EP3350298A1 - Wässrige reinigungszusammensetzung für harte oberflächen - Google Patents

Wässrige reinigungszusammensetzung für harte oberflächen

Info

Publication number
EP3350298A1
EP3350298A1 EP16760453.7A EP16760453A EP3350298A1 EP 3350298 A1 EP3350298 A1 EP 3350298A1 EP 16760453 A EP16760453 A EP 16760453A EP 3350298 A1 EP3350298 A1 EP 3350298A1
Authority
EP
European Patent Office
Prior art keywords
composition
compositions
las
alkyl benzene
fatty alcohol
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.)
Granted
Application number
EP16760453.7A
Other languages
English (en)
French (fr)
Other versions
EP3350298B1 (de
Inventor
Sumanth Kumar ARNIPALLY
Manoj Vilas Dagaonkar
Somnath GOSH
Sujoy MAITY
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
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Priority to PL16760453T priority Critical patent/PL3350298T3/pl
Priority claimed from PCT/EP2016/070512 external-priority patent/WO2017045924A1/en
Publication of EP3350298A1 publication Critical patent/EP3350298A1/de
Application granted granted Critical
Publication of EP3350298B1 publication Critical patent/EP3350298B1/de
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • C11D1/66—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
    • 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
    • C11D17/0013—Liquid compositions with insoluble particles in suspension
    • 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, a non-ionic surfactant and an abrasive.
  • 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, but they are are effective against some of the more common stains.
  • Ca-LAS and Mg-LAS respectively are milder, but they are are effective against some of the more common stains.
  • calcite, magnesium carbonate or other equivalent alkaline substances are used to neutralise 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 cleansing 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 neutralisation of LAS acid.
  • compositions which contain Ca-LAS as well as Mg-LAS and which are obtained by neutralisation of LAS-acid with dolomite do not face such a problem.
  • hard surface cleaning compositions comprising Ca-LAS as a primary surfactant, but which do not contain more than a particular amount of Mg- LAS and which are stable.
  • an aqueous abrasive cleansing composition comprising:
  • magnesium salt of linear alkyl benzene sulphonic acid in an amount not more than 1 % of the amount of said calcium salt
  • HLB of said alkoxylated fatty alcohol is in the range of 11 to 20 and carbon chain length of said fatty alcohol is in the range of 12 to 16.
  • 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.
  • the term 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.
  • the aqueous abrasive cleansing composition of the present invention comprises calcium salt of linear alkyl benzene sulphonic acid (abbreviated as Ca-LAS).
  • abrasive cleansing 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.
  • compositions containing Na-LAS neutralise 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 neutralised. Progress of the reaction is periodically checked by determining pH of samples.
  • Dolomite is a naturally occurring mineral and the principle member of
  • compositions containing Ca-LAS made by 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 which are made by non-dolomite route of neutralisation but for that the problem of instability needs to be addressed.
  • compositions in accordance with this invention comprise calcium salt of linear alkyl benzene sulphonic acid. It is preferred that compositions in accordance with the invention comprise 1 wt% to 15 wt% calcium salt of 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.
  • aqueous abrasive cleansing 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.
  • HLB of the alkoxylated fatty alcohol is in the range of 1 1 to 20 and 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 five to eight moles of ethylene oxide units. Alkoxylated fatty alcohols having degree of ethoxylation from five to eight show particularly good technical effect by stabilizing the compositions which are stored at temperatures higher or lower than the normal room temperature. It is preferred that compositions in accordance with the invention comprise 0.5 wt% to 10 wt% of alkoxylated fatty alcohol. A combination of one or more such non-ionic surfactants may also be used.
  • compositions in accordance with the invention comprise a viscosity building agent which is an abrasive having Moh's index of 0.5 to 7 or a polymer or a combination thereof, in an amount sufficient to provide 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 .
  • a Haake ® AR1000 Rheometer with cone and plate assembly is used for the measurement, but any other equivalent machine may be used.
  • compositions in accordance with the invention preferably comprise an abrasive having Moh's Index of 0.5 to 7.
  • compositions comprise 10 wt% to 50 wt% abrasive.
  • abrasive is at least one of bentonite, china clay, calcite or feldspar but any other suitable abrasive or abrasives may be used. It is preferred that the average particle size of abrasive is 0.5 to 400 ⁇ , more preferably 10 to 200 ⁇ .
  • 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.
  • Amount of water and the pH Compositions in accordance with the invention are aqueous, i.e., water-based. It is preferred that the compositions comprise 20 wt% to 80 wt% water.
  • pH of the compositions in accordance with the invention is in the range of 6 to 8 at 20 °C.
  • 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.
  • Other surfactants are disclosed hereinafter.
  • compositions in accordance with this invention may contain other surfactants.
  • 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 %.
  • total surfactant means the sum total of all surfactants contained in the compositions, which includes calcium salt of linear alkyl benzene sulphonic acid.
  • 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.
  • Other ingredients 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.
  • 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.
  • Example 1 Preparation of aqueous hard surface cleaning cream composition devoid of magnesium salt of linear alkyl benzene sulphonic acid:
  • Step 1
  • a plastic beaker of suitable size was positioned in alignment with an overhead stirrer.
  • 550 g of demineralised 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 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.
  • Caprylic/Capric Glycerides Its HLB value is 13 to 15 and it has carbon chain length of 8 to 10.
  • 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.
  • Lialet® 123-8 Ex. Sasol is fatty alcohol polyethylene glycol ether (alkoxylated fatty alcohol) based on LIAL® 123 and ethylene oxide (8 moles). Its HLB value is about 12 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.
  • compositions outside the scope of the present invention (X, Y and Z) are unstable under all conditions.
  • data pertaining to 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.
  • the right balance of HLB (1 1 to 20) and carbon chain length (C12 to C16) provides optimal stability (Compositions 1 , 2, 3, 4 and 5).

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
EP16760453.7A 2015-09-15 2016-08-31 Wässrige reinigungszusammensetzung für harte oberflächen Active EP3350298B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL16760453T PL3350298T3 (pl) 2015-09-15 2016-08-31 Wodna kompozycja do czyszczenia twardych powierzchni

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP2015185171 2015-09-15
PCT/EP2016/070512 WO2017045924A1 (en) 2015-09-15 2016-08-31 Aqueous hard surface cleaning composition

Publications (2)

Publication Number Publication Date
EP3350298A1 true EP3350298A1 (de) 2018-07-25
EP3350298B1 EP3350298B1 (de) 2018-12-12

Family

ID=62584861

Family Applications (1)

Application Number Title Priority Date Filing Date
EP16760453.7A Active EP3350298B1 (de) 2015-09-15 2016-08-31 Wässrige reinigungszusammensetzung für harte oberflächen

Country Status (3)

Country Link
EP (1) EP3350298B1 (de)
PL (1) PL3350298T3 (de)
TR (1) TR201819968T4 (de)

Also Published As

Publication number Publication date
TR201819968T4 (tr) 2019-01-21
EP3350298B1 (de) 2018-12-12
PL3350298T3 (pl) 2019-07-31

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