EP3268459B1 - Compositions de nettoyage concentrées stables pour surfaces dures - Google Patents

Compositions de nettoyage concentrées stables pour surfaces dures Download PDF

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Publication number
EP3268459B1
EP3268459B1 EP16707122.4A EP16707122A EP3268459B1 EP 3268459 B1 EP3268459 B1 EP 3268459B1 EP 16707122 A EP16707122 A EP 16707122A EP 3268459 B1 EP3268459 B1 EP 3268459B1
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EP
European Patent Office
Prior art keywords
compositions
composition
viscosity
aqueous cleansing
recovery
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP16707122.4A
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German (de)
English (en)
Other versions
EP3268459A1 (fr
Inventor
Sumanth Kumar ARNIPALLY
Manoj Vilas Dagaonkar
Jiji Paul Kottukapally
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Unilever PLC
Unilever NV
Original Assignee
Unilever PLC
Unilever NV
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Publication of EP3268459A1 publication Critical patent/EP3268459A1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/37—Mixtures of compounds all of which are anionic
    • 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
    • C11D3/12—Water-insoluble compounds
    • C11D3/1233—Carbonates, e.g. calcite or dolomite
    • 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
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers

Definitions

  • the invention is in the field of dilutable concentrated aqueous cleansing compositions for hard surface cleaning, especially dishwashing.
  • Aqueous dishwash compositions are now used in many countries and their use is expected to increase in the coming years. Such compositions usually contain about 50 to 70 wt% water. The balance is usually made up of anionic surfactants, in particular alkylbenzene sulphonates and ethoxylated sulphates, some amount of magnesium sulphate for grease removal, perfume, colour and other additives. Some products may also contain an alkaline ingredient like sodium carbonate.
  • thermal stability is very important. However it is observed that the viscosity of such compositions often varies with change in temperature. Such changes are not desirable because during storage and transportation, the compositions invariably get exposed to extreme and rapidly changing temperatures. Thermal stability tests are done to check beforehand whether the compositions meet the stringent requirements or not. Samples are exposed to low temperature for a long time and then allowed to equilibrate with room temperature.
  • composition contains a natural, biopolymeric or synthetic gum thickener along with polyhydric alcohol and urea.
  • the gum provides thickening while the urea and polyhydric alcohol provide stability and controlled flow which is further aided by adjustment of pH.
  • compositions of GB1164854 (Cook et.al., 1969) are stabilised by way of metal salts like chlorides and sulphates of Zinc, Magnesium, Aluminium and Calcium.
  • compositions of EP2770044 A1 (Unilever, 2014 ) are lamellar gels having alkyl benzene sulphonate and (poly)ethoxylated alkyl sulphate in the ratio of 4:1 to 1:1. They are free of any alkali, in particular, sodium carbonate.
  • the compositions contain at least 1 wt% amine oxide and 1 to 12 wt% electrolyte with at least 2 wt% performance additives.
  • US4692275 A discloses powder detergent compositions with a mixed surfactant system containing a C 8 -C 18 alkylbenzene sulphonate and C 12 -C 18 alcohol ethoxysulphate.
  • the total surfactant content is up to 20 wt% and the ratio of sulphonate to sulphate is from 3.5:1 to 1.5:1.
  • An alkaline material such as sodium carbonate is included in aqueous concentrated dishwash compositions in order to increase the pH and provide enough reserve alkalinity for better degreasing. It helps to include high levels of sodium carbonate in order to formulate a stable concentrated cleansing product.
  • the benefits tend to be offset by instability and none of the prior art discussed earlier provide a useful solution for alkaline compositions.
  • a concentrated aqueous cleansing composition comprising:
  • an aqueous cleansing composition comprising one part by weight of the composition of the first aspect and one to three parts by weight of water.
  • the concentrated aqueous cleansing compositions of the invention comprise 14 wt% to 35 wt% of a mixed anionic surfactant system containing alkyl benzenesulphonate and (poly)ethoxylated sulphate.
  • the surfactants assist in removing soil and grease from utensils and also assist in maintaining the soil in solution or suspension in the wash liquor.
  • alkylbenzene sulphonate is a linear alkylbenzene sulphonate having alkyl chain length of C 8 -C 20 .
  • the counter ion for anionic surfactants is an alkali metal, typically sodium, although instead of alkali metals, other amine based counter ions can also be present.
  • Preferred linear alkyl benzene sulphonate surfactants include sodium salt of alkyl benzene sulphonates with an alkyl chain length of from 8 to 15, more preferably 12 to 14.
  • the mixed anionic surfactant system also has a (poly)ethoxylated sulphate.
  • General formula of such surfactants is RO(C 2 H 4 0) x SO 3 - M + where R is an alkyl chain having from 10 to 22 carbon atoms, saturated or unsaturated, M is a cation which makes the compound water-soluble, especially an alkali metal, ammonium or substituted ammonium cation, and x averages from 1 to 15.
  • R is an alkyl chain having from 12 to 16 carbon atoms
  • M is sodium and x averages from 1 to 3, preferably x is 1;
  • SLES sodium lauryl ether sulphate
  • SLES sodium salt of lauryl ether sulphonic acid in which the predominantly C12 lauryl alkyl group has been ethoxylated with an average of 1 mole of ethylene oxide per mole.
  • the ratio of (a):(b), i.e., the ratio of the total amount of alkyl benzene sulphonate to the total amount of (poly)ethoxylated sulphate is from 1:1 to 3:1 parts by weight.
  • compositions according to the invention have 15 wt% to 35 wt% of the mixed anionic surfactant system. More preferred compositions have 15 wt% to 30 wt%. When the total amount of anionic surfactant is more than 35 wt% or less than 12 wt%, there is no appreciable change in viscosity of the composition as a function of temperature.
  • the concentrated aqueous cleansing compositions according to the invention comprise at least 12 wt% of sodium carbonate.
  • the amount of sodium carbonate is 14 wt% to 50 wt% and more preferably it is 14 wt% to 40 wt%.
  • the amount of sodium carbonate is 14 wt% to 25 wt%.
  • Sodium carbonate provides high pH and high reserve alkalinity which is useful for degreasing.
  • Non-carbonate builder
  • compositions comprising the total non-carbonate builder content should be less than 1 wt%.
  • the primary function of a builder is to regulate the hardness of water so as to reduce the extent of scum.
  • the non-carbonate builder is a zeolite, phosphate, pyrophosphate, silica, succinate, carboxylate, malonate, polycarboxylate, nitrilo triacetic acid, citric acid or a salt thereof, a soap or an acetate.
  • the non-carbonate builders usually provide some degree of stability to the compositions. Therefore when the compositions contain more than 1 wt% non-carbonate builder, there is not much difference between the initial and final viscosity of the compositions.
  • the concentrated aqueous cleansing compositions of the invention comprises very limited amount of, i.e., up to 2 wt% insoluble particulate matter other than the non-carbonate builder.
  • particulate matter may include an abrasive or may even be a silicate like sodium silicate.
  • the compositions may contain one type of particulate matter or a mixture of different particles while still being inside the range of up to 2 wt% of the total composition.
  • Moh's index of such particulate matter is in the range of 2.5 to 6.0.
  • the particulate matter could be one or more of clay, calcite, dolomite, olive stone, feldspar, apatite, fluorite and hematite, kyanite, magnetite, orthoclase and pumice.
  • the average particle size of such particles is 0.5 ⁇ m to 400 ⁇ m, more preferably 10 ⁇ m to 200 ⁇ m.
  • the concentrated aqueous cleansing compositions in accordance with the invention comprise 40 wt% to 80 wt% water. More preferred compositions comprise 50 wt% to 75 wt% water. Optimal compositions have 60 wt% to 75 wt% water.
  • the concentrated aqueous cleansing compositions of the invention may further comprise other surfactants over and above the mixed anionic surfactant system described earlier. However, such additional surfactants may have no influence or limited influence on the viscosity profile of the composition.
  • the compositions of this invention may comprise further surfactants selected from amphoteric, zwitterionic and nonionic surfactants and combinations thereof. Cationic surfactants are not preferred.
  • Such additional surfactants preferably are surfactants other than anionic surfactants because the compositions already contain significant amount of anionic surfactants for cleaning performance.
  • the concentrated aqueous cleansing compositions of the invention may optionally comprise other ingredients, such as fragrances, preservatives and colorants, foam boosting agents, preservatives (e.g. bactericides), pH buffering agents, polyelectrolytes, anti-oxidants, anti-corrosion agents, anti-static agents.
  • compositions may further comprise colorants, pearlisers and/or opacifiers.
  • the viscosity of the concentrated aqueous cleansing compositions according to the invention is in the range of 500 cp to 10000 cp.
  • the viscosity is in the range of 700 cP to 10000 cP and more preferably it is in the range of 800 cP to 10000 cP.
  • the concentrated aqueous cleansing composition Upon dilution with one to three parts by weight water, the concentrated aqueous cleansing composition forms a ready-to-use dish wash liquid. This is particularly useful against greasy soil. This diluted composition is non-gelling.
  • Viscosity of the diluted aqueous cleansing composition is in the range of 100 cP to 4000 cP. Preferably it is in the range of 300 cP to 2000 cP. More preferably it is in the range of 500 cP to 1200 cP.
  • the viscosity measurements are done at 25 °C at a shear rate from 1 s -1 to 50 s -1 .
  • a Haake® AR1000 Rheometer with cone and plate assembly is used for the measurements but any equivalent machine may be used.
  • compositions tend to increase or decrease under hot or cold conditions. For this reason, such compositions are often subjected to thermal stability studies. The studies are conducted as follows: The initial viscosity of the compositions is measured at room temperature (25 °C). This viscosity is usually measured as soon as the compositions are prepared. Thereafter the compositions are exposed to low temperature for some time and then allowed to equilibrate again with the room temperature as above. Viscosity is measured again (final viscosity).
  • the pH of the concentrated aqueous cleansing compositions according to the invention is in the range of 11 to 13.
  • the method of cleaning any hard surface such as soiled dishes using the diluted form of the concentrated composition is not different from the usual method.
  • a method would include a step of contacting a soiled plate with an efficacious amount of the composition preferably with the help of a scrubber or implement such as sponge, scouring pad or cloth, followed by scrubbing and later by rinsing with water.
  • the concentrated aqueous cleansing compositions of the invention may be made available to users in the form of a pre-impregnated implement.
  • the concentrated aqueous cleansing compositions according to the invention are formulated to permit easy viscosity control by the consumer upon dilution with water.
  • the cleaning liquid may be sold in concentrated form and, upon dilution by the consumer, display stable viscosity over a wide range of activity levels, the activity levels reducing with increased dilution.
  • the concentrated aqueous cleansing compositions can easily be diluted by the consumer at home by combining with water and inverting or gently shaking the container, which reliably forms a homogeneous non-gelling diluted composition.
  • compositions according to the invention are generally suitable for use in dish wash applications for manual or machine assisted cleaning, the compositions may also be used for other related applications like fabric cleaning and general hard surface cleaning.
  • a series of concentrated aqueous dish wash compositions containing from 18 wt% to 35 wt% of the mixed anionic surfactant system were made.
  • the compositions were formulated with only two anionic surfactants; Na-LAS was the alkyl benzenesulphonate (a) and SLES 1 EO was the (poly)ethoxylated sulphate (b).
  • the total amount of sodium carbonate was kept constant but in order to ascertain the effect of ratio between the said surfactants, the ratio was varied from 1:1 to 3.5:1 parts by weight as described hereinafter. All the compositions did not contain any non-carbonate builder. Further, all the compositions were free of insoluble particulate matter other than the builder.
  • compositions were outside the invention and some were inside.
  • the compositions were prepared in a standard manner well known in the art. Details are provided in table 1.
  • Table 1 Composition/wt% Outside the invention Inside the invention 1 2 3 4 5 6 7 8 9
  • the viscosity was measured at 25°C at shear rate from 1 s -1 to 50 s - as soon as the compositions were prepared. This was recorded as the initial viscosity.
  • compositions were stored at 5 °C for 12 hours and then immediately thawed for 3 hours, i.e., kept at 25°C so as to equilibrate with the room temperature.
  • the viscosity of each composition was then measured again under variable shear rate as above. This was recorded as the final viscosity and these two values were used to determine the extent of "recovery" of viscosity.
  • Table 2 summarises the viscosity profile of composition 1.
  • Table 2 Shear rate/ s -1 Viscosity/cP % recovery Initial Final 1.0 6153 1430 23.2 1.5 4275 1126 26.3 2.5 3051 883.9 29.0 3.9 2271 688.9 30.3 6.3 1702 561.5 33.0 10.0 1329 454.3 22.0 15.8 1028 370.8 36.1 25.1 814.9 312.7 38.4 39.8 650.3 267.3 41.1 50.0 586.8 247.7 42.2
  • Table 3 summarises the viscosity profile of composition 2.
  • Table 3 Shear rate/ s -1 Viscosity/cP % recovery Initial Final 1.0 9786 480 4.9 1.5 6851 390.2 5.7 2.5 4773 320.2 6.7 3.9 3316 267.1 8.1 6.3 2324 229.3 9.9 10.0 1650 195.4 11.8 15.8 1189 169.6 14.3 25.1 874.2 147.7 16.9 39.8 658.8 129.5 19.7 50.0 575.5 120.4 20.9
  • composition 3 The viscosity profile of composition 3 is summarised in table 4.
  • Table 4 Shear rate/ s -1 Viscosity/cP % recovery Initial Final 1.0 92650 85730 92.5 1.5 84910 67490 79.5 2.5 70140 49380 70.4 3.9 50060 34250 68.4 6.3 31940 23540 73.7 10.0 18900 17170 90.8 15.8 11830 13530 114.4 25.1 7916 11490 145.1 39.8 5985 10230 170.9 50.0 7070 10290 145.5
  • composition 4 The viscosity profile of composition 4 is summarised in table 5.
  • Table 5 Shear rate/ s -1 Viscosity/cP % recovery Initial Final 1.0 6222 6386 102 1.5 4228 4669 110 2.5 2976 3378 113 3.9 2123 2470 116 6.3 1548 1803 116 10.0 1141 1314 115 15.8 855.5 963.1 112 25.1 650.3 718.8 110 39.8 501.6 544.7 108 50.0 442.9 476.6 107
  • composition 5 which also is outside the invention (in view of sodium silicate) is shown in table 6.
  • Table 6 Shear rate/ s -1 Viscosity/cP % recovery Initial Final 10.0 1547 1609 101 15.8 1169 1236 104 25.1 933 970 103 39.8 780 778 100 50.0 737 700 96
  • compositions 6, 7, 8 and 9 The data pertaining to viscosity of the compositions within the scope of the invention (i.e., compositions 6, 7, 8 and 9) is shown below.
  • the recovery was at least 70%. This can be attributed to the ratio of a:b which was 2:1.
  • composition 7 The data pertaining to composition 7 is summarized in table 8. In this case the ratio was 1:1 and the total amount of anionic surfactant was 24 wt%. Table 8 Shear rate/ s -1 Viscosity/cP % recovery Initial Final 1.0 23260 20970 90 1.5 16740 16570 99 2.5 12070 13600 112 3.9 8760 11120 126 6.3 6409 8709 135 10.0 4765 6532 137 15.8 3609 4683 129 25.1 2773 3412 123 39.8 2173 2590 119 50.0 1939 2273 117
  • the minimum recovery was close to 90%.
  • composition 8 The data pertaining to composition 8 is summarized in table 9 below. In this case the ratio was 2:1. The total amount of anionic surfactant was 18 wt%. Table 9 Shear rate/ s -1 Viscosity/cP % recovery Initial Final 1.0 8648 8564 99.0 1.5 6077 6031 99.2 2.5 4333 4293 99.1 3.9 3142 3082 98.1 6.3 2298 2243 97.6 10.0 1712 1663 96.6 15.8 1300 1256 95.9 25.1 1009 967.3 95.2 39.8 801 762.2 95.3 50.0 716 682.2 95.2
  • the data indicates about 90% recovery. It was much more than the minimum level of 70%.
  • composition 9 is summarised in table 10.
  • the ratio of a:b was 1:1 and the total amount of anionic surfactant was 18 wt%.
  • Table 10 Shear rate/ s -1 Viscosity/cP % recovery Initial Final 1.0 9888 8834 89.0 1.5 6680 6033 90.0 2.5 4649 4011 86.0 3.9 3275 2900 88.0 6.3 2340 1875 80.0 10.0 1703 1485 87.0 15.8 1258 1135 90.0 25.1 944 864 91.0 39.8 723 662 91.0 50.0 627 580.5 92.0

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)

Claims (5)

  1. Composition nettoyante aqueuse concentrée comprenant :
    (i) de 14 % en masse à 35 % en masse d'un système de tensioactif anionique mixte contenant un benzènesulfonate d'alkyle (a) et un sulfate (poly)éthoxylé (b) ;
    (ii) au moins 12 % en masse de carbonate de sodium ; et,
    (iii) moins de 1 % en masse d'adjuvant de non-carbonate,
    où le rapport de (a) à (b) est de 1:1 à 3:1 parties en masse.
  2. Composition selon la revendication 1, où ledit adjuvant de non-carbonate est une zéolite, un silicate, phosphate, pyrophosphate, succinate, carboxylate, malonate, polycarboxylate, acide nitrilotriacétique, acide citrique ou un sel de ceux-ci, un savon ou un acétate.
  3. Composition selon la revendication 1 ou 2, où ladite composition comprend jusqu'à 2 % en masse de matière particulaire insoluble différente dudit adjuvant de non-carbonate.
  4. Composition nettoyante aqueuse comprenant une partie en masse de la composition selon la revendication 1 et de une à trois parties en masse d'eau.
  5. Composition nettoyante aqueuse selon la revendication 1 ou 2 ou 3, où la viscosité de ladite composition à 25°C sous une vitesse de cisaillement de 1 s-1 est de 500 cP à 10 000 cP.
EP16707122.4A 2015-03-09 2016-03-01 Compositions de nettoyage concentrées stables pour surfaces dures Active EP3268459B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP15158144 2015-03-09
PCT/EP2016/054298 WO2016142211A1 (fr) 2015-03-09 2016-03-01 Compositions de nettoyage concentrées stables pour surfaces dures

Publications (2)

Publication Number Publication Date
EP3268459A1 EP3268459A1 (fr) 2018-01-17
EP3268459B1 true EP3268459B1 (fr) 2018-06-20

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EP16707122.4A Active EP3268459B1 (fr) 2015-03-09 2016-03-01 Compositions de nettoyage concentrées stables pour surfaces dures

Country Status (4)

Country Link
EP (1) EP3268459B1 (fr)
AR (1) AR103878A1 (fr)
WO (1) WO2016142211A1 (fr)
ZA (1) ZA201706042B (fr)

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DK131158A (fr) 1967-08-25
NZ191283A (en) * 1978-08-21 1982-03-09 Colgate Palmolive Co Stable pourable heavy-duty built liquid detergent comprising optical brightening agent or water soluble dye
US4260528A (en) 1979-06-18 1981-04-07 Lever Brothers Company Aqueous high viscosity liquid dishwasher compositions
US4469605A (en) * 1982-12-13 1984-09-04 Colgate-Palmolive Company Fabric softening heavy duty liquid detergent and process for manufacture thereof
US4692275A (en) 1986-04-23 1987-09-08 Lever Brothers Company Detergent compositions containing an alkylbenzene sulfonate and alcohol ethoxysulfate surfactant system
US5602092A (en) 1994-07-06 1997-02-11 Colgate-Palmolive Company Concentrated aqueous liquid detergent compositions containing deflocculating polymers
US6277803B1 (en) 2000-06-28 2001-08-21 Colgate-Palmolive Company Thickened cleaning composition
GB0031827D0 (en) * 2000-12-29 2001-02-14 Unilever Plc Detergent compositions
US6337312B1 (en) * 2001-05-11 2002-01-08 Colgate-Palmolive Co Liquid crystal compositions comprising an abrasive and magnesium sulfate heptahydrate
US20090023625A1 (en) * 2007-07-19 2009-01-22 Ming Tang Detergent composition containing suds boosting co-surfactant and suds stabilizing surface active polymer
DE102012222186A1 (de) * 2012-12-04 2014-06-05 Henkel Ag & Co. Kgaa Strukturiertes Reinigungsmittel mit Fließgrenze
EP2770044A1 (fr) 2013-02-20 2014-08-27 Unilever PLC Gel lamellaire avec un oxyde d'amine

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Also Published As

Publication number Publication date
AR103878A1 (es) 2017-06-07
ZA201706042B (en) 2019-01-30
WO2016142211A1 (fr) 2016-09-15
EP3268459A1 (fr) 2018-01-17

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