EP0112045B1 - Compositions détergentes - Google Patents

Compositions détergentes Download PDF

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Publication number
EP0112045B1
EP0112045B1 EP83306947A EP83306947A EP0112045B1 EP 0112045 B1 EP0112045 B1 EP 0112045B1 EP 83306947 A EP83306947 A EP 83306947A EP 83306947 A EP83306947 A EP 83306947A EP 0112045 B1 EP0112045 B1 EP 0112045B1
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EP
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Prior art keywords
weight
composition according
detergent
detergent composition
active
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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
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EP83306947A
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German (de)
English (en)
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EP0112045A1 (fr
Inventor
Appaya Raghunath Naik
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Unilever NV
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Unilever NV
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Priority to AT83306947T priority Critical patent/ATE25101T1/de
Publication of EP0112045A1 publication Critical patent/EP0112045A1/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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0094—High foaming 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
    • 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
    • C11D1/123—Sulfonic acids or sulfuric acid esters; Salts thereof derived from carboxylic acids, e.g. sulfosuccinates
    • 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
    • C11D3/04—Water-soluble compounds
    • C11D3/046—Salts

Definitions

  • the present invention relates to high-foaming liquid detergent compositions suitable for use in fabric washing, shampoos, and above all, in manual dishwashing operations in both hard and soft water.
  • GB - A-1 429 637 discloses hand dishwashing compositions containing as detergent-active material a water-soluble salt of a di(C,-C 9 ) alkyl ester of sulphosuccinic acid, in combination with an alkyl sulphate or an alkyl ether sulphate.
  • GB-A-1 164 8541Shell discloses the inclusion of 0.5 to 10% by weight of a water-soluble inorganic magnesium salt in aqueous liquid detergent compositions based on an alkyl or aryl sulphonate in conjunction with an alkyl ether sulphate or a nonionic detergent.
  • the present invention is based on the observation that the presence of small quantities of magnesium ions, derived from an added electrolyte, in liquid detergent compositions based on dialkyl sulphosuccinates gives both performance and formulation benefits.
  • the present invention accordingly provides a foaming liquid detergent composition in the form of a clear, stable aqueous solution containing from 2 to 60% by weight of active detergent comprising at least 2% by weight, preferably at least 5% by weight, based on the whole composition, of a water-soluble salt of a dialkyl ester of sulphosuccinic acid as defined below, the composition containing from 0.02 to 0.24% by weight of magnesium ions derived from an added electrolyte.
  • magnesium ions arrive in the composition as part of an added water-soluble magnesium salt, for example, magnesium sulphate, chloride, or toluene or xylene sulphonate.
  • an added water-soluble magnesium salt for example, magnesium sulphate, chloride, or toluene or xylene sulphonate.
  • the amount of added magnesium salt is within the range of from 0.02 to 0.24% by weight of magnesium ions.
  • the optimum level of addition within these limits for any particular formulation will depend on the total active detergent concentration, the total level and type of electrolyte present and the hydrotrope level, and can readily be determined experimentally by one skilled in the art.
  • the magnesium ions are added to the compositions of the invention in the form of water-soluble magnesium salts which are electrolytes.
  • the preferred salts are magnesium sulphate and magnesium chloride.
  • magnesium chloride hexahydrate the limits given above correspond to 0.17 to 2.02% by weight; for magnesium sulphate heptahydrate, the limits given above correspond to 0.21 to 2.46% by weight.
  • the amount of added magnesium salt present in the compositions of the invention is preferably from 0.15 to 2.50% by weight, and more preferably from 0.50 to 1.50% by weight.
  • the total active detergent level of the compositions of the invention ranges from 2 to 60% by weight, preferably from 5 to 40% by weight.
  • the addition of magnesium salts in accordance with the invention is especially beneficial at total active detergent levels of 30% by weight and below. At the low end of the concentration range, 20% and below, the additional benefit of viscosity increase is observed.
  • the present invention alleviates the problem of low viscosities that can arise with low-active-detergent dialkyl sulphosuccinate-based compositions.
  • the dialkyl sulphosuccinate which is an essential detergent-active material in the composition of the invention, may be either symmetrical (both alkyl groups the same) or unsymmetrical. It may if desired be constituted by a mixture of materials of different chain lengths, of which the individual dialkyl sulphosuccinates themselves may be either symmetrical or unsymmetrical.
  • the detergent-active dialkyl sulphosuccinates are compounds of the formula I: wherein each of R 1 and R 2 , which may be the same or different, represents a straight-chain or branched-chain alkyl group having from 3 to 12 carbon atoms, preferably from 4 to 10 carbon atoms and more preferably from 6 to 8 carbon atoms, and X 1 represents a solubilising cation, that is to say, any cation yielding a salt of the formula I sufficiently soluble to be detergent-active.
  • the solubilising cation X 1 will generally be monovalent, for example, alkali metal, especially sodium; ammonium; or substituted ammonium, for example, ethanolamine.
  • the alkyl groups R 1 and R 2 in the dialkyl sulphosuccinate are preferably straight-chain or (in mixtures) predominantly straight-chain.
  • dialkyl sulphosuccinates that may advantageously be used in the composition of the invention are the C a lC s unsymmetrical materials described and claimed in GB-A-2 105 325, corresponding to EP-A 71412 (Unilever); the dioctyl sulphosuccinate/dihexyl sulphosuccinate mixtures described and claimed in GB-A-2 104 913 (Unilever) and the mixtures of symmetrical and unsymmetrical dialkyl sulphosuccinates described and claimed in GB-A-2 108 520 (Unilever) the last two publications corresponding to EP-A-71410 and 71411.
  • composition of the invention may of course with advantage contain other detergent-active agents in addition to the dialkyl sulphosuccinate, provided that the total composition contains at least 2% by weight, preferably at least 5%, of dialkyl sulphosuccinate(s).
  • the composition may, for example, include one or more of the sulphonate-type detergents conventionally used as the main detergent-active agent in liquid compositions, for example, alkylbenzene sulphonates (especially C 9 ⁇ C 15 linear alkylbenzene sulphonates), secondary alkane sulphonates, alpha-olefin sulphonates, alkyl glyceryl ether sulphonates, and fatty acid ester sulphonates.
  • dialkyl sulphosuccinates are themselves sulphonate-type detergents. If such additional sulphonate-type materials are present, the total sulphonate preferably predominates in the active detergent mixture of the composition of the invention. If no such additional sulphonate-type materials are present, the sulphosuccinate alone preferably predominates.
  • alkylbenzene sulphonates and secondary alkane sulphonates are especially preferred.
  • the ratio of dialkyl sulphosuccinate to alkylbenzene sulphonate or secondary alkane sulphonate is preferably within the range of from 4:1 to 0.1:1, more preferably from 2.5:1 to 1:1.
  • composition of the invention advantageously contains one or more further detergent-active materials in addition to the dialkyl sulphosuccinate and optional additional sulphonate already mentioned.
  • one or more alkyl ether sulphates and/or one or more ethoxylated nonionic detergents having an alkyl chain length of C s to C 15 and an average degree of ethoxylation of from 5 to 14.
  • Preferred alkyl ether sulphates are materials of the general formula wherein R 3 is a C 10 to C 18 alkyl group, X 2 is a solubilising cation, and n, the average degree of ethoxylation, is from 1 to 12.
  • R 3 is preferably a C11 to C 15 alkyl group and n is preferably from 1 to 8.
  • alkyl ether sulphate a range of differently ethoxylated materials, and some unethoxylated material, will be present and the value of n represents an average.
  • the unethoxylated material is, of course, alkyl sulphate.
  • additional alkyl sulphate may be admixed with the alkyl ether sulphate, to give a mixture in which the ethoxylation distribution is more weighted towards lower values.
  • alkyl ether sulphates containing less than 20% by weight of C, 4 and above material, as described and claimed in our copending application EP-A-112044, published 27.06.84.
  • Examples of preferred ether sulphates for use in the present invention are Dobanol (Registered Trade Mark) 23-3 and Dobanol (Registered Trade Mark) 23-2 ex Shell, both based on C 12 to C 13 (50% of each) primary alcohol (about 75% straight chain, 25% 2-methyl branched), and having average degrees of ethoxylation n of 3 and 2 respectively.
  • the ratio of dialkyl sulphosuccinate, plus any other sulphonate-type detergent present plus any alkyl sulphate present other than that intrinsically present in the ether sulphate, to ether sulphate, is preferably within the range of from 5:1 to 0.5 to 1, more preferably from 3:1 to 1:1.
  • Nonionic detergents that may be used in the composition of the invention include short-chain high-foaming ethoxylated alcohols of the general formula III: wherein R 4 is an alkyl group, preferably straight-chain, having from 8 to 12 carbon atoms, and the average degree of ethoxylation m is from 5 to 12.
  • the weight ratio of alkyl ether sulphate to nonionic detergent is preferably at least 1:1 and more preferably within the range of from 1.5:1 to 3:1, especially about 2:1.
  • An especially preferred nonionic detergent is Dobanol (Registered Trade Mark) 91-8 ex Shell, in which R 4 is C 9 ⁇ C 11 (predominantly straight-chain) and m is 8.
  • compositions of the invention include within their active detergent mixture a C 10 ⁇ C 18 carboxylic acid (C 2 ⁇ C 3 alkanol)amide, preferably a diethanolamide.
  • a C 10 ⁇ C 18 carboxylic acid (C 2 ⁇ C 3 alkanol)amide preferably a diethanolamide.
  • This material at a level not exceeding 30% by weight of the active detergent mixture, gives both performance and formulation advantages.
  • Our copending application EP-A-112046, published 27.06.84 describes and claims liquid detergent compositions containing a dialkyl sulphosuccinate, an alkyl ether sulphate and/or a nonionic detergent, and a C 10 ⁇ C 18 carboxylic acid di(C 2- C 3 )alkanolamide, the last-mentioned component being present in an amount not exceeding 30% by weight of the total active detergent present.
  • the composition of the invention will generally need to contain one or more hydrotropes.
  • hydrotropes are materials present in a formulation to control solubility, viscosity, clarity and stability, but which themselves make no active contribution to the performance of the product.
  • hydrotropes include lower aliphatic alcohols, especially ethanol; urea; lower alkylbenzene sulphonates such as sodium toluene and xylene sulphonates; and combinations of these. Hydrotropes are expensive and take up room in a formulation without contributing to its performance, and it is therefore desirable to use as small quantities of them as possible.
  • compositions of the invention may also contain the usual minor ingredients such as perfume, colour, preservatives and germicides.
  • liquid detergent compositions of the invention containing 2 to 60% by weight of active detergent in clear, stable aqueous solution, may be used for all normal detergent purposes where foaming is advantageous, for example, fabric washing products, general purpose domestic and industrial cleaning compositions, carpet shampoos, car wash products, personal washing products, shampoos, foam bath products, and, above all, manual dishwashing.
  • the dialkyl sulphosuccinate used was a statistical mixture (mole ratio 1:2:1) of di-n-octyl sulphosuccinate, n-hexyl n-octyl sulphosuccinate and di-n-hexyl sulphosuccinate, prepared from a 1:1 mixture of n-hexanol and n-octanol by the method described in Example 1 of GB-A-2 108 520, corresponding to EP-A-7141 and 71411, (Unilever).
  • This material contained 2.5% of sodium sulphate in a 40% solution, so that in the formulations the sodium sulphate level was 1% by weight.
  • the magnesium was added in the form of magnesium chloride hexahydrate.
  • Examples 1 and 2 were repeated using a dialkyl sulphosuccinate sample containing a lower level (1 %) of sodium sulphate, so that the overall level of that material in the composition was only 0.4% by weight. At this lower electrolyte level the urea content could be reduced to 11 %.
  • Examples 1 and 2 were repeated using a dialkyl sulpho-succinate sample free of electrolyte (sodium sulphate). The urea level was 10%.
  • This Example demonstrates the improvement in soft-water foaming performance obtained by the addition of magnesium chloride hexahydrate to a dialkyl sulphosuccinate/ether sulphate formulation.
  • the dialkyl sulphosuccinate used was the C a /C s statistical mixture of Example 2, at a concentration of 16% by weight, and the ether sulphate was Dobanol 23-2S, at a concentration of 8% by weight.
  • This composition without added magnesium chloride hexahydrate washed 23 plates, and with the addition of 1.0% by weight of magnesium chloride hexahydrate washed 27 plates.
  • This experiment shows the effect of the addition of a magnesium salt to a relatively low-concentration (16%) formulation containing a fatty acid diethanolamide in addition to a dialkyl sulphosuccinate and an alkyl ether sulphate.
  • the dialkyl sulphosuccinate was the Cg/Cg mixture used in Examples 1 and 2, containing 2.5% by weight of electrolyte (sodium sulphate) in a 40% solution.
  • the alkyl ether sulphate was Dobanol 23-3A, and the fatty acid diethanolamide was Empilan (Registered Trade Mark) CDE ex Albright & Wilson, a coconut diethanolamide.
  • This experiment illustrates the effect of the addition of a magnesium salt on a relatively low-concentration (18%) formulation containing an alkylbenzene sulphonate (Dob (Registered Trade Mark) 102 ex Shell) in addition to dialkyl sulphosuccinate and alkyl ether sulphate.
  • the dialkyl sulphosuccinate was as used in Examples 10-14.
  • Comparative Composition H already had excellent low-temperature stability.
  • the addition of 0.5% magnesium chloride increased the viscosity without detriment to the cloud point.
  • the higher level of magnesium chloride (1.0%) improved the viscosity further to the slight, but insignificant, detriment of the low-temperature stability.

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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)
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Claims (17)

1. Composition détergente liquide moussante sous forme d'une solution aqueuse limpide stable contenant de 2 à 60% en poids d'un mélange de détergents actifs, comprenant au moins 2% en poids, par rapport au total de la composition, d'un sel hydrosoluble d'un ester dialkylique d'acide suifosuccinique de formule (I):
Figure imgb0014
dans laquelle R1 et R2, qui peuvent être identiques ou différents, représentent chacun un radical alkyle à chaîne droite ou ramifiée contenant de 3 à 12 atomes de carbone, et X1 représente un cation solubilisant, caractérisée en ce que la composition comprend en outre de 0,02 à 0,24% en poids l'ions magnésium provenant d'un électrolyte ajouté.
2. Composition détergente selon la revendication 1, caractérisée en ce qu'elle comprend de 0,15 à 2,50% d'un sel de magnésium minéral ajouté choisi parmi le sulfate de magnésium, le chlorure de magnésium et des mélanges de ceux-ci.
3. Composition détergente selon la revendication 2, caractérisée en ce qu'elle comprend de 0,50 à 1,50% en poids de sel de magnésium ajouté.
4. Composition détergente selon l'une quelconque des revendications 1 à 3, caractérisée en ce que la concentration totale du détergent actif est de 5 à 40% en poids.
5. Composition détergente selon la revendication 4, caractérisée en ce que la concentration totale du détergent actif est de 5 à 30% en poids.
6. Composition détergente selon la revendication 5, caractérisée en ce que la concentration totale du détergent actif est de 5 à 20% en poids.
7. Composition détergente selon l'une quelconque des revendications 1 à 6, caractérisée en ce que le dialkylsulfosuccinate constitue au moins 5% en poids de la composition totale.
8. Composition détergente selon l'une quelconque des revendications 1 à 7, caractérisée en ce que les radicaux alkyle du dialkylsulfosuccinate contiennent chacun de 4 à 10 atomes de carbone.
9. Composition détergente selon la revendication 8, caractérisée en ce que les radicaux alkyle du dialkylsulfosuccinate contiennent chacun de 6 à 8 atomes de carbone.
10. Composition détergente selon l'une quelconque des revendications 1 à 9, caractérisée en ce que le mélange de détergents actifs comprend en outre un alkylbenzènesulfonate et/ou un s-alcane-sulfonate.
11. Composition détergente selon la revendication 10, caractérisée en ce que le rapport pondéral du dialkylsulfosuccinate à l'alkylbenzènesulfonate et/ou au s-alcanesulfonate est compris entre 2,5:1 et 1:1.
12. Composition détergente selon l'une quelconque des revendications 1 à 11, caractérisée en ce que le mélange des détergents actifs comprend encore un alkylpolyéthoxysulfate en C10-18 présentant un degré moyen d'éthoxylation de 1 à 12.
13. Composition détergente selon la revendication 12, caractérisée en ce que l'alkylpolyéthoxysulfate a une longueur de chaîne alkylique de C11 à C15.
14. Composition détergente selon la revendication 12 ou 13, caractérisée en ce que l'alkylpolyéthoxysulfate contient moins de 20% en poids de matières ayant une longueur de chaîne de C14 et plus.
15. Composition détergente selon l'une quelconque des revendications 12 à 14, caractérisée en ce que le rapport pondéral du dialkylsulfosuccinate plus d'éventuels alkylbenzènesulfonate et/ou s-alcane- sulfonate présents à l'alkylpolyéthoxysulfate est compris entre 5:1 et 0,5:1.
16. Composition détergente selon l'une quelconque des revendications 1 à 15, caractérisée en ce que le mélange des détergents actifs comprend encore un di(alcanol en C2―C3)amide d'acide carboxylique en C10-18 en une proportion ne dépassant pas 30% du poids du mélange des détergents actifs.
17. Composition détergente selon la revendication 1, caractérisée en ce que le système détergent actif comprend essentiellement:
(a) (i) un sel hydrosoluble et l'ester dialkylique d'acide sulfosuccinique de formule (I) et facultativement
(ii) un alkylbenzènesulfonate et/ou un s-alcanesulfonate, et
(b) (i) un alkylpolyéthoxysulfate en C10-18 ayant un degré moyen d'éthoxylation de 1 à 12, et, facultativement,
(ii) un surfactif non ionique éthoxylé en C8-15 ayant un degré moyen d'éthoxylation de 5 à 14, le rapport pondéral de (b) (i) à (b) (ii) étant d'au moins 1:1,

le rapport pondéral de (a) à (b) étant compris entre 5:1 et 0,5:1 et, facultativement,
(c) un di(alcanol en C2-C3)amide d'acide carboxylique en C10-18 en une quantité de 0 à 30% du poids total du système détergent actif.
EP83306947A 1982-11-16 1983-11-14 Compositions détergentes Expired EP0112045B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT83306947T ATE25101T1 (de) 1982-11-16 1983-11-14 Detergenszusammensetzungen.

Applications Claiming Priority (2)

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GB8232687 1982-11-16
GB8232687 1982-11-16

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EP0112045A1 EP0112045A1 (fr) 1984-06-27
EP0112045B1 true EP0112045B1 (fr) 1987-01-21

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EP83306947A Expired EP0112045B1 (fr) 1982-11-16 1983-11-14 Compositions détergentes

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EP (1) EP0112045B1 (fr)
JP (1) JPS6050399B2 (fr)
AT (1) ATE25101T1 (fr)
AU (1) AU550658B2 (fr)
BR (1) BR8306255A (fr)
CA (1) CA1220694A (fr)
DE (1) DE3369343D1 (fr)
DK (1) DK523383A (fr)
GB (1) GB2130237B (fr)
GR (1) GR81252B (fr)
IN (1) IN158158B (fr)
NO (1) NO834151L (fr)
NZ (1) NZ206210A (fr)
PH (1) PH18169A (fr)
PT (1) PT77672A (fr)
ZA (1) ZA838428B (fr)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8301745D0 (en) * 1983-01-21 1983-02-23 Unilever Plc Detergent compositions
JPS59145778A (ja) * 1983-02-09 1984-08-21 Ushio Inc 光化学蒸着装置
GB8420945D0 (en) * 1984-08-17 1984-09-19 Unilever Plc Detergents compositions
FR2622205B1 (fr) * 1987-10-21 1990-04-13 Univ Toulouse Utilisation de sels de metaux alcalins et alcalino-terreux pour rendre visqueuses des solutions aqueuses de surfactifs anioniques, et compositions visqueuses ainsi obtenues
US5279677A (en) * 1991-06-17 1994-01-18 Coral International, Inc. Rinse aid for metal surfaces
WO1995007969A1 (fr) * 1993-09-14 1995-03-23 The Procter & Gamble Company Produit pour laver la vaisselle a la main
CA2629248A1 (fr) * 2005-11-15 2007-05-24 The Procter & Gamble Company Composition detergente de lavage liquide avec un agent tensioactif de sulfate ou sulfonate d'alkyle ou d'hydroxyalkyle d'origine naturelle et des agents tensioactifs de type oxyded'amine a chaine moyenne ramifiee
US8252122B2 (en) 2009-03-17 2012-08-28 Bbt Bergedorfer Biotechnik Gmbh Use of an agent that contains carbamide and/or at least a derivative thereof as a cleaning agent

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DK131158A (fr) * 1967-08-25
GB1513550A (en) * 1975-05-05 1978-06-07 Unilever Ltd Hard surface cleaning compositions
AU543961B2 (en) * 1981-07-24 1985-05-09 Unilever Plc Detergent compositions based on sulphosuccinotes
NZ201308A (en) * 1981-07-24 1985-08-16 Unilever Plc Dialkyl sulphosuccinates and detergent compositions

Also Published As

Publication number Publication date
ATE25101T1 (de) 1987-02-15
DE3369343D1 (en) 1987-02-26
AU2136383A (en) 1984-05-24
ZA838428B (en) 1985-07-31
JPS59126500A (ja) 1984-07-21
GB2130237A (en) 1984-05-31
PH18169A (en) 1985-04-09
GR81252B (fr) 1984-12-11
GB2130237B (en) 1986-06-18
NO834151L (no) 1984-05-18
IN158158B (fr) 1986-09-20
NZ206210A (en) 1986-05-09
JPS6050399B2 (ja) 1985-11-08
DK523383D0 (da) 1983-11-15
DK523383A (da) 1984-05-17
EP0112045A1 (fr) 1984-06-27
CA1220694A (fr) 1987-04-21
GB8330368D0 (en) 1983-12-21
PT77672A (en) 1983-12-01
BR8306255A (pt) 1984-06-19
AU550658B2 (en) 1986-03-27

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