EP3298116A1 - A composition and method for treating substrates - Google Patents

A composition and method for treating substrates

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Publication number
EP3298116A1
EP3298116A1 EP16717966.2A EP16717966A EP3298116A1 EP 3298116 A1 EP3298116 A1 EP 3298116A1 EP 16717966 A EP16717966 A EP 16717966A EP 3298116 A1 EP3298116 A1 EP 3298116A1
Authority
EP
European Patent Office
Prior art keywords
composition
graft
starch
comp
polymethacrylic acid
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
EP16717966.2A
Other languages
German (de)
French (fr)
Other versions
EP3298116B1 (en
Inventor
Aravindakshan Perincheery
Abhishek Rastogi
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
Publication of EP3298116A1 publication Critical patent/EP3298116A1/en
Application granted granted Critical
Publication of EP3298116B1 publication Critical patent/EP3298116B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146Sulfuric acid esters
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29Sulfates of polyoxyalkylene ethers
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005Other compounding ingredients characterised by their effect
    • C11D3/0036Soil deposition preventing compositions; Antiredeposition agents
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/22Carbohydrates or derivatives thereof
    • C11D3/222Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/225Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin etherified, e.g. CMC
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3788Graft polymers

Definitions

  • the present invention relates to a composition and a method for treating substrates, such as fabrics; particularly for improved stain and soil removal and better cleaning upon the subsequent wash without the use of a cleaning implement.
  • 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.
  • US2005-0215449 discloses a textile care agent containing a copolymer of unsaturated carboxylic acids and/or their salts with carbohydrates, as well as a washing method for washing textiles using the textile care agent in an ordinary household washing machine.
  • the invention further concerns the use of the textile care agent to reduce creasing, improve ironing properties, and decrease pilling. This document does not disclose methyl cellulose or the pH values of the present invention for the purpose of providing easier cleaning on the subsequent wash.
  • WO03/010268 discloses a laundry cleaning composition
  • a laundry cleaning composition comprising a graft polymer benefit agent and at least one additional laundry cleaning ingredient, the graft polymer benefit agent comprising a polysaccharide backbone and a plurality of graft chains extending from said backbone, each of said 20 plurality of graft chains having a degree of polymerisation between 5 and 250, preferably between 5 and 50 or between 25 and- 250 wherein said graft polymer is substantially free of cross-linking and has a degree of substitution of grafts across a bulk sample in the range of from 0.02 to 1.0.
  • This composition has a basic pH, a pH of 7 to 1 1.
  • WO 01/88075 discloses Anionic, hydrophobic polysaccharides useful as soil release agents in detergent compositions are graft copolymers of a polysaccharide having anionic substituents with an ethylenically unsaturated monomer, the copolymer having a polysaccharide backbone carrying grafted hydrophobic vinyl polymeric groups derived from the ethylenically unsaturated monomer, and anionic substituents. The polymers exhibit enhanced release of both oily and particulate soil from both polyester and cotton.
  • US5049302 discloses A stable liquid detergent composition having improved clay soil detergency, clay soil anti-redeposition, oily soil anti-redeposition and soil release properties is disclosed.
  • the detergent composition is comprised of an anionic surfactant, a nonionic surfactant, a hydrotrope, a graft copolymer of polyalkylene oxide and an ester monomer, and a nonionic cellulosic anti-redeposition agent.
  • the graft copolymer is comprised of (a) a polyalkylene oxide based upon an alkylene oxide having from 2 to 4 carbon atoms having a molecular weight of 300 to 100,000 and, (b) at least one vinyl ester derived from a saturated monocarboxylic acid containing 1 to 6 carbon atoms, and/or methyl or ethyl ester of acrylic or meth-acrylic acid in a weight ratio of (a):(b) of from 1 :0.2 to 1 :10.
  • the nonionic cellulosic anti-redeposition agent is preferably hydroxypropyl methylcellulose.
  • oily and particulate soil removal can be achieved by depositing a starch-graft-polymethacrylic acid, an anionic surfactant and methyl cellulose at a pH of 1 to 4.5 onto a fabric. Without wishing to be bound by theory, it is thought that this forms an invisible layer on the treated fabric which prevents the deep penetration of soils. This layer acts as a sacrificial layer which gets easily dissolved at high pH during the next-wash, thereby completely removing the soil along with it.
  • the invention provides a composition for treating a substrate, the said composition comprising 4 to 20% by weight of a starch-graft- polymethacrylic acid, 1 to 10% by weight of an anionic surfactant and 0.25 to 5% by weight of methyl cellulose wherein the pH of the composition is between 1 and 4.5.
  • the invention provides a method for treating a substrate comprising the steps in sequence of applying the composition according to the invention onto a substrate and allowing the substrate to dry.
  • the invention provides use of the composition according to the invention for improved stain and soil removal upon the subsequent wash.
  • the improved cleaning upon the subsequent wash benefit is also referred to as next time cleaning benefit.
  • the present invention provides a composition for treating a substrate, comprising a starch-graft-polymethacrylic acid, an anionic surfactant and methyl cellulose.
  • the balance of the composition is made up to 100% by weight with water.
  • the pH of the composition is between 1 and 4.5.
  • the starch-graft-polymethacrylic acid of the present invention is derived from maize or tapioca starch by graft copolymerisation with methacrylic acid.
  • Starch has active sites for grafting. Such sites are -OH and -CH2OH moieties.
  • the level of grafting is defined as a percentage weight of polymethacrylic acid present in graft copolymer.
  • the starch-graft-polymethacrylic acid of the invention has preferably a grafting level of at least 10%, more preferably at least 15%, yet more preferably at least 20%, most preferably at least 25% by weight of the starch-graft-polymethacrylic acid.
  • the starch-graft-polymethacrylic acid is present in a concentration of 4 to 20%, preferably not more than 18%, more preferably not more than 15% but typically not less than 5%, preferably not less than 10% by weight of the composition.
  • More than 20% of starch-graft-polymethacrylic acid is not desired in the composition as the viscosity of the composition increases.
  • composition of the present invention comprises an anionic surfactant.
  • anionic surfactant Preferably any non-soap anionic surfactant known in the art for use in laundry detergents may be used herein.
  • Preferred anionic surfactants are water-soluble salts, particularly alkali metal, ammonium and alkylolammonium salts of organic sulphur reaction products, particularly alkyl sulphonates and alkyl suphates.
  • Non-limiting examples of the anionic surfactants include any of the common anionic surfactants such as sodium lauryl ether sulphate, sodium dodecyl sulphate, sodium alpha olefin sulphate and sodium dodecyl benzene sulphonate.
  • the anionic surfactant is present in a concentration of 1 to 10%, preferably not more than 8%, more preferably not more than 6%, still more preferably not more than 5% but typically not less than 2%, preferably not less than 3% by weight of the composition. Since the composition of the present invention is a leave-on product, a surfactant concentration of more than 10% is not desired as a concentration above 10% may cause irritation to the skin.
  • Anionic surfactant of the present invention may be combined with another surfactant generally chosen from non-ionic surfactants.
  • Non-ionic surfactants are 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.
  • alkylphenols preferably from 12 to 20 carbon atoms
  • the alkyl group contains from about 6 to about 12 carbon atoms
  • dialkylphenols in which each alkyl group contains from 6 to 12 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 alkyl 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.
  • 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, incorporated herein by reference.
  • ethoxylated non-ionics which are condensation products of fatty alcohols with from 9 to 15 carbon atoms condensed with 3 to 12 moles of ethylene oxide (generally understood to be an average value), Tween 20, Span 60 and Toximul 8241 .
  • the ratio of non-ionic surfactant to anionic surfactant is preferably not more than 5:1 , more preferably not more than 4:1 , yet more preferably not more than 3:1 , most preferably not more than 2:1.
  • Methyl cellulose used in the present invention has a methyl content between 27.5% to 31 .5%.
  • Methyl cellulose is present in the composition of the present invention in a concentration of 0.25 to 5%, preferably not more than 4%, still more preferably not more than 3% but typically not less than 0.4%, preferably not less than 1 %, more preferably not less than 2% by weight of the composition.
  • methyl cellulose is not desired in the composition as the viscosity of the composition increases, thereby not being suitable for direct application.
  • the viscosity of the compositions according to the invention is preferably less than 1000 mPa.s (25°C and 20s "1 ), more preferably between 50 to 1000, when measured with a TA instrument rheometer AR-1000, with a cone and plate set-up, acrylic/steel 4 cm diameter, 2° angle, truncation gap 52-56 micrometer, in steady flow operation.
  • composition further comprises a further polymer.
  • soil release polymers such as the Repel-O-Tex range of Rhodia (trade mark) i.e. SF2, PF594, Crystal, notably Repel-O- Tex SF2, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl cellulose, Texcare SRN 170 of Clariant, pluronics and sodium carboxymethyl cellulose.
  • the additional polymer is present in a concentration of 0.1 % to 5% by weight of the composition. pH of the composition
  • the pH of the composition is between 1 and 4.5, preferably between 2 and 3.5, more preferably between 2.5 and 3.5. The best results are obtained when the pH of the composition is less than 4.
  • composition of the present invention is an aqueous composition comprising water.
  • the composition is made upto 100 percent by adding water.
  • the composition preferably comprises 65 to 95% by weight of water.
  • Optional ingredients
  • composition may further comprise softening agents as commonly used in fabric softening compositions, antimicrobial agents, silicone oils and co-solvents like 2- phenoxyethanol (commercially available as ex Dow Chemicals as Dowanol EP- trademark) to improve stability and dispersibility, hydrotropes and preservatives.
  • softening agents as commonly used in fabric softening compositions, antimicrobial agents, silicone oils and co-solvents like 2- phenoxyethanol (commercially available as ex Dow Chemicals as Dowanol EP- trademark) to improve stability and dispersibility, hydrotropes and preservatives.
  • the invention in a second aspect, relates to a method for treating a substrate comprising the steps in sequence of applying the composition according to the invention onto a substrate and allowing the substrate to dry.
  • the composition may be applied by any known method such as by using wipes, spray, including spray guns, atomizers, or other direct application. It is preferred that the surface is not rinsed after the application of the composition and before drying.
  • the invention relates to the use of the composition according to the invention for improved stain and soil removal upon the subsequent wash.
  • the product is typically packed in a bottle, preferably a plastic bottle at volumes of between 250 ml and 5 L, more preferably between 250 ml and 1.5 L.
  • a bottle preferably a plastic bottle at volumes of between 250 ml and 5 L, more preferably between 250 ml and 1.5 L.
  • Common supermarket size bottles are 250 ml, 500 ml, 750ml, 1 L and 1 .5 L.
  • the bottles may optionally have a measuring cup attached, or a measuring scale indicator in the cap, to enable the consumer to dose the right amount.
  • Trigger spray dispenser bottles typically have a volume of between 250 ml and 1.5 L. Common volumes include 400 ml, 500 ml, 750 ml, and 1 L.
  • Alfodet P46 70wt%
  • Tapioca starch was slurried with urea solution in a 500 ml three neck round bottom flask and was mixed for 60 minutes with an overhead stirrer at room temperature. Ferrous ammonium sulfate was added to the slurry and was mixed for 5 minutes. Then, methacrylic acid was added to the slurry and was mixed for 10 minutes. The grafting reaction was initiated with the addition of H2O2 to the slurry. The reaction was continued for 60 minutes. Homo-polymer (PMAA) was removed from grafted starch by repeated water washing and starch-graft-polymethacrylic acid was dried at room temperature for 48 hours.
  • PMAA Homo-polymer
  • a slurry of starch-graft-polymethacrylic acid was prepared by dispersing pre-calculated amount of starch-graft-polymethacrylic acid in desired volume of water.
  • the starch-graft- polymethacrylic acid was cooked at 80 °C temperature for 30 minutes and cooled to room temperature.
  • the pH of the cooked polymer was adjusted to 8 with the addition of 1 M KOH solution.
  • a pre-calculated amount of anionic surfactant was added to the cooked starch-graft-polymethacrylic acid and was mixed at 2000 rpm for 5 minutes. Subsequently, pH of the solution was adjusted to 3.5 with the addition of 1 M HCI solution while mixing at 4000 rpm.
  • a pre-calculated amount of methyl cellulose solution was added to the slurry and was mixed for 15 minutes at 4000 rpm.
  • compositions were stored in 50 ml tarson tube at room temperature. If phase separation was observed after 2 days, the composition was considered unstable. If there was no phase separation, the composition was considered stable. Collar treatment and soiling:
  • the collars were cut into two halves.
  • the control (untreated) and the treated halves were washed separately in different TL machines using 1 .5 g/L Surf Excel, top-load matic (commercial detergent for automatic vertical axis top load washing machines, ex Malawistan Unilever Limited) at 24 FH (2:1 ).
  • top-load matic commercial detergent for automatic vertical axis top load washing machines, ex Malawistan Unilever Limited
  • Example 1 Effect of each component of the composition on stability and cleaning performance
  • composition according to the invention (Ex1 ) is compared to comparative compositions (Comp 1 to Comp 9) with at least one of the components of the composition missing.
  • composition according to the invention provides superior cleaning and is stable when compared to any of the comparative examples.
  • Comp 7 to Comp 9 additionally show that the desired benefit is not achieved even at increased levels of each of the ingredients.
  • Example 2 Effect of concentration of Starch-graft-polymethacrylic acid on stability and cleaning performance
  • This example demonstrates the effect of concentration of starch-graft-polymethacrylic acid on stability and cleaning performance.
  • the example compositions Ex 2 to Ex 4 are compared with comparative examples Comp 10 to Comp 12 comprising starch-graft- polymethacrylic acid in a concentration outside the scope of the invention.
  • Example 3 Effect of polymethacrylic acid grafting level on stability and cleaning performance
  • Example 4 Effect of concentration of surfactant on stability and cleaning performance
  • compositions according to the invention comprising different concentrations of anionic surfactant (Ex 7 to Ex 10) are compared with comparative compositions having anionic surfactant in a concentration outside the scope of the present invention (Comp 16 and Comp 17).
  • Example 5 Effect of concentration of methyl cellulose on stability and cleaning performance
  • This example demonstrates the effect of concentration of methyl cellulose on stability and cleaning performance.
  • the example compositions Ex 1 1 to Ex 15 are compared with comparative examples Comp 18 and Comp 19 comprising methyl cellulose in a concentration outside the scope of the invention.
  • Example 6 Effect of pH of the composition on stability and cleaning performance
  • the effect of the pH of the composition according to the invention (Ex 16 and Ex 19) on cleaning performance is compared to comparative compositions having a pH outside the scope of the invention (Comp 20 to Comp 22).
  • Example 7 Effect of different anionic surfactant and other surfactants of other types on stability
  • This example illustrates the effect of the ratio of anionic to the optional non-ionic surfactant on stability.
  • Non-ionic surfactants are added additionally to the composition of the invention.

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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)
  • Health & Medical Sciences (AREA)
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  • Detergent Compositions (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

The present invention relates to a composition and a method for treating substrates, such as fabrics; particularly for improved stain and soil removal and better cleaning upon the subsequent wash without the use of a cleaning implement. It is therefore an object of the present invention to provide a stable composition that provides improved cleaning upon subsequent wash. It has been found that oily and particulate soil removal can be achieved by depositing a starch-graft-polymethacrylic acid, an anionic surfactant and methyl cellulose at a pH of 1 to 4.5 onto a fabric.

Description

A COMPOSITION AND METHOD FOR TREATING SUBSTRATES Field of the invention
The present invention relates to a composition and a method for treating substrates, such as fabrics; particularly for improved stain and soil removal and better cleaning upon the subsequent wash without the use of a cleaning implement.
Background of the invention
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 collar stains, are tough to remove during main wash. They are better removed when a cleaning implement is used. However cleaning using an implement requires more time and effort.
US2005-0215449 discloses a textile care agent containing a copolymer of unsaturated carboxylic acids and/or their salts with carbohydrates, as well as a washing method for washing textiles using the textile care agent in an ordinary household washing machine. The invention further concerns the use of the textile care agent to reduce creasing, improve ironing properties, and decrease pilling. This document does not disclose methyl cellulose or the pH values of the present invention for the purpose of providing easier cleaning on the subsequent wash. WO03/010268 discloses a laundry cleaning composition comprising a graft polymer benefit agent and at least one additional laundry cleaning ingredient, the graft polymer benefit agent comprising a polysaccharide backbone and a plurality of graft chains extending from said backbone, each of said 20 plurality of graft chains having a degree of polymerisation between 5 and 250, preferably between 5 and 50 or between 25 and- 250 wherein said graft polymer is substantially free of cross-linking and has a degree of substitution of grafts across a bulk sample in the range of from 0.02 to 1.0.This composition has a basic pH, a pH of 7 to 1 1.
US3558499 (Atlas Chem IND, 1971 ), discloses Built detergent compositions containing an anti-redeposition agent selected from the group consisting of graft copolymers of a polymerizable monomer and a water soluble or water dispersible polymeric material or a physical blend of a polymerized monomer and a water soluble or water dispersible polymeric material, vinyl monomer" as used herein is included vinyl monomers capable of free radical catalyzed polymerization. In general, and in accordance with the present invention built detergent compositions contain (1 ) from about g 10% to about 25% of a suitable detergent compound, (2) from about 60% to about 89.9% of "builders" and (3) from about 0.10% to about 10% of an anti-redeposition agent. As set forth above, such formulations may also contain minor amounts of perfume, and other suitable modifiers. WO 01/88075 (Unilever, 2001 ), discloses Anionic, hydrophobic polysaccharides useful as soil release agents in detergent compositions are graft copolymers of a polysaccharide having anionic substituents with an ethylenically unsaturated monomer, the copolymer having a polysaccharide backbone carrying grafted hydrophobic vinyl polymeric groups derived from the ethylenically unsaturated monomer, and anionic substituents. The polymers exhibit enhanced release of both oily and particulate soil from both polyester and cotton.
US5049302 (BASF, 1991 ), discloses A stable liquid detergent composition having improved clay soil detergency, clay soil anti-redeposition, oily soil anti-redeposition and soil release properties is disclosed. The detergent composition is comprised of an anionic surfactant, a nonionic surfactant, a hydrotrope, a graft copolymer of polyalkylene oxide and an ester monomer, and a nonionic cellulosic anti-redeposition agent. The graft copolymer is comprised of (a) a polyalkylene oxide based upon an alkylene oxide having from 2 to 4 carbon atoms having a molecular weight of 300 to 100,000 and, (b) at least one vinyl ester derived from a saturated monocarboxylic acid containing 1 to 6 carbon atoms, and/or methyl or ethyl ester of acrylic or meth-acrylic acid in a weight ratio of (a):(b) of from 1 :0.2 to 1 :10. The nonionic cellulosic anti-redeposition agent is preferably hydroxypropyl methylcellulose. There is a synergism between the nonionic anti- redeposition agent and the graft polyol which imparts improved clay soil detergency, clay anti-deposition and oily soil anti-redeposition properties to the detergent composition. It is therefore an object of the present invention to provide improved stain removal especially of oily and particulate soils. It is another object of the present invention to provide improved cleaning upon subsequent wash.
It is still another object of the present invention to provide a stable composition;
especially a composition that does not phase separate. Surprisingly, it has been found that oily and particulate soil removal can be achieved by depositing a starch-graft-polymethacrylic acid, an anionic surfactant and methyl cellulose at a pH of 1 to 4.5 onto a fabric. Without wishing to be bound by theory, it is thought that this forms an invisible layer on the treated fabric which prevents the deep penetration of soils. This layer acts as a sacrificial layer which gets easily dissolved at high pH during the next-wash, thereby completely removing the soil along with it.
Summary of the invention
Accordingly, in a first aspect, the invention provides a composition for treating a substrate, the said composition comprising 4 to 20% by weight of a starch-graft- polymethacrylic acid, 1 to 10% by weight of an anionic surfactant and 0.25 to 5% by weight of methyl cellulose wherein the pH of the composition is between 1 and 4.5.
In a second aspect, the invention provides a method for treating a substrate comprising the steps in sequence of applying the composition according to the invention onto a substrate and allowing the substrate to dry.
In a third aspect, the invention provides use of the composition according to the invention for improved stain and soil removal upon the subsequent wash. For the avoidance of doubt, the improved cleaning upon the subsequent wash benefit is also referred to as next time cleaning benefit.
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 present invention provides a composition for treating a substrate, comprising a starch-graft-polymethacrylic acid, an anionic surfactant and methyl cellulose. The balance of the composition is made up to 100% by weight with water. The pH of the composition is between 1 and 4.5.
Starch-graft-polymethacrylic acid
The starch-graft-polymethacrylic acid of the present invention is derived from maize or tapioca starch by graft copolymerisation with methacrylic acid.
Starch has active sites for grafting. Such sites are -OH and -CH2OH moieties. The level of grafting is defined as a percentage weight of polymethacrylic acid present in graft copolymer. The starch-graft-polymethacrylic acid of the invention has preferably a grafting level of at least 10%, more preferably at least 15%, yet more preferably at least 20%, most preferably at least 25% by weight of the starch-graft-polymethacrylic acid.
In the composition of the present invention, the starch-graft-polymethacrylic acid is present in a concentration of 4 to 20%, preferably not more than 18%, more preferably not more than 15% but typically not less than 5%, preferably not less than 10% by weight of the composition.
More than 20% of starch-graft-polymethacrylic acid is not desired in the composition as the viscosity of the composition increases.
Anionic surfactant
The composition of the present invention comprises an anionic surfactant. Preferably any non-soap anionic surfactant known in the art for use in laundry detergents may be used herein.
Preferred anionic surfactants are water-soluble salts, particularly alkali metal, ammonium and alkylolammonium salts of organic sulphur reaction products, particularly alkyl sulphonates and alkyl suphates.
Non-limiting examples of the anionic surfactants include any of the common anionic surfactants such as sodium lauryl ether sulphate, sodium dodecyl sulphate, sodium alpha olefin sulphate and sodium dodecyl benzene sulphonate. In the composition of the present invention, the anionic surfactant is present in a concentration of 1 to 10%, preferably not more than 8%, more preferably not more than 6%, still more preferably not more than 5% but typically not less than 2%, preferably not less than 3% by weight of the composition. Since the composition of the present invention is a leave-on product, a surfactant concentration of more than 10% is not desired as a concentration above 10% may cause irritation to the skin.
Anionic surfactant of the present invention may be combined with another surfactant generally chosen from non-ionic surfactants.
Non-ionic surfactants are 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 alkyl group contains from about 6 to about 12 carbon atoms, dialkylphenols in which each alkyl group contains from 6 to 12 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 alkyl 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, incorporated herein by reference. Especially preferred are those ethoxylated non-ionics which are condensation products of fatty alcohols with from 9 to 15 carbon atoms condensed with 3 to 12 moles of ethylene oxide (generally understood to be an average value), Tween 20, Span 60 and Toximul 8241 . When present in the composition, the ratio of non-ionic surfactant to anionic surfactant is preferably not more than 5:1 , more preferably not more than 4:1 , yet more preferably not more than 3:1 , most preferably not more than 2:1.
Methyl cellulose
It is found that the addition of a lower alkyl cellulose, preferably methyl cellulose improves the removal of fatty soils upon the next wash.
Methyl cellulose used in the present invention has a methyl content between 27.5% to 31 .5%. Methyl cellulose is present in the composition of the present invention in a concentration of 0.25 to 5%, preferably not more than 4%, still more preferably not more than 3% but typically not less than 0.4%, preferably not less than 1 %, more preferably not less than 2% by weight of the composition.
More than 5% of methyl cellulose is not desired in the composition as the viscosity of the composition increases, thereby not being suitable for direct application.
The viscosity of the compositions according to the invention is preferably less than 1000 mPa.s (25°C and 20s"1), more preferably between 50 to 1000, when measured with a TA instrument rheometer AR-1000, with a cone and plate set-up, acrylic/steel 4 cm diameter, 2° angle, truncation gap 52-56 micrometer, in steady flow operation.
Further optional polymers
For best cleaning performance upon the subsequent wash, especially for improved cleaning of soils and stains it is preferred that the composition further comprises a further polymer.
It is found that the addition of a second polymer improves the removal of soils and stains upon the next wash. The most preferred are soil release polymers such as the Repel-O-Tex range of Rhodia (trade mark) i.e. SF2, PF594, Crystal, notably Repel-O- Tex SF2, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl cellulose, Texcare SRN 170 of Clariant, pluronics and sodium carboxymethyl cellulose.
When present in the composition, the additional polymer is present in a concentration of 0.1 % to 5% by weight of the composition. pH of the composition
The pH of the composition is between 1 and 4.5, preferably between 2 and 3.5, more preferably between 2.5 and 3.5. The best results are obtained when the pH of the composition is less than 4.
Water
The composition of the present invention is an aqueous composition comprising water. The composition is made upto 100 percent by adding water. The composition preferably comprises 65 to 95% by weight of water. Optional ingredients
The composition may further comprise softening agents as commonly used in fabric softening compositions, antimicrobial agents, silicone oils and co-solvents like 2- phenoxyethanol (commercially available as ex Dow Chemicals as Dowanol EP- trademark) to improve stability and dispersibility, hydrotropes and preservatives.
Process for treating a fabric
In a second aspect, the invention relates to a method for treating a substrate comprising the steps in sequence of applying the composition according to the invention onto a substrate and allowing the substrate to dry.
The composition may be applied by any known method such as by using wipes, spray, including spray guns, atomizers, or other direct application. It is preferred that the surface is not rinsed after the application of the composition and before drying.
Use of the composition
In a third aspect, the invention relates to the use of the composition according to the invention for improved stain and soil removal upon the subsequent wash.
Product Format
The product is typically packed in a bottle, preferably a plastic bottle at volumes of between 250 ml and 5 L, more preferably between 250 ml and 1.5 L. Common supermarket size bottles are 250 ml, 500 ml, 750ml, 1 L and 1 .5 L. The bottles may optionally have a measuring cup attached, or a measuring scale indicator in the cap, to enable the consumer to dose the right amount.
Also considered in the context of the present invention for the purpose of direct application, such as direct application onto a fabric, is a product format in the form of a bottle with a trigger spray dispenser comprising the composition according to the invention. Trigger spray dispenser bottles typically have a volume of between 250 ml and 1.5 L. Common volumes include 400 ml, 500 ml, 750 ml, and 1 L.
Larger containers for industrial scale use are also included the scope of this invention. The invention will now be illustrated by means of the following non-limiting examples.
Examples
Materials
Chemical /Material Grade Manufacturer/
Supplier
Modified Starch-graft-polymethacrylic Lab Synthesized as per starch acid mentioned procedure
Surfactant Sodium Linear Ether Commercial Galaxy Surfactant sulphate (SLES); Galaxy (70wt%
LES-70 paste)
Sodium Technical Sigma-Aldrich dodecylbenzenesulphonate grade
(SDBS); 289957
Sodium dodecyl sulfate Dust free Sigma-Aldrich
(SDS); 74255 pellets
>99%
Alpha Olefin Sulfonate Commercial Godrej Industries (AOS); Alfodet P46 (70wt%
paste)
Ethoxylated Alcohol, Commercial Galaxy Surfactant NI(EO)n(Galaxy MW-253) (100 wt%)
Ethoxylated Alcohol, Commercial Galaxy Surfactant NI(EO)n(Galaxy MW-257) (100 wt%)
C12-15 E09 Commercial Stepan Company, (Biosoft N25-9) (100 wt%) Northfield, IL
Tween 20 Lab grade Sigma-Aldrich
(P1379 ) 97%
Span 60 Lab grade Sigma-Aldrich
(S7010) >95%
Makon TD-18 Commercial Stepan Company,
(100 wt%) Northfield, IL
Toximul 8241 Commercial Stepan Company,
(100 wt%) Northfield, IL Cetylpyridinium chloride Lab grade Sigma-Aldrich
(CPC)
(C9002) >99%
Cetrimonium bromide AR Sigma-Aldrich
(CTAB)
(V8001 13) >99%
Soil Methyl cellulose Lab grade Sigma-Aldrich
release
polymer (M0512)
Preparation of starch-qraft-polvmethacrylic acid:
Tapioca starch was slurried with urea solution in a 500 ml three neck round bottom flask and was mixed for 60 minutes with an overhead stirrer at room temperature. Ferrous ammonium sulfate was added to the slurry and was mixed for 5 minutes. Then, methacrylic acid was added to the slurry and was mixed for 10 minutes. The grafting reaction was initiated with the addition of H2O2 to the slurry. The reaction was continued for 60 minutes. Homo-polymer (PMAA) was removed from grafted starch by repeated water washing and starch-graft-polymethacrylic acid was dried at room temperature for 48 hours.
Preparation of the composition:
A slurry of starch-graft-polymethacrylic acid was prepared by dispersing pre-calculated amount of starch-graft-polymethacrylic acid in desired volume of water. The starch-graft- polymethacrylic acid was cooked at 80 °C temperature for 30 minutes and cooled to room temperature. The pH of the cooked polymer was adjusted to 8 with the addition of 1 M KOH solution. A pre-calculated amount of anionic surfactant was added to the cooked starch-graft-polymethacrylic acid and was mixed at 2000 rpm for 5 minutes. Subsequently, pH of the solution was adjusted to 3.5 with the addition of 1 M HCI solution while mixing at 4000 rpm. A pre-calculated amount of methyl cellulose solution was added to the slurry and was mixed for 15 minutes at 4000 rpm.
Test for stability:
The compositions were stored in 50 ml tarson tube at room temperature. If phase separation was observed after 2 days, the composition was considered unstable. If there was no phase separation, the composition was considered stable. Collar treatment and soiling:
Half of ten cotton shirt collars were treated with the 5g of the sample formulation. The other halves were kept untreated and were used as the control. Post drying, these collars were given to auto-rickshaw drivers for a full day's use.
Washing and Evaluation of collars:
Post-soiling, the collars were cut into two halves. The control (untreated) and the treated halves were washed separately in different TL machines using 1 .5 g/L Surf Excel, top-load matic (commercial detergent for automatic vertical axis top load washing machines, ex Hindustan Unilever Limited) at 24 FH (2:1 ). After drying, the collars were evaluated by trained panelists on the scale of 0 to 10. Lesser the score of collar better is the cleaning.
An average collar line score of less than 1 was considered to be good as it implied that there was no visible collar line.
Example 1 : Effect of each component of the composition on stability and cleaning performance
In this example, the composition according to the invention (Ex1 ) is compared to comparative compositions (Comp 1 to Comp 9) with at least one of the components of the composition missing.
Comp 6 - 1 0.25 98.75 3.5 Yes 1.5
Ex 1 5 1 0.25 93.75 3.5 Yes 0.8
Comp 7 10 - - 90 3.5 No 1.2
Comp 8 - 5 - 95 3.5 Yes 1.8
Comp 9 - - 2 98 3.5 Yes 1.4
*SLES
The above table shows that the composition according to the invention provides superior cleaning and is stable when compared to any of the comparative examples. Comp 7 to Comp 9 additionally show that the desired benefit is not achieved even at increased levels of each of the ingredients.
Example 2: Effect of concentration of Starch-graft-polymethacrylic acid on stability and cleaning performance
This example demonstrates the effect of concentration of starch-graft-polymethacrylic acid on stability and cleaning performance. The example compositions Ex 2 to Ex 4 are compared with comparative examples Comp 10 to Comp 12 comprising starch-graft- polymethacrylic acid in a concentration outside the scope of the invention.
*SLES The table above shows that best results for collar line cleaning is obtained at a starch- graft-polymethacrylic acid concentration within the scope of the present invention.
Example 3: Effect of polymethacrylic acid grafting level on stability and cleaning performance
This example demonstrates the effect of polymethacrylic acid grafting level on stability and cleaning performance. Comp 13 to Comp 15 are comparative examples with a polymethacrylic acid grafting level outside the scope of the invention and Ex 5 and Ex 6 are examples of the invention comprising a polymethacrylic acid grafting level within the scope of the invention.
*SLES
The table above shows that a stable composition with superior collar line cleaning is obtained only with a polymethacrylic acid grafting level within the scope of the present invention.
Example 4: Effect of concentration of surfactant on stability and cleaning performance In this example, compositions according to the invention comprising different concentrations of anionic surfactant (Ex 7 to Ex 10) are compared with comparative compositions having anionic surfactant in a concentration outside the scope of the present invention (Comp 16 and Comp 17). Set Starch- *An ioMethyl Water pH Stabilit Average collar graft- nic cellulo (wt%) y line score polymet surfac se
hacrylic tant (wt%)
acid (wt%) Contr Exp. (wt%) ol
Comp 5 0 0.25 94.75 3.5 No 2.2 1 .2 16
Comp 5 0.5 0.25 94.25 3.5 No 2.1 1 .1 17
Ex 7 5 1 0.25 93.75 3.5 Yes 2.2 0.8
Ex 8 5 2 0.25 92.75 3.5 Yes 2.2 0.8
Ex 9 5 5 0.25 89.75 3.5 Yes 2.1 0.8
Ex 10 5 10 0.25 84.75 3.5 Yes 2.2 0.7
*SLES
It is inferred from the results of the above table that a stable composition with superior cleaning performance is obtained at a anionic surfactant concentration according to the invention.
Example 5: Effect of concentration of methyl cellulose on stability and cleaning performance
This example demonstrates the effect of concentration of methyl cellulose on stability and cleaning performance. The example compositions Ex 1 1 to Ex 15 are compared with comparative examples Comp 18 and Comp 19 comprising methyl cellulose in a concentration outside the scope of the invention.
Set Starch- *An ioMethyl Water pH Stabilit Average collar graft- nic cellulo (wt%) y line score polymet surfac se
hacrylic tant (wt%)
acid (wt%) Contr Exp. (wt%) ol
Comp 5 1 0 94 3.5 Yes 2.1 1 .2 18
Comp 5 1 0.2 93.8 3.5 Yes 2.2 1 .1 19
Ex 11 5 1 0.25 93.75 3.5 Yes 2.2 0.8
Ex 12 5 1 0.4 93.6 3.5 Yes 2.2 0.8
Ex 13 5 1 1 93 3.5 Yes 2.1 0.75
Ex 14 5 1 2 92 3.5 Yes 2.2 0.8
Ex 15 5 1 5 89 3.5 Yes 2.1 0.7
*SLES
The table above shows that best results for collar line cleaning is obtained at a methyl cellulose concentration within the scope of the present invention.
Example 6: Effect of pH of the composition on stability and cleaning performance In this example, the effect of the pH of the composition according to the invention (Ex 16 and Ex 19) on cleaning performance is compared to comparative compositions having a pH outside the scope of the invention (Comp 20 to Comp 22).
Set Starch- *Anio Methyl Water pH Stabilit Average collar graft- nic cellulo (wt%) y line score polymet surfac se
hacrylic tant (wt%)
acid (wt%) Contr Exp. (wt%) ol
Ex 16 5 1 0.25 93.75 1 Yes 2.1 0.8
Ex 17 5 1 0.25 93.75 2.5 Yes 2.2 0.8
Ex 18 5 1 0.25 93.75 3.5 Yes 2.1 0.8
Ex 19 5 1 0.25 93.75 4.5 Yes 2.1 0.9
Comp 5 1 0.25 93.75 5 Yes 2.1 1 .5 20
Comp 5 1 0.25 93.75 6 Yes 2.2 1 .6 21
Comp 5 1 0.25 93.75 9 Yes 2.2 1 .7 22
*SLES
The table above shows that best results for collar line cleaning is obtained at a pH range according to the invention.
Example 7: Effect of different anionic surfactant and other surfactants of other types on stability
This example demonstrates the effect of different anionic surfactants according to the invention (Ex 23 to Ex 26) and the effect of using other surfactants instead of an anionic surfactant (Comp 23 to Comp 32) on stability.
Set Starch- Surfactant Methyl Water pH Stabilit graft- cellulo (wt%) y polymet se
hacrylic (wt%)
acid
(wt%) Type wt%
Ex 23 5 Anionic SDBS 1 0.25 93.75 3.5 Yes
Ex 24 5 SDS 1 0.25 93.75 3.5 Yes
Ex 25 5 SLES 1 0.25 93.75 3.5 Yes
Ex 26 5 AOS 1 0.25 93.75 3.5 Yes Comp 5 Non- E03 0.25 93.75 3.5 No
1
23 ionic
Comp 5 E05 0.25 93.75 3.5 No 24 1
Comp 5 E07 0.25 93.75 3.5 No
1
25
Comp 5 E09 0.25 93.75 3.5 No 26 1
Comp 5 Tween 0.25 93.75 3.5 No 27 1
20
Comp 5 Span 0.25 93.75 3.5 No 28 1
60
Comp 5 Makon 0.25 93.75 3.5 No 29 1
TD-18
Comp 5 Toximul 0.25 93.75 3.5 No 30 8241 1
Comp 5 Cationic CPC 0.25 93.75 3.5 No
1
31
Comp 5 CTAB 0.25 93.75 3.5 No 32 1
The table above shows that a stable composition is obtained by any anionic surfactant according to the invention. It is also noted that a stable composition is not obtained by the use of other surfactants like cationic and non-ionic.
Example 8: Effect of non-ionic surfactants on the stability
This example illustrates the effect of the ratio of anionic to the optional non-ionic surfactant on stability. Non-ionic surfactants are added additionally to the composition of the invention.
The above table shows that a stable composition is not obtained at all ratios of anionic surfactant and non-ionic surfactant.

Claims

A composition for treating a substrate, the said composition comprising:
a 4 to 20% by weight of a starch-graft-polymethacrylic acid;
b 1 to 10% by weight of an anionic surfactant; and
c 0.25 to 5% by weight of methyl cellulose;
wherein the pH of the composition is between 1 and 4.5.
A composition according to claim 1 , wherein the starch-graft-polymethacrylic acid has a grafting level of at least 10% by weight.
A composition according to claim 1 or 2, wherein the anionic surfactant is selected from sodium lauryl ether sulphate, sodium dodecyl sulphate, sodium alpha olefin sulphate and sodium dodecyl benzene sulphonate.
A composition according to any one of the preceding claims, wherein the composition further comprises a non-ionic surfactant.
The composition according to any one of the preceding claims, wherein composition further comprises water.
A method for treating a substrate comprising the steps in sequence of
a Applying the composition according to claims 1 to 5 onto the substrate; and b Allowing the substrate to dry.
Use of the composition according to claims 1 to 5 for improved stain and soil removal upon the subsequent wash.
EP16717966.2A 2015-05-20 2016-04-25 A composition and method for treating substrates Active EP3298116B1 (en)

Applications Claiming Priority (2)

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PCT/EP2016/059151 WO2016184643A1 (en) 2015-05-20 2016-04-25 A composition and method for treating substrates

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AU (1) AU2016264794B2 (en)
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TR (1) TR201909933T4 (en)
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US3558499A (en) * 1969-07-01 1971-01-26 Atlas Chem Ind Anti-redeposition agents
GB8527772D0 (en) 1985-11-11 1985-12-18 Unilever Plc Non-aqueous built liquid detergent composition
US5049302A (en) * 1988-10-06 1991-09-17 Basf Corporation Stable liquid detergent compositions with enchanced clay soil detergency and anti-redeposition properties
EP1280879B1 (en) * 2000-05-09 2005-07-27 Unilever Plc Soil release polymers and laundry detergent compositions containing them
EP1409627B1 (en) 2001-07-20 2005-11-09 Unilever Plc Use of compounds in products for laundry applications
US20050215449A1 (en) 2002-11-20 2005-09-29 Josef Penninger Textile care product
EP2473590B2 (en) * 2009-09-02 2018-01-17 Unilever N.V. Process for treatment of a fabric
ES2560607T3 (en) * 2010-05-31 2016-02-22 Unilever N.V. Laundry treatment composition

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BR112017024402A2 (en) 2018-07-24
AU2016264794B2 (en) 2019-04-11
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TR201909933T4 (en) 2019-07-22
ZA201706716B (en) 2019-04-24

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