EP0292193B1 - Composition détergente - Google Patents

Composition détergente Download PDF

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Publication number
EP0292193B1
EP0292193B1 EP19880304291 EP88304291A EP0292193B1 EP 0292193 B1 EP0292193 B1 EP 0292193B1 EP 19880304291 EP19880304291 EP 19880304291 EP 88304291 A EP88304291 A EP 88304291A EP 0292193 B1 EP0292193 B1 EP 0292193B1
Authority
EP
European Patent Office
Prior art keywords
detergent active
carbonate
weight
composition
water
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.)
Revoked
Application number
EP19880304291
Other languages
German (de)
English (en)
Other versions
EP0292193A1 (fr
Inventor
John Lloyd
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
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Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Publication of EP0292193A1 publication Critical patent/EP0292193A1/fr
Application granted granted Critical
Publication of EP0292193B1 publication Critical patent/EP0292193B1/fr
Anticipated expiration legal-status Critical
Revoked legal-status Critical Current

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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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/1233—Carbonates, e.g. calcite or dolomite
    • 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
    • C11D10/00—Compositions of detergents, not provided for by one single preceding group
    • C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
    • C11D3/126—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite in solid compositions

Definitions

  • This invention relates to a detergent composition, particularly to a detergent composition for washing and softening fabrics.
  • Detergent compositions generally contain in addition to a detergent active material to remove soil from fabrics, a detergency builder material whose role is primarily to prevent calcium ions in hard water from reducing the efficiency of the detergent active material.
  • a detergency builder material whose role is primarily to prevent calcium ions in hard water from reducing the efficiency of the detergent active material.
  • phosphates such as sodium tripolyphosphate have been used as detergency builders.
  • Harshening is a phenomena which occurs with many detergent compositions, where the feel of the fabric becomes harsh after washing. This occurs particularly with fabrics formed of natural fibres such as cotton and may be due in part to the removal of natural lubricating materials from the fibres of the fabric.
  • a number of materials are suggested in the art as fabric softeners, capable of reducing the degree of harshening obtained in the wash.
  • Such a class of materials are the smectite clays having a high exchange capacity as disclosed in GB1400898 (Procter & Gamble). It has been found however that such clays are most effective when used in the presence of a peptising agent, such as sodium tripolyphosphate. Such clays are less effective however in the absence of tripolyphosphate ions.
  • the art has not therefore recommended clays as effective fabric softening or anti-harshening agents for use with detergent compositions in which alkali metal carbonates are used in place of tripolyphosphate salts.
  • compositions containing a sodium carbonate/calcite builder mixture can be substantially overcome by the presence of a fabric softening clay material.
  • a detergent composition for washing and softening fabrics which is essentially free of phosphate builder and comprises:
  • compositions of the invention necessarily contain at least one non-soap detergent active material, preferably at a level of 5 to 40% by weight. These materials are preferably selected from non-soap anionic and nonionic detergent actives and mixtures thereof.
  • detergent active materials including soaps, may also be used but this will normally be in admixture with non-soap anionic and/or nonionic materials.
  • the non-soap (synthetic) anionic detergent active compound is usually the water-soluble alkali metal salt of an organic sulphate and sulphonate having alkyl radicals containing from about 8 to about 22 carbon atoms, the term alkyl being used to include the alkyl portion of higher acyl radicals.
  • suitable synthetic anionic detergent compounds are sodium and potassium alkyl sulphates, especially those obtained by sulphating higher (C8-C18) alcohols produced for example from tallow or coconut oil, sodium and potassium alkyl (C9-C20) benzene sulphonates, particularly sodium linear secondary alkyl (C10-C15) benzene sulphonates; sodium alkyl glyceryl ether sulphates, especially those ethers of the higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum; sodium coconut oil fatty monoglyceride sulphates and sulphonates; sodium and potassium salts of sulphuric acid esters of higher (C8-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 neutralised with sodium hydroxide; sodium and potassium salts of fatty acid amides of methyl taurine; alkane monos
  • Suitable nonionic detergent compounds include in particular the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for example aliphatic alcohols, acids, amides or alkyl phenols with alkylene oxides, especially ethylene oxide either alone or with propylene oxide.
  • Specific nonionic detergent compounds are alkyl (C6-C22) phenols-ethylene oxide condensates, generally up to 25 EO, ie up to 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 up to 40 EO, and products made by condensation of ethylene oxide with the reaction products of propylene oxide and ethylenediamine.
  • Other so-called nonionic detergent compounds include long chain tertiary amine oxides, long chain tertiary phosphine oxides and dialkyl sulphoxides.
  • the detergent active system is a mixture of soap and a non-soap anionic detergent active, and optionally with the further inclusion of a nonionic detergent active material.
  • Particularly preferred detergent active systems contain from 2 - 17% non-soap anionic detergent active, up to 8% nonionic detergent active, up to 8% soap and a ratio of nonionic to soap of from 3:1 to 1:3, most preferably from 2:1 to 1:2.
  • the term "soap" includes not only the usual alkali metal and alkaline earth metal salts of fatty acids, but also the organic salts which can be formed by complexing fatty acids with organic nitrogen-containing materials such as amines and derivatives thereof.
  • the soap comprises salts of higher fatty acids containing from 8 to 24 carbon atoms, preferably from 10 to 20 carbon atoms in the molecule, or mixtures thereof.
  • soaps include sodium stearate, sodium palmitate, sodium salts of tallow, coconut oil and palm oil fatty acids and complexes between stearic and/or palmitic fatty acid and/or tallow and/or coconut oil and/or palm oil fatty acids with water-soluble alkanolamines such as ethanolamine, di- or triethanolamine, and 2,2-dimethyl ethanolamine and N-containing ring compounds such as morpholine, 2′-pyrrolidone and their methyl derivatives.
  • water-soluble alkanolamines such as ethanolamine, di- or triethanolamine
  • 2,2-dimethyl ethanolamine and N-containing ring compounds such as morpholine, 2′-pyrrolidone and their methyl derivatives.
  • An essential ingredient of the composition is a water-soluble carbonate material as a builder. This is preferably sodium or potassium carbonate or a mixture thereof.
  • the water-soluble carbonate material includes some bicarbonate salt.
  • the carbonate salt may be fully neutralised but it is preferably partially neutralised, for example a sesquicarbonate may be used in partial replacement of the normal carbonate salt.
  • a preferred carbonate to bicarbonate weight ratio is from 10:1 to 1:2, most preferably from 6:1 to 1:1.
  • the amount of water-soluble carbonate material in the detergent composition can be varied widely, but the amount should be at least 5% by weight, such as from 10% to 40%, preferably 10% to 35% by weight.
  • the amount of the water-soluble carbonate material is determined on an anhydrous basis, though the salts may be hydrated either before or when incorporated into the detergent composition. It should be noted that it may also be desirable to limit the carbonate content to a lower level within the range mentioned, so as to decrease the risk of internal damage following any accident ingestion, for example by children.
  • further builder materials may be present, although materials which act as seed crystal poisons are best avoided.
  • further builder materials include fatty acids, selected water-soluble soaps, alkyl malonates, alkenyl or alkyl succinates, sodium fatty acid sulphonates, alkali metal orthophosphates, polyacetates, carboxylates, polycarboxylates, succinates and zeolites or their amorphous equivalents.
  • the composition necessarily contains a water-insoluble particulate carbonate material.
  • This material must be capable of acting as a seed crystal for the precipitate which results from the reaction between the calcium hardness ions of the water and the water-soluble carbonate.
  • this water-insoluble particulate materials is a seed crystal for calcium carbonate, such as calcium carbonate itself.
  • the water-insoluble particulate carbonate material must be finely divided, with a surface area of at least 10 m2/g, and preferably at least 15 m2/g.
  • the particularly preferred material has surface area from 30-100 m2/g. Insoluble carbonate material with surface areas in excess of 100 m2/g may be used, if such materials are economically available.
  • the high surface area material be prepared in the absence of poisons, so as to retain its seed activity.
  • the insoluble carbonate material will usually have an average particle size of less than 10 ⁇ m, as measured by sieve analysis, but may be granulated for ease of handling.
  • any crystalline form thereof may be used or a mixture thereof, but calcite is preferred as aragonite and vaterite are less readily available commercially, and calcite is a little less soluble than aragonite or vaterite at most usual wash temperatures.
  • any aragonite or vaterite is used it is generally in admixture with calcite.
  • the term 'calcite' is used to mean either calcite itself or any other suitable water-insoluble calcium carbonate seed material.
  • the selected level of calcite in the overall composition depends on the specific surface area as described above.
  • the amount of calcite used in the compositions should be from 10% to 60%, more preferably from 15% to 30%.
  • a weight ratio of water soluble carbonate material to calcite of less than about 4:1 is preferred.
  • a further essential component of the compositions of the present invention is a fabric softening clay material.
  • This clay material should be a phyllosilicate clay with a 2:1 layer structure, the non-silicate layer being either dioctahedrally or trioctahedrally coordinated and includes the species Saponite, Hectorite, Montmorillonite or Mauricellite.
  • Other 2:1 clay minerals such as Talc, Vermiculite, Mica and Chlorite have been proved to be unsuitable for fabric softening as have been the unaltered minerals of the 1:1 layered clays of the Kaolin group.
  • Other aluminosilicate materials which do not have a layer structure, such as zeolites are also unsuitable as fabric softening clay materials.
  • Particularly suitable clay materials are the smectite clays described in detail in United States Patent Specification US 3 959 155 (MONTGOMERY et al assigned to THE PROCTER & GAMBLE COMPANY), especially smectite clays such as described in United States Patent Specification US 3 936 537 (BASKERVILLE).
  • Other disclosures of suitable clay materials for fabric softening purposes include European patent specification EP 26528-A (PROCTER & GAMBLE LIMITED).
  • the most preferred clay fabric softening materials include those materials of bentonitic origin, bentonites being primarily montmorillonite type clays together with various impurities, the level and nature of which depends on the source of the clay material.
  • the level of fabric softening clay material in the compositions of the invention should be sufficient to provide the fabrics with a softening benefit.
  • a level of up to 35% by weight of the composition is suitable, preferably from 8% to 15%, these percentages referring to the level of the clay mineral per se .
  • Levels of clay raw material higher than this may be necessary when the raw material is derived from a particularly impure source.
  • the weight ratio of the seed crystal to the clay is less than 1.8 to 1. If a higher ratio is used, such as 3.0 to 1, we have found that the fabric softening benefit obtained from the clay is insufficient.
  • the detergent composition can optionally contain any of the conventional ingredients in the amounts in which such ingredients are normally employed in fabric washing detergent compositions.
  • One such optional ingredient is an alkali metal silicate, particularly sodium neutral, alkaline, meta- or orthosilicate.
  • a low level of silicate for example 5-10% by weight, is usually advantageous in decreasing the corrosion of metal parts in fabric washing machines, and it may give processing benefits. If higher levels of silicate are used up to a practical maximum of 30%, for example from 10% to 20% by weight, there can be a more noticeable improvement in detergency, which may permit some decrease in the water-soluble carbonate material content. This effect appears to be particularly beneficial when the wash liquor is used in water with appreciable levels of magnesium hardness.
  • the amount of silicate can also be used to some extent to control the equilibrium pH of the wash liquor, which is generally above 9, preferably 10-11 for an aqueous solution of the composition at the recommended concentration. Sodium silicate is commonly supplied in concentrated aqueous solution, but the amounts are calculated on an anhydrous basis.
  • lather boosters such as alkanolamides, particularly the monoethanolamides derived from palm kernel fatty acids and coconut fatty acids, lather depressants, oxygen-releasing bleaching agents such as sodium perborate and sodium percarbonate, peracid bleach precursors, chlorine-releasing bleaching agents such as trichloroisocyanuric acid, other fabric softening agents, inorganic salts such as sodium sulphate, and, usually present in very minor amounts, fluorescent agents, perfumes, enzymes such as proteases and amylases, germicides and colourants.
  • lather boosters such as alkanolamides, particularly the monoethanolamides derived from palm kernel fatty acids and coconut fatty acids
  • lather depressants oxygen-releasing bleaching agents such as sodium perborate and sodium percarbonate, peracid bleach precursors, chlorine-releasing bleaching agents such as trichloroisocyanuric acid, other fabric softening agents, inorganic salts such as sodium sulphate, and, usually present in
  • the detergent compositions may be produced by any of the techniques commonly employed in the manufacture of fabric washing detergent compositions, including slurry-making and spray-drying processes.
  • the composition may comprise spray-dried beads containing at least a part, such as all, of the detergent active system and the water-soluble carbonate, while the calcite or other seed crystal is added thereto as separate particles, which may be pre-granulated.
  • the clay material may be included in the slurry for the spray-dried beads or added separately to the composition either as a powder or as a pre-granulated material.
  • the composition may contain sodium silicate, it may be prepared by granulating a carbonate/silicate powder with the seed crystal material, ideally in the presence of a liquid binder such as sucrose solution, as described in more detail in South African patent 87/8350 (Unilever PLC).
  • compositions were prepared by spray-drying some ingredients to form a base powder and then adding other ingredients thereto.
  • Composition A was tested in the following manner. A 2.5kg fabric load comprising a mixture of prewashed and preharshened terry cotton monitors were washed for 30 minutes at 40°C or 95°C in an automatic washing machine. The water hardness was 24°FH and the product dosage was 140g into 20 litres of wash liquor. A similar wash liquor was prepared containing the same amount of composition A together with 17g of clay, being therefore equivalent to a composition (B) containing about 12% clay. After each wash the monitors were line dried and washed again. After 5 such washes the softness of the monitors was determined by a panel of trained assessors. Results are expressed as the number of preferences - the higher the score the softer the cloth. The results were:
  • compositions A and D were tested in the same manner as in Example 1 except that the wash load comprised naturally soiled articles, the wash temperature was 60°C and for each wash 70g of product was used for a pre-wash followed by 140g of product as a main wash.
  • the water hardness was 40°FH and softness assessments were made after 2 and 6 washes. The results were:
  • composition D was modified by post-dosing the clay and the calcite and the modified composition was tested, it was found to be very similar in softness performance to composition D.
  • compositions G to J were tested in the same manner as Example 1 except that the wash temperature was 60°C and the product dosage was 7.7 g/l.
  • a laboratory scale apparatus fitted with an impellor agitator was used, the fabric load consisting of pre-washed terry cotton monitors. Softness was assessed after 1 wash. The initial pH of the wash liquor was measured in each case. The results were:
  • compositions G and J were tested in the same way, either at 40°C or at 60°C and the fabric load included two different standard cotton detergency test cloths, and the observed % detergency results were: where ⁇ 95 is the confidence limit for a significant difference of 95% probability. It will be seen that although composition J exhibited the lower pH and was preferred in terms of softening, the observed detergency results are not significantly different.
  • compositions K to P were tested in the same manner as Example 3 and softness was assessed after 1 wash. The results were: These results show not only the benefit of adding bicarbonate to the compositions, but also that in the absence of bicarbonate there is a benefit for the inclusion of higher levels of soap and nonionic actives.

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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)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)

Claims (6)

  1. Composition détergente pour laver et adoucir des articles textiles, qui est sensiblement exempte de phosphates adjuvants et qui comprend :
    (i) de 2 à 40% en poids d'un système détergent actif comprenant au moins un détergent actif non savonneux ;
    (ii) de 5 à 40% en poids d'un adjuvant qui comprend un carbonate hydrosoluble en une quantité telle qu'il représente au moins 5% en poids de la composition ; et
    (iii) de 10 à 60% en poids d'un carbonate non hydrosoluble ayant une surface de contact d'au moins 10 m²/g sous forme de germe cristallin de carbonate de calcium ;
    caractérisée en ce que la composition comprend en outre :
    (iv) jusqu'à 35% en poids d'une argile d'adoucissement de textile ;
    le rapport pondéral des germes cristallins à l'argile étant inférieur à 1,8:1.
  2. Composition selon la revendication 1, dans laquelle le carbonate adjuvant hydrosoluble comprend un mélange d'un carbonate de métal alcalin et d'un bicarbonate de métal alcalin.
  3. Composition selon la revendication 1 ou 2, dans laquelle le système détergent actif comprend un détergent actif anionique non savonneux ou un mélange d'un détergent actif anionique non savonneux avec un détergent actif non ionique, la quantité du détergent actif anionique non savonneux étant supérieure à la quantité du détergent actif non ionique.
  4. Composition selon l'une quelconque des revendications précédentes, dans laquelle le système détergent actif comprend un mélange de savon et d'un détergent actif anionique non savonneux.
  5. Composition selon la revendication 4, dans laquelle le système détergent actif comprend également un détergent actif non ionique.
  6. Composition selon l'une quelconque des revendications précédentes, dans laquelle une partie au moins du système détergent actif et de l'adjuvant carbonate hydrosoluble est sous forme de granules séchés par pulvérisation, les autres ingrédients dont une partie au moins du germe cristallin étant présents sous forme de particules séparées.
EP19880304291 1987-05-14 1988-05-12 Composition détergente Revoked EP0292193B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB878711423A GB8711423D0 (en) 1987-05-14 1987-05-14 Detergent composition
GB8711423 1987-05-14

Publications (2)

Publication Number Publication Date
EP0292193A1 EP0292193A1 (fr) 1988-11-23
EP0292193B1 true EP0292193B1 (fr) 1992-09-23

Family

ID=10617340

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19880304291 Revoked EP0292193B1 (fr) 1987-05-14 1988-05-12 Composition détergente

Country Status (14)

Country Link
EP (1) EP0292193B1 (fr)
JP (1) JPS63301300A (fr)
KR (1) KR910004891B1 (fr)
AU (1) AU595115B2 (fr)
BR (1) BR8802263A (fr)
DE (1) DE3874806T2 (fr)
ES (1) ES2035286T3 (fr)
GB (1) GB8711423D0 (fr)
IN (1) IN166786B (fr)
MY (1) MY103564A (fr)
NO (1) NO170495C (fr)
PH (1) PH23926A (fr)
TR (1) TR23435A (fr)
ZA (1) ZA883402B (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2223028A (en) * 1988-06-28 1990-03-28 Unilever Plc Detergent composition including fabric softening clay
GB8904750D0 (en) * 1989-03-02 1989-04-12 Unilever Plc Agglomerates for addition to detergent powders
GB9303721D0 (en) * 1993-02-24 1993-04-14 Unilever Plc Detergent composition
GB2415964B (en) * 2004-07-03 2008-04-16 Appaya Raghunath Naik Detergent formulations based on soap and fatty acid N-methyl glucamides
CN102257113B (zh) * 2008-12-16 2013-05-08 荷兰联合利华有限公司 固体助洗剂组合物
IN2014MN00943A (fr) * 2011-12-01 2015-04-24 Unilever Plc

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1400898A (en) * 1972-07-14 1975-07-16 Procter & Gamble Detergent compositions

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1437950A (en) * 1972-08-22 1976-06-03 Unilever Ltd Detergent compositions
GB1583081A (en) * 1977-05-18 1981-01-21 Unilever Ltd Production of detergent compositions
US4141841A (en) * 1977-07-18 1979-02-27 The Procter & Gamble Company Antistatic, fabric-softening detergent additive
US4626364A (en) * 1985-01-28 1986-12-02 Colgate-Palmolive Company Particulate fabric softening and antistatic built detergent composition and particulate agglomerate for use in manufacture thereof
GB8603667D0 (en) * 1986-02-14 1986-03-19 Unilever Plc Detergent composition

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1400898A (en) * 1972-07-14 1975-07-16 Procter & Gamble Detergent compositions

Also Published As

Publication number Publication date
AU595115B2 (en) 1990-03-22
EP0292193A1 (fr) 1988-11-23
NO882050L (no) 1988-11-15
IN166786B (fr) 1990-07-14
DE3874806D1 (de) 1992-10-29
NO170495C (no) 1992-10-21
NO882050D0 (no) 1988-05-11
MY103564A (en) 1993-08-28
JPS63301300A (ja) 1988-12-08
AU1587788A (en) 1988-11-17
JPH0471960B2 (fr) 1992-11-17
NO170495B (no) 1992-07-13
PH23926A (en) 1990-01-23
ZA883402B (en) 1990-01-31
GB8711423D0 (en) 1987-06-17
TR23435A (tr) 1989-12-29
KR880014091A (ko) 1988-12-22
BR8802263A (pt) 1988-12-06
KR910004891B1 (ko) 1991-07-15
ES2035286T3 (es) 1993-04-16
DE3874806T2 (de) 1993-04-08

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