EP0820503B1 - Improvements relating to light duty cleaning - Google Patents

Improvements relating to light duty cleaning Download PDF

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Publication number
EP0820503B1
EP0820503B1 EP96909119A EP96909119A EP0820503B1 EP 0820503 B1 EP0820503 B1 EP 0820503B1 EP 96909119 A EP96909119 A EP 96909119A EP 96909119 A EP96909119 A EP 96909119A EP 0820503 B1 EP0820503 B1 EP 0820503B1
Authority
EP
European Patent Office
Prior art keywords
alkyl
surfactant composition
surfactant
carrier
electrolyte
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
EP96909119A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0820503A1 (en
Inventor
Beatrice Michelin Helfant
Amauri Zanini Luna
Eduardo Luppy, Jr.
Pablo Andres Marques Marchant
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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=27160129&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0820503(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Priority claimed from BR9501520A external-priority patent/BR9501520A/pt
Priority claimed from BR9502064A external-priority patent/BR9502064A/pt
Priority claimed from BR9503351A external-priority patent/BR9503351A/pt
Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Publication of EP0820503A1 publication Critical patent/EP0820503A1/en
Application granted granted Critical
Publication of EP0820503B1 publication Critical patent/EP0820503B1/en
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
    • 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
    • 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
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/94—Mixtures with anionic, cationic or non-ionic 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
    • 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
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • 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
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/90—Betaines
    • C11D2111/18—

Definitions

  • the present invention is concerned with improvements relating to light duty cleaning and in particular to improvements relating to manual dishwashing.
  • EP 254653 (Cotelle SA and Henkel: 1986) relates to dilution-thickening concentrates in general and covers compositions which are thickened with excess NaCl.
  • WO 95/02664 discloses a liquid concentrate for dilution with water to give a thickened product.
  • the concentrate comprises: an alkyl ether sulphate, optional further anionic or nonionic or amphoteric, optional cationic alone or in combination with nonionic, electrolyte and/or hydrotrope.
  • the compositions disclosed in the above-mentioned documents can be sold as concentrates and are intended for dilution before use to give a thickened composition. Such rheological properties are considered advantageous for the cleaning of hard surfaces as they prevent the product running off the surface. With shampoo compositions, it is also advantageous for the product to thicken in the presence of water such that it is not washed of the skin rapidly.
  • WO-A-9416680 relates to dilution-thickening personal washing compositions which comprise 20-60% surfactant other than soap or primary alcohol sulphate and 1-20% electrolyte it has a sufficiently low viscosity for packing and dispensing but will thicken in use to a sufficiently high viscosity that it does not run off skin or hair when applied.
  • the compositions which are disclosed in detail in WO-A-9416680 comprise ether sulphate and betaine surfactants and sodium chloride as an electrolyte.
  • WO-A-9416680 refers to JP63-270533 which teaches dilution-thickening compositions based on soaps or primary alcohol sulphates as polyhydric alcohols.
  • compositions useful for this purpose may take the form of gels or pastes and may be applied to the surface of the articles with a cloth or sponge.
  • adsorbent carrier includes articles such as a cloth or sponge. The operative consideration is that the carrier can be used to carry the washing solution to the articles to be cleaned.
  • the present invention provides a light duty cleaning process which comprises the steps of:
  • a dilution thickening composition in combination with a carrier causes the surfactant to be retained on the carrier and released over a significantly longer period of time. Therefore in the method of the present invention the increased viscosity on dilution of selected compositions is beneficially combined with the delivering features of a porous substrate to extend the working lifetime of the substrate during the cleaning process
  • the present invention also provides a kit of parts comprising:
  • the compositions of the present invention comprise at least one surfactant whose solution viscosity is strongly influenced by the prevailing electrolyte concentration. While other means by which the viscosity can be increased on dilution are known, the use of an electrolyte is preferred.
  • the thickening of the diluted concentrate is effected by the presence of selected surface active agents whose thickening effect, in the concentrate, is reduced by the presence of an excess of dissolved electrolyte.
  • the concentration of dissolved electrolyte is reduced and the surface active agent component is then capable of exerting its thickening effect.
  • the carrier which is preferably a sponge
  • the carrier is treated with the surfactant composition either by dipping at least a part of the carrier in the composition or by otherwise exposing the carrier to the surfactant composition, such as by pouring or otherwise dispensing the surfactant composition onto the carrier.
  • the combination of the carrier and the composition is treated with water by dipping the combination into water.
  • Preferred surfactant concentrations range from 2-40%wt on product. Levels of total surfactant in the range 7.5-30%wt are particularly preferred.
  • Preferred electrolyte concentrations range from 1-30%wt with levels of 4-9%wt being most particularly preferred.
  • the surfactants include at least one anionic, zwitterionic or amphoteric surfactant.
  • Particularly preferred surfactants include one or more of ethoxylated alkyl ether sulphate, lauryl sulphate and amido propyl betaine.
  • alkyl ether sulphates of the general formula: R-O-(CH 2 -CH 2 O) n SO 3 - where R is C 8-18 alkyl and n is 1 - 5.
  • R is lauryl-.
  • the alkyl ether sulphate surfactants are preferably present at a level of 2-30%wt.
  • a particular preferred electrolyte sensitive surfactant is lauryl ammonium ether sulphate.
  • this component is present in the formulations of the invention at levels of 2-20%wt, more preferably 3-7%wt on product for relatively dilute products or 8-18% for concentrates.
  • Anionic surfactants which may be used in combination with the ether sulphate surface active agents include alkylaryl sulphonates, alcohols sulphates, phosphate esters, sulphosuccinates, sulphosuccinamates, alkane sulphonates, olefin sulphonates, petroleum sulphonates, sarcosinates, taurates, isethionates, and soaps.
  • anionic surfactants include those sold under the trade names Eltesol SX30[TM] (sodium xylene sulphonate), Empicol L2 [TM] (sodium lauryl sulphate), Triton H55[TM] (potassium phosphate ester), Marlinat DF8 (sodium sulphosuccinate), Hostapur SAS 30X[TM] (sodium alkane sulphonate), Hostapur OS[TM] (sodium olefin sulphonate), Petronate S[TM] (sodium petroleum sulphonate), Hamposyl L30[TM) (sodium lauroyl sarcosinate), Fenopon T33[TM] (sodium N-methyl-N-oleyl taurate), and Fenopon AC 78[TM] (sodium coconut isethionate).
  • Eltesol SX30[TM] sodium xylene sulphonate
  • these surfactants additional are alcohol sulphates, particularly C 8 - 18 alcohol sulphates and alkyl benezene sulphonates.
  • Typical levels of alcohol sulphates in compositions of the present invention range from 5-15%wt on product, more preferably 6-10%wt on product.
  • Typical levels of alkyl benzene sulphonate in compositions of the present invention range from 10-30% on product.
  • nonionic surfactant in combination with the ether sulphates surface active agents.
  • One particular class of nonionic surfactants for use in combination with the ether sulphate surface active agents comprises the amine oxides of the formula: R 1 R 2 R 3 -NO in which R 1 is a long chain alkyl group, typically containing 8 to 20 carbon atoms; and R 2 and R 3 are the same or different, lower alkyl group, typically containing 1-4 carbon atoms.
  • R 1 is a long chain alkyl group, typically containing 8 to 20 carbon atoms
  • R 2 and R 3 are the same or different, lower alkyl group, typically containing 1-4 carbon atoms.
  • alkyl dimethyl amine oxides such as sold under the trade name "Empigen OB" [TM] by Albright & Wilson.
  • nonionic surface active agents comprise polyalkoxylated fatty alcohols and their esters; polyalkoxylated fatty acids; polyalkoxylated alkyl phenols; alkanolamides; polyalkoxylated alkanolamides, glucosides, polyglucosides, sucrose and sugar esters, fatty esters, ethoxylated alkanolamides, ethoxylated long chain amines; alkyl amines, alkyl polyglucosides and alkyl polyglycosides.
  • nonionic surfactants are those sold under the trade names Synperonic A[TM] (alcohol ethoxylates), Crodet L24 [TM] (polyoxyethylene-24-lauric acid), Synperonic NP[TM] (nonyl phenyl ethoxylates), Empilan CME[TM] (coconut monoethanolamide), Triton CG110 [TM] (alkyl glucoside), Glucam E10 [TM] (10 mole ethoxylate of methyl glucoside), Crodesta SL 40[TM] (sucrose cocoate), Empilan MAA[TM] (ethoxylated coconut monoethanolamide), Ethomeen C12[TM] (ethoxylated coconut amine), and Tagosoft 16B[TM] (cetyl isooctanoate).
  • Synperonic A[TM] alcohol ethoxylates
  • Crodet L24 [TM] polyoxyethylene-24-lauric acid
  • Suitable amphoteric surfactants for use in combination with the ether sulphate surfactants include alkyl betaines, alkyl aminopropionates, alkyl iminodipropionates; alkyl glycinates; carboxyglycinates; alkyl imidazolines sulphobetaines; alkyl polyaminocarboxylates and polyamphocarboxyglycinates.
  • amphoteric surfactants are those sold under the trade names Tegobetain A4080[TM] (alkyl dimethyl betaine), Ampholax XCU[TM] (coco-amphoglycolate), Amphotensid CT[TM] (alkyl imidazoline based amphoteric), Ampholax XCO 30[TM] (cocoamphocarboxyglycinate) and Sandobet SC[TM] (cocoamide-sulphobetaine); and sodium N-coco-aminopropionate, disodium N-coco-iminodiproprionate, and cocoglycinate.
  • Tegobetain A4080[TM] alkyl dimethyl betaine
  • Ampholax XCU[TM] coco-amphoglycolate
  • Amphotensid CT[TM] alkyl imidazoline based amphoteric
  • Ampholax XCO 30[TM] cocoamphocarboxyglycinate
  • surfactants are betaines, preferably alkyl amido propyl betaines with an alkyl chain length of C 8 -C 18 . Coco amido propyl betaine is particularly preferred.
  • Typical levels of betaine in compositions according to the present invention range from 0.5-5.0%wt, more preferably 1-3%wt on product.
  • Suitable cationic surfactants for use in the concentrates of the invention includes alkyl quaternary ammonium halides; primary, secondary and tertiary amines and their salts; and polyamines.
  • Particular examples of such cationic surfactants are those sold under the trade names Empigen BAC[TM] (alkyl dimethyl benzalkonium chloride), Armac 1[TM] (tallow amine acetate-amine salts), Synprolam 35N3[TM] (N-alkyl propane propane diamine), and Synprolam 35X10[TM] (10 mole ethoxylated primary amine).
  • nonionic surfactants can be used in combination with the cationic surfactant.
  • the nonionic surfactant is preferably a nonionic surfactant as described above for use in combination with the ether sulphates.
  • the surfactants are sensitive to the presence of electrolyte
  • a broad range of electrolytes can be employed, provided that the electrolyte causes thickening of the surfactant at a first concentration and thinning of the surfactant, relative to the viscosity peak at a second, higher concentration.
  • Preferred electrolytes of present inventions are NaCl, MgCl 2 , MgSO 4 and mixtures thereof.
  • Other water-soluble electrolytes may be employed, including builders such as sodium, sodium phosphates and alkali metal silicates.
  • Typical electrolyte concentration is from 4.0 to 20% %w/w, preferred electrolyte concentration is from 4-15 %w/w, particularly preferred concentration is from 4-10% %w/w.
  • Preferred carriers comprise a porous or fibrous material.
  • porous materials are sponges which can be natural and/or synthetic.
  • fibrous materials are cloths, which can be woven and/or non-woven. Synthetic sponges as are widely available in the marketplace are particularly preferred.
  • compositions useful in present invention can include, optionally, perfumes, solvents, colorants and mixtures thereof. It is also possible for the compositions of the invention to contain a compound which provides a particularly unpleasant taste so as to prevent inadvertent consumption of the product.
  • Preservatives and other antimicrobial components are optional components of the compositions according to the invention.
  • Typical antimicrobial agents include formaldehyde.
  • Guar gum is a suitable polymer. Typical inclusion levels of polymer range from 0.001-2%.
  • Hydrotropes are another optional component of the present invention.
  • Ethanol is a suitable hydrotrope as are the xylene, cumeme and benzene sulphonates.
  • ethanol is present at a level of up to 10%wt, preferable up to a level of 6%wt.
  • compositions of the dilution thickening compositions according to the present invention are:
  • compositions comprise:
  • composition according to the present invention comprises:
  • the minors comprise:
  • porous and/or fibrous material useful in the present invention are synthetic sponges, available in the marketplace from the Minesota Mining and Manufacturing (3M) company.
  • compositions were prepared by simple mixing of the components listed in Table 1 to form compositions I and II.
  • Composition I is a composition for use in the method of the present invention and composition II is a control. Both compositions had an initial viscosity of 600cp as measured using a Haake viscometer at 75.04 reciprocal seconds shear rate.
  • the product retention was measured by applying first 3 g of the composition I or II plus, subsequently, 15 g of water to a sponge. After application the sponge was manually compressed to as to generate foam and expel a washing liquor which was allowed to fall into a beaker. The sponge was then treated with a further 15 g of water and the process repeated, each time gathering the liquor in a fresh beaker, until no further foam was generated as the liquor was expelled. The contents of the beakers was subjected to chemical analysis to determine the surfactant concentration. The concentrations are given in table 2 below. SURFACTANT RELEASED ( concentration in ppm) SOLUTION I II 1 1645 6999 2 6792 7055 3 5901 2090 4 1802 966 5 936 464 10 177 86 15 48 60 20 33 36 25 21 29
  • composition I showed a clear retention of the product on the sponge and an extended release of the surfactant from the sponge: i.e. with composition I, which embodies the invention, a more extended washing procedure could be conducted without excessive wastage of the surfactant containing product.
  • compositions I and II Table 3 below gives viscosity/dilution data for the compositions I and II. It can be seen that composition I exhibits an increase in viscosity as it is diluted. Whereas composition II shows a continuous fall in viscosity with dilution. Active concentration ( %) Viscosity (cp) I II 620 13.5 12.5 1 045 - 11.5 1 685 11.0 410 10.5 1 549 10.0 366 9.5 275 9.0 275 8.5 1 123 8.0 149 7.5 794 7.0 54 6.5 484 6.0 20 5.5 193 5.0 14 4.5 19
EP96909119A 1995-04-10 1996-03-22 Improvements relating to light duty cleaning Revoked EP0820503B1 (en)

Applications Claiming Priority (7)

Application Number Priority Date Filing Date Title
BR9501520 1995-04-10
BR9501520A BR9501520A (pt) 1995-04-10 1995-04-10 Composição de detergente
BR9502064A BR9502064A (pt) 1995-05-17 1995-05-17 Composção detergente
BR9502064 1995-05-17
BR9503351A BR9503351A (pt) 1995-07-17 1995-07-17 Processo para lavagem manual de louça
BR9503351 1995-07-17
PCT/EP1996/001283 WO1996032464A1 (en) 1995-04-10 1996-03-22 Improvements relating to light duty cleaning

Publications (2)

Publication Number Publication Date
EP0820503A1 EP0820503A1 (en) 1998-01-28
EP0820503B1 true EP0820503B1 (en) 1999-09-15

Family

ID=27160129

Family Applications (1)

Application Number Title Priority Date Filing Date
EP96909119A Revoked EP0820503B1 (en) 1995-04-10 1996-03-22 Improvements relating to light duty cleaning

Country Status (14)

Country Link
EP (1) EP0820503B1 (xx)
JP (1) JPH11503477A (xx)
KR (1) KR19980703746A (xx)
CN (1) CN1186512A (xx)
AR (1) AR001563A1 (xx)
AU (1) AU695764B2 (xx)
BR (1) BR9604824A (xx)
CA (1) CA2215795A1 (xx)
DE (1) DE69604282T2 (xx)
ES (1) ES2136396T3 (xx)
NZ (1) NZ304863A (xx)
PL (1) PL322767A1 (xx)
TR (1) TR199701154T1 (xx)
WO (1) WO1996032464A1 (xx)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9626622D0 (en) * 1996-12-20 1997-02-05 Unilever Plc Improvements relating to surface cleaning
US5854145A (en) * 1997-05-14 1998-12-29 Cortec Corporation Corrosion inhibitor solution applicator
WO1999013044A1 (en) * 1997-09-10 1999-03-18 Albemarle Corporation Dish-cleaning block
JP3255637B1 (ja) * 2001-01-23 2002-02-12 花王株式会社 液体洗浄剤組成物
JP5008664B2 (ja) 2005-07-11 2012-08-22 トムソン ライセンシング マクロブロック適応型レイヤ間テクスチャ内予測の方法及び装置
BRPI0503023A (pt) * 2005-07-22 2007-03-06 Unilever Nv composição de limpeza, método para limpar superfìcies domésticas, processo para melhorar a retenção de agentes de limpeza em veìculos absorventes, veìculo absorvente com retenção melhorada de agentes de limpeza, e, processo para produção de uma composição de limpeza
PL2094827T3 (pl) † 2006-12-20 2011-04-29 Unilever Nv Kompozycja do mycia naczyń
EP1939274A1 (en) 2006-12-20 2008-07-02 Unilever N.V. Dishwashing composition
BRPI0906013A2 (pt) * 2008-02-22 2015-06-30 Unilever Nv "composição de limpeza líquida, kit e uso do tensoativo de monoalcanolamida"
KR101442998B1 (ko) * 2010-08-11 2014-09-23 콜게이트-파아므올리브캄파니 포밍 클렌저
JP7038587B2 (ja) * 2018-04-02 2022-03-18 ライオン株式会社 食器洗い用の洗浄剤組成物
CN116410727A (zh) * 2023-04-13 2023-07-11 武汉大学 稀释增稠型表面活性剂球形胶束超浓分散体系及其制备方法与应用

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63270533A (ja) * 1987-04-30 1988-11-08 Shiseido Co Ltd 界面活性剤組成物
WO1994028108A1 (en) * 1993-06-01 1994-12-08 Ecolab Inc. Thickened hard surface cleaner

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US3949137A (en) * 1974-09-20 1976-04-06 Akrongold Harold S Gel-impregnated sponge
GB8809161D0 (en) * 1988-04-19 1988-05-25 Top Line Developments Ltd Cleaning aid
GB8817728D0 (en) * 1988-07-26 1988-09-01 Unilever Plc Wiping article
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BR9307795A (pt) * 1992-12-28 1995-11-21 Procter & Gamble Géis detergente claros
GB9301270D0 (en) * 1993-01-22 1993-03-17 Unilever Plc Dilution-thickening,personal washing composition
GB9314410D0 (en) * 1993-07-13 1993-08-25 Jeyes Group Plc Cleansing compositions

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Publication number Priority date Publication date Assignee Title
JPS63270533A (ja) * 1987-04-30 1988-11-08 Shiseido Co Ltd 界面活性剤組成物
WO1994028108A1 (en) * 1993-06-01 1994-12-08 Ecolab Inc. Thickened hard surface cleaner

Non-Patent Citations (1)

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Title
DATABASE WPI Week 8851, Derwent World Patents Index; AN 88-363107 *

Also Published As

Publication number Publication date
DE69604282D1 (de) 1999-10-21
TR199701154T1 (xx) 1998-02-21
AU695764B2 (en) 1998-08-20
DE69604282T2 (de) 1999-12-30
AR001563A1 (es) 1997-11-26
EP0820503A1 (en) 1998-01-28
CN1186512A (zh) 1998-07-01
WO1996032464A1 (en) 1996-10-17
KR19980703746A (ko) 1998-12-05
ES2136396T3 (es) 1999-11-16
NZ304863A (en) 1999-01-28
PL322767A1 (en) 1998-02-16
CA2215795A1 (en) 1996-10-17
AU5273796A (en) 1996-10-30
JPH11503477A (ja) 1999-03-26
BR9604824A (pt) 1999-01-05

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