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
  • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
  • C11D17/0047—Detergents in the form of bars or tablets
  • C11D17/0065—Solid detergents containing builders
  • C11D17/0069—Laundry bars
• • 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
  • C11D3/37—Polymers
  • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/3726—Polyurethanes
• • 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
  • C11D3/37—Polymers
  • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
  • C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions

Definitions

• the present invention relates to the use of associative shear thinning polymers in solid detergent compositions.
• the invention relates to detergent compositions comprising associative, shear thinning hydrophobic alkoxylated acrylic polymers and/or hydrophobic alkoxylated urethane polymers.
• the detergent compositions of the invention provide for enhanced lather generation during wash.
• Solid detergent compositions are popular as they are much cheaper than liquids. They are a popular cleaning form in developing countries as product dosage in the solid form is easier. In particular, amongst the solid forms, bars have gained popularity because of better value delivery. Detergent bars avoid spillage and the product application can be better controlled. Also, the dosage per swipe from the bar is highly controlled.
• Ease of use in direct application detergent compositions like bars is preferred by consumers in developing countries.
• the consumer has to put in a lot of effort and scrub, brush and knead the garment to get lather. This is because bars show localised transfer of material.
• the high local concentration of bar material does not aerate easily during rubbing, brushing, scrubbing and kneading of fabric giving poor lather and localised cleaning. Further the lather generated during the main wash is not readily removed during rinsing.
• Shear thinning polymers have been known to be added to liquid detergent formulations to provide for thickened compositions that are easily pourable and shear thinning during usage. Their use in solid detergent compositions is limited.
• WO-A- 95/31528 discloses liquid detergent compositions comprising substantially linear, water soluble, ionic polymers of MW 10,000 to 1,000,000 Daltons which, when added to structured heavy duty liquids, makes the liquid highly shear thinning. The pour viscosity of the composition does not decrease or increase to a point where it is too thick. The compositions are also stable.
• EP-A-1 010 422 discloses clear cleansing detergent systems comprising a hydrophobically modified acrylic copolymer and a polyol alkoxy ester as thickeners.
• the Aculyn class of polymers hydrophobically modified acrylic polymers and hydrophobic ethoxylated urethane polymers from Rohm and Haas, are widely used in the personal care industry, in particular in hair care compositions and nail polishes for their thickening properties. Aculyn polymers are also used in liquid skin compositions as thickeners.
• WO-A-01/12153 relates to an aqueous composition
• a a skin cleansing surfactant (b) a silicone (c) a hydrocarbonaceous material (d) a cationic polymer and (e) a combination of a polyacrylate thickening polymer and an acrylate methacrylate copolymer wherein the ester group of the methacrylate is alkyl of about 12 to about 20 carbon atoms, said alkyl having about fourteen to about twenty six ethoxy groups and the acrylate has one or more monomers of acrylic acid, methacrylic acid or one of their simple esters in quantities sufficient to provide both viscosity and visual phase stabilization.
• the polyacrylate polymer is a mixture of Aculyn 33 and Aculyn 22.
• WO-A-00/65020 aims at providing a pourable hand dish washing detergent that can be precisely dosed, provides excellent cleaning properties, is skin tolerable and stable to temperature and storage.
• the compositions comprise a thick, aqueous surfactant-containing agent with anionic surfactant, amphoteric surfactant, polymer and icrocapsules, in which one or more ingredients of the hand dish washing detergent are totally or partially included. Aculyn may be used in the formulation.
• WO-A-01/22929 relates to hair care compositions providing for good conditioning and shine to the hair comprising polysiloxane resins and at least one associative polymer.
• the associative polymer can be a hydrophobically modified nonionic ethoxylated urethane polymer, examples of which are Aculyn 44 and Aculyn 46.
• WO-A-97/42291 provides for laundry detergent compositions comprising dye transfer inhibitors and a modified polyamine fabric surface modifying agent. Suitable dye transfer agents include polyethoxylated urethanes disclosed in US-A-4079028 and US-A-4155892. Such polymers have hydrophobic end groups as well as hydrophobic residues in the urethane linkage.
• solid detergent compositions comprising associative, shear thinning polymers chosen from hydrophobic alkoxylated acrylic polymers and hydrophobic alkoxylated urethane polymers show increased lather during the washing process as well as increased detergency.
• the lather quantity, lather stability and lather creaminess are improved when the said polymers are incorporated in solid detergent formulations.
• the lather can also be readily removed during the rinsing stage.
• synergistic solid detergent composition comprising:
• the present invention relates to the use of hydrophobic alkoxylated acrylic polymers and/or hydrophobic alkoxylated urethane polymers in solid detergent compositions.
• the hydrophobic acrylic copolymer preferably has a substantially linear acrylic backbone comprising acid and ester monomers and a pendant group that has alkoxy groups terminated by a hydrophobic group, such that the hydrophobic group has carbon number equal to or greater than 15.
• the hydrophobic alkoxylated urethane polymer preferably has alkoxy residues and urethane residues in the backbone and is terminated by an alkyl group of carbon number equal to or greater than 10.
• hydrophobic alkoxylated acrylic polymers and/or hydrophobic alkoxylated urethane polymers synergistically interact with the detergent active.
• lather formation is enhanced during wash and the lather generated is creamy and thick in nature.
• the lather is also stable. Further the lather generated is easily rinsed.
• the detergent bars of the invention also show enhanced cleaning.
• the invention pertains to detergent bars comprising acrylates/beheneth-25-methacylate copolymer, acrylates/steareth-20 methacrylate copolymer, acrylates/ceteth-20 itaconate copolymer, acrylates/steareth-20 methacrylate copolymer, PEG-150/Decyl alcohol/SMDI polymer, PEG-150/Stearyl alcohol/SMDI copolymer or their mixtures thereof. More specifically the invention provides for a synergistic solid detergent composition comprising
• hydrophobic alkoxylated acrylic copolymer is of the general formula (I) :
• A is a monomer unit obtainable from an acrylic monomer represented by
• R 3 COOR 4 wherein R X R 2 , R 3 and R may or may not be the same and can be H or a C1-C5 alkyl group,
• Ri , R 2 and R 3 can be H or a C1 -C5 alkyl group, such that a) the molecular weight of the acrylic polymer consisting of A and B units is from 50,000 to 500,000 and
• hydrophobic alkoxylated polyurethane is of the general formula (II) :
• n is equal to or greater than 10
• R' is an alkoxy group and m is at least 5 and R is an aliphatic or aromatic residue or a substituted aliphatic/aromatic residue.
• the solid detergent composition is a detergent bar comprising
• an associative, shear thinning polymer selected from acrylates/beheneth-25-methacylate copolymer, acrylates/steareth-20 methacrylate copolymer, acrylates/ceteth-20 itaconate copolymer, acrylates/steareth- 20 methacrylate copolymer, PEG-150/Decyl alcohol/SMD
• the solid detergent composition of the invention as described above comprises from 1% to 50% by weight builder.
• Preferred builders are alkali metal carbonates and sodium tripolyphosphate (STPP) .
• the present invention relates to solid detergent compositions comprising a detergent active, an inorganic filler and a associative, shear thinning polymer chosen from one or more polymers as represented in formulae (I) and (II) and mixtures thereof .
• the polymer may be a random copolymer or a block copolymer.
• the weight average molecular weight of the polymer is preferably from 50,000 to 500,000, more preferably from 100,000 to 250,000.
• An associative, shear thinning polymer suitable for the invention is a hydrophobic, alkoxylated acrylic polymer, preferably as given by formula (I) .
• the polymer as represented in formula (I) , has a substantially linear backbone comprising acid and ester monomers.
• the acid may be present as a free acid or as the corresponding salt . More than one acid and more than one ester maybe present in the copolymer. Especially preferred are acrylic and methacrylic acid and their corresponding esters .
• the acrylic polymer has a pendant group attached to the acid or ester group that is an alkoxy group terminated by a hydrophobic group.
• the number of alkoxy groups is from 5 to 1000, more preferably from 10-500 and most preferably from 10 to 50.
• the alkoxy groups are preferably independently selected C 2 -C 4 alkoxy groups, most preferably, ethoxy groups.
• the hydrophobic group is preferably a saturated hydrocarbon of carbon number equal to or greater than 15. More preferably the hydrophobic group is a saturated hydrocarbon of carbon number greater than 20.
• Suitable examples of such polymers are polymers such as acrylates/beheneth-25 methacrylate copolymer (AculynTM 28) , acrylates/steareth-20 methacrylate copolymer (AculynTM 22, acrylates/ceteth-20 itaconate copolymer (STRUCTURE 11 3001) , acrylates/steareth-20 methacrylate copolymer (STRUCTURE R 2001) and mixtures thereof .
• An especially preferred polymer is Aculyn 28.
• the hydrophobic, alkoxylated acrylic polymer can be made by any suitable method as known in the art .
• Another associative, shear thinning polymer suitable for the invention is a hydrophobic, alkoxylated acrylic polymer preferably as shown in formula (II) .
• the polymer is preferably a linear copolymer, preferably a linear block copolymer.
• the linear backbone consists of urethane linkages containing aliphatic or aromatic residues or substituted aliphatic/aromatic residues linked together by alkoxy groups. At least 5 alkoxy groups are required to link the urethane groups.
• the alkoxy groups are independently selected C 2 -C 4 alkoxy groups, most preferably ethoxy groups.
• the urethane groups are linked together by polyethylene glycol of weight average molecular weight from 200 to 10,000.
• the aliphatic or aromatic residues of the urethane linkage may arise from the isocyanate used to prepare the polymer.
• isocyanates, diisocyanates and triisocyanates are known in the art and are suitable to prepare the polymer. Without being limited by the same, isocyanates and method of making the hydrophobic, alkoxylated urethane polymer are disclosed in US 4 079 028, the disclosure of which is incorporated herein by reference.
• the end group is a saturated hydrocarbon with a carbon chain length at least 10, more preferably from 10 to 20.
• Especially preferred polymers are AculynTM 44 and AculynTM 46, and mixtures thereof .
• the hydrophobic alkoxylated acrylic polymer or the hydrophobic alkoxylated urethane polymer and their mixtures are preferably present in an amount of from 0.001% to 10% by weight of the solid detergent composition. More preferably, the polymer is present in an amount of from 0.1% to 6% and more preferably in an amount of from 0.5% to 4% by weight of the detergent composition.
• the solid detergent composition of the invention can be a granular composition, powder, bar or tablet. Especially preferred is a detergent bar.
• the pH of the detergent composition is preferably above 8.0, more preferably above 9.0. Further, when a detergent solution of lOg/litre is used, the typical ionic strength of the detergent composition when transferred onto the fabric is greater than 50 mmoles.
• the detergent composition of the invention essentially comprises detergent active, builder/filler and the hydrophobically modified acrylic polymer.
• the detergent active is generally chosen from an anionic, nonionic, cationic, zwitterionic detergent active or mixtures thereof. 0.5-80% of the active by weight of the detergent composition can be incorporated in the formulation. More preferably the amount of surfactant is from 2 to 70% and most preferably from 5 to 70% by weight of the detergent composition.
• Anionic surfactants which can be used in the compositions of the invention are both soap and non-soap detergent compounds.
• Especially suitable anionic detergent active compounds are water soluble salts of organic sulphuric reaction products having in the molecular structure an alkyl radical containing from 8 to 22 carbon atoms, and a radical chosen from sulphonic acid or sulphur acid ester radicals and mixtures thereof.
• soap denotes salts of carboxylic fatty acids.
• the soap may be derived from any of the triglycerides conventionally used in soap manufacture - consequently the carboxylate anions in the soap may contain from 8 to 22 carbon atoms.
• the soap may be obtained by saponifying a fat and/or a fatty acid.
• the fats or oils generally used in soap manufacture may be such as tallow, tallow stearines, palm oil, palm stearines, soya bean oil, fish oil, castor oil, rice bran oil, sunflower oil, coconut oil, babassu oil, palm kernel oil, and others.
• the fatty acids are derived from oils/fats selected from coconut, rice bran, groundnut, tallow, palm, palm kernel, cotton seed, soya bean, castor etc.
• the fatty acid soaps can also be synthetically prepared (e.g. by the oxidation of petroleum or by the hydrogenation of carbon monoxide by the Fischer-Tropsch process) .
• Resin acids such as those present in tall oil, may be used. Naphthenic acids are also suitable.
• Tallow fatty acids can be derived from various animal sources and generally comprise about 1-8% myristic acid, about 21-32% palmitic acid, about 14-31% stearic acid, about 0-4% palmitoleic acid, about 36-50% oleic acid and about 0-5% linoleic acid.
• a typical distribution is 2.5% myristic acid, 29% palmitic acid, 23% stearic acid, 2% palmitoleic acid, 41.5% oleic acid, and 3% linoleic acid.
• Other similar mixtures, such as those from palm oil and those derived from various animal tallow and lard are also included.
• coconut oil refers to fatty acid mixtures having an approximate carbon chain length distribution of 8% C 8 , 7% Cin, 48% C 12 , 17% Ci 4 , 8% C 16 , 2% Ci ⁇ , 7% oleic and 2% linoleic acids (the first six fatty acids listed being saturated) .
• Other sources having similar carbon chain length distributions such as palm kernel oil and babassu kernel oil, are included within the term coconut oil.
• the term total fatty matter usually abbreviated to TFM is used to denote the percentage by weight of fatty acid and triglyceride residues present without taking into account the accompanying cations.
• the total fatty matter is preferably between 20 to 85% by weight of the soap bar.
• an accompanying sodium cation will generally amount to about 8% by weight.
• Other cations may be employed as desired for example zinc, potassium, magnesium, alkyl ammonium and aluminium.
• Suitable nonionic detergent active compounds can be broadly described as compounds produced by the condensation of alkylene oxide groups, which are hydrophilic in nature, with an organic hydrophobic compound which may be aliphatic or alkyl aromatic in nature.
• the length of the hydrophilic or polyoxyalkylene radical which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.
• Suitable amphoteric detergent-active compounds that optionally can be employed are derivatives of aliphatic secondary and tertiary amines containing an alkyl group of 8 to 18 carbon atoms and an aliphatic radical substituted by an anionic water- solubilizing group, for instance sodium 3-dodecylamino- propionate, sodium 3-dodecylaminopropane sulphonate and sodium N-2-hydroxydodecyl-N-methyltaurate.
• Suitable cationic detergent-active compounds are quaternary ammonium salts having an aliphatic radical of from 8 to 18 carbon atoms, for instance cetyltrimethyl ammonium bromide.
• Suitable zwitterionic detergent-active compounds that optionally can be employed are derivatives of aliphatic quaternary ammonium, sulphonium and phosphonium compounds having an aliphatic radical of from 8 to 18 carbon atoms and an aliphatic radical substituted by an anionic water-solubilising group, for instance 3- (N-N-dimethyl-N-hexadecylammonium) , propane-1-sulphonate betaine, 3- (dodecylmethyl sulphonium) propane-1-sulphonate betaine and 3- (cetylmethylphosphonium) ethane sulphonate betaine .
• detergent-active compounds are compounds commonly used as surface-active agents given in the well-known textbooks "Surface Active Agents", Volume I by Schwartz and Perry and “Surface Active Agents and Detergents", Volume II by Schwartz, Perry and Berch.
• Fillers suitable for use in the formulation include kaolin, calcium carbonate (calcite) , soapstone, china clay and the like, used singly or in combination.
• the filler is present in an amount of from 5 to 75% by weight of the detergent composition, preferably from 30 to 70 wt%.
• Preferably builders are used in the detergent composition.
• the detergency builders used in the formulation are preferably inorganic and suitable builders include alkali metal aluminosilicates (zeolites) , alkali metal carbonate, sodium tripolyphosphate (STPP) , tetrasodium pyrophosphate (TSPP) , citrates, sodium nitrilotriacetate (NTA) and combinations of these .
• Builders are preferably used in an amount ranging from 1 to 50% by wt . Zeolite if used as builder is present at levels not exceeding 10% by wt .
• Inorganic particulates are an optional ingredient of the formulation and may be incorporated especially for hard surface cleaning compositions.
• the particulate phase comprises a particulate structuring system and/or abrasive, which is insoluble in water.
• the abrasive may be soluble and present in such excess to any water present in the composition that the solubility of the abrasive in the aqueous phase is exceeded and consequently solid abrasive exists in the composition.
• Suitable inorganic particulate material can be selected from, particulate zeolites, calcite 's, dolomites, feldspars, siliceous, silicates, other carbonates, bicarbonates, sulphates and polymeric materials such as polyethylene.
• the most preferred inorganic particulate materials are dolomite, sodium hydrogen carbonate, borax, sodium/potassium sulfate, zeolite and feldspars.
• additives such as one or more water insoluble particulate materials like polysaccharides such as starch or modified starches and cellulose may be incorporated.
• ingredients preferably selected from enzymes, antiredeposition agents, fluorescers, colour, preservatives and perfumes, also bleaches, bleach precursors, bleach stabilisers, sequestrants, soil release agents (usually polymers) and other polymers may optionally be incorporated in the solid detergent composition.
• the solid detergent composition of the invention can be made by any conventional process known in the art.
• the anionic surfactant is neutralised in a Sigma mixer by using a suitable base. Fillers like sodium carbonate and china clay and builder are added and the mass is completely mixed. Thereafter, a solution of alkaline silicate and optionally more fillers are added. Optional ingredients like colourant, enzyme, perfume, flourescer are then added.
• the hydrophobically modified acrylic polymer is added at any stage of processing, preferably before the addition of a base like calcium hydroxide.
• the hydrophobically modified acrylic polymer builds rheology so as to facilitate processing. Further, when the bar containing the polymer is applied onto the fabric, the bar material is transferred in such a way that it spreads on fabric rather than getting transferred locally.
• Soda ash was taken in the sigma mixer to neutralise 92% Linear Alkyl Benzene Sulphonic (LAS) Acid. The acid was then completely neutralised with sodium carbonate to get sodium LAS. Thereafter more sodium carbonate was added to the mass followed by the addition of china clay, aluminium sulphate, and sodium tripoly phosphate (STPP) . Half of the total calicte was also added and the mass was completely mixed. Thereafter, 40% solution of alkaline silicate, and the rest of the calcite are added. AculynTM 22, AculynTM 28, AculynTM 44 and AculynTM 46 were added at this stage in Examples 1, 2, 3 and 4 respectively. This was followed by the addition of calcium hydroxide, color, perfume and fluorescer.
• LAS Linear Alkyl Benzene Sulphonic
• Cotton fabric of size 30 cm by 10cm was fixed onto a trough using screws to hold the fabric in place.
• a dispersion of 0.5 g/litre antifoam in water (of zero hardness) was prepared.
• the model antifoam was prepared using an equal composition of oleic acid, triolein, palmitic acid, and tripalmitin. 15 ml of this solution was added to the trough to soak the fabric.
• the cloth to liquor ratio was 1:5.
• the bar was fixed onto a suitable holder and the fabric was rubbed for 10 seconds. More water containing the antifoam was then added to the trough to give a cloth to liquor ratio of 1:10.
• the fabric was then rubbed with a plastic brush in a controlled manner for 10 seconds.
• the solution with the dissolved surfactant and foam was carefully transferred from the trough to a 100 ml graduated cylinder taking care not to disturb the lather.
• the fabric piece was gently squeezed to drain the solution into the cylinder
• the cylinder top was closed with the help of a stopper and the solution was shaken for 20 seconds.
• the cylinder was allowed to stand for 10 seconds and then the height of the foam was measured. This represents the volume of the lather (expressed in ml) .
• the foam and the solution in the cylinder was left undisturbed for another 5 mins and the foam height was measured again.
• the drop in height indicates the foam stability.
• the quality of the foam - bubble size and thickness was also determined qualitatively.
• the lather after rinsing was measured as follows. The fabric piece treated as above was dipped in 60 ml of water. The cloth to liquor ratio was 1:20. The procedure was repeated thrice and the lather solution transferred into a 100 ml cylinder. The fabric piece was gently squeezed to drain the solution into the cylinder. The above mentioned cylinder shake procedure was followed to get the amount of lather after rinsing.
• the detergent bars of Comparative Example A and Examples 1 to 4 were also evaluated by a trained in-house panel of 19 members. All members used each sample for 3 days and evaluated the bars at the end of this period for attributes like brightness of the bar, soapiness, economy of use of the bar, water required for rinsing the fabric after washing and perfume impact.
• Soapiness was evaluated by generating lather using water manually. Increased soapiness indicated a thicker and creamier lather. Perfume impact was evaluated during washing of the fabric .
• the evaluation was done on a 10 point scale. The higher the score, the better the attribute. The statistical significance of the data was 99.9%.
• the bar according to the invention was perceived to be brighter, more 'soapy'and to have a higher impact of perfume during use.
• the water required for rinsing, economy of use and fabric softness was similar to the control bar.
• the overall performance of the bar of the invention was found to be superior to the bar of Comparative Example A.
• the present invention provides for solid detergent compositions that provide for good lather and better detergency. Further the overall attributes and performance of these compositions is superior to conventional formulations.

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• Chemical & Material Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Wood Science & Technology (AREA)
• Organic Chemistry (AREA)
• Detergent Compositions (AREA)
• Compositions Of Macromolecular Compounds (AREA)

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Citations (7)

• 2002
  • 2002-10-02 WO PCT/EP2002/011065 patent/WO2003033638A1/en not_active Application Discontinuation
  • 2002-10-02 CN CNA028200993A patent/CN1568363A/zh active Pending
  • 2002-10-02 BR BR0212751-2A patent/BR0212751A/pt not_active Application Discontinuation
  • 2002-10-10 MY MYPI20023782A patent/MY128699A/en unknown

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