WO1997025401A1 - Cleaning compositions - Google Patents
Cleaning compositions Download PDFInfo
- Publication number
- WO1997025401A1 WO1997025401A1 PCT/US1996/020219 US9620219W WO9725401A1 WO 1997025401 A1 WO1997025401 A1 WO 1997025401A1 US 9620219 W US9620219 W US 9620219W WO 9725401 A1 WO9725401 A1 WO 9725401A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- composition
- amine oxide
- composition according
- acid
- limescale
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 101
- 238000004140 cleaning Methods 0.000 title description 6
- 239000004094 surface-active agent Substances 0.000 claims abstract description 20
- 239000002562 thickening agent Substances 0.000 claims abstract description 18
- 150000001412 amines Chemical class 0.000 claims abstract description 15
- 238000003860 storage Methods 0.000 claims abstract description 14
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 8
- 229920001285 xanthan gum Polymers 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 6
- SYELZBGXAIXKHU-UHFFFAOYSA-N dodecyldimethylamine N-oxide Chemical group CCCCCCCCCCCC[N+](C)(C)[O-] SYELZBGXAIXKHU-UHFFFAOYSA-N 0.000 claims description 5
- 230000000694 effects Effects 0.000 claims description 5
- 150000003973 alkyl amines Chemical group 0.000 claims description 4
- 239000004310 lactic acid Substances 0.000 claims description 4
- 235000014655 lactic acid Nutrition 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 239000004908 Emulsion polymer Substances 0.000 claims description 2
- 229920002310 Welan gum Polymers 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims 6
- -1 alkyl dimethyl amine oxide Chemical compound 0.000 claims 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 5
- 239000006260 foam Substances 0.000 description 22
- 239000004579 marble Substances 0.000 description 9
- 239000000230 xanthan gum Substances 0.000 description 6
- 229940082509 xanthan gum Drugs 0.000 description 6
- 235000010493 xanthan gum Nutrition 0.000 description 6
- 239000002253 acid Substances 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 239000003205 fragrance Substances 0.000 description 4
- 238000000518 rheometry Methods 0.000 description 4
- 230000004580 weight loss Effects 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- 238000009825 accumulation Methods 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 3
- 239000011976 maleic acid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- 241000195940 Bryophyta Species 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000002009 alkene group Chemical group 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 235000011929 mousse Nutrition 0.000 description 2
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 150000001261 hydroxy acids Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 235000000396 iron Nutrition 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- FTUYQIPAPWPHNC-UHFFFAOYSA-M sodium;4-[[4-[benzyl(ethyl)amino]phenyl]-[4-[benzyl(ethyl)azaniumylidene]cyclohexa-2,5-dien-1-ylidene]methyl]benzene-1,3-disulfonate Chemical compound [Na+].C=1C=C(C(=C2C=CC(C=C2)=[N+](CC)CC=2C=CC=CC=2)C=2C(=CC(=CC=2)S([O-])(=O)=O)S([O-])(=O)=O)C=CC=1N(CC)CC1=CC=CC=C1 FTUYQIPAPWPHNC-UHFFFAOYSA-M 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
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
- C11D3/16—Organic compounds
- C11D3/34—Organic compounds containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/042—Acids
-
- 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
- C11D1/75—Amino oxides
-
- 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
-
- 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
- C11D17/003—Colloidal solutions, e.g. gels; Thixotropic solutions or pastes
-
- 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
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
-
- 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
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
- C11D3/2086—Hydroxy carboxylic acids-salts thereof
Definitions
- This invention relates to cleaning compositions particularly for use in removing limescale stains from surfaces, particularly compositions that are dispensable as foams.
- EP- A-0,589,761 discloses a thickened acidic aqueous cleaner for bathtubs and other hard surfaced items, which removes limescale, soap scum and greasy soil from surfaces of such items without damaging such surfaces.
- composition of the reference comprises:
- a nonionic surfactant (b) a nonionic surfactant; (c) a xanthan gum thickener having a molecular weight of about 1 ,000,000 to
- the composition of the reference does not include either sulfamic acid or amine oxide surfactants.
- EP-A-0,606,712 discloses a thickened buffered aqueous acidic composition.
- composition of the reference comprises citric acid and sodium citrate, and in the composition suitable thickeners include conventional thickeners such as xanthan gum, polymers, alkyl amines, and surfactant based thickeners as well as nonionic and amine oxide surfactants.
- suitable thickeners include conventional thickeners such as xanthan gum, polymers, alkyl amines, and surfactant based thickeners as well as nonionic and amine oxide surfactants.
- the composition of the reference does not include sulphamic acid.
- EP-A-0,666,304 discloses compositions comprising as a first essential ingredient an organic acid such as maleic acid. It is preferred in the invention of the reference to use maleic acid either alone or together with sulfonic acids such as sulfamic acid.
- compositions according to the reference invention comprise as a second essential ingredient a surfactant or mixtures thereof.
- the compositions comprise said surfactant in an appropriate amount below 1% by weight of the total composition.
- the composition of the reference does not include amine oxide surfactants.
- the compositions of the reference comprise thickeners.
- WO-A-94 28108 concerns oven cleaning compositions and does not deal with acidic limescale removing compositions.
- the subject invention is directed to a limescale removing composition which can be delivered as a foam.
- the subject invention provides an aqueous liquid storage- stable limescale removing foamable composition
- aqueous liquid storage- stable limescale removing foamable composition comprising: a. a mixture of sulphamic acid and at least one organic carboxylic acid; b. a thickening agent; c. an amine oxide surfactant.
- the subject invention provides a method of removing limescale from a substrate using the composition as set out above. Disclosure of Invention
- the composition of the invention comprises a mixture of sulphamic acid and at least one organic carboxylic acid.
- the sulphamic acid and the at least one other acid are preferably mixed in synergistically effective limescale removing amounts.
- the organic carboxylic acid has a molecular weight of 60-250. More preferably, the carboxylic acid is lactic acid, citric acid, or another hydroxy acid where the hydroxy group is ⁇ to at least one of the acid moieties.
- the mixture of acids is present in the range 5-20 weight percent of the aqueous cleaning composition and more preferably 10-20 weight percent.
- the composition of the invention can be dispensed as a foam through a foam dispenser.
- the composition may tend to be difficult to dispense in this way if the composition in use has a final viscosity which is much above 300 cps. All viscosity measurements stated herein are taken using a Brookfield viscometer, at 20°C using #3 spindle at 30 rpm. Preferably, the final viscosity is in the range 200-300 cps.
- the maximum viscosity of the composition of the invention is limited by the need for the composition to be dispensable through a foam dispenser, one aspect of particular importance is storage stability.
- the composition of the subject invention relies on a complex blend of components and inevitably the composition will be placed into its final package some long time before it comes into use in the hands of the ultimate consumer. It is important that the viscosity of the composition is maintained within parameters during storage to allow delivery through the foam dispenser. Long term stability of the viscosity is mainly determined by the optimized level and type of thickening agents. Thickeners which can be effective in the composition of the subject invention can be selected from the group consisting of acrylic emulsion polymer thickeners, xanthan gums, rhamsan gums, welan gums and polyurethanes. The preferred thickener is xanthan gum with altered rheology.
- the thickener is present in an amount of 0.001-5 weight percent based on the weight of the cleaning composition.
- the storage stable composition of the subject invention will preferably be dispensable as a foam through a foam dispenser after storage at room temperature for 6 months, and more preferable after storage at room temperature for 1 year.
- the storage stable composition of the subject invention will not show phase separation or precipitation after said storage, the viscosity of the composition remaining constant during said storage.
- the foaminess index ⁇ is between 15-50 and more typically between 20-30.
- the amount of thickener is instrumental in allowing the composition to remain storage stable, it should also be noted that the presence of particular amounts of other components in the composition may effect viscosity.
- the amine oxide surfactant can be expected to have an effect on the viscosity of the composition.
- Another important feature of the limescale removing composition of the invention is that the composition is dispensable as a foam. Dispensing as a foam allows the composition to remain on the limescale stain for an effective time. The composition should be able to remain in contact with and be able to wet and penetrate the limescale stain for a sufficient time to have an effective descaling effect. Subsequently, the composition must be able to be washed away easily with water.
- foams can be loose airy type foams, while at the other extreme, foams can be tight mousse like type foams.
- the composition of the subject invention ideally produces a foam which is roughly halfway between a loose airy type foam and a tight mousse type foam in order to give maximum descaling and a good cling parameter. Cling is measured by spraying about lOg of product onto the underside of a preweighed suspended plate weighing about 200g. The plate is left to hang for 5 minutes and is then re-weighed. The cling is determined by the amount of product remaining on the plate after 5 minutes.
- the cling parameter of the composition of the subject invention is 50 - 70% of product remaining on the surface after 5 minutes.
- the nature and amount of the amine oxide surfactant present in the composition of the invention will generally determine the foam profile and cling parameter of the composition. Additionally, however, the cling parameter is dependent on the amount of thickener present in the composition.
- the amine oxide preferably has the formula RR' R"NO, where R is a substituted or unsubstituted alkyl or alkene group contaimng from about 8 to about 30, preferably from about 10 to about 20, more preferably about 10 to 16 carbon atoms.
- R is an unsubstituted alkyl group.
- Groups R' and R" are each substituted or unsubstituted alkyl or alkene groups containing from about 1 to about 18, preferably from about 1 to about 4, carbon atoms. More preferably, R' and R" are each methyl groups.
- the amine oxide detergent surfactant can be prepared by known and conventional methods.
- One such method involves the oxidation of tertiary amines in the manner set forth in U.S. Patent No. 3,223,647 and British Patent 437,566.
- amine oxides are prepared by the controlled oxidation of the corresponding tertiary amines.
- the surfactant will be lauryl dimethyl amine oxide.
- the amine oxide surfactant is present in the amount of 2.0-8.0% by weight of the total composition.
- composition can contain other optional components appropriate to limescale removing compositions including dyes and fragrances.
- the balance of the composition of the invention (to 100 weight percent) is deionized water.
- composition of the invention is dispensable through a conventional foam dispenser.
- composition ofExample 3 had a viscosity of 250 cps and on dispensing through a conventional foam dispenser produced a foam with a cling parameter of 50 - 70% over a 5 minute period.
- the composition was stable on storage at room temperature for one year.
- the composition of Example 3 was tested for effectiveness by the marble cube test as follows:
- the average % weight loss (for the 3 cubes) ranged from 35 - 40%.
- a commercially available maleic acid limescale removing composition was tested in the same way as above and the % weight loss ranged from 20 - 30%.
- the subject invention provides a limescale removing composition which may be produced using conventional manufacturing methods and packaging.
- the foamable limescale removing composition maintains its foaming and rheological properties after shelf storage at room temperature for 6 months, preferably one year. This shelf stability will allow a consumer to effectively utilize the descaling composition even though the composition may be placed into its final package a long time prior to its purchase and use.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Inorganic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Detergent Compositions (AREA)
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Abstract
An aqueous liquid storage stable foamable limescale removing composition comprising a mixture of sulphamic acid and at least one organic carboxylic acid, a thickening agent and an amine oxide surfactant.
Description
CLEANING COMPOSITIONS
Technical Field
This invention relates to cleaning compositions particularly for use in removing limescale stains from surfaces, particularly compositions that are dispensable as foams.
Background Art Tap water always contains a certain amount of solubilized ions which eventually deposit as salts, on surfaces in contact with the water, as it evaporates. Such salts include calcium carbonate, commonly referred to as limescale. This phenomenon of limescale accumulation on surfaces which are often in contact with water may damage surfaces and affects the functioning of taps or appliances, such as irons. Also, the accumulation of limescale in the toilet bowl is aesthetically unpleasant and favors the deposition of further soil and the growth of microorganisms. It is therefore important to control this limescale accumulation.
Many limescale removing compositions are known in the art. For example, EP- A-0,589,761 discloses a thickened acidic aqueous cleaner for bathtubs and other hard surfaced items, which removes limescale, soap scum and greasy soil from surfaces of such items without damaging such surfaces.
One composition of the reference comprises:
(a) an anionic surfactant;
(b) a nonionic surfactant; (c) a xanthan gum thickener having a molecular weight of about 1 ,000,000 to
10,000,000 such as Kelzan® T sold by Merck & Co.; and
(d) 2 to 8 percent of an acid mixture of succinic acid; glutaric acid and adipic acid of about 1 :1:1; and
(e) balance being water, wherein the composition has a pH of about 1 to about 4, more preferably about 2.7 to about 3.3 and a Brookfield viscosity of about 200
to 1,000 cps at room temperature, using a #2 spindle and 50 φm. The composition of the reference does not include either sulfamic acid or amine oxide surfactants.
EP-A-0,606,712 discloses a thickened buffered aqueous acidic composition.
The composition of the reference comprises citric acid and sodium citrate, and in the composition suitable thickeners include conventional thickeners such as xanthan gum, polymers, alkyl amines, and surfactant based thickeners as well as nonionic and amine oxide surfactants. The composition of the reference does not include sulphamic acid.
EP-A-0,666,304 discloses compositions comprising as a first essential ingredient an organic acid such as maleic acid. It is preferred in the invention of the reference to use maleic acid either alone or together with sulfonic acids such as sulfamic acid.
The compositions according to the reference invention comprise as a second essential ingredient a surfactant or mixtures thereof. The compositions comprise said surfactant in an appropriate amount below 1% by weight of the total composition. The composition of the reference does not include amine oxide surfactants. Optionally, the compositions of the reference comprise thickeners.
WO-A-94 28108 concerns oven cleaning compositions and does not deal with acidic limescale removing compositions.
The subject invention is directed to a limescale removing composition which can be delivered as a foam.
In one embodiment, the subject invention provides an aqueous liquid storage- stable limescale removing foamable composition comprising: a. a mixture of sulphamic acid and at least one organic carboxylic acid; b. a thickening agent; c. an amine oxide surfactant.
In another embodiment, the subject invention provides a method of removing limescale from a substrate using the composition as set out above.
Disclosure of Invention
All amounts of components set out herein are given as percentages by weight of the limescale removing composition. The composition of the invention comprises a mixture of sulphamic acid and at least one organic carboxylic acid. The sulphamic acid and the at least one other acid are preferably mixed in synergistically effective limescale removing amounts. Preferably, the organic carboxylic acid has a molecular weight of 60-250. More preferably, the carboxylic acid is lactic acid, citric acid, or another hydroxy acid where the hydroxy group is α to at least one of the acid moieties.
Preferably, the mixture of acids is present in the range 5-20 weight percent of the aqueous cleaning composition and more preferably 10-20 weight percent.
The composition of the invention can be dispensed as a foam through a foam dispenser. The composition may tend to be difficult to dispense in this way if the composition in use has a final viscosity which is much above 300 cps. All viscosity measurements stated herein are taken using a Brookfield viscometer, at 20°C using #3 spindle at 30 rpm. Preferably, the final viscosity is in the range 200-300 cps. When the maximum viscosity of the composition of the invention is limited by the need for the composition to be dispensable through a foam dispenser, one aspect of particular importance is storage stability. The composition of the subject invention relies on a complex blend of components and inevitably the composition will be placed into its final package some long time before it comes into use in the hands of the ultimate consumer. It is important that the viscosity of the composition is maintained within parameters during storage to allow delivery through the foam dispenser. Long term stability of the viscosity is mainly determined by the optimized level and type of thickening agents. Thickeners which can be effective in the composition of the subject invention can be selected from the group consisting of acrylic emulsion polymer thickeners, xanthan gums, rhamsan gums, welan gums and polyurethanes. The preferred thickener is xanthan gum with altered rheology. Preferably, the thickener is present in an amount of 0.001-5 weight percent based on the weight of the cleaning composition.
The storage stable composition of the subject invention will preferably be dispensable as a foam through a foam dispenser after storage at room temperature for 6 months, and more preferable after storage at room temperature for 1 year. Preferably, the storage stable composition of the subject invention will not show phase separation or precipitation after said storage, the viscosity of the composition remaining constant during said storage.
Typically, the foaminess index Σ is between 15-50 and more typically between 20-30.
While the amount of thickener is instrumental in allowing the composition to remain storage stable, it should also be noted that the presence of particular amounts of other components in the composition may effect viscosity. In particular, the amine oxide surfactant can be expected to have an effect on the viscosity of the composition. Another important feature of the limescale removing composition of the invention is that the composition is dispensable as a foam. Dispensing as a foam allows the composition to remain on the limescale stain for an effective time. The composition should be able to remain in contact with and be able to wet and penetrate the limescale stain for a sufficient time to have an effective descaling effect. Subsequently, the composition must be able to be washed away easily with water. Of importance, therefore, in the effectiveness of the composition is the quality of the foam which is produced. At one extreme, foams can be loose airy type foams, while at the other extreme, foams can be tight mousse like type foams. The composition of the subject invention ideally produces a foam which is roughly halfway between a loose airy type foam and a tight mousse type foam in order to give maximum descaling and a good cling parameter. Cling is measured by spraying about lOg of product onto the underside of a preweighed suspended plate weighing about 200g. The plate is left to hang for 5 minutes and is then re-weighed. The cling is determined by the amount of product remaining on the plate after 5 minutes. Preferably, the cling parameter of the composition of the subject invention is 50 - 70% of product remaining on the surface after 5 minutes.
The nature and amount of the amine oxide surfactant present in the composition of the invention will generally determine the foam profile and cling parameter of the composition. Additionally, however, the cling parameter is dependent on the amount of thickener present in the composition. The amine oxide preferably has the formula RR' R"NO, where R is a substituted or unsubstituted alkyl or alkene group contaimng from about 8 to about 30, preferably from about 10 to about 20, more preferably about 10 to 16 carbon atoms. Preferably, R is an unsubstituted alkyl group. Groups R' and R" are each substituted or unsubstituted alkyl or alkene groups containing from about 1 to about 18, preferably from about 1 to about 4, carbon atoms. More preferably, R' and R" are each methyl groups.
The amine oxide detergent surfactant can be prepared by known and conventional methods. One such method involves the oxidation of tertiary amines in the manner set forth in U.S. Patent No. 3,223,647 and British Patent 437,566. In general terms, amine oxides are prepared by the controlled oxidation of the corresponding tertiary amines. Most preferably, the surfactant will be lauryl dimethyl amine oxide. Preferably, the amine oxide surfactant is present in the amount of 2.0-8.0% by weight of the total composition.
The composition can contain other optional components appropriate to limescale removing compositions including dyes and fragrances. The balance of the composition of the invention (to 100 weight percent) is deionized water.
The composition of the invention is dispensable through a conventional foam dispenser.
Modes for Carrvinp: Out the Invention Exemplary compositions of the invention are now set out below:
Exam le 1
Material % w/w
Deionized Water To balance
Xanthan gum with altered rheology (Kelco) 0.50
Sulphamic Acid (GelpKe and Bate Ltd.) 10.00
Citric Acid 4.00
Lauryl dimethyl amine oxide 2.00
1% Dye Solution - Blue 0.50
Fragrance 0.10
Exam le 2
Material % w/w
Deionized Water To balance
Xanthan gum with altered rheology (Kelco) 0.70
Sulphamic Acid (GelpKe and Bate Ltd.) 9.00
Lactic Acid (Purac®) 5.00
Lauryl dimethyl amine oxide 4.00
1% Dye Solution - Blue 0.30
Fragrance 0.20
Example 3
Material % w/
Deionized Water To balance
Xanthan gum with altered rheology (Kelco) 0.60
Sulphamic Acid (GelpKe and Bate Ltd.) 13.00
Lactic Acid (Purac®) 1.00
Lauryl dimethyl amine oxide 5.00
1% Dye Solution Acid Blue 7 0.40
Fragrance 0.10
The composition ofExample 3 had a viscosity of 250 cps and on dispensing through a conventional foam dispenser produced a foam with a cling parameter of 50 - 70% over a 5 minute period.
The composition was stable on storage at room temperature for one year. The composition of Example 3 was tested for effectiveness by the marble cube test as follows:
Marble Cube Test
1) 3 marble cubes weighing approximately 20g were washed with distilled water and dried in an oven until their weight was constant at room temperature.
2) Each marble cube was weighed (W0).
3) 150g of product being tested was weighed into a conical flask.
4) The pre-weighed marble cubes were placed into the test product. 5) The marble cubes were left on test for 18 hours.
6) After 18 hours, the marble cubes were removed from the test product and rinsed thoroughly with deionized water.
7) Each marble cube was dried in an oven for 12 hours and weighed at room temperature. (Wj) The percentage descaling was calculated as follows:
W0 - W, x 100% = % weight loss.
Interpretation of Results
The higher the percentage weight loss the greater the limescale removal activity of the product.
Results of the above Marble Cube Test
For the composition ofExample 3, the average % weight loss (for the 3 cubes) ranged from 35 - 40%.
Comparative Example 1
A commercially available maleic acid limescale removing composition was tested in the same way as above and the % weight loss ranged from 20 - 30%.
Industrial Applicability
The subject invention provides a limescale removing composition which may be produced using conventional manufacturing methods and packaging. The foamable limescale removing composition maintains its foaming and rheological properties after shelf storage at room temperature for 6 months, preferably one year. This shelf stability will allow a consumer to effectively utilize the descaling composition even though the composition may be placed into its final package a long time prior to its purchase and use.
Claims
1. An aqueous liquid storage stable foamable limescale removing composition comprising: a. a mixture of sulphamic acid and at least one organic carboxylic acid; b. a thickening agent; c. an amine oxide surfactant.
2. The composition according to claim 1 wherein the viscosity of the composition is 300 cps or less.
3. The composition according to claim 1 wherein the viscosity of the composition is in the range of 200 cps to 300 cps.
4. The composition according to claim 1 wherein the composition has a cling parameter of 50 - 70%.
5. The composition according to claim 1 wherein at least one carboxylic acid is lactic acid.
6. The composition according to claim 1 wherein at least one carboxylic acid is citric acid.
7. The composition according to claim 1 wherein the thickening agent is selected from the group consisting of acrylic emulsion polymers, xanthan gums, rhamsan gums, welan gums and polyurethane.
8. The composition according to claim 1 wherein the amine oxide surfactant is an alkyl amine oxide surfactant.
9. The composition according to claim 8 wherein the alkyl amine oxide surfactant is a C10-C16 alkyl dimethyl amine oxide.
10. The composition according to claim 9 wherein the alkyl amine oxide surfactant is lauryl dimethyl amine oxide.
11. The composition according to claim 1 wherein said mixture of sulphamic acid and at least one organic carboxylic acid are admixed together in synergistically effective limescale removing amounts.
12. An aqueous liquid storage stable foamable limescale removing composition comprising:
5-20% by weight of a mixture of sulphamic acid and at least one organic carboxylic acid; 0.001 -5% by weight of a thickening agent;
2.0-8.0% by weight of an amine oxide surfactant wherein the balance of the composition is deionized water.
13. A method of removing limescale from a substrate comprising the steps of applying the composition of claim 1 to a substrate containing limescale; allowing the composition to remain in contact with the substrate for a sufficient amount of time to have a descaling effect; and removing the composition from the substrate.
14. The method of removing limescale from a substrate according to claim 13 wherein the composition comprises: 5-20% by weight of a mixture of sulphamic acid and at least one organic carboxylic acid; 0.001-5% by weight of a thickening agent; 2.0- 8.0% by weight of an amine oxide surfactant wherein the balance of the composition is deionized water.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE69620158T DE69620158T2 (en) | 1996-01-03 | 1996-12-19 | CLEANING SUPPLIES |
| DK96944872T DK0813585T3 (en) | 1996-01-03 | 1996-12-19 | Cleaning Compositions |
| AT96944872T ATE215121T1 (en) | 1996-01-03 | 1996-12-19 | CLEANING SUPPLIES |
| AU13374/97A AU713065B2 (en) | 1996-01-03 | 1996-12-19 | Cleaning compositions |
| BR9607812A BR9607812A (en) | 1996-01-03 | 1996-12-19 | Cleaning compositions |
| EP96944872A EP0813585B1 (en) | 1996-01-03 | 1996-12-19 | Cleaning compositions |
| MXPA/A/1997/006712A MXPA97006712A (en) | 1996-01-03 | 1997-09-03 | Limpi compositions |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB9600030.2 | 1996-01-03 | ||
| GBGB9600030.2A GB9600030D0 (en) | 1996-01-03 | 1996-01-03 | Cleaning compositions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1997025401A1 true WO1997025401A1 (en) | 1997-07-17 |
Family
ID=10786532
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/US1996/020219 WO1997025401A1 (en) | 1996-01-03 | 1996-12-19 | Cleaning compositions |
Country Status (12)
| Country | Link |
|---|---|
| EP (1) | EP0813585B1 (en) |
| KR (1) | KR19980702727A (en) |
| CN (1) | CN1181105A (en) |
| AT (1) | ATE215121T1 (en) |
| AU (1) | AU713065B2 (en) |
| BR (1) | BR9607812A (en) |
| CA (1) | CA2214524A1 (en) |
| DE (1) | DE69620158T2 (en) |
| DK (1) | DK0813585T3 (en) |
| ES (1) | ES2170887T3 (en) |
| GB (1) | GB9600030D0 (en) |
| WO (1) | WO1997025401A1 (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999023194A1 (en) * | 1997-10-31 | 1999-05-14 | The Procter & Gamble Company | Liquid acidic limescale removal compositions packaged in a spray-type dispenser |
| WO1999032592A1 (en) * | 1997-12-22 | 1999-07-01 | S. C. Johnson & Son, Inc. | Cleaning compositions for ceramic and porcelain surfaces and related methods |
| US6333299B1 (en) | 1997-10-31 | 2001-12-25 | The Procter & Gamble Co. | Liquid acidic limescale removal composition packaged in a spray-type dispenser |
| WO2004078901A1 (en) * | 2003-02-28 | 2004-09-16 | The Procter & Gamble Company | Foam-generating kit containing a foam-generating dispenser and a high viscosity composition |
| WO2004078903A1 (en) * | 2003-02-28 | 2004-09-16 | The Procter & Gamble Company | A cleaning kit and/or a dishwashing kit containing a foam-generating dispenser and a cleaning and/or dishwashing composition |
| WO2005103218A1 (en) * | 2004-04-21 | 2005-11-03 | Henkel Kommanditgesellschaft Auf Aktien | Highly acidic sanitary cleaner having stabilised viscosity and time behaviour |
| US7402554B2 (en) | 2003-02-28 | 2008-07-22 | The Procter & Gamble Company | Foam-generating kit containing a foam-generating dispenser and a composition containing a high level of surfactant |
| CN100519726C (en) * | 2003-02-28 | 2009-07-29 | 宝洁公司 | Foam-generating kit containing a foam-generating dispenser and a high viscosity composition |
| US7651992B2 (en) | 2003-02-28 | 2010-01-26 | The Procter & Gamble Company | Foam-generating kit containing a foam-generating dispenser and a composition containing a high level of surfactant |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2841802B1 (en) * | 2002-07-08 | 2005-03-04 | Commissariat Energie Atomique | COMPOSITION, FOAM AND METHOD FOR DECONTAMINATING SURFACES |
| JP4732115B2 (en) * | 2005-10-14 | 2011-07-27 | 花王株式会社 | Acid detergent composition for hard surfaces |
| CN110498867B (en) * | 2018-05-17 | 2021-08-03 | 中国石油化工股份有限公司 | Modified welan gum, preparation method thereof, water-based fracturing fluid composition and water-based fracturing fluid |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1240469A (en) * | 1967-08-08 | 1971-07-28 | Atlas Preservative Company Ltd | Improvements in or relating to cleaning compositions |
| FR2469450A1 (en) * | 1979-11-12 | 1981-05-22 | Solitaire Produits Entretien F | Aq. aerosol descaling and cleaning compsn. - contg. organic acid, surfactant, gelling agent and hygroscopic agent |
| EP0130786A2 (en) * | 1983-07-05 | 1985-01-09 | Ecolab Inc. | Foamable, acidic cleaning compositions |
| EP0253676A2 (en) * | 1986-07-17 | 1988-01-20 | R & C PRODUCTS PTY. LIMITED | Amine-acid thickening compositions |
| EP0656417A1 (en) * | 1993-11-29 | 1995-06-07 | The Procter & Gamble Company | Limescale removal compositions |
-
1996
- 1996-01-03 GB GBGB9600030.2A patent/GB9600030D0/en active Pending
- 1996-10-19 KR KR1019970706134A patent/KR19980702727A/en active IP Right Grant
- 1996-12-19 CA CA002214524A patent/CA2214524A1/en not_active Abandoned
- 1996-12-19 DE DE69620158T patent/DE69620158T2/en not_active Expired - Fee Related
- 1996-12-19 CN CN96193159A patent/CN1181105A/en active Pending
- 1996-12-19 EP EP96944872A patent/EP0813585B1/en not_active Expired - Lifetime
- 1996-12-19 AT AT96944872T patent/ATE215121T1/en not_active IP Right Cessation
- 1996-12-19 BR BR9607812A patent/BR9607812A/en not_active Application Discontinuation
- 1996-12-19 AU AU13374/97A patent/AU713065B2/en not_active Ceased
- 1996-12-19 ES ES96944872T patent/ES2170887T3/en not_active Expired - Lifetime
- 1996-12-19 WO PCT/US1996/020219 patent/WO1997025401A1/en active IP Right Grant
- 1996-12-19 DK DK96944872T patent/DK0813585T3/en active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1240469A (en) * | 1967-08-08 | 1971-07-28 | Atlas Preservative Company Ltd | Improvements in or relating to cleaning compositions |
| FR2469450A1 (en) * | 1979-11-12 | 1981-05-22 | Solitaire Produits Entretien F | Aq. aerosol descaling and cleaning compsn. - contg. organic acid, surfactant, gelling agent and hygroscopic agent |
| EP0130786A2 (en) * | 1983-07-05 | 1985-01-09 | Ecolab Inc. | Foamable, acidic cleaning compositions |
| EP0253676A2 (en) * | 1986-07-17 | 1988-01-20 | R & C PRODUCTS PTY. LIMITED | Amine-acid thickening compositions |
| EP0656417A1 (en) * | 1993-11-29 | 1995-06-07 | The Procter & Gamble Company | Limescale removal compositions |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999023194A1 (en) * | 1997-10-31 | 1999-05-14 | The Procter & Gamble Company | Liquid acidic limescale removal compositions packaged in a spray-type dispenser |
| EP0919610A1 (en) * | 1997-10-31 | 1999-06-02 | The Procter & Gamble Company | Liquid acidic limescale removal compositions packaged in a spray-type dispenser |
| US6333299B1 (en) | 1997-10-31 | 2001-12-25 | The Procter & Gamble Co. | Liquid acidic limescale removal composition packaged in a spray-type dispenser |
| WO1999032592A1 (en) * | 1997-12-22 | 1999-07-01 | S. C. Johnson & Son, Inc. | Cleaning compositions for ceramic and porcelain surfaces and related methods |
| WO2004078901A1 (en) * | 2003-02-28 | 2004-09-16 | The Procter & Gamble Company | Foam-generating kit containing a foam-generating dispenser and a high viscosity composition |
| WO2004078903A1 (en) * | 2003-02-28 | 2004-09-16 | The Procter & Gamble Company | A cleaning kit and/or a dishwashing kit containing a foam-generating dispenser and a cleaning and/or dishwashing composition |
| US7402554B2 (en) | 2003-02-28 | 2008-07-22 | The Procter & Gamble Company | Foam-generating kit containing a foam-generating dispenser and a composition containing a high level of surfactant |
| CN100519726C (en) * | 2003-02-28 | 2009-07-29 | 宝洁公司 | Foam-generating kit containing a foam-generating dispenser and a high viscosity composition |
| US7651992B2 (en) | 2003-02-28 | 2010-01-26 | The Procter & Gamble Company | Foam-generating kit containing a foam-generating dispenser and a composition containing a high level of surfactant |
| WO2005103218A1 (en) * | 2004-04-21 | 2005-11-03 | Henkel Kommanditgesellschaft Auf Aktien | Highly acidic sanitary cleaner having stabilised viscosity and time behaviour |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0813585A1 (en) | 1997-12-29 |
| CA2214524A1 (en) | 1997-07-17 |
| EP0813585B1 (en) | 2002-03-27 |
| AU1337497A (en) | 1997-08-01 |
| BR9607812A (en) | 1998-07-07 |
| DE69620158D1 (en) | 2002-05-02 |
| KR19980702727A (en) | 1998-08-05 |
| CN1181105A (en) | 1998-05-06 |
| ES2170887T3 (en) | 2002-08-16 |
| AU713065B2 (en) | 1999-11-25 |
| DK0813585T3 (en) | 2002-07-08 |
| ATE215121T1 (en) | 2002-04-15 |
| DE69620158T2 (en) | 2002-08-14 |
| GB9600030D0 (en) | 1996-03-06 |
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