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
  • C11D11/00—Special methods for preparing compositions containing mixtures of detergents ; Methods for using cleaning compositions
  • C11D11/04—Special methods for preparing compositions containing mixtures of detergents ; Methods for using cleaning compositions by chemical means, e.g. by sulfonating in the presence of other compounding ingredients followed by neutralising
• • 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
  • C11D1/83—Mixtures of non-ionic with anionic 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
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/02—Inorganic compounds ; Elemental compounds
  • C11D3/12—Water-insoluble compounds
  • C11D3/14—Fillers; Abrasives ; Abrasive compositions; Suspending or absorbing agents not provided for in one single group of C11D3/12; Specific features concerning abrasives, e.g. granulometry or mixtures
• • 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
  • C11D1/66—Non-ionic compounds
  • C11D1/72—Ethers of polyoxyalkylene glycols

Definitions

• the invention relates to a composition for cleaning hard surfaces.
• the invention relates to a composition comprising calcium-based anionic surfactant.
• Hard surface cleaning compositions are available in various formats. There was a time when powders were widely used. Then came bars which were shaped like soap bars. Bars are being gradually replaced by liquids and pastes. Abrasive pastes usually contain an anionic surfactant, generally sodium salt of linear alkyl benzene sulphonic acids, as well as a non-ionic surfactant and an abrasive.
• an anionic surfactant generally sodium salt of linear alkyl benzene sulphonic acids
• Calcium and magnesium salts of alkyl benzene sulphonic acids provided alternatives to the sodium salts which has been used for several decades.
• sodium salts are prepared by neutralizing the corresponding acids with soda ash or sodium hydroxide.
• the surfactants which are calcium or magnesium salts of linear alkyl benzene sulphonic acids (Ca-LAS and Mg-LAS respectively) are milder. They are effective against some of the more common stains.
• calcite i.e. calcium carbonate
• magnesium carbonate or other equivalent alkaline substances are used to neutralize the corresponding precursor sulphonic acids.
• Dolomite is an alternative neutralizing agent which results into a mixture of Mg-LAS and Ca-LAS in varying proportions which depends on the concentration and type/grade of dolomite.
• Some amount of magnesium sulphate and calcium sulphate is also generated which act as in-situ structuring agents in cleaning compositions, especially dish wash bars.
• WO2014/044639 A1 discloses aqueous hand dish wash pastes which contain Na-LAS, calcium carbonate as abrasive and a non-ionic surfactant.
• the compositions do not contain Mg-LAS.
• the combination of Na-LAS and the additional surfactant produces ductile pastes at a constant total surfactant.
• the exemplified compositions are highly alkaline due to presence of significant amount of soda and silicate, a part of which gets used up in neutralization of LAS acid.
• compositions which contain Ca-LAS as well as Mg-LAS and which are obtained by neutralization of LAS-acid with dolomite do not face such a problem.
• an aqueous abrasive cleaning composition comprising:
• Aqueous abrasive cleaning composition comprising:
• composition has a pH in the range of 6 to 8 at 20 °C;
• the composition comprises an amount of magnesium salt of linear alkyl benzene sulphonic acid that is 0 to 1 % of the amount of said calcium salt;
• composition comprises less than 1 wt% sodium salt of linear alkyl benzene sulphonic acid
• said abrasive has a Moh's index of 0.5 to 7;
• the amount of surfactant on the surface of the abrasive particles is 0 to 10 % of the total surfactant of the composition; and (f) said alkoxylated fatty alcohol has an HLB in the range of 1 1 to 20 and carbon chain length in the range of 12 to 16.
• compositions of the present invention comprising the step of preparing calcium salt of linear alkyl benzene sulphonic acid by reacting linear alkyl benzene sulphonic acid with calcium oxide and/or calcium hydroxide.
• Hard surfaces include floors, walls, tiles, windows, cupboards, sinks, showers, shower plastified curtains, wash basins, WCs, fixtures and fittings made of different materials like ceramic, vinyl, no-wax vinyl, linoleum, melamine, glass, Formica®, vitroceramic, plastified wood, metal or any painted or varnished or sealed surface. It also includes household appliances including, but not limited to refrigerators, freezers, washing machines, automatic dryers, ovens, microwave ovens and dishwashers.
• dishes includes glasses, pots, pans, baking dishes and flatware made from ceramic, china, metal, glass, plastic (polyethylene, polypropylene, polystyrene), wood, enamel, Inox®, teflon, or any other material commonly used in the making of articles used for eating and/or cooking.
• plastic polyethylene, polypropylene, polystyrene
• wood enamel, Inox®, teflon, or any other material commonly used in the making of articles used for eating and/or cooking.
• wt% as used herein is defined as percentage by weight based on total weight of the composition.
• the aqueous abrasive cleaning composition of the present invention comprises calcium salt of linear alkyl benzene sulphonic acid (abbreviated as Ca-LAS).
• abrasive cleaning compositions for hard surface cleaning contain sodium salt of linear alkyl benzene sulphonic acid, often abbreviated as Na-LAS. While such compositions are efficacious, they are also very strong and thereby tend to be harsh to the user's skin, e.g. hands.
• compositions containing Na-LAS neutralize linear alkyl benzene sulphonic acid (LAS) with an alkali like sodium carbonate, sodium silicate or sodium hydroxide.
• LAS linear alkyl benzene sulphonic acid
• the material which is widely used is sodium carbonate (also known as soda ash or soda).
• soda ash or soda sodium carbonate
• a stoichiometric excess of soda is made to react with a given amount of LAS-acid to produce Na-LAS.
• Excess soda remains in the formulation and serves as a builder or alkaline material. Alkaline compositions provide better grease removal; however, as indicated earlier, they tend to be significantly harsh.
• Ca-LAS provides a milder alternative to Na-LAS but the usual way of making
• compositions containing Ca-LAS is to react LAS-acid with dolomite.
• the known way to make a hard surface cleaning composition containing Ca-LAS as the primary surface- active agent is to mix LAS-acid with water to prepare a slurry.
• Dolomite usually stoichiometric excess, is then added to the slurry. Sufficient amount of time is allowed to ensure that the acid gets neutralized. Progress of the reaction is periodically checked by determining the pH.
• Dolomite is a naturally occurring mineral and the principle member of
• compositions containing Ca-LAS made by a non- dolomite route leads to unstable products.
• compositions devoid of Mg-LAS are especially prone to separation into solid and liquid phases and this is particularly observed in the case of samples stored at high temperatures, e.g. 40 °C, or low temperatures, e.g. 5 °C.
• compositions in accordance with this invention comprise calcium salt of linear alkyl benzene sulphonic acid (i.e. Ca-LAS). It is preferred that compositions in accordance with the invention comprise 0.1 to 15 wt% calcium salt of linear alkyl benzene sulphonic acid, more preferably 0.5 to 10 wt% and even more preferably 1 to 5 wt%.
• Ca-LAS linear alkyl benzene sulphonic acid
• Magnesium salt of linear alkyl benzene sulphonic acid is in an amount not more than 1 % of the amount of said calcium salt. For example, if the total amount of Ca-LAS is 15 wt%, then the maximum amount of Mg-LAS is 0.15 wt%, which amounts to not more than 1 % of the amount of the calcium salt.
• the aqueous abrasive cleaning compositions of the invention do not contain magnesium salt of linear alkyl benzene sulphonic acid.
• the amount of magnesium salt of linear alkyl benzene sulphonic is from 0 to 1 % of the amount of the calcium salt.
• compositions in accordance with the invention comprise one or more alkoxylated fatty alcohol.
• These are non-ionic surfactants.
• the HLB of the alkoxylated fatty alcohol is in the range of 1 1 to 20 and the carbon chain length of said fatty alcohol is in the range of 12 to 16. All non-ionic surfactants have an HLB value. The higher the number, the more hydrophilic the surfactant. On the other hand, surfactants having lower HLB value are more lipophilic.
• Alkoxylated fatty alcohols lend stability to the compositions even in the total absence of Mg-LAS or when the Mg-LAS content is minimal. It is particularly preferred that the degree of ethoxylation in said alkoxylated fatty alcohol is from 5 to 8 moles of ethylene oxide units. Alkoxylated fatty alcohols having a degree of ethoxylation from 5 to 8 show particularly good technical effect by stabilizing the compositions which are stored at temperatures higher or lower than the normal room temperature (i.e. a temperature around 20
• compositions in accordance with the invention comprise 0.05 to 10 wt% of alkoxylated fatty alcohol, more preferably 0.1 to 8 and even more preferably 1 to 5 wt%.
• a combination of one or more such non-ionic surfactants may also be used.
• the ratio calcium salt linear alkyl benzene sulphonic acid to alkoxylated fatty alcohols is 1 :1 to 2:1.
• compositions in accordance with the invention comprise an abrasive having a Moh's Index of 0.5 to 7.
• compositions comprise 1 to 50 wt% abrasive, preferably 5 to 40 wt% and more preferably 10 to 30 wt%.
• the abrasive preferably is at least one of bentonite, china clay, calcite, dolomite or feldspar but any other suitable abrasive or abrasives may be used. It is preferred that the abrasive comprises at least calcite and preferably in an amount of at least 50 wt% of the total amount of abrasives in the composition.
• the average particle size of abrasive is 0.5 to 400 ⁇ , more preferably 10 to 200 ⁇ .
• compositions in accordance with the invention have a viscosity of 500 to 2000 cP at 20 °C.
• the viscosity may be measured by any suitable method. It is preferably measured at 20 °C at a shear rate from 1 s "1 to 50 s "1 , using a Haake ® AR1000 Rheometer with cone and plate assembly.
• any known method can be used to build the required viscosity, including for example by using the abrasive particles present in the composition.
• the compositions in accordance with this invention preferably comprise a polymer.
• the purpose of the polymer is to provide some viscosity to the compositions. It is preferred that the polymer is a water-swellable polymer or an associative polymer. It is preferred that the polymer provides the desired viscosity when the pH of the compositions is in the range of 6 to 8. Whenever the polymer is present, it is preferred that the amount thereof is 0.005 to 10 wt%.
• the polymer is one or more of polyacrylic acid, polyacrylates, cross-linked acrylates, guar gum or its derivatives, starch-acrylic grafted copolymers, hydrolysate of starch-acrylonitrile grafted copolymers, crosslinked polyoxyethylene, cross-linked methyl cellulose, sodium carboxymethylcellulose or partially cross-linked water-swellable polymers of polyethylene oxides and polyacrylamide or
• compositions in accordance with the invention comprise 0.008 wt% to 5 wt% polymer, more preferably 0.01wt% to 2.5 wt% of the polymer.
• a particularly preferred polymer is Acusol® 880/882.
• compositions in accordance with the invention are aqueous, i.e. water-based. It is preferred that the compositions comprise 20 to 80 wt% water and more preferably 30 to 75 wt%, even more preferably 40 to 70 wt% and still even more preferably 50 to 60 wt%.
• the pH of the compositions in accordance with the invention is in the range of 6 to 8 at 20 °C.
• the compositions in accordance with this invention comprise less than 1 wt% of strong alkalis which include sodium hydroxide, sodium silicate and sodium carbonate. If the pH of the composition is more than 8, it is likely to adversely affect stability of the product. Similarly, at pH less than 6, there could be protonation of the nonionic surfactants, which eventually could result in unstable compositions.
• compositions in accordance with this invention may contain other ingredients which are disclosed hereinafter.
• compositions in accordance with this invention may contain other surfactants.
• compositions comprise less than 1 wt% sodium salt of linear alkyl benzene sulphonic acid (Na-LAS). Any excess amount of Na-LAS could tend to destabilise the compositions due to exchange of calcium ions with the sodium ions. Further, the compositions may also become more alkaline and thereby less milder.
• Na-LAS linear alkyl benzene sulphonic acid
• the cleaning composition may further comprise other anionic surfactants, amphoteric and zwitterionic surfactants, provided they do not interfere with the performance or stability of the compositions. It is preferred that the amount of such other surfactants is from 0.1 to 20 wt %.
• compositions in accordance with the invention comprise less than 1 wt% cationic surfactant.
• the total amount of surfactants is not greater than 40 wt%.
• the Active Detergent (AD) level is not greater than 40 %.
• the term total surfactant means the sum total of all surfactants contained in the compositions, which includes calcium salt of linear alkyl benzene sulphonic acid.
• the AD level is not more than 30 wt%, with a preferred level being not more than 20 wt%, and even more preferred not more than 10 wt%.
• Suitable amphoteric surfactants are derivatives of aliphatic secondary and tertiary amines containing an alkyl group of 8 to 20 carbon atoms and an aliphatic group substituted by an anionic water-solubilising group, for instance sodium 3- dodecylamino-propionate, sodium 3- dodecylaminopropane-sulphonate and sodium N 2-hydroxy-dodecyl-N-methyltaurate.
• Suitable zwitterionic surfactants include derivatives of aliphatic quaternary ammonium, sulphonium and phosphonium compounds having an aliphatic group of from 8 to 18 carbon atoms and an aliphatic group substituted by an anionic water- solubilising group, for instance betaine and betaine derivatives such as alkyl betaine, in particular C12-C16 alkyl betaine, 3-(N,N-dimethyl-N-hexadecylammonium)-propane 1 - sulphonate betaine, 3- (dodecylmethyl-sulphonium)-propane 1 -sulphonate betaine, 3- (cetylmethyl-phosphonium)- propane-1 -sulphonate betaine and N,N-dimethyl-N- dodecyl-glycine.
• betaines are the alkylamidopropyl betaines e.g. those wherein the alkylamido group is derived from coconut oil
• surfactants can be found in the well-known textbooks: 'Surface Active Agents' Vol.1 , by Schwartz & Perry, Interscience 1949; 'Surface Active Agents' Vol.2 by Schwartz, Perry & Berch, Interscience 1958; the current edition of 'McCutcheon's Emulsifiers and Detergents' published by Manufacturing Confectioners Company; Tenside-Taschenbuch', H. Stache, 2nd Edn., Carl Hauser Verlag, 1981.
• compositions according to this invention may include additional ingredients to improve or enhance the in-use performance.
• Such ingredients include colour, fragrance, soil suspending agents, detersive enzymes, compatible bleaching agents, freeze-thaw stabilisers, bactericides, preservatives, hydrotropes and perfumes.
• aqueous hard surface cleaning compositions according to the invention are liquids or creams or pastes, which may be directly applied to the hard surface.
• An example of a commercial cream is CIF ® from Unilever. Packaging
• the aqueous hard surface cleaning composition according to the invention can be packaged in any suitable container.
• the composition is packaged in a plastic bottle with a detachable closure /pouring spout.
• the bottle may be rigid or deformable.
• a deformable bottle allows the bottle to be squeezed for dispensing.
• clear bottles they may be made of PET or Polyethylene.
• the bottle may be provided with one or more labels, or with a shrink-wrap sleeve, which is desirably at least partially transparent, for example 50% of the area of the sleeve is transparent.
• the adhesive used for any transparent label should preferably not adversely affect the transparency.
• the compositions can also be packed in other formats like sachets and pouches.
• Method of preparing Methods to prepare Ca-LAS containing cleaning compositions include the step of neutralizing acid-LAS with Dolomite or e.g. calcite. This way any deliberate excess of the neutralizing agent (i.e. Dolomite or calcite) will act as the abrasive in the final composition.
• Dolomite or calcite any deliberate excess of the neutralizing agent (i.e. Dolomite or calcite) will act as the abrasive in the final composition.
• Dolomite or calcite any deliberate excess of the neutralizing agent (i.e. Dolomite or calcite) will act as the abrasive in the final composition.
• Dolomite or calcite any deliberate excess of the neutralizing agent (i.e. Dolomite or calcite) will act as the abrasive in the final composition.
• these methods may not always result in a composition comprising abrasive particles with the required cleaning properties, as the surface of the remaining abrasive particles
• the amount of surfactant on the surface of the abrasive particles is from 0 to 10 % of the total surfactant of the composition.
• the amount of surfactant present on the surface of the abrasive particles is determined according to the method described in the Examples below.
• the present invention further provides a method of preparing a composition of the present invention comprising the step of preparing the calcium salt of linear alkyl benzene sulphonic acid by reacting linear alkyl benzene sulphonic acid with calcium oxide and/or calcium hydroxide.
• a method of preparing a composition of the present invention comprising the step of preparing the calcium salt of linear alkyl benzene sulphonic acid by reacting linear alkyl benzene sulphonic acid with calcium oxide and/or calcium hydroxide.
• said step takes place in the absence of the abrasive particles present in the final composition.
• the cleaning composition comprising the abrasive particles and Ca-LAS is centrifuged twice at 7500 rpm for 20 min. The particles are removed from the supernatant and washed thoroughly with Dl water to ensure removal of all soluble ingredients deposited on the particle. The washed particles are then dried in a hot air oven. To remove the calcium salt of linear alkyl benzene sulfonate from the surface of the particles, the dried particles are washed with methyl alcohol. The stock solution comprising methyl alcohol and leached calcium salt of linear alkyl benzene sulfonate is titrated against 0.4 mM hyamine solution in presence of chloroform and mixed indicator.
• the amount of surfactant present in the stock solution is determined. Based on this, the amount of surfactant deposited on the particle surface is calculated. The % of surfactant deposited on the particle is then calculated using the formula below:
• % surfactant deposited on the particle surface (amount of surfactant deposited on the particle surface/total amount of surfactant present in the composition) * ! 00
• Example 1 Preparation of aqueous hard surface cleaning cream composition devoid of magnesium salt of linear alkyl benzene sulphonic acid to show alkoxylated fatty alcohol requirements:
• Step 1
• a plastic beaker of suitable size was positioned in alignment with an overhead stirrer.
• 550 g of demineralized water was heated to 65 to 75 ° C. About half the quantity of water was then added to the first mentioned beaker and it was stirred at about 150 rpm. This was followed by addition of 5 g coco fatty acids and 0.2 g silicone oil to suppress the foam. Thereafter, 200 g calcite was added to it to form a mix, which was stirred for about five minutes. Thereafter, 33 g of commercial linear alkyl benzene sulphonic acid (LAS-acid) was added slowly. A nonionic surfactant was then added and the mix was stirred for few minutes.
• LAS-acid commercial linear alkyl benzene sulphonic acid
• step 2 A compositions containing a polymer (in addition to calcite) were also prepared.
• the procedure (step 2) was as follows:
• the balance amount of water 450 g was added. To this 0.3 g of polymer was added and stirred for 5 minutes at 150 rpm. To this, the premix was added and stirred for five minutes. This was followed by addition of 350 g of calcite and the contents were stirred for twenty minutes.
• Span® 80 is Sorbitan monooleate, a type of non-ionic surfactant from Croda.
• HLB value of this surfactant is 4.3 ⁇ 1. Its carbon chain length is 24 to 26
• PEG-200 is polyethylene glycol of molecular weight 200 Daltons coupled with oleic acid.
• Polyethylene glycol mono-oleate is also a non-ionic surfactant and its HLB value is 8 to 9.3.
• Lialet® 125-5 Ex. Sasol is fatty alcohol polyethylene glycol ether (alkoxylated fatty alcohol) based on LIAL® 125 and ethylene oxide (5 moles). Its HLB value is about 1 1 and its carbon chain length is 12 to 16.
• compositions separated into an aqueous phase and solid phase. It was not possible to measure viscosity.
• composition Z indicates that alkoxylated fatty alcohols having HLB of 1 1 to 20 do not provide desired results. Comparison of the data for composition Z and composition 1 indicates that it is a combination of the right chain length and the right HLB which provides technical effect.
• HLB HLB
• C12 to C16 carbon chain length
• Example 2 Preparation of aqueous hard surface cleaninq cream composition devoid of magnesium salt of linear alkyl benzene sulphonic acid and comprising abrasive particles having an amount of surfactant on the surface thereof of 0 to 10% of the total amount of surfactant: Table 3
• compositions outside the invention (A-l and A-ll)
• a model bathroom soil composition containing calcium stearate was sprayed on enamel tiles for uniform deposition and then baked at a certain temperature for a fixed amount of time.

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Citations (10)

• 2017
  • 2017-10-23 BR BR112019010101A patent/BR112019010101A2/pt not_active Application Discontinuation
  • 2017-10-23 CN CN201780065713.8A patent/CN110199012B/zh active Active
  • 2017-10-23 EP EP17797251.0A patent/EP3541909B1/en active Active
  • 2017-10-23 AU AU2017362556A patent/AU2017362556B2/en active Active
  • 2017-10-23 WO PCT/EP2017/076963 patent/WO2018091226A1/en unknown
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  • 2017-11-16 AR ARP170103187A patent/AR110805A1/es active IP Right Grant
• 2019
  • 2019-04-05 ZA ZA2019/02154A patent/ZA201902154B/en unknown

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