982-06-30 1984-10-22 Procter & Gamble
DE3318110C2 (de) * 1983-05-18 1986-12-18 Siemens AG, 1000 Berlin und 8000 München Vorrichtung zum Bestücken von Leiterplatten
US4483778A (en) * 1983-12-22 1984-11-20 The Procter & Gamble Company Peroxygen bleach activators and bleaching compositions
US4772290A (en) * 1986-03-10 1988-09-20 Clorox Company Liquid hydrogen peroxide/peracid precursor bleach: acidic aqueous medium containing solid peracid precursor activator

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB836988A (en) * 1955-07-27 1960-06-09 Unilever Ltd Improvements in or relating to bleaching and detergent compositions
EP0120591A1 (fr) * 1983-02-23 1984-10-03 The Procter & Gamble Company Ingrédients de détergents et leur utilisation dans des compositions de nettoyage et des procédés de lavage

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Publication number Publication date
EP0337274A3 (en) 1990-08-29
AU614350B2 (en) 1991-08-29
EP0337274A2 (fr) 1989-10-18
NO172593B (no) 1993-05-03
AU3259989A (en) 1989-10-19
BR8901766A (pt) 1989-11-28
TR23958A (tr) 1991-01-11
NO891502L (no) 1989-10-16
NO172593C (no) 1993-08-11
JPH01306498A (ja) 1989-12-11
DE68919506D1 (de) 1995-01-12
NO891502D0 (no) 1989-04-12

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