WO2015193203A1 - Stain treatment compositions - Google Patents

Stain treatment compositions Download PDF

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Publication number
WO2015193203A1
WO2015193203A1 PCT/EP2015/063230 EP2015063230W WO2015193203A1 WO 2015193203 A1 WO2015193203 A1 WO 2015193203A1 EP 2015063230 W EP2015063230 W EP 2015063230W WO 2015193203 A1 WO2015193203 A1 WO 2015193203A1
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WO
WIPO (PCT)
Prior art keywords
substrate
fabric
stain removal
stain
removal composition
Prior art date
Application number
PCT/EP2015/063230
Other languages
French (fr)
Inventor
Ravine Anthony Gungabissoon
Jordan Todorov Petkov
Original Assignee
Unilever Plc
Unilever N.V.
Conopco, Inc., D/B/A Unilever
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 N.V., Conopco, Inc., D/B/A Unilever filed Critical Unilever Plc
Priority to EP15730114.4A priority Critical patent/EP3158037A1/en
Priority to CN201580032807.6A priority patent/CN106661519A/en
Priority to BR112016029718A priority patent/BR112016029718A2/en
Publication of WO2015193203A1 publication Critical patent/WO2015193203A1/en
Priority to ZA2016/08407A priority patent/ZA201608407B/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/30—Amines; Substituted amines ; Quaternized amines
    • C11D2111/12—

Definitions

  • This invention relates to ambient-active fabric stain removal compositions and ambient- active domestic stain removal compositions.
  • aqueous substrate cleaning is performed at cold or ambient temperatures. These temperatures are a challenge for stain removal technology which relies on water temperatures of 40 - 70 degrees. In the case of modern washing machines, stain removal mainly relies largely on the heating of water above ambient temperatures in the washing machine. This accounts for a large proportion of the laundry and other domestic cleaning related greenhouse gas footprint which needs reducing for environmental reasons.
  • the objective of the invention is the removal of fabric stains from stained fabric and stains from other substrates as defined herein.
  • a fabric or other substrate stain removal composition comprising a diamine compound and a surfactant.
  • a fabric or other substrate stain removal composition comprising a compound of structure:
  • X1 and X2 are hydrogen bond donor or acceptor groups independently selected from
  • R is a linker independently selected from:
  • a method for removing a stain from a stained fabric or other substrate comprising the step of applying to the stain, the composition of the first aspect of the invention.
  • a pre-treatment device comprising (i) a storage chamber storing the composition of the first aspect of the invention and a (i) dispenser for applying said composition to a stain on a fabric or other substrate, the pre- treatment device preferably being suitable for use in the method of the second aspect.
  • the invention provides use of a diamine compound, preferably in combination with a surfactant, in the removal of stains from a stained fabric or other substrate.
  • a diamine compound preferably in combination with a surfactant
  • the removal of stains at low temperatures is radically improved and so offers cost effective improved laundry/other domestic cleaning in regions where ambient washing occurs out of habit or necessity.
  • Improved washing performance at lower temperatures is generally desirable but increased low temperature performance may also help inhibit the adoption of hot water washing in these countries, a rising trend as standards of living increase and more people are able to afford washing machines.
  • the invention provides stain removal performance of soil and/or stains in an ambient temperature cleaning processes (with low temperature wash liquor) without serious consideration to the temperature sensitivity of ingredients during storage.
  • the formulation can therefore be designed more freely, on the basis of other considerations.
  • the term “substrate” includes fabric, and clothing and other surfaces such as cutlery, crockery and other domestic/household hard surfaces.
  • the term “diamine compound” is intended to include any suitable diamine compound, including stereoisomeric and racemic forms, derivatives, and substituted derivative and mixtures thereof.
  • the term “ambient-active” is intended to mean less that 25 degrees Celcius and preferably 22 degrees Celcius or less, more preferably 15 degrees or less but always greater than 1 degree Celcius and "active" means effective in achieving stain removal.
  • stain removal is means removal as measured in terms of Remission units or a Remission index. For a visible (by the human eye) effect, effective stain removal is represented by remission equal to or greater than 2 Remission units and preferably greater or equal to 5 units.
  • wt% means “% by weight”. Unless specified otherwise, all percentages mentioned herein are by weight calculated relative to the total composition.
  • the diamine preferably comprises anyone of the following structures:
  • Diaminopropane (Sigma, CAS Number 109-76-2), propane-1 ,2-diamine, propane-1 ,3- diamine, pentane-1 ,3-diamine, 2-aminoethanol, 2-aminopropan-1 -ol, 2-aminobutan-1-ol, 2-aminopentan-1-ol, 2-aminohexan-1-ol, 2-aminodecan-1 -ol, 2-aminoundecan-1-ol, 2- aminododecan-1-ol, 3-aminopropan-1-ol, 2-aminoethanethiol, 2-aminoethanol, 1- aminopropan-2-ol, 3-aminopropan-1-ol, 4-aminobutan-2-ol, ethane-1 ,2-diol, propane-1 ,2- diol, butane-1 ,2-diol, pentane-1 ,2-diol, hexane-1 ,2-dio
  • the method of the invention preferably comprises an aqueous washing process.
  • the method comprises the step of adding water to the composition to form an aqueous wash liquor.
  • the method comprises localised application of the composition to a stain or stained area of the fabric or substrate.
  • the method may be pre-treatment method, and be followed by a subsequent aqueous washing step. Pre-treatment steps may take place without further addition of any water (beyond any contained in the composition).
  • the pre-treatment process may comprise the step of soaking the substrate in an aqueous solution to which the treatment composition has been added.
  • the pre-treatment process may comprise the step of applying the
  • composition by spraying, brushing, rubbing or scrubbing etc.
  • the second step of the method of the invention may be a 'main' wash and may be a manual washing process or a washing process in a washing machine.
  • the second step may use any suitable detergent composition.
  • this detergent composition comprises one or more surfactants and/or other functional ingredients, adjuncts etc. as described below.
  • subsequent steps may not require further application of the diamine compound.
  • the washing process of the invention is less than 90 minutes in duration, more preferably less than 60 minutes and most preferably less than 30 minutes.
  • the pre-treatment step is preferably less than 5 minutes, and more preferably less than 2 minutes.
  • the diamine compound is present in wash liquor in a concentration in the range 0.01 mg/ml - 10mg/ml and more preferably in the range 0.31 mg/ml - 0.62mg/ml.
  • concentration of the diamine compound in the wash liquor is in the range 0.15mg/ml to 10mg/ml.
  • the diamine compound is present in any composition of the invention in a concentration in the range 40 mg - 5000 mg per dose, preferable 320mg - 4000 mg per dose.
  • the composition may be provided as a single dose format or as multiple dose, free flowing format (powder, liquid, gel, paste etc) which is measured out by the consumer using a dosing device.
  • the dose may range from 10 ml to 100ml.
  • the pre-treatment device may be by any suitable device such as roll-on applicator or tube, sprays, aerosols, pastes, a pump-operated dispenser or stain treatment pen or brush or the like.
  • the pre-treatment device may comprise a scrubbing member having brush, bristles, tufts, projections, embossments etc or any combination thereof to further aid application of the detergent composition to a substrate.
  • the treatment composition is ambient-active. Accordingly, the temperature of the wash liquor step of aqueous washing process is therefore less than 40 °C and preferably less than 30°C and more preferably less than 25°C and more preferably less than or equal to 22°C further more preferably 15°C or less at all times during the washing but excluding drying. Encouraging low temperature wash liquor is advantageous environmentally and financially.
  • the treatment composition of the invention and/or any detergent composition used subsequently may comprise any of the following ingredients.
  • the surfactant may be a synthetic surfactant.
  • the surfactant comprises a biosurfactant which is mircrobially synthesized e.g. from bacteria, fungi or other microbe.
  • the biosurfactant comprises a glycolipid biosurfactant which may be a rhamnolipid or sophorolipid or trehalolipid or a mannosylerythritol lipid (MEL).
  • a glycolipid biosurfactant which may be a rhamnolipid or sophorolipid or trehalolipid or a mannosylerythritol lipid (MEL).
  • the biosurfactant may advantageously comprise a cellobiose, peptide based biosurfactants, lipoproteins and lipopeptides e.g. surfactin, fatty acids e.g. corynomucolic acids (preferably with hydrocarbon chain C12-C14) , phospholipids e.g.
  • Phosphatidylethanolamine produced by Rhodococcus erythropolis grown on n-alkane resulted in the lowering of interfacial tension between water and hexadecane to less than 1 mN m-1 and CMC of 30 mg L-1 (Kretschner et al., 1982) and Spiculisporic acid;
  • polymeric biosurfactants including emulsan, liposan, mannoprotein and polysaccharide- protein complexes.
  • the biosurfactant comprises a rhamnolipid.
  • the surfactant may be present by weight in the compositions at a level of from 3 to 85% by weight, preferably from 3 to 60% by weight, more preferably from 3 to 40% by weight, most preferably from 3 to 35% by weight.
  • the anionic surfactant is present at a level of from 0.1 to 95% by weight, preferably from 1 to 50% by weight, more preferably from 1.5 to 25% by weight based on total weight of surfactants present.
  • the surfactant is or at least comprises an anionic surfactant.
  • Anionic surfactants are defined herein as amphiphilic molecules comprising one or more functional groups that exhibit a net anionic charge when in aqueous solution at the normal wash pH of between 6 and 1 1.
  • Preferred anionic biosurfactants are rhamnolipds and lactonic forms of sophorolipids. Biosurfactants which are not expressed biologically in anionic form but have been modified to provide/improve anionic properties are included in the invention.
  • Preferred synthetic anionic surfactants are the alkali metal salts of organic sulphur reaction products having in their molecular structure an alkyl radical containing from about 6 to 24 carbon atoms and a radical selected from the group consisting of sulphonic and sulphuric acid ester radicals.
  • anionic surfactant hereinafter described can be used, such as alkyl ether sulphates, soaps, fatty acid ester sulphonates, alkyl benzene sulphonates,
  • sulphosuccinate esters primary alkyl sulphates, olefin sulphonates, paraffin sulphonates and organic phosphate
  • preferred anionic surfactants are the alkali and alkaline earth metal salts of fatty acid carboxylates, fatty alcohol sulphates, preferably primary alkyl sulfates, more preferably they are ethoxylated, for example alkyl ether sulfates; and alkylbenzene sulfonates or mixtures thereof.
  • Amphoteric surfactants and/or zwitterionic surfactants may be present in the
  • compositions according to the invention are amphoteric.
  • the pH of the wash liquor is preferably of between 6 and 10.
  • an amphoteric or zwitterionic surfactant is present at a level of from 0.1 to 20% by weight, more preferably from 0.25 to 15% by weight, even more preferably from 0.5 to 10% by weight.
  • Suitable zwitterionic surfactants are exemplified as those which can be broadly described as derivatives of aliphatic quaternary ammonium, sulfonium and phosphonium
  • Ri contains an alkyl, alkenyl or hydroxyalkyl group with 8 to 18 carbon atoms, from 0 to 10 ethylene-oxy groups or from 0 to 2 glyceryl units;
  • Y is a nitrogen, sulfur or phosphorous atom;
  • R2 is an alkyl or hydroxyalkyl group with 1 to 3 carbon atoms;
  • x is 1 when Y is a sulfur atom and 2 when Y is a nitrogen or phosphorous atom;
  • R3 is an alkyl or hydroxyalkyl group with 1 to 5 carbon atoms and Z is a radical selected from the group consisting of sulfate, sulfonate, carboxylate, phosphate or phosphonate.
  • Preferred amphoteric surfactants are amine oxides, for example coco dimethyl amine oxide.
  • Preferred zwitterionic surfactants are betaines, and especially amidobetaines.
  • Preferred betaines are Cs to C18 alkyl amidoalkyl betaines, for example coco amido betaine. These may be included as co-surfactants, preferably present in an amount of from 0 to 10 wt %, more preferably 1 to 5 wt %, based on the weight of the total composition.
  • Preferred amphoteric or zwitterionic surfactants for incorporation in the composition according to the present invention are betaine surfactants. Examples of these are mentioned in the following list.
  • the sulfatobetaines such as 3-(dodecyldimethylammonium)-1 -propane sulfate; and 2- (cocodimethylammonium)-l -ethane sulfate.
  • the sulfobetaines such as: 3-(dodecyldimethyl-ammonium)-2-hydroxy-1 -propane sulfonate; 3-(tetradecyl-dimethylammonium)-1 -propane sulfonate; 3-(Ci2-Ci 4 alkyl- amidopropyldimethylammonium)-2-hydroxy-1 -propane sulfonate; and 3- (cocodimethylammonium)-l -propane sulfonate.
  • carboxybetaines such as (dodecyldimethylammonium) acetate (also known as lauryl betaine); (tetradecyldimethylammonium) acetate (also known as myristyl betaine);
  • oleyldimethylammonium also known as oleyl betaine
  • the sulfoniumbetaines such as: (dodecyldimethylsulfonium) acetate; and 3- (cocodimethyl-sulfonium)-l -propane sulfonate.
  • the phosphoniumbetaines such as 4-(trimethylphosphonium)-1 -hexadecane sulfonate; 3-(dodecyldimethylphosphonium)-1 -propanesulfonate; and
  • compositions according to the present invention preferably comprise
  • compositions may further comprise, colorants, pearlisers and/or opacifiers, and shading dye.
  • Fluorescent Agents The invention is highly advantageous if carried out in water with a high water hardness, preferably of greater than 5°FH preferably greater than 40°FH, more preferably greater than 90°FH.
  • Figures 1 -3 show the results of diamine compounds in a laundry detergent composition tested for ability to treat various fat stains as follows:
  • Fig 1 Various soiled cotton fabrics (a) Used Frying Fat (b) Butterfat (c) Beef Fat (d) Lard were washed for 1 hour at room temperature in a range of 1 ,4 Diaminobutane dihydrochloride concentrations (0.15 - 10 mg/ml) and Laundry detergent composition. The "0" value shows washing in Laundry detergent composition without diamine.
  • Fig2 Various soiled cotton fabrics (a) Used Frying Fat (b) Butterfat (c) Beef Fat (d) Lard were washed for 1 hour at room temperature in a range of 1 ,3 Diaminopropane concentrations (0.15 - 10 mg/ml) and Laundry detergent composition. The "0" value shows washing in Laundry detergent composition without diamine.
  • Fig 3 Various soiled cotton fabrics were pre-treated in either 5 mg/ml 1 ,4 Diaminobutane dihydrochloride and Laundry detergent composition (Test) or Laundry detergent composition alone (Control). The fabrics were then washed in Laundry detergent composition for 1 hour at room temperature. Washing of the test and controls was carried out in triplicate for each soiled fabric.
  • diamine compounds in laundry detergent laundry detergent compositions were tested to determine their ability to treat i.e. stains from cotton fabric in various ways. All values throughout are wt%. End-point Stain Removal Assay
  • Fat soils Violet Dyed Used Frying Fat (CS-46), Coloured Beef Fat (CS-61 ), Coloured Lard (CS-62), Butterfat (CS-10)
  • the soiled fabric discs were pre-washed to remove any residual free stain as follows:
  • the soiled fabric was incubated in the pre-treatment solution for 5 mins at room temperature with no agitation. The pre-treatment wash liquor was then removed.
  • the soiled fabric was washed (250 rpm, 1 hour, room
  • wash liquor was then removed and fabric washed 4 X 5 mins with 200 ul distilled water on a plate shaker at 250 rpm. The fabric was then left to dry over night at room temperature before scanning.
  • the soiled fabrics were washed at 250 rpm for 1 hour at room temperature. After washing, the wash liquor was then removed and fabric washed 4 X 5 mins with 200 ul distilled water on a plate shaker at 250 rpm. The fabric was then left to dry over night at room temperature before scanning.

Abstract

A fabric stain removal composition comprising a diamine compound and a surfactant.

Description

STAIN TREATMENT COMPOSITIONS
This invention relates to ambient-active fabric stain removal compositions and ambient- active domestic stain removal compositions.
In many climates and in developing countries, aqueous substrate cleaning is performed at cold or ambient temperatures. These temperatures are a challenge for stain removal technology which relies on water temperatures of 40 - 70 degrees. In the case of modern washing machines, stain removal mainly relies largely on the heating of water above ambient temperatures in the washing machine. This accounts for a large proportion of the laundry and other domestic cleaning related greenhouse gas footprint which needs reducing for environmental reasons.
The objective of the invention is the removal of fabric stains from stained fabric and stains from other substrates as defined herein.
In a first aspect of the present invention there is provided a fabric or other substrate stain removal composition comprising a diamine compound and a surfactant. In a further aspect of the present invention there is provided a fabric or other substrate stain removal composition comprising a compound of structure:
i
\
R X,
(CH2)n /
wherein
X1 and X2 are hydrogen bond donor or acceptor groups independently selected from
NH2, OH, SH and NH; and
R is a linker independently selected from:
a. -CH- la. -CH-CH2- c. -CH-CH2-CH2- and n is an integer where n=0 to 10.
Preferably X1 =X2=NH2 and R= -CH- and n=1 (i.e. 1 ,3 diaminopropane) and n=2 (i.e. 1 ,4 diaminobutane)
In a third aspect of the invention there is provided a method for removing a stain from a stained fabric or other substrate, comprising the step of applying to the stain, the composition of the first aspect of the invention.
In a fourth aspect of the invention there is provided a pre-treatment device comprising (i) a storage chamber storing the composition of the first aspect of the invention and a (i) dispenser for applying said composition to a stain on a fabric or other substrate, the pre- treatment device preferably being suitable for use in the method of the second aspect.
In a further aspect the invention provides use of a diamine compound, preferably in combination with a surfactant, in the removal of stains from a stained fabric or other substrate. With the invention, the removal of stains at low temperatures is radically improved and so offers cost effective improved laundry/other domestic cleaning in regions where ambient washing occurs out of habit or necessity. Improved washing performance at lower temperatures is generally desirable but increased low temperature performance may also help inhibit the adoption of hot water washing in these countries, a rising trend as standards of living increase and more people are able to afford washing machines. The invention provides stain removal performance of soil and/or stains in an ambient temperature cleaning processes (with low temperature wash liquor) without serious consideration to the temperature sensitivity of ingredients during storage. The formulation can therefore be designed more freely, on the basis of other considerations.
As used herein, the term "substrate" includes fabric, and clothing and other surfaces such as cutlery, crockery and other domestic/household hard surfaces. As used herein, the term "diamine compound" is intended to include any suitable diamine compound, including stereoisomeric and racemic forms, derivatives, and substituted derivative and mixtures thereof. The term "ambient-active" is intended to mean less that 25 degrees Celcius and preferably 22 degrees Celcius or less, more preferably 15 degrees or less but always greater than 1 degree Celcius and "active" means effective in achieving stain removal.
As used herein "stain removal" is means removal as measured in terms of Remission units or a Remission index. For a visible (by the human eye) effect, effective stain removal is represented by remission equal to or greater than 2 Remission units and preferably greater or equal to 5 units.
As used herein, the abbreviation "wt%" means "% by weight". Unless specified otherwise, all percentages mentioned herein are by weight calculated relative to the total composition.
The diamine preferably comprises anyone of the following structures:
1 ,4 Diaminobutane dihydrochloride (Sigma, CAS Number 333-93-7) ; 1 ,3
Diaminopropane (Sigma, CAS Number 109-76-2), propane-1 ,2-diamine, propane-1 ,3- diamine, pentane-1 ,3-diamine, 2-aminoethanol, 2-aminopropan-1 -ol, 2-aminobutan-1-ol, 2-aminopentan-1-ol, 2-aminohexan-1-ol, 2-aminodecan-1 -ol, 2-aminoundecan-1-ol, 2- aminododecan-1-ol, 3-aminopropan-1-ol, 2-aminoethanethiol, 2-aminoethanol, 1- aminopropan-2-ol, 3-aminopropan-1-ol, 4-aminobutan-2-ol, ethane-1 ,2-diol, propane-1 ,2- diol, butane-1 ,2-diol, pentane-1 ,2-diol, hexane-1 ,2-diol, octane-1 ,2-diol, decane-1 ,2-diol, dodecane-1 ,2-diol, propane-1 ,3-diol, butane-1 ,3-diol, 2-mercaptoethanol, 1- mercaptopropan-2-ol, 3-mercaptopropan-1 -ol, 2-aminoethanethiol, 2-mercaptoethanol, 3- mercaptopropan-1-ol, ethane-1 ,2-dithiol, propane-1 ,3-dithiol, butane-1 ,3-dithiol. The stain may comprise biological material such as fat, oil, blood, starch and
combinations thereof. The method of the invention preferably comprises an aqueous washing process.
Accordingly it is preferred that the method comprises the step of adding water to the composition to form an aqueous wash liquor. Preferably the method comprises localised application of the composition to a stain or stained area of the fabric or substrate. The method may be pre-treatment method, and be followed by a subsequent aqueous washing step. Pre-treatment steps may take place without further addition of any water (beyond any contained in the composition).
Alternatively or additionally, the pre-treatment process may comprise the step of soaking the substrate in an aqueous solution to which the treatment composition has been added. Alternatively the pre-treatment process may comprise the step of applying the
composition by spraying, brushing, rubbing or scrubbing etc.
The second step of the method of the invention may be a 'main' wash and may be a manual washing process or a washing process in a washing machine. The second step may use any suitable detergent composition. Preferably this detergent composition comprises one or more surfactants and/or other functional ingredients, adjuncts etc. as described below. In the case of pre-treatment according to the invention, subsequent steps may not require further application of the diamine compound.
Preferably the washing process of the invention is less than 90 minutes in duration, more preferably less than 60 minutes and most preferably less than 30 minutes. In pre- treatment embodiments, the pre-treatment step is preferably less than 5 minutes, and more preferably less than 2 minutes.
For the treatment of beef and lard fat stains, preferably the diamine compound is present in wash liquor in a concentration in the range 0.01 mg/ml - 10mg/ml and more preferably in the range 0.31 mg/ml - 0.62mg/ml. For the treat of frying fat and butter fat, preferably the concentration of the diamine compound in the wash liquor is in the range 0.15mg/ml to 10mg/ml. Preferably the diamine compound is present in any composition of the invention in a concentration in the range 40 mg - 5000 mg per dose, preferable 320mg - 4000 mg per dose. The composition may be provided as a single dose format or as multiple dose, free flowing format (powder, liquid, gel, paste etc) which is measured out by the consumer using a dosing device. The dose may range from 10 ml to 100ml.
The pre-treatment device may be by any suitable device such as roll-on applicator or tube, sprays, aerosols, pastes, a pump-operated dispenser or stain treatment pen or brush or the like. The pre-treatment device may comprise a scrubbing member having brush, bristles, tufts, projections, embossments etc or any combination thereof to further aid application of the detergent composition to a substrate.
Preferably the treatment composition is ambient-active. Accordingly, the temperature of the wash liquor step of aqueous washing process is therefore less than 40 °C and preferably less than 30°C and more preferably less than 25°C and more preferably less than or equal to 22°C further more preferably 15°C or less at all times during the washing but excluding drying. Encouraging low temperature wash liquor is advantageous environmentally and financially. The treatment composition of the invention and/or any detergent composition used subsequently may comprise any of the following ingredients.
The surfactant may be a synthetic surfactant. Preferably the surfactant comprises a biosurfactant which is mircrobially synthesized e.g. from bacteria, fungi or other microbe.
Preferably the biosurfactant comprises a glycolipid biosurfactant which may be a rhamnolipid or sophorolipid or trehalolipid or a mannosylerythritol lipid (MEL).
Alternatively, the biosurfactant may advantageously comprise a cellobiose, peptide based biosurfactants, lipoproteins and lipopeptides e.g. surfactin, fatty acids e.g. corynomucolic acids (preferably with hydrocarbon chain C12-C14) , phospholipids e.g.
Phosphatidylethanolamine produced by Rhodococcus erythropolis grown on n-alkane resulted in the lowering of interfacial tension between water and hexadecane to less than 1 mN m-1 and CMC of 30 mg L-1 (Kretschner et al., 1982) and Spiculisporic acid;
polymeric biosurfactants including emulsan, liposan, mannoprotein and polysaccharide- protein complexes.
Preferably the biosurfactant comprises a rhamnolipid.
The surfactant may be present by weight in the compositions at a level of from 3 to 85% by weight, preferably from 3 to 60% by weight, more preferably from 3 to 40% by weight, most preferably from 3 to 35% by weight.
Preferably the anionic surfactant is present at a level of from 0.1 to 95% by weight, preferably from 1 to 50% by weight, more preferably from 1.5 to 25% by weight based on total weight of surfactants present.
Preferably the surfactant is or at least comprises an anionic surfactant.
Anionic surfactants are defined herein as amphiphilic molecules comprising one or more functional groups that exhibit a net anionic charge when in aqueous solution at the normal wash pH of between 6 and 1 1.
Preferred anionic biosurfactants are rhamnolipds and lactonic forms of sophorolipids. Biosurfactants which are not expressed biologically in anionic form but have been modified to provide/improve anionic properties are included in the invention.
Preferred synthetic anionic surfactants are the alkali metal salts of organic sulphur reaction products having in their molecular structure an alkyl radical containing from about 6 to 24 carbon atoms and a radical selected from the group consisting of sulphonic and sulphuric acid ester radicals.
Although any anionic surfactant hereinafter described can be used, such as alkyl ether sulphates, soaps, fatty acid ester sulphonates, alkyl benzene sulphonates,
sulphosuccinate esters, primary alkyl sulphates, olefin sulphonates, paraffin sulphonates and organic phosphate; preferred anionic surfactants are the alkali and alkaline earth metal salts of fatty acid carboxylates, fatty alcohol sulphates, preferably primary alkyl sulfates, more preferably they are ethoxylated, for example alkyl ether sulfates; and alkylbenzene sulfonates or mixtures thereof.
Amphoteric surfactants and/or zwitterionic surfactants may be present in the
compositions according to the invention. For amphoteric the pH of the wash liquor is preferably of between 6 and 10. Preferably an amphoteric or zwitterionic surfactant is present at a level of from 0.1 to 20% by weight, more preferably from 0.25 to 15% by weight, even more preferably from 0.5 to 10% by weight.
Suitable zwitterionic surfactants are exemplified as those which can be broadly described as derivatives of aliphatic quaternary ammonium, sulfonium and phosphonium
compounds with one long chain group having about 8 to about 18 carbon atoms and at least one water solubilizing radical selected from the group consisting of sulfate, sulfonate, carboxylate, phosphate or phosphonate. A general formula for these compounds is:
Figure imgf000008_0001
wherein Ri contains an alkyl, alkenyl or hydroxyalkyl group with 8 to 18 carbon atoms, from 0 to 10 ethylene-oxy groups or from 0 to 2 glyceryl units; Y is a nitrogen, sulfur or phosphorous atom; R2 is an alkyl or hydroxyalkyl group with 1 to 3 carbon atoms; x is 1 when Y is a sulfur atom and 2 when Y is a nitrogen or phosphorous atom; R3 is an alkyl or hydroxyalkyl group with 1 to 5 carbon atoms and Z is a radical selected from the group consisting of sulfate, sulfonate, carboxylate, phosphate or phosphonate.
Preferred amphoteric surfactants are amine oxides, for example coco dimethyl amine oxide. Preferred zwitterionic surfactants are betaines, and especially amidobetaines. Preferred betaines are Cs to C18 alkyl amidoalkyl betaines, for example coco amido betaine. These may be included as co-surfactants, preferably present in an amount of from 0 to 10 wt %, more preferably 1 to 5 wt %, based on the weight of the total composition. Preferred amphoteric or zwitterionic surfactants for incorporation in the composition according to the present invention are betaine surfactants. Examples of these are mentioned in the following list.
The sulfatobetaines, such as 3-(dodecyldimethylammonium)-1 -propane sulfate; and 2- (cocodimethylammonium)-l -ethane sulfate.
The sulfobetaines, such as: 3-(dodecyldimethyl-ammonium)-2-hydroxy-1 -propane sulfonate; 3-(tetradecyl-dimethylammonium)-1 -propane sulfonate; 3-(Ci2-Ci4 alkyl- amidopropyldimethylammonium)-2-hydroxy-1 -propane sulfonate; and 3- (cocodimethylammonium)-l -propane sulfonate.
The carboxybetaines, such as (dodecyldimethylammonium) acetate (also known as lauryl betaine); (tetradecyldimethylammonium) acetate (also known as myristyl betaine);
(cocodimethylammonium) acetate (also known as coconut betaine);
(oleyldimethylammonium) acetate (also known as oleyl betaine);
(dodecyloxymethyldimethylammonium) acetate; and (cocoamido- propyldimethylammonium) acetate (also known as cocoamido-propyl betaine or CAPB).
The sulfoniumbetaines, such as: (dodecyldimethylsulfonium) acetate; and 3- (cocodimethyl-sulfonium)-l -propane sulfonate.
The phosphoniumbetaines, such as 4-(trimethylphosphonium)-1 -hexadecane sulfonate; 3-(dodecyldimethylphosphonium)-1 -propanesulfonate; and
2-(dodecyldimethylphosphonium)-1 -ethane sulfate. The compositions according to the present invention preferably comprise
carboxybetaines or sulphobetaines as amphoteric or zwitterionic surfactants, or mixtures thereof. Especially preferred is lauryl betaine.
Further optional ingredients include additional surfactants e.g non ionic and cationic surfactants, viscosity modifiers, foam boosting agents, enzymes, preservatives (e.g. bactericides), pH buffering agents, polyelectrolytes, anti-shrinking agents, anti-wrinkle agents, anti-oxidants, sunscreens, anti-corrosion agents, drape imparting agents, antistatic agents and ironing aids. The compositions may further comprise, colorants, pearlisers and/or opacifiers, and shading dye. Fluorescent Agents. The invention is highly advantageous if carried out in water with a high water hardness, preferably of greater than 5°FH preferably greater than 40°FH, more preferably greater than 90°FH.
Examples
The invention will now be further described with reference to the following non-limiting examples in which
Figures 1 -3 show the results of diamine compounds in a laundry detergent composition tested for ability to treat various fat stains as follows:
Fig 1 : Various soiled cotton fabrics (a) Used Frying Fat (b) Butterfat (c) Beef Fat (d) Lard were washed for 1 hour at room temperature in a range of 1 ,4 Diaminobutane dihydrochloride concentrations (0.15 - 10 mg/ml) and Laundry detergent composition. The "0" value shows washing in Laundry detergent composition without diamine.
Fig2: : Various soiled cotton fabrics (a) Used Frying Fat (b) Butterfat (c) Beef Fat (d) Lard were washed for 1 hour at room temperature in a range of 1 ,3 Diaminopropane concentrations (0.15 - 10 mg/ml) and Laundry detergent composition. The "0" value shows washing in Laundry detergent composition without diamine.
Fig 3: Various soiled cotton fabrics were pre-treated in either 5 mg/ml 1 ,4 Diaminobutane dihydrochloride and Laundry detergent composition (Test) or Laundry detergent composition alone (Control). The fabrics were then washed in Laundry detergent composition for 1 hour at room temperature. Washing of the test and controls was carried out in triplicate for each soiled fabric.
In these examples, diamine compounds in laundry detergent laundry detergent compositions were tested to determine their ability to treat i.e. stains from cotton fabric in various ways. All values throughout are wt%. End-point Stain Removal Assay
Reagents: • The following soiled cotton fabric samples (Centre from Testmaterials BV) were hole punched into discs and transferred to 300 μΙ 96 well plates:
• Fat soils: Violet Dyed Used Frying Fat (CS-46), Coloured Beef Fat (CS-61 ), Coloured Lard (CS-62), Butterfat (CS-10)
Laundry detergent composition as below: Working concentration stock dilution = 1 :428 (i.e. the below stock was diluted 1 :428 times in the wash liquor)
Laundry Detergent Composition
Ingredient % by weight
Non-ionic surfactant Neodol 25-9* 6.2
Alcohol ethoxy sulphate 1 1.8
Linear alkylbenzene sulfonate 6.5
Sodium citrate dihydrate 5.2
Sorbitol 5.0
Propylene Glycol 9.0
Sodium tetraborate pentahydrate 3.0
Minor additives and water balance to 100
*Ci2-Ci5 alkoxylated (9EO) chain group
• Diamines:
1 ,4 Diaminobutane dihydrochloride (Sigma, CAS Number 333-93-7) 1 ,3 Diaminopropane (Sigma, CAS Number 109-76-2)
Procedure:
Pre-washing of soiled fabric
The soiled fabric discs were pre-washed to remove any residual free stain as follows:
• 200 μΙ of distilled water was added to each well
• Plates agitated on a plate shaker at 250 rpm for 2 mins • Water removed
Pre-treatment of soiled fabric with diamines followed by main wash The following Test and Control Mixtures were added to the wells:
• Test Mixture:
• Laundry detergent composition 100 ul
· Distilled Water 80 ul
• Diamine dilution* 20 ul
*The diamines were diluted to a final concentration of 5 mg/ml
• Control Mixture (Laundry detergent composition only negative control)
• Laundry detergent composition 100 ul
• Distilled Water 100 ul
The soiled fabric was incubated in the pre-treatment solution for 5 mins at room temperature with no agitation. The pre-treatment wash liquor was then removed.
Following pre-treatment, the soiled fabric was washed (250 rpm, 1 hour, room
temperature) in the following mixture:
• Laundry detergent composition 100 ul
· Distilled Water 100 ul
After washing, the wash liquor was then removed and fabric washed 4 X 5 mins with 200 ul distilled water on a plate shaker at 250 rpm. The fabric was then left to dry over night at room temperature before scanning.
(2b) Main wash of soiled fabric with diamines
The following Test and Control Mixtures were added to the wells: • Test Mixture
• Laundry detergent composition 100 ul
· Distilled Water 80 ul
• Diamine* 20 ul
*The diamines were diluted to final concentrations of: 10, 5, 2.5, 1.25, 0.62, 0.31 and 0.15 mg/ml
• Control Mixture (Laundry detergent composition only negative control)
• Laundry detergent composition 100 ul
• Distilled Water 100 ul
The soiled fabrics were washed at 250 rpm for 1 hour at room temperature. After washing, the wash liquor was then removed and fabric washed 4 X 5 mins with 200 ul distilled water on a plate shaker at 250 rpm. The fabric was then left to dry over night at room temperature before scanning.
(3) Visual inspection of washed fabric
After drying, the soiled fabric 96 well plates were visually inspected and photographed. The whiteness of the cloth represents efficacy of the stain treatment composition. The results are shown in Figures 1 - 3. Conclusions:
The results show that diamines can improve the cleaning of fat soiled fabrics in combination with a laundry detergent composition when applied both as both a pre- treatment before the main wash and when included directly in the main wash. Generally, cleaning improvement is dose dependent but in so far as beef and lard fat stains 1 ,3- diaminopropane forms best at concentrations 0.31 mg/ml and 0.62mg/ml respectively in a main wash test.

Claims

1. A substrate stain removal composition comprising a diamine compound and a
surfactant.
2. A substrate stain removal composition according to claim 1 wherein the substrate is a fabric.
3. A substrate stain removal composition according to claim 1 or claim 2 wherein the diamine comprises the structure:
Xi
\
R X2
(CH2)n / CH3 wherein
X1 and X2 are hydrogen bond donor or acceptor groups independently selected from NH2, OH, SH and NH; and R is a linker independently selected from:
a. -CH- b. -CH-CH2- c. -CH-CH2-CH2- and n is an integer where n=0 to 10.
4. A substrate stain removal composition according to any preceding claim wherein the diamine comprises 1 ,4 diaminobutane or 1 ,3 diaminopropoane or mixtures thereof.
5. A substrate stain removal composition according to any preceding claim wherein the surfactant comprises a biosurfactant.
6. A substrate stain removal composition according to claim 5 where the biosurfactant comprises a rhamnolipid.
7. A substrate stain removal composition according to any preceding claim, wherein composition is ambient-active.
8. A pre-treatment device comprising (i) a storage chamber storing the fabric stain removal composition of any of claims 1-7 and a (ii) dispenser for locally applying said substrate stain removal composition to a stain on a fabric or other substrate.
9. A method for removing a stain from a stained fabric or other substrate, comprising the step of applying to the stain, the fabric stain removal composition of any of claims 1 -7 wherein the step takes place at ambient temperature being less than 40 degrees C.
10. A method according to claim 8 comprising the step of adding water to the fabric stain removal composition to form an aqueous wash liquor wherein the liquor is at ambient temperature being less than 40 degrees C.
1 1 . A method according to any of claims 9 or 10 comprising localised application to a stain on a stained fabric or other substrate, of the composition of any of the claims
1 -6.
12. A method according to any of claims 9-1 1 wherein the step of applying the
composition is a pre-treatment step using the pre-treatment device of claim 8.
13. A method according to any of claims 9-12 wherein the compound is present in a wash liquor in the range of 0.01 - 10mg/ml.
14. Use of a diamine compound in the removal of oil/fat stains, preferably in
combination with surfactant.
15. Use of a diamine compound as claimed in claim 14 wherein the diamine comprises the structure:
i
\
R X2
(CH2)n / CH3 wherein X1 and X2 are hydrogen bond donor or acceptor groups independently selected from NH2, OH, SH and NH; and R is a linker independently selected from a. -CH-, b - CH-CH2- and c. -CH-CH2-CH2- and whereand n is an integer where n=0 to 10; in the removal of oil/fat stains, preferably in combination with surfactant .
PCT/EP2015/063230 2014-06-19 2015-06-12 Stain treatment compositions WO2015193203A1 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP15730114.4A EP3158037A1 (en) 2014-06-19 2015-06-12 Stain treatment compositions
CN201580032807.6A CN106661519A (en) 2014-06-19 2015-06-12 Stain treatment compositions
BR112016029718A BR112016029718A2 (en) 2014-06-19 2015-06-12 tissue stain removal composition, pretreatment device, method of removing a stain from a tissue and use of 1,4-diaminobutane in combination with surfactant
ZA2016/08407A ZA201608407B (en) 2014-06-19 2016-12-06 Stain treatment compositions

Applications Claiming Priority (2)

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WO2017215978A1 (en) * 2016-06-16 2017-12-21 Unilever Plc Methods and compositions
CN109312266A (en) * 2016-06-16 2019-02-05 荷兰联合利华有限公司 Method and composition
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US11001790B2 (en) 2016-06-16 2021-05-11 Conopco, Inc. Methods and compositions
US11046911B2 (en) 2016-06-16 2021-06-29 Conopco, Inc. Methods and compositions

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