EP0647264B1 - Improvements relating to cleaning compositions - Google Patents
Improvements relating to cleaning compositions Download PDFInfo
- 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
- Authority
- EP
- European Patent Office
- Prior art keywords
- solvent
- composition according
- solvent component
- composition
- water
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 111
- 238000004140 cleaning Methods 0.000 title claims abstract description 51
- 230000006872 improvement Effects 0.000 title description 4
- 239000002904 solvent Substances 0.000 claims abstract description 101
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000004094 surface-active agent Substances 0.000 claims abstract description 28
- 239000000839 emulsion Substances 0.000 claims abstract description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 239000003945 anionic surfactant Substances 0.000 claims description 15
- 159000000003 magnesium salts Chemical class 0.000 claims description 14
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 13
- 238000009472 formulation Methods 0.000 claims description 13
- -1 glycol ethers Chemical class 0.000 claims description 10
- 239000002736 nonionic surfactant Substances 0.000 claims description 10
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 claims description 9
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 8
- NTKBNCABAMQDIG-UHFFFAOYSA-N 3-butoxypropan-1-ol Chemical compound CCCCOCCCO NTKBNCABAMQDIG-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 238000005191 phase separation Methods 0.000 claims description 5
- 150000001298 alcohols Chemical class 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- 239000007921 spray Substances 0.000 claims description 4
- 229910021653 sulphate ion Inorganic materials 0.000 claims description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- GQCZPFJGIXHZMB-UHFFFAOYSA-N 1-tert-Butoxy-2-propanol Chemical compound CC(O)COC(C)(C)C GQCZPFJGIXHZMB-UHFFFAOYSA-N 0.000 claims description 2
- WMDZKDKPYCNCDZ-UHFFFAOYSA-N 2-(2-butoxypropoxy)propan-1-ol Chemical compound CCCCOC(C)COC(C)CO WMDZKDKPYCNCDZ-UHFFFAOYSA-N 0.000 claims description 2
- GZMAAYIALGURDQ-UHFFFAOYSA-N 2-(2-hexoxyethoxy)ethanol Chemical compound CCCCCCOCCOCCO GZMAAYIALGURDQ-UHFFFAOYSA-N 0.000 claims description 2
- GYIXQTJAIAZSHP-UHFFFAOYSA-N 2-[2-[(2-methylpropan-2-yl)oxy]propoxy]propan-1-ol Chemical compound OCC(C)OCC(C)OC(C)(C)C GYIXQTJAIAZSHP-UHFFFAOYSA-N 0.000 claims description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 2
- 150000001299 aldehydes Chemical class 0.000 claims description 2
- 238000007046 ethoxylation reaction Methods 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 abstract description 6
- 230000008020 evaporation Effects 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 5
- 238000003860 storage Methods 0.000 abstract description 4
- 230000009471 action Effects 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000012071 phase Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical group CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 125000000129 anionic group Chemical group 0.000 description 9
- 239000000271 synthetic detergent Substances 0.000 description 6
- 239000003599 detergent Substances 0.000 description 5
- 239000004530 micro-emulsion Substances 0.000 description 5
- 239000002689 soil Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- IDQBJILTOGBZCR-UHFFFAOYSA-N 1-butoxypropan-1-ol Chemical compound CCCCOC(O)CC IDQBJILTOGBZCR-UHFFFAOYSA-N 0.000 description 3
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003752 hydrotrope Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 229940091250 magnesium supplement Drugs 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- JYVLIDXNZAXMDK-UHFFFAOYSA-N pentan-2-ol Chemical compound CCCC(C)O JYVLIDXNZAXMDK-UHFFFAOYSA-N 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 235000015096 spirit Nutrition 0.000 description 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- XGPGFVIAZHLWBN-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical group CCCCOCC(C)O.CCCCOCC(C)O XGPGFVIAZHLWBN-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- UPGSWASWQBLSKZ-UHFFFAOYSA-N 2-hexoxyethanol Chemical compound CCCCCCOCCO UPGSWASWQBLSKZ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- LDMRLRNXHLPZJN-UHFFFAOYSA-N 3-propoxypropan-1-ol Chemical compound CCCOCCCO LDMRLRNXHLPZJN-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- 239000003082 abrasive agent Substances 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 229940117927 ethylene oxide Drugs 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 230000008571 general function Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 150000002681 magnesium compounds Chemical class 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 229960000869 magnesium oxide Drugs 0.000 description 1
- 235000012245 magnesium oxide Nutrition 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000002888 zwitterionic surfactant Substances 0.000 description 1
Images
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
- C11D3/43—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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Abstract
Description
- The present invention relates to improvements relating to cleaning compositions and in particular to improvements relating to cleaning compositions comprising surfactants and solvents.
- Many cleaning 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.
- Many of these 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.
- One such emulsion is disclosed in US-A-4689168 (The Drackett Company) which discloses anisotropic hard surface cleaning compositions containing volatile silicones, a non-volatile surfactant preferably selected from amongst anionic, nonionic surfactants and mixtures thereof and a polar organic solvent having a boiling point in the range 75-250°C which is preferably ethyl, propyl or butyl alcohol and water.
- 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. As consumers prefer stable, 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). In that document are described 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. In that specification it is stated that the use of sprays to deliver the compositions to a surface is to be avoided due to odour problems.
- A related later application EP-A-0428816 (P&G: 1989/90) 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.
- Other systems have comprised emulsions. 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.
- Similar emulsion systems are disclosed in EP-A-0347110 (Colgate: 1988): which relates to clear liquid detergents comprising anionics and nonionics, polar solvent consisting of C1-C4 alkyl ethers of ethylene or diethylene glycol of mono, di or tripropylene glycol and 2.5-5% fragrance at pH 6-7 The last above-mentioned specification also discusses the detergency enhancing effect of magnesium in formulations containing anionic surfactants.
- 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.
- Despite the research which has been conducted in this field a number of technical problems remain.
- Where microemulsions are employed they are difficult to produce, but where they are not used insufficient solvent may be present for effective cleaning.
- In addition, the use of certain surfactants may lead to a product which are unstable, or appear so, on even short term storage. These products may be discarded by consumers thereby pointlessly releasing surfactants and solvents into the environment.
- Moreover, normal use of a surfactanVsolvent cleaning composition will increase the environmental loading of solvent and surfactant.
- It is therefore desirable to ensure that of the surfactants released into the environment some are readily biodegradable and consequently use of environmentally preferable surfactants in cleaning compositions is preferred. Unfortunately, it has proved difficult to formulate homogeneous solvent-containing systems which comprise these surfactants.
- Additionally, the use of lower rather than higher levels of solvent is preferred as this reduces both cost and environmental release of solvent. However as mentioned above, the use of low levels of solvent can give poor cleaning results.
- From the above it can be seen that it is desirable to prepare stable, biodegradable, products which comprise relatively low levels of solvent and which provide the effective cleaning performance associated with higher levels of solvent.
- We have now devised homogeneneous solvent and surfactant-containing systems which, in use, decompose into emulsions.
- Accordingly, the present invention provides a homogeneous, isotropic, aqueous, solvent-containing, cleaning composition wherein the solvent system comprises:
- a) a first, glycol ether solvent component in an amount such that it is present at a level above the miscibility limit of that solvent component with water, and,
- b) a second solvent component present at a level such that the first solvent component is solubilised in the composition, said second solvent component being sufficiently volatile that, in use, said second solvent component evaporates from the composition to leave a solvent-water emulsion comprising the first solvent component and water.
- By using the second, volatile solvent to assist in the solution of the first solvent it is possible to obtain compositions which are clear, stable, isotropic compositions and do not constitute microemulsions. In use of the product, 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. This yields the advantages of astable non-emulsion product as regards storage, dosing and manufacture, employs a relatively low level of solvent and provides the cleaning benefits of a free-solvent system.
- The presence of a first solvent component in an amount such that it is present at a level above the miscibility limit of said solvent component with water is an essential feature of the invention.
- Preferably, 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.
- Most preferably, 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 presence of a second, volatile solvent component is an essential feature of the invention.
- Preferably, the second solvent component is selected from volatile alcohols; water miscible, volatile glycol ethers, aldehydes, ketones, di-alkyl ethers and mixtures thereof.
- More preferably, said second solvent component is selected from the group comprising: methanol, ethanol, isopropyl alcohol, ethylene glycol monobutyl ether and mixtures thereof.
- Most preferably, 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.
- Surfactants 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.
- In embodiments 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.
- In particularly preferred embodiments of the present invention the cleaning composition further comprises an 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.
- Preferably the 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 C10-C18 alkylbenzene sulphonates, C10-C18 alkanesulphonates, sulphonated C10-C22 fatty acids or esters thereof, C8-C18 olefinsulphonates, di-(C6-C10 alkyl) sulphosuccinates, C10-C18 alkylsulphates, C10-C18 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).
- Particularly, preferred amongst 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:
- ROS03X
- In general, 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.
- In addition to, or as an alternative to, anionic surfactants, nonionic surfactants can be employed. The preferred nonionic surfactant is selected from the group comprising ethoxylated alcohols of the general formula:
- R1-(OCH2CH2)m-OH
- As is illustrated by reference to examples given below, we have determined that particularly effective 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.
- Preferred compositions according to the present invention therefore comprise:
- a) the magnesium salt of an anionic surfactant, preferably the magnesium salt of primary alcohol sulphate,
- b) 6%-12% wt n-butoxy propanol,
- c) water, and,
- d) sufficient volatile alcohol to prevent phase separation between the water and the n-butoxy propanol.
- The 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.
- It is preferable to spray the 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.
- Accordingly, a further aspect of the present invention comprises a process including the steps of:
- a) directly treating a surface with a composition according to the present invention,
- b) permitting the second solvent component to at least partially evaporate, and,
- c) performing a mechanical cleaning operation.
- A yet further aspect of the present invention relates to 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.
- In order that the present invention may be further understood it will be described hereafter by way of example and with reference to the accompanying figures 1 and 2 wherein;
- Figure 1 is a graph showing the cleaning efficiency of commercial n-butoxy propan-2-ol (DOWANOL PnB) with concentration, and,
- Figure 2 illustrates the cleaning efficiency of the compositions prepared as examples in graphical form.
- Cleaning compositions were prepared as in Table 1 below, all figures being given in wt% on product and being made up to 100% with water. The following abbreviations are used to identify the components mentioned in Tables 1, 2 and 3:
- PnB: Dowanol PnB [RTM]: n-butoxy propan-2-ol,
- P2L: Pentan-2-ol,
- IMS: Industrial methylated spirits: ethanol,
- BD: Butyl Digol [RTM]: di ethylene glycol butyl ether
- DOB: Dobanol 91-8 [RTM]: nonionic surfactant
- NH3: Ammonia
- LAS: Linear alkyl sulphonate: surfactant (as ammonium salt).
- PAS: Magnesium salt of Clo-C,8 primary alcohol sulphate: anionic surfactant.
- NON: Dobanol 91-350FA [RTM]: nonionic surfactant.
- From figure 1 it can be seen that the cleaning efficiency of PnB-based compositions is particularly dependent on PnB concentration in the range between 5 and 7 wt% concentration on product. To obtain these results 1.0 ml of each neat sample was applied with a sponge on to soiled Decamel [RTM] tiles (soiled with 80/20 fat/particulate soil at 0.25mg/cm.cm) and wiped using 10 reciprocal Sheen rubbing cycles (76 g/cm.cm applied load). The percentage cleaning efficiency was calculated from reflectance measurements.
- The maximum miscibility of PnB with water is around 6%wt and consequently formulations comprising >6%wt are normally phase separated into an aqueous and an excess solvent phase. From Figure 1 it is clear that free solvent is far more effective in cleaning operations than solvent which is dissolved in an aqueous medium.
- 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.
- In order to determine the effectiveness of the compositions, 0.6ml of each neat sample was sprayed on to soiled Decamel [RTM] tiles (soiled with 80/20 fat/particulate soil at 0.25mg/cm.cm) and left for one minute before wiping with a sponge cloth using 10 reciprocal Sheen rubbing cycles (76 g/cm.cm applied load). The percentage cleaning efficiency was calculated from tile-surface reflectance measurements. Comparative examples are marked with an asterisk.
- Percentage cleaning efficiency results for the above mentioned formulations are shown in figure 2. In decreasing order, cleaning efficiency was 3>2>1>4.
- 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.
- A significant improvement is attained when the starting concentration of PnB is above the maximum miscibility level, as in example 3. The 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.
- In order to further demonstrate the characteristic features of the present invention a number of known compositions as described in EP-A-0428816 were prepared with the formulations given below in Table 2 and their phase-behaviour on evaporation noted. The balance of each composition was water and the figures quoted are weight percentages on product. Examples 5-12, as marked with an asterisk, are these comparative examples whereas example 13 is an embodiment of the invention, identical to example 3 given above.
- All samples were clear isotropic liquids at room temperature apart from sample 8 which was cloudy This sample was therefore excluded from the following.
- In separate experiments 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.
- Further examples are given in Table 3 below. Examples 14-27 illustrate the effect of the choice of surfactant on product performance.
- To obtain the results listed in Table 3, 1.0 ml of each neat sample was applied with a sponge on to soiled Decamel [RTM] tiles (soiled with 80/20 fat/particulate soil at 0.25mg/cm.cm) and wiped by hand using reciprocal rubbing cycles. The cleaning efficiency was determined in relation to the effort required: 1 corresponds to little effort whereas 5 corresponds to some difficulty in removing the soil. Comparative examples are indicated by an asterisk.
- As noted above, the maximum miscibility of PnB with water is around 6%wt and consequently formulations comprising >6%wt PnB are normally phase separated into an aqueous phase and an excess solvent phase. However, in the presence of the cosolvent the formulations of examples 16-19 exhibited a single phase.
- 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.
- It can be seen from embodiments 17 and 19 that the addition of IPA or IMS as co-solvents in the presence of a slightly increased level of PnB improves the cleaning performance greatly. This is in agreement with the results discussed above comparing examples 1 and 3 as 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.
- From the examples given above it can be seen that homogeneous, solvent systems which phase separate to form an emulsion on evaporation of a portion of the solvent give improved cleaning performance over homogeneous systems which comprise similar quantities of solvent but which do not exhibit the phase separation behaviour in use.
wherein R is a C8 to C18 primary alkyl group and X is a solubilising cation. Suitable cations include sodium, magnesium, potassium, ammonium and mixtures thereof.
wherein R1 is straight or branched, C8 to C18 alkyl and the average degree of ethoxylation (i.e. the ethylene oxide chain length) m is 1-14.
Claims (14)
Applications Claiming Priority (7)
Application Number | Priority Date | Filing Date | Title |
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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 (en) | 1992-06-18 | 1993-05-27 | Improvements relating to cleaning compositions |
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EP0647264A1 EP0647264A1 (en) | 1995-04-12 |
EP0647264B1 true EP0647264B1 (en) | 1996-04-24 |
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CZ (1) | CZ319594A3 (en) |
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ES (1) | ES2087743T3 (en) |
HU (1) | HUT70082A (en) |
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MY (1) | MY109133A (en) |
SK (1) | SK154894A3 (en) |
WO (1) | WO1993025654A1 (en) |
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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 |
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US3764544A (en) * | 1971-08-06 | 1973-10-09 | L Haworth | Spot remover for wearing apparel |
EP0005309A1 (en) * | 1978-02-14 | 1979-11-14 | Dawley Brook Papers Limited | Cleaning composition and method of removing printing ink from surfaces |
US4212758A (en) * | 1978-10-20 | 1980-07-15 | Belkevich Petr I | Cleansing agents containing oleic acid, isopropanol and ethylacetate |
SE438162B (en) * | 1979-05-29 | 1985-04-01 | Tepab Tek Prod Ab | PROCEDURE FOR CLEANING A SURFACE, IN PARTICULAR REMOVAL OF COATING LAYERS AND LAYOUTS FROM A SURFACE |
CA1178160A (en) * | 1981-09-10 | 1984-11-20 | Donald B. Compton | Liquid hard-surface cleaner |
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 (en) * | 1989-11-23 | 1991-05-29 | The Procter & Gamble Company | Hard-surface cleaning compositions |
ZA925727B (en) * | 1991-08-09 | 1993-03-10 | Bristol Myers Squibb Co | Glass cleaning composition. |
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1993
- 1993-05-27 BR BR9306574A patent/BR9306574A/en not_active Application Discontinuation
- 1993-05-27 SK SK1548-94A patent/SK154894A3/en unknown
- 1993-05-27 HU HU9403634A patent/HUT70082A/en unknown
- 1993-05-27 DE DE69302384T patent/DE69302384T2/en not_active Expired - Fee Related
- 1993-05-27 JP JP6501062A patent/JPH07507584A/en active Pending
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- 1993-05-27 ES ES93912803T patent/ES2087743T3/en not_active Expired - Lifetime
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- 1993-05-27 EP EP93912803A patent/EP0647264B1/en not_active Expired - Lifetime
- 1993-05-27 WO PCT/EP1993/001330 patent/WO1993025654A1/en not_active Application Discontinuation
- 1993-05-27 CZ CZ943195A patent/CZ319594A3/en unknown
- 1993-06-16 MY MYPI93001174A patent/MY109133A/en unknown
- 1993-06-17 IN IN194BO1993 patent/IN176902B/en unknown
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EP0647264A1 (en) | 1995-04-12 |
CA2136850A1 (en) | 1993-12-23 |
SK154894A3 (en) | 1995-07-11 |
CZ319594A3 (en) | 1995-05-17 |
DE69302384T2 (en) | 1996-09-26 |
WO1993025654A1 (en) | 1993-12-23 |
BR9306574A (en) | 1998-12-08 |
DE69302384D1 (en) | 1996-05-30 |
HUT70082A (en) | 1995-09-28 |
JPH07507584A (en) | 1995-08-24 |
AU678360B2 (en) | 1997-05-29 |
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