EP0753048B1 - Compositions detergentes - Google Patents

Compositions detergentes Download PDF

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Publication number
EP0753048B1
EP0753048B1 EP95911339A EP95911339A EP0753048B1 EP 0753048 B1 EP0753048 B1 EP 0753048B1 EP 95911339 A EP95911339 A EP 95911339A EP 95911339 A EP95911339 A EP 95911339A EP 0753048 B1 EP0753048 B1 EP 0753048B1
Authority
EP
European Patent Office
Prior art keywords
detergent composition
nonionic surfactant
surfactant
water
alcohol
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
EP95911339A
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German (de)
English (en)
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EP0753048A1 (fr
Inventor
Peter Robert Garrett
Dennis Giles
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
Priority claimed from GB9406460A external-priority patent/GB9406460D0/en
Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Publication of EP0753048A1 publication Critical patent/EP0753048A1/fr
Application granted granted Critical
Publication of EP0753048B1 publication Critical patent/EP0753048B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime 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
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/0017—Multi-phase liquid compositions
    • C11D17/0021—Aqueous microemulsions
    • 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
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/18—Hydrocarbons

Definitions

  • the present invention relates to detergent compositions containing a surfactant and a solvent in the form of an oil-in-water microemulsion.
  • Liquid detergent and cleaning compositions in the form of microemulsions both oil-in-water and water-in-oil, have been disclosed in the prior art.
  • EP 137 616A discloses liquid detergent compositions prepared from conventional detersive surfactants and other conventional detergent ingredients, plus a grease-cutting solvent.
  • the compositions contain fatty acids or soaps (5-50 wt%) as detergency builders and are formulated as stable oil-in-water microemulsions.
  • the preferred surfactant systems comprise sulphonate or sulphate type anionic surfactants with minor amounts of ethoxylated nonionic surfactants such as C 14-15 alcohol ethoxylates (7EO).
  • Detergency builders may be present in amounts of 0.5-15 wt%, citrates being preferred.
  • EP 164 467A (Procter & Gamble) discloses laundry detergents and hard surface cleaners comprising oil-in-water microemulsions, containing alkylbenzene and olefin solvents, plus surfactants and substantial amounts of fatty acid soap.
  • the compositions may contain ethoxylated nonionic surfactants, for example, C 14-15 alcohol ethoxylate (7EO).
  • Compositions containing sodium citrate as builder are disclosed.
  • GB 2 194 547A discloses a clear single-phase liquid pre-spotting composition in the form of a microemulsion (oil-in-water or water-in-oil), solution or gel, comprising 10-70 wt% alkane (solvent), 4-60 wt% nonionic surfactant, optional cosurfactants and/or cosolvents, and 1-80 wt% water. It is suggested that builders such as sodium sesquicarbonate might be included, preferably at levels of 5 wt% and above. Unbuilt water-in-oil microemulsions are specifically disclosed which contain the short-chain nonionic surfactant Neodol 91-6 alone or in conjunction with a longer-chain (C 14-15 ) ethoxylated nonionic surfactant.
  • CA 2 013 431A Patent Application Company discloses unbuilt microemulsion cleaners for engine cleaning and degreasing, containing solvents and nonionic surfactants.
  • GB 2 259 518A (Shell) discloses unbuilt microemulsion cleaning compositions for use in seawater, containing anionic and nonionic surfactants, aromatic hydrocarbon and water.
  • the present invention provides a fabric washing detergent composition
  • a fabric washing detergent composition comprising an organic surfactant system and a non-aqueous solvent which together with water form a stable oil-in-water microemulsion, the composition comprising:
  • Rapidity of cleaning effect is of critical importance for a pretreatment product which is required to work within a short time period.
  • the present invention enables detergent compositions to be formulated which are highly effective main wash products and yet which also offer a potent pretreatment facility.
  • compositions are also suitable for use in machine washing employing automatic dosing systems, for example, as described and claimed in US 4 489 455 (Procter & Gamble).
  • This patent describes and claims apparatus and process for washing textiles based on utilising strictly limited or controlled quantities of an aqueous wash liquor, ranging from (at least) just enough to be distributed evenly and completely over the whole wash load, to (at most) about five times the dry weight of the washload.
  • compositions of the invention which are preferably liquid, the ethoxylated nonionic surfactant and the solvent are so chosen, and are present in amounts such that, together with water, they form a stable oil-in-water microemulsion in which the solvent is within the micelles of the surfactant.
  • the ethoxylated nonionic surfactant has an average alkyl chain length which is less than 12 carbon atoms.
  • the average alkyl chain length is within the range of from 9 to 11 carbon atoms, and most preferably the average alkyl chain length is about C 10 .
  • the ethoxylated nonionic surfactant is also characterised by a high content of C 10 material: at least 45 wt%, preferably at least 50 wt% and most preferably at least 70 wt% (all based on the alcohol).
  • the remainder of the ethoxylated nonionic surfactant may be of predominantly shorter or longer chain length, but advantageously the total content of C 10 and shorter-chain material is at least 60 wt%, and more preferably at least 75 wt% (all based on the alcohol).
  • Suitable materials are the Novel (Trade Mark) 1012 series ex Vista, which are narrow-range-ethoxylated materials consisting mainly of C 10 chains, available in various average degrees of ethoxylation.
  • the chain length distribution of these materials is typically C 10 84 ⁇ 4%, C 12 8.5 ⁇ 2%, C 14 6.5 ⁇ 2%.
  • a class of broader-range-ethoxylated materials suitable for use in the invention is the Dobanol (Trade Mark) 91 series ex Shell, which consist mainly of C 9 , C 10 and C 11 chains.
  • the chain length distribution of these materials is typically C 9 18%, C 10 50%, C 11 32%.
  • ethoxylated nonionic surfactants are generally mixtures containing a spread of chain lengths about an average value. If desired, a mixture of two or more commercial materials may be used provided that the overall average chain length of all nonionic surfactant present is less than C 12 and provided that sufficient C 10 material is present in the overall mixture.
  • the average degree of ethoxylation may suitably range from 2 to 8, and preferably from 2 to 6, in order to give optimum HLB (hydrophilic-lipophilic balance) values corresponding to optimum oily soil detergency.
  • the HLB value suitably ranges from 8 to 14, preferably from 8 to 12.5, and more preferably from 9 to 10.
  • a cosurfactant which is not an ethoxylated alcohol may be present, provided that at least 50 wt% of the surfactant system is constituted by ethoxylated nonionic surfactant.
  • the co-surfactant may be, for example, a nonionic surfactant other than an ethoxylated alcohol, or an anionic sulphate or sulphonate type detergent, such as alkylbenzene sulphonate or primary alcohol sulphate. It is generally preferred that the surfactant system should contain not more than 40 wt% of anionic surfactant.
  • the surfactant system as a whole constitutes from 2 to 40 wt% of the composition, preferably from 5 to 40 wt%, more preferably from 5 to 30 wt% and advantageously from 5 to 25 wt%, of the composition.
  • the non-aqueous solvent which constitutes from 0.5 to 55 wt%, preferably from 0.5 to 20 wt%, of the composition, may be any solvent valuable in the removal of oily soil which exhibits a sufficiently low interfacial tension towards the ethoxylated nonionic surfactant to form a stable oil-in-water microemulsion.
  • the solvent may range from wholly non-polar paraffinic materials, for example, alkanes, to more polar materials such as esters.
  • Preferred solvents are C 12-16 alkanes, for example, dodecane, tetradecane and hexadecane, hexadecane being especially preferred.
  • the optimum amount present depends on the chain length.
  • hexadecane from 0.5 to 20 wt%, preferably from 5 to 15 wt% and more preferably from 7.5 to 15 wt%, is suitable; for tetradecane, 15 to 30 wt% is preferred, and for dodecane, 25 to 55 wt% is preferred.
  • the weight ratio of non-aqueous solvent (alkane) to ethoxylated nonionic surfactant is also dependent on chain length.
  • alkane alkane
  • ethoxylated nonionic surfactant ethoxylated nonionic surfactant
  • the detergency of the microemulsion system is significantly increased if there is also present a detergency builder selected from sodium tripolyphosphate and polymeric detergency builders.
  • a detergency builder selected from sodium tripolyphosphate and polymeric detergency builders.
  • the amount of builder that can be incorporated without destabilising the microemulsion is not, however, unlimited.
  • the builder present in an amount of from is 0.1 to 5 wt%, preferably from 0.2 to 3 wt%, more preferably from 0.5 to 3 wt% and is selected from sodium tripolyphosphate and polymeric detergency builders.
  • Preferred polymeric builders for use in the present invention are polymeric polycarboxylate builders, for example, acrylic, maleic and itaconic acid polymers.
  • Polymers that may be used include polyacrylates, acrylic/maleic copolymers such as Sokalan (Trade Mark) CP5 and CP7 ex BASF, and the polyvinyl acetate/polyitaconic acid polymers described and claimed in WO 93 23444A (Unilever). These polymers are highly weight-effective builders which can be used in amounts that give significant building without destabilising the microemulsion.
  • Oily soil detergencies were assessed by measuring the percentage removal of radio-labelled model soils by means of a scintillation counter.
  • Soiled cloths (5 cm x 5 cm squares of knitted polyester) carrying a mixture of radiolabelled triolein and radiolabelled palmitic acid were prepared as follows. Each cloth was soaked in 0.18 ml of a toluene solution containing 3.33 g 95% triolein (radiolabelled) and 1.67 g 99% palmitic acid (radiolabelled) per 100 ml. The cloths were then allowed to equilibrate for 3 hours.
  • composition under test was applied to a fabric square at ambient temperature at a level designed to give a liquor to cloth ratio of 1:1.
  • the contact time was varied from 5 to 30 minutes to examine kinetic effects.
  • the cloth was then transferred, using tweezers, to an open bottle containing 15 ml of water (20° French hard) held within a shaker bath maintained at 25°C.
  • the cloth was then rinsed for 2 minutes at a 100 rpm setting of the shaker bath (this gave a gentle to and fro motion to the rinse liquor within the bottle).
  • Liquid detergent compositions were prepared to the formulations (in parts by weight) given in the tables that follow. Soil removal (detergency) results are shown after the tables of compositions.
  • compositions of Examples 1 to 3 and Comparative Examples A, X, P, D, M, N and H containing a solvent (hexadecane) were in microemulsion form, while the compositions of Comparative Examples B, Y, C, Q, E, F and G, which did not contain a solvent, were not.
  • the ingredients used may be identified as follows:
  • microemulsion system X finally gave results comparable with those obtained from microemulsion system A, but required the full 30 minutes to do so; the use of short-chain nonionic surfactant clearly gives a significant kinetic advantage.
  • the non-microemulsion system Y was poor, comparable to the non-microemulsion system B.
  • Example 1 Comparative Examples C, P and O: sodium tripolyphosphate builder
  • Example 1 C P Q Nonionic: C 10 EO 4 1 7.5 7.5 - - C 9-11 EO 2.5 2 2.5 2.5 - - C 12-14 EO 4.4 3 - - 10.0 10.0 Hexadecane 10.0 - 10.0 - STP 4 0.8 0.9 0.8 0.9 Water (20°FH) 80.0 90.0 80.0 90.0 100.8 100.9 100.8 100.9
  • Examples 1 and C containing short-chain nonionic surfactant were as follows: Soak/contact time (minutes) Soil removal (%) Triolein Palmitic acid 1 C 1 C 5 36.2 22.2 49.6 47.3 10 50.7 26.3 60.1 50.7 15 58.7 26.9 60.7 50.0 20 60.8 28.5 63.6 54.7 30 63.8 26.1 63.5 55.6
  • the microemulsion P gave significantly worse results than the microemulsion 1, and was also slow to reach the maximum value. Of the four systems only 1 gave really high values.
  • the non-microemulsion systems Q and C gave similar results, showing no benefit for the use of short-chain nonionic surfactant in the non-microemulsion system.
  • Example D E Nonionic: C 10 EO 4 1 7.5 7.5 C 9-11 EO 2.5 2 2.5 2.5 Hexadecane 10.0 - EDTA 5 0.8 0.9 Water (20°FH) 80.0 90.0 100.8 100.9
  • Soil removal results were as follows: Soak/contact time (minutes) Soil removal (%) Triolein Palmitic acid D E D E 5 32.0 16.4 44.5 39.7 10 45.0 17.0 48.7 40.7 15 45.6 19.3 46.2 45.7 20 48.4 21.2 47.4 46.2 30 36.0 18.8 44.3 53.4
  • Example 2 Comparative Examples F and M: acrylate/maleate copolymer builder
  • Example 3 Comparative Examples G and N: polyvinyl acetate/itaconate) builder
  • Example 3 G N Nonionic: C 10 EO 4 1 7.5 7.5 - C 9-11 EO 2.5 2 2.5 2.5 - C 12-14 EO 4.4 3 - - 10.0 Hexadecane 10.0 - 10.0 PVA/IA 7 0.8 0.9 0.8 Water (20°FH) 80.0 90.0 80.0 100.8 100.9 100.8
  • Example H Nonionic: C 10 EO 4 1 7.5 C 9-11 EO 2.5 2 2.5 Hexadecane 10.0 Sodium citrate 0.8 Water (20°FH) 80.0 100.8
  • Soil removal results were as follows: Soak/contact time (minutes) Soil removal (%) Triolein Palmitic acid 5 42.0 31.6 10 41.9 33.0 15 39.7 35.1 20 40.8 35.9 30 38.3 38.9

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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)
  • Detergent Compositions (AREA)

Claims (14)

  1. composition détergente de lavage des textiles comprenant un système tensioactif organique et un solvant non aqueux qui ensemble avec l'eau forment une microémulsion stable huile-dans-eau, ladite composition comprenant :
    (i) de 2 à 40% en poids d'un système tensioactif organique comprenant:
    (a) 50 à 100% en poids de tensioactif non ionique alcool éthoxylé ayant une longueur moyenne de chaíne alkyle inférieure à C12 et une teneur en matière en C10 (à base de l'alcool) d'au moins 45% en poids ;
    (b) facultativement jusqu'à 50% en poids d'un cotensioactif autre qu'un tensioactif non ionique alcool éthoxylé,
    (ii) de 0,5 à 55% en poids d'un solvant non aqueux,
    (iii) de 0,1 à 5% en poids d'un adjuvant de détergence hydrosoluble et caractérisée en ce que ledit adjuvant de détergence hydrosoluble est choisi parmi les adjuvants de détergence tripolyphosphates et polymères,
    (iv) de l'eau et des ingrédients secondaires facultatifs jusqu'à 100% en poids.
  2. Composition détergente selon la revendication 1, dans laquelle le tensioactif non ionique (i)(a) contient au moins 70% en poids (à base de l'alcool) de matière en C10.
  3. Composition détergente selon la revendication 1 ou 2, dans laquelle le tensioactif non ionique (i)(a) contient au moins 60% en poids (à base de l'alcool) de matière ayant une longueur de chaíne en C10 ou moins.
  4. Composition détergente selon l'une quelconque des revendications précédentes, dans laquelle le tensioactif non ionique (i)(a) contient au moins 75% en poids (à base de l'alcool) de matière ayant une longueur de chaíne en C10 ou moins.
  5. Composition détergente selon l'une quelconque des revendications précédentes, dans laquelle le tensioactif non ionique (i)(a) a un I.A dans la gamme de 8 à 12,5.
  6. Composition détergente selon la revendication 5, dans laquelle le tensioactif non ionique (i)(a) a un I.A dans la gamme de 9 à 10.
  7. Composition selon l'une quelconque des revendications précédentes, qui comprend de 5 à 40% en poids du système tensioactif (i).
  8. Composition détergente selon l'une quelconque des revendications précédentes, dans laquelle le solvant non aqueux (ii) comprend un alcane en C12-16.
  9. Composition détergente selon la revendication 8, dans laquelle le solvant (ii) comprend l'hexadécane.
  10. Composition détergente selon la revendication 9, dans laquelle l'hexadécane (ii) est présent en une quantité de 0,5 à 20% en poids.
  11. Composition détergente selon la revendication 10, dans laquelle l'hexadécane (ii) est présent en une quantité de 5 à 15% en poids.
  12. Composition détergente selon l'une quelconque des revendications 9 à 11, dans laquelle le rapport pondéral de l'hexadécane (ii) au tensioactif non ionique (i)(a) est dans la gamme de 0,5:1 à 2:1.
  13. Composition détergente selon la revendication précédente, qui comprend de 0,2 à 3% en poids d'adjuvant de détergence (iii).
  14. Composition détergente selon l'une quelconque des revendications précédentes, dans laquelle le système tensioactif organique (i) contient moins de 40% en poids de tensioactif anionique.
EP95911339A 1994-03-31 1995-03-16 Compositions detergentes Expired - Lifetime EP0753048B1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
GB9406460A GB9406460D0 (en) 1994-03-31 1994-03-31 Detergent compositions
GB9406460 1994-03-31
GB9414323A GB9414323D0 (en) 1994-03-31 1994-07-15 Detergent compositions
GB9414323 1994-07-15
PCT/EP1995/000990 WO1995027034A1 (fr) 1994-03-31 1995-03-16 Compositions detergentes

Publications (2)

Publication Number Publication Date
EP0753048A1 EP0753048A1 (fr) 1997-01-15
EP0753048B1 true EP0753048B1 (fr) 1998-07-15

Family

ID=26304617

Family Applications (1)

Application Number Title Priority Date Filing Date
EP95911339A Expired - Lifetime EP0753048B1 (fr) 1994-03-31 1995-03-16 Compositions detergentes

Country Status (7)

Country Link
EP (1) EP0753048B1 (fr)
AU (1) AU1894695A (fr)
CA (1) CA2173137A1 (fr)
DE (1) DE69503489T2 (fr)
ES (1) ES2119405T3 (fr)
IN (1) IN184051B (fr)
WO (1) WO1995027034A1 (fr)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU762731B2 (en) * 1998-11-12 2003-07-03 Colgate-Palmolive Company, The Microemulsion liquid cleaning composition containing a short chain amphiphile
US6645929B2 (en) * 2001-12-10 2003-11-11 Colgate-Palmolive Company Cleaning composition
BR0309484A (pt) 2002-04-26 2005-02-01 Basf Ag Uso de alcoxilatos, alcoxilato, processo para a preparação do mesmo, e, agente de limpeza, umedecimento, revestimento, adesão, desengraxamento de couro, retenção de umidade ou de tratamento de têxtil, ou formulação cosmética, farmacêutica ou para tratamento de plantas
US7371716B2 (en) 2002-04-26 2008-05-13 Basf Aktiengesellschaft C10-alkanolalkoxylate mixtures and the use thereof
BRPI0720231A2 (pt) * 2006-12-14 2013-12-24 Basf Se Composto químico, emulsificante, concentrado em emulsão, emulsão, e, uso de um concentrado em emulsão ou de uma emulsão
TW201031743A (en) 2008-12-18 2010-09-01 Basf Se Surfactant mixture comprising branched short-chain and branched long-chain components
WO2011003904A1 (fr) 2009-07-10 2011-01-13 Basf Se Mélange de tensioactifs contenant des constituants à chaîne courte et à chaîne longue
ES2551384T3 (es) 2009-12-16 2015-11-18 Unilever N.V. Composición de detergente en microemulsión bicontinua
EP2361963A1 (fr) 2010-02-01 2011-08-31 Unilever N.V. Composition de détergent à micro-émulsion bi-continue
EA022865B1 (ru) 2010-09-28 2016-03-31 Юнилевер Нв Моющая композиция
EP3514207A1 (fr) * 2018-01-18 2019-07-24 Henkel AG & Co. KGaA Procédé de décoration à l'aide d'une microémulsion à faible teneur en huile

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8409055D0 (en) * 1984-04-07 1984-05-16 Procter & Gamble Cleaning compositions
ZA876158B (en) * 1986-09-02 1989-04-26 Colgate Palmolive Co Laundry pre-spotter composition providing improved oily soil removal
US5108643A (en) * 1987-11-12 1992-04-28 Colgate-Palmolive Company Stable microemulsion cleaning composition
CA2013431A1 (fr) * 1989-03-30 1990-09-30 Arpad M. Magyar Degraisseur et nettoyeur de moteur a microemulsion
US5035826A (en) * 1989-09-22 1991-07-30 Colgate-Palmolive Company Liquid crystal detergent composition
GB2259518B (en) * 1991-09-05 1996-02-14 Shell Int Research Micro-emulsion cleaner composition suitable for use in seawater

Also Published As

Publication number Publication date
IN184051B (fr) 2000-06-03
DE69503489D1 (de) 1998-08-20
CA2173137A1 (fr) 1995-10-12
EP0753048A1 (fr) 1997-01-15
WO1995027034A1 (fr) 1995-10-12
ES2119405T3 (es) 1998-10-01
AU1894695A (en) 1995-10-23
DE69503489T2 (de) 1998-12-03

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