EP0647264B1 - Ameliorations relatives a des compositions de nettoyage - Google Patents

Ameliorations relatives a des compositions de nettoyage Download PDF

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Publication number
EP0647264B1
EP0647264B1 EP93912803A EP93912803A EP0647264B1 EP 0647264 B1 EP0647264 B1 EP 0647264B1 EP 93912803 A EP93912803 A EP 93912803A EP 93912803 A EP93912803 A EP 93912803A EP 0647264 B1 EP0647264 B1 EP 0647264B1
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EP
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Prior art keywords
solvent
composition according
solvent component
composition
water
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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.)
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EP93912803A
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German (de)
English (en)
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EP0647264A1 (fr
Inventor
Terry Instone
John Francis Wells
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Unilever PLC
Unilever NV
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Unilever PLC
Unilever NV
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Priority claimed from GB929213073A external-priority patent/GB9213073D0/en
Priority claimed from GB929215902A external-priority patent/GB9215902D0/en
Priority claimed from GB929218080A external-priority patent/GB9218080D0/en
Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Publication of EP0647264A1 publication Critical patent/EP0647264A1/fr
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    • 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
    • C11D3/43—Solvents
    • 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
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146—Sulfuric acid esters
    • 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

Definitions

  • the present invention relates to improvements relating to cleaning compositions and in particular to improvements relating to cleaning compositions comprising surfactants and solvents.
  • compositions for use in cleaning of household and industrial hard surfaces comprise solvent components, in addition to surfactants. These solvents are generally intended to improve cleaning performance by assisting in the removal of greasy or waxy soils. The advantages associated with the presence of solvents in such compositions are particularly marked at low surfactant levels, such as are found in compositions for use on highly reflective surfaces upon which high levels of surfactant residues cannot be tolerated.
  • solvent components are immiscible with water or have a relatively low level of miscibility above which they form emulsions and therefore those compositions which comprise levels of solvent above the miscibility limit either need to be shaken vigorously prior to use or the solvent needs to be present as a stable emulsion.
  • compositions On shaking these compositions form semi-stable emulsions which break on contact with a hard surface to release the components.
  • Stable emulsions can be difficult to prepare and are prone to phase-separation.
  • single phase systems and single phase systems are more readily formulated, processed, stored and dispensed than emulsions, the use of immiscible solvents in single phase compositions has been limited to relatively low levels.
  • compositions comprising a binary solvent system of terpenes and polar solvents are described in EP-A-0040882 and EP-A-0080749.
  • Typical compositions for cleaning glass are described in EP-A-261874 (The Procter and Gamble Company: 1986/87).
  • cleaning compositions which comprise a specific isomer of n-butoxy propan-2-ol, available commercially as 'DOWANOL PnB' (RTM, from the DOW Chemical Company).
  • n-butoxy propan-2-ol is miscible with water up to a level of around 6% dependent on temperature and levels of isomers.
  • sprays to deliver the compositions to a surface is to be avoided due to odour problems.
  • EP-A-0428816 discloses in general terms formulations comprising as a first solvent from 1-9% of ethanol, 0.5-3% of n-butoxy propan-2-ol, 0.5-3% of n-propoxy propanol and, as a second solvent, 0.5-3% of a primary or secondary monoalcohol having a five carbon alkyl chain.
  • GB-A-2144763 (P&G: 1983) relates to hard-surface cleaners in the form of a so-called 'microemulsion' of solvent, comprising at least 5% solvent and a magnesium salt.
  • the use of microemulsions has been considered advantageous due to the improved cleaning performance of free solvent as compared with solutions of solvent in water or other aqueous media.
  • Microemulsions are described in that document as very fine emulsions which appear as homogeneous compositions.
  • WO-A-80/02693 discloses compositions of ethyl acetate, glycerol and water with optional surfactant in mixtures which are normally two phase systems except in a narrow formulation band.
  • EP-A-105063 discloses cleaning compositions which comprise a principal solvent and, when necessary, an auxiliary solvent which is utilized to solubilise the principal solvent.
  • the examples of EP-A-105063 employ, as the water- miscible solvent, diethylene glycol mono-n-butyl ether (commercially available as 'BUTYL DIGOL' (TM)).
  • US-A-4212758 discloses a cleansing agent which comprises as water-soluble components isopropyl alcohol and 1,2-propandiol, together with oleic acid and water-insoluble ethyl acetate.
  • US-A-3764544 discloses the use of ethyl acetate or other related acetates as an estersolvent, in combination with a coupling agent such as a glycol ether solvent.
  • EP-A-0527625 published on 17.02.93, discloses aqueous liquid compositions comprising ethylene glycol monohexyl ether in an amount which appears to be above its miscibility limit with water and a second volatile solvent (isopropanol) in an amount sufficient to give an isotropic composition.
  • EP-B-0479908 discloses stable, non-emulsion, cleaning and degreasing compositions which can comprise a relatively insoluble glycol ether solvent present above it's solubility limit and an solubilizing additive which includes and optional non-volatile hydrotropes.
  • microemulsions are employed they are difficult to produce, but where they are not used insufficient solvent may be present for effective cleaning.
  • surfactanVsolvent cleaning composition normal use of a surfactanVsolvent cleaning composition will increase the environmental loading of solvent and surfactant.
  • the present invention provides a homogeneous, isotropic, aqueous, solvent-containing, cleaning composition wherein the solvent system comprises:
  • the second solvent component evaporates from the overall composition and the remaining first solvent component and water phase-separate, thus forming an emulsion, whereby the cleaning action of the first solvent component is potentiated.
  • the emulsion thus formed generally has a coarse dispersed phase.
  • the first solvent component is selected from the group comprising propylene glycol mono n-butyl ether, dipropylene glycol mono n-butyl ether, propylene glycol mono t-butyl ether, dipropylene glycol mono t-butyl ether, diethylene glycol hexyl ether, and mixtures thereof.
  • the first solvent component is propylene glycol mono n-butyl ether (n-butoxy propan-2-ol), preferably present at a level of 6%-12%.
  • the second solvent component is selected from volatile alcohols; water miscible, volatile glycol ethers, aldehydes, ketones, di-alkyl ethers and mixtures thereof.
  • said second solvent component is selected from the group comprising: methanol, ethanol, isopropyl alcohol, ethylene glycol monobutyl ether and mixtures thereof.
  • the second solvent component comprises, ethanol, isopropanol or mixtures thereof.
  • Ethanol in the form of industrial methylated spirits is suitable for the practice of the invention.
  • compositions according to the present invention are optional components of formulations according to the present invention although it is desirable that compositions according to the invention further comprise one or more surfactant species.
  • the nature of the surfactant is not critical to the general function of the invention.
  • the surfactant species are generally anionic or nonionic, although it is envisaged that cationic, zwitterionic and amphoteric surfactants can be employed. Mixtures of both anionic and nonionic can be employed.
  • the cleaning composition further comprises an anionic surfactant.
  • anionic surfactant it is envisaged that a broad range of anionic surfactants can be used in the embodiments of the present invention, some of which are listed below. In each case the anionic surfactant will be present together with a suitable counter-ion.
  • compositions further comprise magnesium ions in an amount corresponding to at least 0.02 M where M is the molar amount of anionic surfactant in the composition
  • the magnesium salt of the anionic synthetic detergent to be used in the present invention can be a magnesium salt of the well-known types of anionic detergent surfactants, such as the C 10 -C 18 alkylbenzene sulphonates, C 10 -C 18 alkanesulphonates, sulphonated C 10 -C 22 fatty acids or esters thereof, C 8 -C 18 olefinsulphonates, di-(C 6 -C 10 alkyl) sulphosuccinates, C 10 -C 18 alkylsulphates, C 10 -C 18 alkylethersulphates containing from 1 to 10 moles of ethylene-oxide. Further examples can be found in Schwartz-Perry "Surface Active Agents and Detergents", Vol. I (1949) and Vol. II (1958).
  • the anionic detergents are the magnesium salts of primary alcohol sulphates. These are believed to be more readily biodegradable than other surfactants and are available in commercial quantities from renewable resources.
  • Primary alcohol sulphates are mixture of materials of the general formulation:
  • the final composition should comprise from 0.05 to 10% by weight of the magnesium salt of the anionic synthetic detergent, preferably from 0.1 to 7.5% by weight.
  • the magnesium salt of the anionic synthetic detergent may be incorporated as such in the final composition, or may be formed by in-situ neutralisation of the anionic synthetic detergent in acid from with a suitable neutralising magnesium compound such as magnesium-oxide, -hydroxide, - carbonate, etc.
  • the magnesium salt of the anionic synthetic detergent may also be formed in situ by the addition of a magnesium salt such as magnesium sulphate to the alkali-metal ammonium or alkanolamine salt of the anionoic synthetic detergent in the composition.
  • nonionic surfactants can be employed.
  • the preferred nonionic surfactant is selected from the group comprising ethoxylated alcohols of the general formula:
  • compositions are formed when the surfactant system consists solely of the magnesium salt of an anionic surfactant, particularly the magnesium salt of a primary alcohol sulphate.
  • compositions according to the present invention therefore comprise:
  • compositions of the invention can further comprise other components selected from the group comprising: further surfactant species, perfumes, electrolytes, colours and dyes, abrasives, hygiene agents, further solvent components, foam-control agents, viscosity modifying agents, hydrotropes and mixtures thereof. Provided that these components are present at sufficiently low levels they do not interfere with the function of the invention.
  • compositions directly onto a soiled surface rather than cleaning the surface with a cloth or sponge dampened with the compositions. It is believed that the evaporation of one of the components of the cleaning composition is critical to the use of the inventive compositions in practice and that evaporation proceeds more effectively during the spraying operation and from a surface than from a cloth.
  • a further aspect of the present invention comprises a process including the steps of:
  • a yet further aspect of the present invention relates to a homogeneneous composition
  • a homogeneneous composition comprising solvent and surfactant which decomposes into a solvent-water emulsion as a portion of the solvent evaporates, packaged in a container adapted to produce a spray.
  • Single phase compositions were formed by simple mixing of the components according to the formulations given in Table 1, the balance of the formulation being water.
  • Example 1 is a control experiment to illustrate the base-line cleaning effect of a single phase system containing PnB.
  • the level of PnB in this example has been selected such that it lies below the maximum miscibility with water and consequently the system forms a homogeneous mixture. It can be seen from comparative example 2 that the addition of IMS improves the cleaning performance only slightly.
  • compositions of example 3 are clear, homogeneous systems which, in use, lose the alcoholic solvent to the ambient and reach a composition at which there is just sufficient alcohol present to solubilise all of the PnB present. At this composition, further loss of volatile solvent results in phase separation of the PnB.
  • Comparative example 4 shows that when BD, is present below its maximum miscibility in the starting composition cleaning is less effective.
  • each sample was applied to a black ceramic tile and spread over the surface with a clean, dry cloth to form a thin film which was allowed to evaporate to dryness.
  • the film was observed closely by eye to determine the formation of any emulsion (indicated by a transformation from a transparent film to an opaque film).
  • the only sample observed to form an emulsion was that of example 13, an embodiment of the invention.
  • Examples 14-27 illustrate the effect of the choice of surfactant on product performance.
  • Examples 14 and 15 are control experiments to illustrate the cleaning effect of a single phase system containing PnB, below the maximum miscibility.
  • the cleaning performance of these compositions appears slightly better in the presence of the nonionic surfactant (comparative example 14) than the anionic surfactant (comparative example 15). This is in agreement with the results noted in respect of comparative example 1 mentioned above.
  • Examples 16 and 18 are examples using a nonionic surfactant. Although these compositions had a cleaning performance approaching that of embodiments 17 and 19, the compositions became cloudy on storage. It is to be noted that the anionic surfactant in compositions according to the preferred embodiment of the present invention exhibits better cleaning performance than the nonionic surfactant (compare examples 16 and 17).
  • Comparative examples 20-27 shows that combinations of solvent which fall outside of the scope of the present invention did not have effective cleaning performance. In these comparative compositions no emulsion was formed on the evaporation of the volatile solvent component.

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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 de nettoyage homogène, isotrope, aqueuse contenant un solvant, dans laquelle le système solvant comprend :
(a) un premier solvant éther glycolique en une quantité telle qu'il est présent en une proportion au dessus de la limite de miscibilité de ce solvant avec l'eau et,
(b) un second solvant autre que le monohexyléther d'éthylène-glycol, présent en une proportion telle que le premier solvant est solubilisé dans la composition, ledit second solvant étant suffisamment volatil pour que, à l'emploi, ledit second solvant s'évapore de la composition pour laisser une émulsion solvant/eau comprenant le premier solvant et l'eau.
2. Composition selon la revendication 1, dans laquelle le premier solvant est choisi parmi le mono-n-butyléther de propylène-glycol, le mono-n-butyléther de dipropylène-glycol, le mono-t-butyléther de propylène-glycol, le mono-t-butyléther de dipropylène-glycol, l'hexyléther de diéthylèneglycol et leurs mélanges.
3. Composition selon la revendication 1, dans laquelle le second solvant est choisi parmi les alcools volatils; les éthers glycoliques, aldéhydes, cétones, éthers dialkyliques et leurs mélanges miscibles avec l'eau, volatils.
4. Composition selon la revendication 3, dans laquelle le second composant est choisi parmi le méthanol, l'éthanol, l'alcool isopropylique, le monobutyléther d'éthylène-glycol et leurs mélanges.
5. Composition selon la revendication 1, qui comprend en outre un tensioactif.
6. Composition selon la revendication 5, qui comprend un tensioactif anionique.
7. Composition selon la revendication 6, dans laquelle le tensioactif anionique est le sel d'alkylsulfate primaire des matières de formule générale :
Figure imgb0014
dans laquelle R est un groupe alkyle primaire en C8-18 et X est un contre-ion approprié.
8. Composition selon la revendication 7, comprenant en outre des ions magnésium en une quantité correspondant à au moins 0,02 M ; M étant la quantité molaire de tensioactif anionique dans la composition.
9. Composition selon la revendication 5, comprenant un tensioactif non ionique.
10. Composition selon la revendication 9, comprenant un tensioactif non ionique choisi parmi les alcools éthoxylés de formule générale :
Figure imgb0015
dans laquelle R1 est alkyle en Cs-1s droit ou ramifié et le degré moyen d'éthoxylation (c'est à dire la longueur de la chaîne oxyde d'éthylène) m est 1-14.
11. Composition de nettoyage selon la revendication 1, comprenant :
(a) de 6 à 12% en poids de n-butoxy-propanol
(b) de l'eau,
(c) un alcool suffisamment volatil pour empêcher la séparation de phases entre l'eau et le n-butoxy-propanol.
12. Composition selon la revendication 11, comprenant en outre :
(a) le sel de magnésium d'un tensioactif anionique.
13. Procédé de nettoyage comprenant les étapes :
a) traiter directement une surface avec une composition selon l'une quelconque des revendications 1 à 12,
b) laisser le second solvant s'évaporer au moins partiellement, et,
c) effectuer une opération de nettoyage mécanique.
14. Composition selon l'une quelconque des revendications 1 à 12, emballée dans un récipient adapté pour produire une pulvérisation de ladite composition.
EP93912803A 1992-06-18 1993-05-27 Ameliorations relatives a des compositions de nettoyage Expired - Lifetime EP0647264B1 (fr)

Applications Claiming Priority (7)

Application Number Priority Date Filing Date Title
GB9213073 1992-06-18
GB929213073A GB9213073D0 (en) 1992-06-18 1992-06-18 Improvements relating to cleaning composition
GB929215902A GB9215902D0 (en) 1992-07-27 1992-07-27 Improvements relating to cleaning compositions
GB9215902 1992-07-27
GB9218080 1992-08-25
GB929218080A GB9218080D0 (en) 1992-08-25 1992-08-25 Improvements relating to cleaning compositions
PCT/EP1993/001330 WO1993025654A1 (fr) 1992-06-18 1993-05-27 Ameliorations relatives a des compositions de nettoyage

Publications (2)

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EP0647264A1 EP0647264A1 (fr) 1995-04-12
EP0647264B1 true EP0647264B1 (fr) 1996-04-24

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EP93912803A Expired - Lifetime EP0647264B1 (fr) 1992-06-18 1993-05-27 Ameliorations relatives a des compositions de nettoyage

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EP (1) EP0647264B1 (fr)
JP (1) JPH07507584A (fr)
AU (1) AU678360B2 (fr)
BR (1) BR9306574A (fr)
CA (1) CA2136850A1 (fr)
CZ (1) CZ319594A3 (fr)
DE (1) DE69302384T2 (fr)
ES (1) ES2087743T3 (fr)
HU (1) HUT70082A (fr)
IN (1) IN176902B (fr)
MY (1) MY109133A (fr)
SK (1) SK154894A3 (fr)
WO (1) WO1993025654A1 (fr)

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9319125D0 (en) * 1993-09-15 1993-11-03 Dow Europ Sa Cleaning composition
AU675833B2 (en) * 1994-03-23 1997-02-20 Amway Corporation Concentrated all-purpose light duty liquid cleaning composition and method of use
US5531939A (en) * 1994-03-23 1996-07-02 Amway Corporation Concentrated glass and window cleaning composition and method of use
US5942484A (en) * 1995-03-30 1999-08-24 The Procter & Gamble Company Phase-stable liquid fabric refreshment composition
US5681355A (en) * 1995-08-11 1997-10-28 The Procter & Gamble Company Heat resistant dry cleaning bag
US5789368A (en) * 1996-01-26 1998-08-04 The Procter & Gamble Company Fabric care bag
US6233771B1 (en) 1996-01-26 2001-05-22 The Procter & Gamble Company Stain removal device
US5840675A (en) * 1996-02-28 1998-11-24 The Procter And Gamble Company Controlled released fabric care article
US5891197A (en) * 1996-08-02 1999-04-06 The Proctor & Gamble Company Stain receiver for dry cleaning process
US5872090A (en) * 1996-10-25 1999-02-16 The Procter & Gamble Company Stain removal with bleach
US5849039A (en) * 1997-01-17 1998-12-15 The Procter & Gamble Company Spot removal process
US5762648A (en) * 1997-01-17 1998-06-09 The Procter & Gamble Company Fabric treatment in venting bag
US7008458B2 (en) 1997-04-04 2006-03-07 Hayday William A Biodegradable ether dry cleaning solvent
US6273919B1 (en) 1997-04-04 2001-08-14 Rynex Holdings Ltd. Biodegradable ether dry cleaning solvent
US5888250A (en) * 1997-04-04 1999-03-30 Rynex Holdings Ltd. Biodegradable dry cleaning solvent
NZ503088A (en) * 1997-09-03 2001-11-30 S Method and cleaning composition for sanitizing, disinfecting and inhibiting mold and mildew growth on non-porous hard surfaces

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3764544A (en) * 1971-08-06 1973-10-09 L Haworth Spot remover for wearing apparel
EP0005309A1 (fr) * 1978-02-14 1979-11-14 Dawley Brook Papers Limited Composition détergente et méthode pour l'enlèvement d'encre d'imprimerie de surfaces
US4212758A (en) * 1978-10-20 1980-07-15 Belkevich Petr I Cleansing agents containing oleic acid, isopropanol and ethylacetate
SE438162B (sv) * 1979-05-29 1985-04-01 Tepab Tek Prod Ab Forfarande for rengoring av en yta, i synnerhet avlegsnande av beleggningsskikt och fergskikt fran en yta
CA1178160A (fr) * 1981-09-10 1984-11-20 Donald B. Compton Produit liquide pour le nettoyage de surfaces dures
GB2144763B (en) * 1983-08-11 1987-10-28 Procter & Gamble Liquid detergent compositions with magnesium salts
US4689168A (en) * 1984-06-08 1987-08-25 The Drackett Company Hard surface cleaning composition
US5075026A (en) * 1986-05-21 1991-12-24 Colgate-Palmolive Company Microemulsion all purpose liquid cleaning composition
US4921629A (en) * 1988-04-13 1990-05-01 Colgate-Palmolive Company Heavy duty hard surface liquid detergent
EP0428816A1 (fr) * 1989-11-23 1991-05-29 The Procter & Gamble Company Composition de nettoyage pour surfaces dures
ZA925727B (en) * 1991-08-09 1993-03-10 Bristol Myers Squibb Co Glass cleaning composition.

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MY109133A (en) 1996-12-31
AU4318493A (en) 1994-01-04
ES2087743T3 (es) 1996-07-16
IN176902B (fr) 1996-10-05
EP0647264A1 (fr) 1995-04-12
CA2136850A1 (fr) 1993-12-23
SK154894A3 (en) 1995-07-11
CZ319594A3 (en) 1995-05-17
DE69302384T2 (de) 1996-09-26
WO1993025654A1 (fr) 1993-12-23
BR9306574A (pt) 1998-12-08
DE69302384D1 (de) 1996-05-30
HUT70082A (en) 1995-09-28
JPH07507584A (ja) 1995-08-24
AU678360B2 (en) 1997-05-29

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