WO2015101454A1 - Detergent composition - Google Patents

Detergent composition Download PDF

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Publication number
WO2015101454A1
WO2015101454A1 PCT/EP2014/076195 EP2014076195W WO2015101454A1 WO 2015101454 A1 WO2015101454 A1 WO 2015101454A1 EP 2014076195 W EP2014076195 W EP 2014076195W WO 2015101454 A1 WO2015101454 A1 WO 2015101454A1
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WO
WIPO (PCT)
Prior art keywords
composition
mud
kojic acid
detergent
comp
Prior art date
Application number
PCT/EP2014/076195
Other languages
French (fr)
Inventor
Paul Damien Price
Srinivasa Gopalan Raman
Original Assignee
Unilever N.V.
Unilever Plc
Conopco, Inc., D/B/A Unilever
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Publication date
Application filed by Unilever N.V., Unilever Plc, Conopco, Inc., D/B/A Unilever filed Critical Unilever N.V.
Publication of WO2015101454A1 publication Critical patent/WO2015101454A1/en

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    • 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
    • C11D3/2096—Heterocyclic compounds
    • C11D2111/12—

Definitions

  • the present invention is in the field of a detergent composition and more particularly relates to a detergent composition for removing mud stains.
  • Fabric stains run the gamut from food spills to household substances and can be of different types; mainly aqueous, oily, particulate and bleachable. Stains are something that people try to avoid, yet they are unavoidable. Nonetheless, people still prefer to wear clothes with lesser stains or no stains at all. In fact, people prefer to avoid stains not just on clothes but in general in kitchens, bathrooms and also on various household surfaces.
  • Polyacrylate polymers are also known for mud stain removal. However, polyacrylates are not preferred to be used in laundry compositions due to biodegradability issues.
  • a detergent composition comprising a kojic acid derivative of formula A provides mud removal and reduces re-deposition of mud stains and soils.
  • the present invention provides a detergent composition for mud stain removal comprising 0.1 to10 %w of a compound of formula A
  • R is a C 2 to Ci 2 alkyl group; and 5 to 50%w of one or more surfactants.
  • the invention provides a process for treating a substrate for mud stain removal comprising the steps in sequence of preparing 0.05 - 1 % by weight solution of the composition according to the invention in water, treating the substrate with the prepared solution; and rinsing the substrate.
  • substrate typically means any kind of fabric.
  • the detergent composition according to the invention comprises a kojic acid derivative of formula A and one or more surfactants.
  • the detergent composition comprises a compound of formula A.
  • R is a C 2 to C12 alkyl group; preferably C 2 to C 7 alkyl group.
  • the compound of formula A is a derivative of kojic acid with long acyl groups.
  • the composition comprises 0.1 to10 % by weight of the compound of formula A, preferably not less than 1 %, more preferably not less than 2%, still more preferably not less than 3%, even more preferably not less than 4% or even not less than 5% but typically not more than 9%, preferably not more than 8%, more preferably not more than 7%, still more preferably not more than 6% by weight of the composition.
  • the composition comprises between 5-50% by weight of one or more surfactants.
  • the surfactant may be chosen from any commercially available surfactants suitable for laundry purposes.
  • Such surfactants may be chosen from the surfactants described in well known textbooks like "Surface Active Agents” Vol. 1 , by Schwartz & Perry, Interscience 1949, Vol. 2 by Schwartz, Perry & Berch, Interscience 1958, and/or the current edition of "McCutcheon's Emulsifiers and Detergents” published by Manufacturing Confectioners Company or in “Tenside Taschenbuch", H. Stache, 2nd Edn., Carl Hauser Verlag, 1981 .
  • the surfactant may be anionic, non-ionic, cationic, amphoteric and/or zwitterionic.
  • Anionic surfactants or a combination of anionic and non-ionic surfactant are the most preferred.
  • Anionic surfactants Suitable anionic surfactants for the detergent compounds which may be used are linear alkyi benzene sulfonate (LAS), (usually) water-soluble alkali metal salts of organic sulphates and sulphonates having alkyi radicals containing from about 8 to about 22 carbon atoms, the term alkyi being used to include the alkyi portion of higher acyl radicals, including alkyi sulphates, alkyi ether sulphates, alkaryl sulphonates, alkanoyl isethionates, alkyi succinates, alkyi sulphosuccinates, N-alkoyl sarcosinates, alkyi phosphates, alkyi ether phosphates, alkyi ether carboxylates, alpha-olefin sulphonates and acyl methyl taurates, especially their sodium, magnesium ammonium and mono , di- and triethanolamine salts.
  • LAS linear
  • the alkyi and acyl groups generally contain from 8 to 22 carbon atoms, preferably 8 to 18 carbon atoms, still more preferably 12 to 15 carbon atoms and may be unsaturated.
  • the alkyi ether sulphates, alkyi ether phosphates and alkyi ether carboxylates may contain from one to 10 ethylene oxide or propylene oxide units per molecule, and preferably contain 1 to 3 ethylene oxide units per molecule.
  • anionics examples include linear alkyi benzene sulfonate, sodium lauryl sulphate, sodium lauryl ether sulphate, ammonium lauryl sulphosuccinate, ammonium lauryl sulphate, ammonium lauryl ether sulphate, sodium cocoyl isethionate, sodium lauroyl isethionate, and sodium N-lauryl sarcosinate.
  • Non-ionic surfactants include linear alkyi benzene sulfonate, sodium lauryl sulphate, sodium lauryl ether sulphate, ammonium lauryl sulphosuccinate, ammonium lauryl sulphate, ammonium lauryl ether sulphate, sodium cocoyl isethionate, sodium lauroyl isethionate, and sodium N-lauryl sarcosinate.
  • Non-ionic surfactants include linear alkyi benzene sulfon
  • Non-ionic surfactants are also well-known in the art. They normally consist of a water- solubilising polyalkoxylene (preferably from 3 to10 ethoxy and/or propoxy groups) or a mono- or di-alkanolamide group in chemical combination with an organic hydrophobic group derived from, for example, fatty alcohols with from 9 to 15 carbon atoms
  • alkylphenols (preferably from 12 to 20 carbon atoms) in which the alkyi group contains from about 6 to about 12 carbon atoms, dialkylphenols in which each alkyi group contains from 6 to 2 carbon atoms, primary, secondary or tertiary aliphatic alcohols (or alkyl-capped derivatives thereof) monocarboxylic acids having from 10 to about 24 carbon atoms in the alkyi group and polyoxypropylenes.
  • Fatty acid mono- and dialkanolamides in which the alkyl group of the fatty acid radical contains from 10 to about 20 carbon atoms and the alkyloyl group having from 1 to 3 carbon atoms are also common.
  • polyalkoxylene moiety usually consists of an average of from 2 to 20 groups of ethylene oxide, propylene oxide groups or mixtures thereof.
  • the latter class includes those described in European Patent Specification EP-A-0,225,654, especially for use as all or part of the liquid phase.
  • ethoxylated non-ionics which are condensation products of fatty alcohols with from 9 to 15 carbon atoms condensed with 3 to 9 moles of ethylene and/or propylene oxide per mole of fatty alcohol. Examples of these are the
  • condensation products of C12 to C15 alcohols with 3 or 7 moles of ethylene oxide may be used as the sole non-ionic surfactant or in combination with those described in EP-A-0,225,654.
  • non-ionic surfactant is DOBANOL® 25-3, which is a C5 alcohol ethoxylated with on average three ethoxy groups.
  • Other useful non-ionic surfactants are from the PLURAFAC® series from BASF.
  • SYNPERONIC® non-ionic surfactant such as SYNPERONIC® LF D25 or LF RA 30 are especially preferred non-ionic surfactants that can be used in the non-aqueous liquid automatic dishwasher detergent compositions.
  • Other useful non-ionic surfactants are SYNPERONIC® RA 30,
  • surfactants are especially preferred because they are biodegradable and low foaming.
  • Other useful surfactants are NEODOL® 25-7 and NEODOL® 23-6.5, which products are made by Shell Chemical Company Inc. The latter is a condensation product of a mixture of higher fatty alcohols averaging about 12 to 13 carbon atoms and the number of ethylene oxide groups present averages about 6.5.
  • the higher alcohols are primary alkanols.
  • Other examples of such detergents include TERGITOL® 15-S-7 and
  • TERGITOL® 15-S-9 both of which are linear secondary alcohol ethoxylates made by Union Carbide Corp.
  • the former is mixed ethoxylation product of 1 1 to 15 carbon atoms linear secondary alkanol with seven moles of ethylene oxide and the latter is a similar product but with nine moles ethylene oxide being reacted.
  • Another useful surfactant is TERGITOL® MDS-42 a mixed ethoxylation product of 13-15 cations alcohols with 10 moles of EO and 5 moles of PO.
  • non-ionics include the alkyl saccharides (polyglycosides /oligosaccharides) and, in particular those described in the following patent
  • the alkyl polysaccharides surfactants have a hydrophobic group containing from about 8 to about 20 carbon atoms, preferably from about 10 to about 16 carbon atoms, most preferably from 12 to 14 carbon atoms, and polysaccharide hydrophilic group containing from about 1 .5 to about 10, preferably from 1.5 to 4, most preferably from 1 .6 to 2.7 saccharide units (e.g., galactoside, glucoside, fructoside, glucosyl, fructosyl; and/or galactosyl units). Mixtures of saccharide moieties may be used in the alkyl polysaccharide surfactants.
  • the number x indicates the number of saccharide units in a particular alkyl polysaccharide surfactant.
  • x can only assume integral values.
  • the physical sample can be characterized by the average value of x and this average value can assume non-integral values.
  • the values of x are to be understood to be average values.
  • the hydrophobic group (R) can be attached at the 2- , 3-, or 4- positions rather than at the 1 -position, (thus giving e.g. a glucosyl or galactosyl as opposed to a glucoside or galactoside).
  • glucosides i.e., glucosides, galactoside, fructosides, etc.
  • additional saccharide units are predominately attached to the previous saccharide unit's 2-position. Attachment through the 3-, 4-, and 6-positions can also occur.
  • the preferred alkoxide moiety is ethoxide.
  • Typical hydrophobic groups include alkyi groups, either saturated or unsaturated, branched or unbranched containing from about 8 to about 20, preferably from about 10 to about 18 carbon atoms.
  • the alkyi group is a straight chain saturated alkyi group.
  • the alkyi group can contain up to 3 hydroxy groups and/or the polyalkoxide chain can contain up to about 30, preferably less than 10, alkoxide moieties.
  • Suitable alkyi polysaccharides are decyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, and octadecyl, di-, tri-, tetra-, penta- and hexaglucosides, galactosides, lactosides, fructosides, fructosyls, lactosyls, glucosyls and/or galactosyl and mixtures thereof.
  • non-ionic surfactants may also be used.
  • Mixtures of non-ionic detergent surfactants with other surfactants such as anionic, cationic or ampholytic surfactants and soaps may also be used.
  • Another class of non-ionic surfactants is the Sorbitan esters and their ethoxylated derivatives. These are commercially available under the well-known brands SPAN® (e.g. SPAN® 20, 40, 60 and 80) and TWEEN®.
  • Ethoxylated amines may also be used. Several grades of amine ethoxylates are commercially available.
  • the composition preferably comprises at least 10% by weight of one or more surfactants, more preferably at least 12%, or even at least 15% but typically not more than 40%, still more preferably not more than 35%, or even not more than 30% by weight of the composition.
  • the composition further comprises a builder.
  • the purpose of a builder is to remove hardness ions from the wash liquor.
  • the builder may be selected from any common builder material, including carbonate builders, such as soda (Na 2 C0 3 ), bicarbonate, phosphates, such as STPP, alkaline sodium silicate, sodium metasilicate and zeolytes, and combinations thereof.
  • carbonate builders such as soda (Na 2 C0 3 )
  • bicarbonate such as soda (Na 2 C0 3 )
  • phosphates such as STPP
  • alkaline sodium silicate sodium metasilicate and zeolytes
  • the builder is preferably an alkaline builder.
  • the builder is present in the detergent composition in a concentration of 10 -60%, depending on water hardness and the type of builder.
  • the composition comprises at least 20% by weight of a builder or even at least 25%, but generally less than 50% by weight of the composition.
  • Alkaline builder materials include, but are not limited to carbonate builders, such as soda (Na 2 C0 3 ) and bicarbonate, alkaline sodium silicate and sodium metasilicate.
  • the detergent composition of the present invention preferably comprises 0.1 -20% by weight of a seed material.
  • the seed material is typically present in a concentration of 0.1 -20% by weight of the builder composition, preferably at least 1 %, more preferably at least 2% or even at least 5%, but generally less than 15%, or even less than 10% by weight of the builder composition.
  • a ratio of alkaline builder: seed material in the range of 4:1 and 10:1 is the most preferred.
  • the detergent composition optionally comprises 2 - 30% by weight of an electrolyte, preferably at least 5%, but typically less than 20% by weight of the composition.
  • the electrolyte may be preferably selected from sodium chloride, sodium sulphate; chloride being the most preferred.
  • the electrolyte may also act as filler material. This electrolyte excludes the builder material.
  • the mud stain removal and anti-re-deposition composition according to the invention may be applied in solid or liquid detergent composition.
  • Solid detergent compositions may be in the form of a powder, granule, tablet or pods. Hand wash detergent bars are also considered.
  • the dosage of a solid detergent composition to a standard washing machine of 4-8 kg wash load is typically between 10 and 150 g, preferably at least 20 g, or even at least 30 g, but preferably less than 100 g, or even less than 80 g.
  • the dosage is between 30 and 50g and for vertical axis washing machines, the dosage is between 50 and 80g.
  • liquid compositions both alkaline and neutral pH compositions are considered. Built liquid compositions are preferred, as the effect of the mud removal from non-cotton fabrics is further improved when the composition is built.
  • the dosage of a liquid detergent composition to a standard washing machine of 4-8 kg wash load is typically between 10 and 150 ml, preferably at least 20 ml, or even at least 30 ml, but preferably less than 100 ml, or even less than 80 ml.
  • the dosage is between 30 and 50ml and for vertical axis washing machines, the dosage is between 50 and 80ml.
  • the invention provides a process for treating a substrate for mud stain removal comprising the steps in sequence of preparing a 0.05- 1 % by weight solution of the composition according to the invention in water, treating the substrate with the prepared solution; and rinsing the substrate.
  • the solution is preferably 0.1 - 0.5% by weight of the composition in water for handwash and horizontal axis washing machines and preferably 0.05 - 0.2% for vertical axis washing machines.
  • a detergent base composition was prepared by mixing the surfactants, builder, electrolyte, seed and perfume in a sigma mixture. For washing experiments, required amount of the kojic acid/kojic acid ester was added to the tergotometer along with the detergent base formulation.
  • Washing was carried out using a tergotometer.
  • Protocol 1 .5 g/l appropriate detergent dose, liquor to cloth ratio of 50, water hardness, 24 FH, 100 rpm speed.
  • the detergent base composition and kojic acid/kojic acid ester were dissolved in 24 FH (2:1 Calcium to magnesium) water using a tergotometer operating at 100 rpm for 2 minutes to give a final concentration of 3 g per litre of the final detergent.
  • Five mud soiled fabrics (10 cm x 10 cm fabric, 10g) were added to 500 ml of wash liquor containing the formulation and soaked in it for 20 minutes. The fabrics were then washed for 20 minutes with tergotometer operating at 100 rpm speed. After wash, the fabrics were rinsed with 24 FH water at liquor to cloth ratio of 50 for two minutes twice in the tergotometer operating at 100 rpm.
  • Reflectance measurement The reflectance of the fabric was measured at AR460 (values at 460 nanometer, UV excluded) using a Macbeth 7000 color eye reflectometer. A SAV aperture and SAV lens were used for the measurement. Reflectance measured of the fabrics (control and experimental) were recorded each time after washing. Four readings were taken of the washed stained spot of the fabric and the average value was calculated.
  • Example 1 Effect of the compound of formula A (Kojic acid octyl ester) on mud stain removal
  • Example 3 Effect of the compound of formula A (Kojic acid octyl ester) in comparison to Kojic acid on mud removal
  • compositions comprising the kojic acid derivative (Ex 9 to Ex 1 1 ) than the compositions with kojic acid (Comp B to Comp D).
  • Example 4 Effect of increase in the concentration of the compound of formula A ln this example, the effect of the increase in the concentration of kojic acid octyl ester (Ex 18 to Ex 23), kojic acid propyl ester (Ex 12 to Ex 17) and kojic acid (Comp E to Comp J) are compared.
  • Base composition used in this example is the same formulation as in Comp A.

Abstract

The invention is in the field of detergent compositions, particularly to detergent compositions for removing mud stains. There is a need for detergent compositions comprising biodegradable mud removing agents which provide benefits under alkaline wash conditions. It is therefore an object of the present invention to provide a detergent composition having biodegradable mud removing agents for mud stain removal from fabrics and that reduces re-deposition of mud stains and soils. It has been found that a detergent composition comprising a kojic acid derivative of formula A provides mud removal and reduces re-deposition of mud stains and soils. Formula A wherein R is a C2 to C12 alkyl group.

Description

DETERGENT COMPOSITION
Field of the invention The present invention is in the field of a detergent composition and more particularly relates to a detergent composition for removing mud stains.
Background of the invention Fabric stains run the gamut from food spills to household substances and can be of different types; mainly aqueous, oily, particulate and bleachable. Stains are something that people try to avoid, yet they are unavoidable. Nonetheless, people still prefer to wear clothes with lesser stains or no stains at all. In fact, people prefer to avoid stains not just on clothes but in general in kitchens, bathrooms and also on various household surfaces.
Consequently, improved stain removal is one of the constant goals of the detergent industry. There is always an interest to improve the detergency effect, especially on fabric stains. Fabric stains such as particulate stains, especially mud or clay containing iron oxides, aqueous/ bleachable stains such as tea stains or oily stains such as motor oil stains, grease are difficult to remove during main wash. Even if such stains are removed during the wash process, re-deposition of the removed dirt onto the fabric is hard to avoid. Hydroxamates have been well known for mud stain removal. However, hydroxamates are not preferred to be used in laundry compositions as they do not provide benefits under alkaline wash conditions.
Polyacrylate polymers are also known for mud stain removal. However, polyacrylates are not preferred to be used in laundry compositions due to biodegradability issues.
However, a detergent composition comprising biodegradable mud removing agents and that provide benefits under alkaline wash conditions still remains to be desired. US 3,597,226 (The Procter & Gamble Company) discloses kojyl acylate high temperature batter stabilizers being used in combination with liquid glyceride oil shortenings and alpha-phase crystal-tending emulsifiers as ingredients in cake preparation to provide cakes improved volume, texture, and eating quality. Kojyl acylates of US 3,597,226 has an alkyl group having about 13 to 21 carbon atoms.
Accordingly, it is an object of the present invention to provide a detergent composition for mud stain removal from fabrics. It is another object of the invention to provide a detergent composition that reduces re- deposition of mud stains and soils.
It is yet another object of the invention to provide a detergent composition having biodegradable mud removing agents.
Surprisingly it has now been found that a detergent composition comprising a kojic acid derivative of formula A provides mud removal and reduces re-deposition of mud stains and soils.
Summary of the invention
Accordingly, in a first aspect, the present invention provides a detergent composition for mud stain removal comprising 0.1 to10 %w of a compound of formula A
Figure imgf000004_0001
Formula A wherein R is a C2 to Ci2 alkyl group; and 5 to 50%w of one or more surfactants.
In a second aspect, the invention provides a process for treating a substrate for mud stain removal comprising the steps in sequence of preparing 0.05 - 1 % by weight solution of the composition according to the invention in water, treating the substrate with the prepared solution; and rinsing the substrate.
In the context of the present invention, the reference to "substrate" typically means any kind of fabric.
These and other aspects, features and advantages will become apparent to those of ordinary skill in the art from a reading of the following detailed description and the appended claims. For the avoidance of doubt, any feature of one aspect of the present invention may be utilised in any other aspect of the invention. The word "comprising" is intended to mean "including" but not necessarily "consisting of" or "composed of." In other words, the listed steps or options need not be exhaustive. It is noted that the examples given in the description below are intended to clarify the invention and are not intended to limit the invention to those examples per se. Similarly, all percentages are weight/weight percentages unless otherwise indicated. Except in the operating and comparative examples, or where otherwise explicitly indicated, all numbers in this description indicating amounts of material or conditions of reaction, physical properties of materials and/or use are to be understood as modified by the word "about".
Numerical ranges expressed in the format "from x to y" are understood to include x and y. When for a specific feature multiple preferred ranges are described in the format "from x to y", it is understood that all ranges combining the different endpoints are also contemplated.
Detailed description of the invention
The detergent composition according to the invention comprises a kojic acid derivative of formula A and one or more surfactants.
Kojic acid derivative
The detergent composition comprises a compound of formula A.
Figure imgf000006_0001
Formula A
where R is a C2 to C12 alkyl group; preferably C2 to C7 alkyl group.
The compound of formula A is a derivative of kojic acid with long acyl groups.
The composition comprises 0.1 to10 % by weight of the compound of formula A, preferably not less than 1 %, more preferably not less than 2%, still more preferably not less than 3%, even more preferably not less than 4% or even not less than 5% but typically not more than 9%, preferably not more than 8%, more preferably not more than 7%, still more preferably not more than 6% by weight of the composition.
Surfactant
The composition comprises between 5-50% by weight of one or more surfactants. The surfactant may be chosen from any commercially available surfactants suitable for laundry purposes.
Such surfactants may be chosen from the surfactants described in well known textbooks like "Surface Active Agents" Vol. 1 , by Schwartz & Perry, Interscience 1949, Vol. 2 by Schwartz, Perry & Berch, Interscience 1958, and/or the current edition of "McCutcheon's Emulsifiers and Detergents" published by Manufacturing Confectioners Company or in "Tenside Taschenbuch", H. Stache, 2nd Edn., Carl Hauser Verlag, 1981 .
The surfactant may be anionic, non-ionic, cationic, amphoteric and/or zwitterionic. Anionic surfactants or a combination of anionic and non-ionic surfactant are the most preferred.
Anionic surfactants Suitable anionic surfactants for the detergent compounds which may be used are linear alkyi benzene sulfonate (LAS), (usually) water-soluble alkali metal salts of organic sulphates and sulphonates having alkyi radicals containing from about 8 to about 22 carbon atoms, the term alkyi being used to include the alkyi portion of higher acyl radicals, including alkyi sulphates, alkyi ether sulphates, alkaryl sulphonates, alkanoyl isethionates, alkyi succinates, alkyi sulphosuccinates, N-alkoyl sarcosinates, alkyi phosphates, alkyi ether phosphates, alkyi ether carboxylates, alpha-olefin sulphonates and acyl methyl taurates, especially their sodium, magnesium ammonium and mono , di- and triethanolamine salts. The alkyi and acyl groups generally contain from 8 to 22 carbon atoms, preferably 8 to 18 carbon atoms, still more preferably 12 to 15 carbon atoms and may be unsaturated. The alkyi ether sulphates, alkyi ether phosphates and alkyi ether carboxylates may contain from one to 10 ethylene oxide or propylene oxide units per molecule, and preferably contain 1 to 3 ethylene oxide units per molecule. Examples of suitable anionics include linear alkyi benzene sulfonate, sodium lauryl sulphate, sodium lauryl ether sulphate, ammonium lauryl sulphosuccinate, ammonium lauryl sulphate, ammonium lauryl ether sulphate, sodium cocoyl isethionate, sodium lauroyl isethionate, and sodium N-lauryl sarcosinate. Non-ionic surfactants
Non-ionic surfactants are also well-known in the art. They normally consist of a water- solubilising polyalkoxylene (preferably from 3 to10 ethoxy and/or propoxy groups) or a mono- or di-alkanolamide group in chemical combination with an organic hydrophobic group derived from, for example, fatty alcohols with from 9 to 15 carbon atoms
(optionally branched, e.g. methyl branched), alkylphenols (preferably from 12 to 20 carbon atoms) in which the alkyi group contains from about 6 to about 12 carbon atoms, dialkylphenols in which each alkyi group contains from 6 to 2 carbon atoms, primary, secondary or tertiary aliphatic alcohols (or alkyl-capped derivatives thereof) monocarboxylic acids having from 10 to about 24 carbon atoms in the alkyi group and polyoxypropylenes. Fatty acid mono- and dialkanolamides in which the alkyl group of the fatty acid radical contains from 10 to about 20 carbon atoms and the alkyloyl group having from 1 to 3 carbon atoms are also common. In any of the mono- and dialkanolamide derivatives, optionally, there may be a polyoxyalkylene moiety joining the latter groups and the hydrophobic part of the molecule.
In all polyalkoxylene containing surfactants, the polyalkoxylene moiety usually consists of an average of from 2 to 20 groups of ethylene oxide, propylene oxide groups or mixtures thereof. The latter class includes those described in European Patent Specification EP-A-0,225,654, especially for use as all or part of the liquid phase.
Especially preferred are ethoxylated non-ionics which are condensation products of fatty alcohols with from 9 to 15 carbon atoms condensed with 3 to 9 moles of ethylene and/or propylene oxide per mole of fatty alcohol. Examples of these are the
condensation products of C12 to C15 alcohols with 3 or 7 moles of ethylene oxide. These may be used as the sole non-ionic surfactant or in combination with those described in EP-A-0,225,654.
An example of a non-ionic surfactant is DOBANOL® 25-3, which is a C5 alcohol ethoxylated with on average three ethoxy groups. Other useful non-ionic surfactants are from the PLURAFAC® series from BASF. SYNPERONIC® non-ionic surfactant such as SYNPERONIC® LF D25 or LF RA 30 are especially preferred non-ionic surfactants that can be used in the non-aqueous liquid automatic dishwasher detergent compositions. Other useful non-ionic surfactants are SYNPERONIC® RA 30,
SYNPERONIC® RA 40 and SYNPERONIC® RA 340. The SYNPERONIC®
surfactants are especially preferred because they are biodegradable and low foaming. Other useful surfactants are NEODOL® 25-7 and NEODOL® 23-6.5, which products are made by Shell Chemical Company Inc. The latter is a condensation product of a mixture of higher fatty alcohols averaging about 12 to 13 carbon atoms and the number of ethylene oxide groups present averages about 6.5. The higher alcohols are primary alkanols. Other examples of such detergents include TERGITOL® 15-S-7 and
TERGITOL® 15-S-9), both of which are linear secondary alcohol ethoxylates made by Union Carbide Corp. The former is mixed ethoxylation product of 1 1 to 15 carbon atoms linear secondary alkanol with seven moles of ethylene oxide and the latter is a similar product but with nine moles ethylene oxide being reacted. Another useful surfactant is TERGITOL® MDS-42 a mixed ethoxylation product of 13-15 cations alcohols with 10 moles of EO and 5 moles of PO.
Another class of suitable non-ionics include the alkyl saccharides (polyglycosides /oligosaccharides) and, in particular those described in the following patent
specifications, US-A-3,640,998; US-A-3,346,558; US-A4,223,129; EP-A-0,092,355; EP-A-0,099,183; EP-A-0,070,074; EP-A-0,070,075; EP-A-0,070,075; EP-A-0,070,076; EP-A-0,070,077; EP-A-0,075,994; EP-A-0,075,995 and EP-A-0,075,996. The alkyl polysaccharides surfactants have a hydrophobic group containing from about 8 to about 20 carbon atoms, preferably from about 10 to about 16 carbon atoms, most preferably from 12 to 14 carbon atoms, and polysaccharide hydrophilic group containing from about 1 .5 to about 10, preferably from 1.5 to 4, most preferably from 1 .6 to 2.7 saccharide units (e.g., galactoside, glucoside, fructoside, glucosyl, fructosyl; and/or galactosyl units). Mixtures of saccharide moieties may be used in the alkyl polysaccharide surfactants. The number x indicates the number of saccharide units in a particular alkyl polysaccharide surfactant. For a particular alkyl polysaccharide molecule x can only assume integral values. In any physical sample of alkyl polysaccharide surfactants there will be in general molecules having different x values. The physical sample can be characterized by the average value of x and this average value can assume non-integral values. In this specification the values of x are to be understood to be average values. The hydrophobic group (R) can be attached at the 2- , 3-, or 4- positions rather than at the 1 -position, (thus giving e.g. a glucosyl or galactosyl as opposed to a glucoside or galactoside). However, attachment through the 1 -position, i.e., glucosides, galactoside, fructosides, etc., is preferred. In the preferred product the additional saccharide units are predominately attached to the previous saccharide unit's 2-position. Attachment through the 3-, 4-, and 6-positions can also occur. Optionally and less desirably there can be a polyalkoxide chain joining the hydrophobic moiety (R) and the polysaccharide chain. The preferred alkoxide moiety is ethoxide. Typical hydrophobic groups include alkyi groups, either saturated or unsaturated, branched or unbranched containing from about 8 to about 20, preferably from about 10 to about 18 carbon atoms. Preferably, the alkyi group is a straight chain saturated alkyi group. The alkyi group can contain up to 3 hydroxy groups and/or the polyalkoxide chain can contain up to about 30, preferably less than 10, alkoxide moieties.
Suitable alkyi polysaccharides are decyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, and octadecyl, di-, tri-, tetra-, penta- and hexaglucosides, galactosides, lactosides, fructosides, fructosyls, lactosyls, glucosyls and/or galactosyl and mixtures thereof.
Mixtures of different non-ionic surfactants may also be used. Mixtures of non-ionic detergent surfactants with other surfactants such as anionic, cationic or ampholytic surfactants and soaps may also be used. Another class of non-ionic surfactants is the Sorbitan esters and their ethoxylated derivatives. These are commercially available under the well-known brands SPAN® (e.g. SPAN® 20, 40, 60 and 80) and TWEEN®.
Ethoxylated amines may also be used. Several grades of amine ethoxylates are commercially available.
The composition preferably comprises at least 10% by weight of one or more surfactants, more preferably at least 12%, or even at least 15% but typically not more than 40%, still more preferably not more than 35%, or even not more than 30% by weight of the composition.
Builder
The composition further comprises a builder.
The purpose of a builder is to remove hardness ions from the wash liquor. The builder may be selected from any common builder material, including carbonate builders, such as soda (Na2C03), bicarbonate, phosphates, such as STPP, alkaline sodium silicate, sodium metasilicate and zeolytes, and combinations thereof. For liquid compositions citrate based builder compositions are also considered.
The builder is preferably an alkaline builder.
The builder is present in the detergent composition in a concentration of 10 -60%, depending on water hardness and the type of builder. Preferably the composition comprises at least 20% by weight of a builder or even at least 25%, but generally less than 50% by weight of the composition.
The best results are obtained, when at least part of the builder in the detergent composition is alkaline builder material. Alkaline builder materials include, but are not limited to carbonate builders, such as soda (Na2C03) and bicarbonate, alkaline sodium silicate and sodium metasilicate.
Seed material
Some builders, such as soda, perform better in the presence of a seed material. Soda is thought to remove calcium ions from solution by precipitation as calcium carbonate. This precipitation kinetics can be either enhanced by increasing the concentration of soda in solution or by using a seed that acts as a nucleus for the precipitating species. It is always preferred to use fine powder of the seed material to increase the available surface area and reduce the amount of seed required for effective building of calcium ions.
Common seed materials, suitable for use in the granule of the invention, include dolomite and calcite; calcite being the most preferred. The detergent composition of the present invention preferably comprises 0.1 -20% by weight of a seed material. The seed material is typically present in a concentration of 0.1 -20% by weight of the builder composition, preferably at least 1 %, more preferably at least 2% or even at least 5%, but generally less than 15%, or even less than 10% by weight of the builder composition. A ratio of alkaline builder: seed material in the range of 4:1 and 10:1 is the most preferred.
Electrolyte
The detergent composition optionally comprises 2 - 30% by weight of an electrolyte, preferably at least 5%, but typically less than 20% by weight of the composition.
The electrolyte may be preferably selected from sodium chloride, sodium sulphate; chloride being the most preferred. The electrolyte may also act as filler material. This electrolyte excludes the builder material.
Product format
The mud stain removal and anti-re-deposition composition according to the invention may be applied in solid or liquid detergent composition.
Solid detergent compositions may be in the form of a powder, granule, tablet or pods. Hand wash detergent bars are also considered. The dosage of a solid detergent composition to a standard washing machine of 4-8 kg wash load is typically between 10 and 150 g, preferably at least 20 g, or even at least 30 g, but preferably less than 100 g, or even less than 80 g. Typically for handwash and horizontal axis washing machines, the dosage is between 30 and 50g and for vertical axis washing machines, the dosage is between 50 and 80g.
In liquid compositions, both alkaline and neutral pH compositions are considered. Built liquid compositions are preferred, as the effect of the mud removal from non-cotton fabrics is further improved when the composition is built. The dosage of a liquid detergent composition to a standard washing machine of 4-8 kg wash load is typically between 10 and 150 ml, preferably at least 20 ml, or even at least 30 ml, but preferably less than 100 ml, or even less than 80 ml. Typically for handwash and horizontal axis washing machines, the dosage is between 30 and 50ml and for vertical axis washing machines, the dosage is between 50 and 80ml.
Process for treating a fabric
In another aspect, the invention provides a process for treating a substrate for mud stain removal comprising the steps in sequence of preparing a 0.05- 1 % by weight solution of the composition according to the invention in water, treating the substrate with the prepared solution; and rinsing the substrate.
The solution is preferably 0.1 - 0.5% by weight of the composition in water for handwash and horizontal axis washing machines and preferably 0.05 - 0.2% for vertical axis washing machines.
The invention will now be illustrated by means of the following non-limiting examples Examples
Table 1 : Materials
Figure imgf000013_0001
Preparing the compositions A detergent base composition was prepared by mixing the surfactants, builder, electrolyte, seed and perfume in a sigma mixture. For washing experiments, required amount of the kojic acid/kojic acid ester was added to the tergotometer along with the detergent base formulation.
Staining Protocol 10 cm x 10 cm woven cotton fabrics were soiled using 1 g of 50% red mud (0.5 g of red mud dispersed in 0.5 g of water) using a spatula. The mud slurry was spread in the shape of a circle using the same spatula. The fabrics were placed horizontally and dried overnight and were used for washing. Washing Protocol
Washing was carried out using a tergotometer.
Protocol: 1 .5 g/l appropriate detergent dose, liquor to cloth ratio of 50, water hardness, 24 FH, 100 rpm speed.
The detergent base composition and kojic acid/kojic acid ester were dissolved in 24 FH (2:1 Calcium to magnesium) water using a tergotometer operating at 100 rpm for 2 minutes to give a final concentration of 3 g per litre of the final detergent. Five mud soiled fabrics (10 cm x 10 cm fabric, 10g) were added to 500 ml of wash liquor containing the formulation and soaked in it for 20 minutes. The fabrics were then washed for 20 minutes with tergotometer operating at 100 rpm speed. After wash, the fabrics were rinsed with 24 FH water at liquor to cloth ratio of 50 for two minutes twice in the tergotometer operating at 100 rpm.
Reflectance measurement: The reflectance of the fabric was measured at AR460 (values at 460 nanometer, UV excluded) using a Macbeth 7000 color eye reflectometer. A SAV aperture and SAV lens were used for the measurement. Reflectance measured of the fabrics (control and experimental) were recorded each time after washing. Four readings were taken of the washed stained spot of the fabric and the average value was calculated.
Example 1 : Effect of the compound of formula A (Kojic acid octyl ester) on mud stain removal
In this example, the effect of kojic acid octyl ester at different concentrations (Ex1 to Ex 4) is compared to a control composition (Comp A) without kojic acid octyl ester.
Table 2
Figure imgf000015_0001
Note: *Perfume and fluorescer concentration remains constant and water is added to a 100 percent in each example.
The above table shows that better results on mud stain removal are obtained for Ex 1 to Ex 4 having a kojic acid derivative according to the invention when compared to the Comp A with no kojic acid derivative. However, improved cleaning performance is seen when the kojic acid derivative is present in the composition in a concentration of 5% or more. Example 2: Effect of the compound of formula A (Kojic acid propyl ester) on mud stain removal
In this example, the effect of kojic acid propyl ester at different concentrations (Ex 5 to Ex 8) is compared to a control composition (Comp A) without kojic acid propyl ester.
Table 3
Figure imgf000016_0001
Note: *Perfume and fluorescer concentration remains constant and water is added to a 100 percent in each example.
The above table shows that better results on mud stain removal are obtained for Ex 5 to Ex 8 having a kojic acid derivative according to the invention when compared to the Comp A with no kojic acid derivative. However, improved cleaning performance is seen when the kojic acid derivative is present in the composition in a concentration of 5% or more. Example 3: Effect of the compound of formula A (Kojic acid octyl ester) in comparison to Kojic acid on mud removal
In this example, the effect of kojic acid octyl ester at different concentrations (Ex 9 to Ex 1 1 ) is compared to compositions comprising kojic acid at different concentrations (Comp B to Comp D).
Table 4
Figure imgf000017_0001
Note: *Perfume and fluorescer concentration remains constant and water is added to a 100 percent in each example.
The above table shows that better cleaning of mud stains are obtained for
compositions comprising the kojic acid derivative (Ex 9 to Ex 1 1 ) than the compositions with kojic acid (Comp B to Comp D).
Example 4: Effect of increase in the concentration of the compound of formula A ln this example, the effect of the increase in the concentration of kojic acid octyl ester (Ex 18 to Ex 23), kojic acid propyl ester (Ex 12 to Ex 17) and kojic acid (Comp E to Comp J) are compared.
Base composition used in this example is the same formulation as in Comp A.
Table 5
Set Final Std % in
Reflectance deviation formulation
Comp 3 g/l Base composition 67.6 0.5 0.0
E
Comp 3 g/l Base composition + 0.1 g/l 68.1 0.6 3.3
F kojic acid
Comp 3 g/l Base composition + 0.15 g/l 68.2 0.4 5.0
G kojic acid
Comp 3 g/l Base composition + 0.3 g/l 68.3 0.5 10.0
H kojic acid
Comp I 3 g/l Base composition + 0.75 g/l 68.2 0.5 25.0
kojic acid
Comp 3 g/l Base composition + 1 .5 g/l 68.4 0.5 50.0
J kojic acid
Ex 12 3 g/l Base composition + 0.03 g/l 69.4 0.3 1 .0
kojic acid isopropyl ester
Ex 13 3 g/l Base composition + 0.1 g/l 69.6 0.6 3.3
kojic acid isopropyl ester
Ex 14 3 g/l Base composition + 0.15 g/l 70.3 0.5 5.0
kojic acid isopropyl ester
Ex 15 3 g/l Base composition + 0.3 g/l 70.8 0.4 10.0
kojic acid isopropyl ester
Comp 3 g/l Base composition + 0.75 g/l 71.0 0.5 25.0
K Kojic acid isopropyl ester
Comp 3 g/l Base composition + 1 .5 g/l 71.0 0.5 50.0
L Kojic acid isopropyl ester
Ex 18 3 g/l Base composition + 0.03 g/l 69.9 0.6 1 .0 kojic acid octyl ester
Ex 19 3 g/l Base composition + 0.1 g/l 70.1 0.5 3.3
kojic acid octyl ester
Ex 20 3 g/l Base composition + 0.15 g/l 70.6 0.6 5.0
kojic acid octyl ester
Ex 21 3 g/l Base composition + 0.3 g/l 70.4 0.3 10.0
kojic acid octyl ester
Comp 3 g/l Base composition + 0.75 g/l 70.6 0.5 25.0
M Kojic acid octyl ester
Comp 3 g/l Base composition + 1 .5 g/l 70.5 0.5 50.0
N Kojic acid octyl ester
It is inferred from the above table that even at significantly high concentrations of kojic acid (Comp I and Comp J), the cleaning performance on mud sustains is not as good as the compositions comprising kojic acid derivatives according to the invention.
It is also inferred that at concentrations above 10% of kojic acid derivatives (Comp K, Comp L, Comp M and Comp N), the cleaning performance does not substantially improve while the cost of the composition increases. This is not desired.

Claims

Claims
1 . A detergent composition for mud stain removal comprising
ound of formula A
Figure imgf000020_0001
Formula A
wherein R is a C2 to Ci2 alkyl group; and
b. 5 to 50%w of one or more surfactants.
2. A composition according to claim 1 , wherein said R is a C2 to C7 alkyl group.
3. A composition according to claim 1 or 2, wherein the composition comprises 5 to 10 %w of compound of formula A.
4. A composition according to any one of the preceding claims 1 to 3, wherein the surfactant is anionic and/or non-ionic surfactant.
5. A composition according to any one of the preceding claims 1 to 4, wherein the composition comprises 10 to 30%w of the surfactant.
6. A composition according to any one of the preceding claims 1 to 5, wherein the composition is in the form of a liquid, powder, granules, tablets or pods.
7. A composition according to any one of the preceding claims 1 to 6, wherein the composition further comprises 10 to 60%w of a builder.
8. A process for treating a substrate for mud stain removal comprising the steps in sequence of: a. preparing a 0.05 to 1 % by weight solution of the composition
according to claims 1 to 7 in water, treating the substrate with the prepared solution; and rinsing the substrate.
PCT/EP2014/076195 2013-12-30 2014-12-02 Detergent composition WO2015101454A1 (en)

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