EP2379689B1 - Highly viscous detergent emulsion - Google Patents
Highly viscous detergent emulsion Download PDFInfo
- Publication number
- EP2379689B1 EP2379689B1 EP08879278.3A EP08879278A EP2379689B1 EP 2379689 B1 EP2379689 B1 EP 2379689B1 EP 08879278 A EP08879278 A EP 08879278A EP 2379689 B1 EP2379689 B1 EP 2379689B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- composition
- viscosity
- emulsion
- amount
- shear
- 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.)
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- 239000000839 emulsion Substances 0.000 title claims description 91
- 239000003599 detergent Substances 0.000 title description 31
- 239000000203 mixture Substances 0.000 claims description 166
- 229920002125 Sokalan® Polymers 0.000 claims description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 54
- 239000012071 phase Substances 0.000 claims description 45
- 239000004094 surface-active agent Substances 0.000 claims description 38
- 239000007788 liquid Substances 0.000 claims description 37
- 239000004584 polyacrylic acid Substances 0.000 claims description 37
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 28
- 239000000194 fatty acid Substances 0.000 claims description 28
- 229930195729 fatty acid Natural products 0.000 claims description 28
- 150000004665 fatty acids Chemical class 0.000 claims description 28
- 239000002736 nonionic surfactant Substances 0.000 claims description 27
- 125000000217 alkyl group Chemical group 0.000 claims description 24
- 239000002689 soil Substances 0.000 claims description 24
- 239000012141 concentrate Substances 0.000 claims description 22
- 150000002191 fatty alcohols Chemical class 0.000 claims description 21
- 230000003287 optical effect Effects 0.000 claims description 21
- 239000003784 tall oil Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 19
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- 230000003750 conditioning effect Effects 0.000 claims description 17
- 238000004140 cleaning Methods 0.000 claims description 16
- 239000003352 sequestering agent Substances 0.000 claims description 14
- 230000008719 thickening Effects 0.000 claims description 14
- 239000008346 aqueous phase Substances 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- 230000000087 stabilizing effect Effects 0.000 claims description 10
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- 238000004519 manufacturing process Methods 0.000 claims description 8
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- 239000007844 bleaching agent Substances 0.000 claims description 3
- BAERPNBPLZWCES-UHFFFAOYSA-N (2-hydroxy-1-phosphonoethyl)phosphonic acid Chemical compound OCC(P(O)(O)=O)P(O)(O)=O BAERPNBPLZWCES-UHFFFAOYSA-N 0.000 claims description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 66
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- ZTVCAEHRNBOTLI-UHFFFAOYSA-L Glycine, N-(carboxymethyl)-N-(2-hydroxyethyl)-, disodium salt Chemical compound [Na+].[Na+].OCCN(CC([O-])=O)CC([O-])=O ZTVCAEHRNBOTLI-UHFFFAOYSA-L 0.000 description 5
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- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 3
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- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 3
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 3
- URDCARMUOSMFFI-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(2-hydroxyethyl)amino]acetic acid Chemical compound OCCN(CC(O)=O)CCN(CC(O)=O)CC(O)=O URDCARMUOSMFFI-UHFFFAOYSA-N 0.000 description 2
- 239000004166 Lanolin Substances 0.000 description 2
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- XYZGDYPGGXDMGG-QVTWQEFQSA-J [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CC[C@H](NC(C([O-])=O)C([O-])=O)C([O-])=O Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CC[C@H](NC(C([O-])=O)C([O-])=O)C([O-])=O XYZGDYPGGXDMGG-QVTWQEFQSA-J 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 2
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- 239000012736 aqueous medium Substances 0.000 description 2
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- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
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- 239000007791 liquid phase Substances 0.000 description 2
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- 229920001223 polyethylene glycol Polymers 0.000 description 2
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- 210000002374 sebum Anatomy 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
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- VPTUPAVOBUEXMZ-UHFFFAOYSA-N (1-hydroxy-2-phosphonoethyl)phosphonic acid Chemical compound OP(=O)(O)C(O)CP(O)(O)=O VPTUPAVOBUEXMZ-UHFFFAOYSA-N 0.000 description 1
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- QGJDXUIYIUGQGO-UHFFFAOYSA-N 1-[2-[(2-methylpropan-2-yl)oxycarbonylamino]propanoyl]pyrrolidine-2-carboxylic acid Chemical compound CC(C)(C)OC(=O)NC(C)C(=O)N1CCCC1C(O)=O QGJDXUIYIUGQGO-UHFFFAOYSA-N 0.000 description 1
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 description 1
- PQHYOGIRXOKOEJ-UHFFFAOYSA-N 2-(1,2-dicarboxyethylamino)butanedioic acid Chemical compound OC(=O)CC(C(O)=O)NC(C(O)=O)CC(O)=O PQHYOGIRXOKOEJ-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
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- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 0.000 description 1
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- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011369 resultant mixture Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000000176 sodium gluconate Substances 0.000 description 1
- 235000012207 sodium gluconate Nutrition 0.000 description 1
- 229940005574 sodium gluconate Drugs 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- DZCAZXAJPZCSCU-UHFFFAOYSA-K sodium nitrilotriacetate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CC([O-])=O DZCAZXAJPZCSCU-UHFFFAOYSA-K 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 150000003432 sterols Chemical class 0.000 description 1
- 235000003702 sterols Nutrition 0.000 description 1
- KBVBZJLGCBJUSU-UHFFFAOYSA-N stilbene;triazine Chemical class C1=CN=NN=C1.C=1C=CC=CC=1C=CC1=CC=CC=C1 KBVBZJLGCBJUSU-UHFFFAOYSA-N 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- JSPLKZUTYZBBKA-UHFFFAOYSA-N trioxidane Chemical class OOO JSPLKZUTYZBBKA-UHFFFAOYSA-N 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
Images
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
- C11D3/37—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
- C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/04—Carboxylic acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/662—Carbohydrates or derivatives
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/83—Mixtures of non-ionic with anionic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D10/00—Compositions of detergents, not provided for by one single preceding group
- C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
- C11D10/045—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap based on non-ionic surface-active compounds and soap
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
- C11D17/003—Colloidal solutions, e.g. gels; Thixotropic solutions or pastes
-
- 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
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/044—Hydroxides or bases
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
- C11D3/2079—Monocarboxylic acids-salts thereof
Definitions
- the invention relates to a high viscosity, phase stable alkaline cleaning concentrate or composition characterized by a reduced water concentration (a high concentration of active materials such as alkalinity and surfactants) and to methods of their use and preparation.
- the materials are phase stable, have very high viscosity yet remain dispensable from automatic or programmable dispensers to a use locus where they are easily mixed with water in a use locus to form an aqueous cleaner.
- the thickened emulsions are easily made and are effective in soil removal in laundry, ware washing, clean-in-place and dairy applications.
- the compositions provide improved or enhanced soil removal properties because of high alkaline and surfactant contact.
- Cleaning compositions have been formulated in solid block, particulate and liquid form. Solid forms provide high concentrations of actives, but must be dissolved in water to form a cleaning liquid.
- WO 96/27000 refers to a concentrated liquid gel ware wash detergent composition which contains 5% to 30% by weight of an alkali polyphosphate, 8% to 50% by weight of a source of alkalinity, 0% to 5% by weight of a surface active agent, 0.1% to 2% by weight of a hydrophilic crosslinkled polycarboxylate thickening agent, 0.1% to 2% by weight of a hydrogen bonding agent for the polycarboxylate, and 0 to 15% of a polyacrylate, the balance being water.
- WO 2007/101470 A1 refers to a liquid detergent concentrate composition
- a liquid detergent concentrate composition comprising an emulsion having a water phase and an oil phase, the composition comprising 5-30 wt-% of one or more alkalinity source 1-70 wt-% of at least one nonionic surfactant 0.01-10 wt-% of at least one crosslinked or partly crosslinked polyacrylic acid or polymethacrylic acid.
- EP 0953631 A1 refers to an alkaline emulsion detergent composition with improved phase stability, useful viscosity and excellent soil removal properties can comprise in an aqueous phase, an emulsion comprising a source of alkalinity, a nonionic surfactant blend, a water conditioning agent and an alkyl polyglucoside.
- the improved stable emulsions can be used in laundry applications or other soil removal processes.
- the compositions are typically prepared by forming an alkaline nonionic blend combining the blend with a water conditioning agent and the alkyl polyglucoside and shearing the resulting aqueous mixture to form an emulsion characterized by a preferred particle size and viscosity.
- liquid detergent concentrates typically are not as highly active as solids and are often greater than 50% water.
- Detergent emulsion concentrates have been employed as all-purpose cleaners, ware washing detergents and in formulations for cleaning hard surfaces by diluting the concentrate with water.
- the typical emulsion liquid is less than 60% actives, less than 10% surfactant less than 30-40% alkalinity.
- Many of the prior art emulsions are not sufficiently phase stable meaning that they do not remain globally homogenous for storage and use in a variety of applications, have reduced actives concentration (comprise greater than 50% water) or display reduced properties compared to other useful forms of detergent or are difficult to manufacture, dispense or store.
- Many prior art emulsions contain relatively low caustic content and relatively low sequestrant and surfactant contents.
- Substantial attention has been directed to concentrate materials having substantially increased active content that can be manufactured as stable liquids.
- a need has existed to push the active concentrate of detergent components in the emulsion to 60 to 65% in order to provide the efficacy and performance of solids.
- These liquids must have a stable viscosity and a handleable viscosity such that the liquid can be reliably dispensed from a source of the material to a use locus such as a laundry machine.
- the composition comprises a thickening system compatible with the high alkaline formula resulting in a high viscosity composition that exhibits shear thinning.
- the composition of the invention is particularly novel in that its rheology is unique.
- the composition may be defined as a solid when no shear is applied but once shear is applied, the composition begins to flow.
- the composition comprises 15 to 50 wt.-% of a source of alkalinity, 10 to 30 wt.-% of nonionic surfactant(s), 0.1 to 10 wt.-% of a water conditioning or sequestering agent, an optional alkyl polyglucoside surfactant, and a thickening system comprising 0.25 to 5 wt.-% of a fatty acid and 5 to 25 wt.-% of a polyacrylic acid, wherein the resulting stable compositions are characterized by a low water content, high actives concentration of greater than 60 wt % based on the concentrate composition, high alkalinity, and a viscosity greater than 250 Pa ⁇ s (250,000 centipoise) at 20° C using a Bohlin CVO rheometer measured in rotating shear mode at the shear rate of 0.2 per second.
- This improved detergent can be used for a variety of applications but preferably is used in laundry applications. We have achieved cleaner formulations that comprise greater than 30
- a liquid cleaner concentrate composition in the form of an aqueous thickened emulsion having a continuous aqueous phase and a dispersed phase, the composition comprising a phase stable thickened emulsion comprising:
- soiled articles are contacted with an aqueous liquid cleaning liquor comprising a major proportion of water and 0.5 to 3.0 ppm of the emulsion detergent.
- the clothes are contacted with the washing liquor at an elevated temperature of from 25°C to 80°C for a period of time to remove soil.
- the soil and used liquor are then rinsed from the clothing in a rinse cycle.
- the improved detergents of the invention are made by a process that comprises the steps of combining the nonionic surfactant or surfactant blend with anionic surfactants, chelating components, and various other textile detergent components. To this blend, the sources of alkalinity are added followed by the polyacrylic acid.
- the term "thickened emulsion" connotes a substance that behaves as a solid until a sufficiently large load or stress is applied, at which point it flows like a fluid.
- a thickened emulsion is a viscoplastic material that behaves as a rigid body at low stresses but flows as a viscous fluid at high stress.
- Thickened emulsions of the invention comprise two immiscible liquids.
- the continuous phase is comprised substantially of caustic salts and other dissolved components in an aqueous medium.
- compositions of the invention since no additional water is added to compositions of the invention, thickened emulsions of the invention result in a composition having a substantially low aqueous phase or low water content.
- emulsion and “thickened emulsion” are used interchangeably.
- emulsion refers to compositions having substantially lower viscosities than those of the present invention.
- thickened emulsions of the invention are comprised of two limitedly miscible liquid phases.
- Compositions of the invention may comprise a third solid particulate comprised substantially of the carboxymethylcellulose or optical brightener(s), if any is used, to formulate the thickened emulsions of the invention. If a third phase exists, this discrete phase is believed to include particles in the range of between 1 micrometer up to 100 microns; however, compositions of the invention may include substantially larger particles including above 100 microns.
- the insoluble or non-water soluble portion typically a liquid nonionic surfactant, forms dispersed droplets having a particle size less than 10, less than 5 microns, preferably between 0.5 and 8 microns.
- Phase stable connotes that under typical manufacturing, storage and use conditions, the dispersed phase does not substantially lose its finely divided form and separate from the aqueous phase to a degree that the material becomes not useful in a laundry or other cleaning purpose. Some small amount of separation can be tolerated as long as the thickened emulsion retains greater than 98% of the discontinuous phase (predominantly organic materials) in small emulsified form and provides cleaning activity.
- the aqueous materials of the invention typically involve the emulsification of a relatively insoluble, typically organic phase and an aqueous phase.
- the organic phase can contain one or more components such as surfactants, water conditioning agents, brighteners, etc. while the aqueous phase can contain, in an aqueous medium, aqueous soluble components such as sodium hydroxide, water conditioning agents, brighteners, dyes and other components.
- the materials are typically made by dispersing the relatively "oily" organic insoluble phase in the aqueous phase stabilized by an emulsion stabilizer composition with the application of shear.
- the emulsion stabilizer typically comprises the polyacrylic acid in combination with a fatty acid at an amount that can promote a stable thickened emulsion.
- alkylpolyglucoside (APG) surfactants may be added to enhance the stabilization of the emulsion.
- the emulsion stabilizers are polyacrylic acid in combination with an anionic surfactant that are sufficiently soluble in sodium hydroxide and promote small particle size formation in the typical organic phase used in the thickened emulsions of the invention.
- anionic surfactant such as a alkyl ethoxylate without an emulsion stabilizer will rapidly separate into two separate phases.
- Such surfactants have low solubility in sodium hydroxide while sodium hydroxide is insoluble in this organic compound.
- the useful procedure for forming the dispersions of the invention involves combining fatty alcohol ethoxylate(s) with alkyl polyglucoside, carboxymethyl cellulose and tall oil.
- the APG can be added at this time and the contents of the vessel can be agitated strongly.
- Any optical brighteners are added to the described combination followed by adding aqueous caustic, typically 50 wt % aqueous caustic to a large metal vessel containing agitation apparatus.
- Monoethanolamine is added to the combination followed by polyacrylic acid as the final ingredient.
- this emulsion concept could be applied elsewhere as well. This would include warewashing, clean in place cleaners and sanitizers, food and dairy formulations. In general, this emulsion concept could be used in any formulation where relatively insoluble nonionic surfactants are mixed with caustic solutions to form a thickened emulsion with properties balanced for the selected end use.
- the low foaming surfactants can comprise nonionics such as linear alcohol ethoxylates (Lutensol® available from BASF located in Ludwigshafen, Germany), particularly the fatty alcohol C 13 -C 15 ethoxylates having 2 to 10 polyethylene oxide groups.
- Thickeners useful in the invention include a combination of linear polyacrylic acid such as Acusol® (Rohm & Haas) and a fatty acid such as tall oil.
- surfactant or "surface active agent” refers to an organic chemical that when added to a liquid changes the properties of that liquid at a surface.
- EO, PO, or EO/PO refer to ethylene oxide and propylene oxide, respectively.
- EO/PO refers to ethylene oxide and propylene oxide groups.
- substantially free may refer to any component that the composition of the invention lacks or mostly lacks. When referring to “substantially free” it is intended that the component is not intentionally added to compositions of the invention. Use of the term “substantially free” of a component allows for trace amounts of that component to be included in compositions of the invention because they are present in another component. However, it is recognized that only trace or de minimus amounts of a component will be allowed when the composition is said to be “substantially free” of that component.
- Weight percent, percent by weight, % by weight, and the like are synonyms that refer to the concentration of a substance as the weight of that substance divided by the weight of the composition and multiplied by 100.
- weight percentages provided herein reflect the weight percentage of the raw material as provided from the manufacturer.
- the active weight percent of each component is easily determined from the provided information by use of product data sheets as provided from the manufacturer.
- emulsions have concerned systems of two isotropic, substantially Newtonian liquids, one being dispersed in the other in the form of small droplets.
- the system is stabilized by absorbed amphiphiles which modify interfacial properties.
- emulsions act in more than two phases.
- An emulsion forms when two immiscible liquids, usually water and oil, for example, are agitated so that one liquid forms droplets dispersed within the other liquid.
- Emulsions are stabilized by a compound adsorbed at the interface.
- emulsifier This compound is termed an "emulsifier.”
- emulsifier are molecules that possess both polar and nonpolar regions and which serve to bridge the gap between the two immiscible liquids.
- the polar portion of an emulsifier is soluble in the water phase, while the nonpolar region is soluble in the oil phase.
- formation of an emulsion or emulsification involves breaking large droplets into smaller ones due to shear forces.
- emulsion failure In order to discuss the stability of emulsions, it is necessary to first discuss how an emulsion fails.
- the initial step in emulsion failure is known as flocculation, in which individual droplets become attached to each other but are still separated by a thin film of the continuous phase.
- the next step is coalescence, in which the thin liquid film between the individual droplets destabilizes, allowing large droplets to form. As coalescence continues, the emulsion separates into an oil layer and an aqueous layer.
- emulsions are stabilized by slowing the destabilization or flocculation process. This can be done either by reducing the droplet mobility, by increasing viscosity or by the insertion of an energy barrier between droplets.
- the size of droplets or particles of the dispersed phase are less than 10 microns, preferably less than 5 microns in diameter.
- compositions of the invention are particularly unique in the rheological characteristics they exhibit.
- the inventors have characterized their invention as a "thickened emulsion" despite the fact that compositions of the invention behave differently than any presently known emulsions.
- the compositions are characterized as emulsions because they are comprised of at least two immiscible phases as is commonly known in the emulsion art.
- the thickened emulsions of the invention exhibit characteristics of a solid when they are not under shear.
- the thickened emulsions of the invention exhibit a viscosity of greater than 1,000 Pa ⁇ s at zero shear. As shear increases, the rheology of the invention composition changes substantially until, when the compositions of the invention are under high shear, they exhibit properties of a liquid.
- compositions of the invention exhibit unusually high viscosity.
- thickened emulsions of the invention exhibit a viscosity of greater than 100 Pa ⁇ s at 20 degrees centigrade when using a Bohlin CVO rheometer measured in rotating shear mode at the shear rate of 0.2 per second.
- thickened emulsions of the invention exhibit a viscosity of greater than 300 Pa ⁇ s, greater than 500 Pa ⁇ s, greater than 700 Pa ⁇ s, greater than 900 Pa ⁇ s, greater than 1,100 Pa ⁇ s, greater than 1,300 Pa ⁇ s, up to greater than 1,500 Pa ⁇ s at 20 degrees centigrade when measured using a Bohlin CVO rheometer measured in rotating shear mode at the shear rate of 0.2 per second.
- the viscosity of the invention compositions may be engineered to suit a specific use or dispensing system. Generally, as the amount of thickening agents such as fatty acid and polyacrylic acid are increased, the viscosity of the composition increases.
- compositions otherwise prepared according to the invention except they lack fatty acids are viscous fluids with viscosities of 10 Pas when taken at 0.2s -1 .
- Increasing the content of fatty acids from 0% to 1% results in a continuous increase of shear viscosity up to several hundreds of Pas along with the appearance changing from a flowing liquid to a solid gel or paste.
- Similar observations are made when modifying the concentration of polyacrylic acid. As previously mentioned, without polyacrylic acid the composition appears as a viscous liquid with shear viscosity below 10 Pas (0.2s -1 ). With the concentration of polyacrylic acid between 5 and 8 weight percent, the composition turns into a paste resulting in viscosities in the range of 100-1000 Pas (0.2s -1 ).
- a source of alkalinity is needed to control the pH of the use detergent solution.
- the alkalinity source is selected from the group consisting of alkali metal hydroxide, such as sodium hydroxide, potassium hydroxide or mixtures thereof; an alkali metal silicate such as sodium metasilicate and carbonate salts may also be used.
- the preferred source which is the most cost-effective, is commercially available sodium hydroxide which can be obtained in aqueous solutions in a concentration of 50 wt-% and in a variety of solid forms in varying particle sizes.
- the sodium hydroxide can be employed in the invention in either liquid or solid form or a mixture of both.
- alkali metal carbonates alkali metal bicarbonates, alkali metal sesquicarbonates, alkali metal borates and alkali metal silicate.
- alkali metal carbonates between 40 to 80 weight percent, between 45 to 75 weight percent, and between 50 to 70 weight percent sodium hydroxide (50% actives) is included in the composition of the invention.
- nonionic detersive surfactants that can be used with the invention include the alcohol ethoxylates.
- a combination of nonionic surfactants is preferred.
- These include linear and branched alcohol ethoxylates.
- Suitable alcohol ethoxylates include those having between 5 and 10 EO, between 6 and 8 EO and a linear alcohol ethoxylate having between 1 and 6 EO, between 2 and 5 EO. Examples of these include the fatty alcohol C13-C15 ethoxylate (7EO) commercially available as Lutensol® AO7 and the fatty alcohol C13-C15 ethoxylate (3EO) commercially available as Lutensol® AO3, both available from BASF.
- Lutensol® surfactants are ethoxylates of oxo-alcohols which are synthetic alcohols.
- nonionic surfactants suitable for use in the present invention include but are not limited to ethylene oxide/propylene oxide copolymers, ethylene oxide/propylene oxide/ethylene oxide copolymers, propylene oxide/ethylene oxide/propylene oxide copolymers (such as those available under the Pluronics mark and Pluronics R from BASF, those surfactants sold under the Plurafacs mark from BASF and those sold under the Polytergents mark also from BASF).
- compositions of the invention include between 5 and 35 weight percent nonionic surfactant or nonionic surfactant mixture, between 10 and 30 weight percent, and between 15 and 25 weight percent.
- the composition comprises between 2 to 25 weight percent, between 5 and 20 weight percent, and between 8 and 17 weight percent of a first nonionic surfactant; and between 0.5 and 15 weight percent, between 2 and 13 weight percent, and between 5 and 10 weight percent of a second nonionic surfactant.
- the thickened emulsions of the invention are stabilized using a soap and polyacrylic acid and alkyl polyglucosides optionally improve consistency, stability, and homogeneity of the thickened emulsions of the invention.
- Such surfactants have a strongly hydrophobic alkyl group with a strongly hydrophilic glycoside group that can have its hydrophilicity modified by the presence of ethylene oxide groups.
- these materials are effective emulsion stabilizers when the material is soluble in the aqueous phase and can promote small particle size emulsions.
- the alkyl polyglucoside, Glucopon 215 contains a hydrophobic group with an alkyl straight chain of C8 to C10. This material has good solubility in sodium hydroxide solutions.
- alkyl polyglucosides with different alkyl groups and DP's.
- the general class of alkyl polyglucosides produces low interfacial tension between mineral oil and water. Low interfacial tension is probably responsible for the success of these surfactants in stabilizing the thickened emulsion.
- the system that is being used is different than the typical emulsion.
- the oil phase is the surfactant (fatty alcohol ethoxylate) while the aqueous phase is the sodium hydroxide solution along with other materials.
- the surfactant fatty alcohol ethoxylate
- the surfactant has essentially no solubility in the sodium hydroxide solution and the sodium hydroxide has essentially no solubility in the surfactant phase.
- compositions of the invention optionally comprise between 0.01 to 10 weight percent alkyl polyglucoside, between 0.5 to between 8 weight percent, and between 1 and 5 weight percent (50% active).
- alkylpolyglucosides have a synergistic thickening, stabilizing, and homogenizing effect when used in combination with certain other thickening agents.
- APG is used in combination with a fatty acid and/or a polyacrylic acid.
- APG is used in combination with a polyacrylate copolymer.
- APG is used in combination with an alcohol ethoxylate and/or an acrylic acid polymer and/or a polyacrylic acid.
- the combination of fatty acid with polyacrylic acid and optionally alkylpolyglucoside in the present formulation provides a composition having a sufficiently high viscosity, improved homogeneity and stability even at the high alkalinity required.
- other thickening agents widely known in the industry such as CMC, guar gums, xanthan gums, polyethylene glycol to name a few break down and are therefore ineffective at creating a high viscosity formulation. It is unusual for a composition having such a high caustic content and alkalinity to achieve a high viscosity as exhibited by compositions of the present invention.
- a fatty acid of choice in compositions of the invention comprises tall oil.
- Tall oil is also referred to as liquid resin and is a resinous yellow-black oily liquid composed of a mixture of rosins, fatty acids, sterols, high-molecular alcohols, and other alkyl chain materials.
- the crude tall oil is distilled into tall oil rosin (having the rosin content of 10 - 35%), further refinery gives to tall oil fatty acid (the rosin content of 1 - 10%).
- Tall oil fatty acid is particularly preferred in compositions of the invention due to its low cost and flowability. Unlike many other fatty acids, tall oil remains a liquid at ambient temperature making it easier to handle than other fatty acids.
- Tall oil is an unsaturated fatty acid containing primarily a combination of oleic and linolic acids and in lesser amounts palmitic and stearic acids among others.
- tall oil fatty acid comprises from 0.01 to 5 weight percent, from 0.1 to 4 weight percent, and from 0.2 to 3 weight percent.
- ACUSOL® 445 is a partially neutralized, liquid detergent polymer.
- the polyacrylate comprises ACUSOL® 445, a polyacrylic acid with a molecular weight of 4500 manufactured by Rohm and Haas, Philadelphia, Pennsylvania.
- Other polyacrylic acids of molecular weight 4500 (CRITERION 2005) and 8000 (CRITERION 2108) can be purchased from Kemira Chemicals, Kennesaw, Georgia. It is believed that other suitable examples include Soakalan CP5 available from BASF, Coatex DE185, or Isol Dispersant HN44.
- polyacrylic acid comprises from 5 to 25 weight percent.
- Alcohol ethoxylates are also useful as thickening agents in compositions of the invention.
- Isotridecanol ethoxylate is a nonionic surfactant available as Lutensol® TO 8 from BASF that has been found effective at providing thickening, stabilizing, and homogeneity in compositions of the invention.
- Alcohol ethoxylates such as isotridecanol ethoxylate have improved performance as a thickening agent when combined with either a polyacrylic acid such as Accusol ® 445 discussed above, and/or an acrylic acid polymer such as Carbopol® ETD 2691 available from Lubrizol Corporation.
- Carbopol® is a lightly crosslinked polyacrylic acid polymer.
- alcohol ethoxylates are present in an amount from 0.5 to 10 weight percent, from 0.75 to 9.5 weight percent, and from 0.9 to 9.0 weight percent.
- Polyacrylate copolymers are also useful thickening, stabilizing, and homogenizing agents when incorporated into compositions of the invention.
- An example of such a copolymer is Cosmedia® available from Cognis.
- Cosmedia® is an emulsifying copolymer consisting of methacrylic acid and acryclic acid ethyl and butyl ester.
- polyacrylate copolymers are present in an amount from 0.5 to 10 weight percent, from 0.75 to 9.5 weight percent, and from 0.9 to 9.0 weight percent.
- compositions of the invention preferably include water conditioning agents.
- the thickened emulsion compositions of the invention can comprise a polyvalent metal complexing, sequestering or chelating agent that aids in metal compound soil removal and in reducing harmful effects of hardness components in service water.
- a polyvalent metal cation or compound such as a calcium, a magnesium, an iron, a manganese, a molybdenum, etc. cation or compound, or mixtures thereof, can be present in service water and in complex soils.
- Such compounds or cations can comprise a stubborn soil or can interfere with the action of either washing compositions or rinsing compositions during a cleaning regimen.
- a chelating agent can effectively complex and remove such compounds or cations from soiled surfaces and can reduce or eliminate the inappropriate interaction with active ingredients including the nonionic surfactants and anionic surfactants of the invention.
- Both organic and inorganic chelating agents are common and can be used.
- Inorganic chelating agents include such compounds as sodium tripolyphosphate and other higher linear and cyclic polyphosphates species.
- Organic chelating agents include both polymeric and small molecule chelating agents.
- Organic small molecule chelating agents are typically organocarboxylate compounds or organophosphate chelating agents.
- Polymeric chelating agents commonly comprise polyanionic compositions such as polyacrylic acid compounds.
- Small molecule organic chelating agents include sodium gluconate, sodium glucoheptonate, N-hydroxyethylenediaminetriacetic acid (HEDTA), ethylenediaminetetraacetic acid (EDTA), nitrilotriaacetic acid (NTA), diethylenetriaminepentaacetic acid (DTPA), ethylenediaminetetraproprionic acid, triethylenetetraaminehexaacetic acid (TTHA), and the respective alkali metal, ammonium and substituted ammonium salts thereof, ethylenediaminetetraacetic acid tetrasodium salt (EDTA), nitrilotriacetic acid trisodium salt (NTA), ethanoldiglycine disodium salt (EDG), diethanolglycine sodium-salt (DEG), and 1,3-propylenediaminetetraacetic acid (PDTA), dicarboxymethyl glutamic acid tetrasodium salt (GLDA), methylglycine-N-N-di
- Small molecule organic chelating agents also include biodegradable sequestrants having combinations of chelating and hydrotroping functionalities from EDG, MGDA and GLDA-type molecules.
- Preferred sequestrants include ethanoldiglycine disodium salt (EDG), dicarboxymethyl glutamic acid tetrasodium salt (GLDA), and methylglycine-N-N-diacetic acid trisodium salt (MGDA), due to their biodegradability and their ability to bind easily with hydrotropes to form ultra-compact concentrates.
- EDG ethanoldiglycine disodium salt
- GLDA dicarboxymethyl glutamic acid tetrasodium salt
- MGDA methylglycine-N-N-diacetic acid trisodium salt
- sequestrants that are suitable to include in compositions of the invention include anionic polyelectrolytes such as polyacrylates and acrylic acid copolymers, itaconic acid copolymers such as an acrylic/itaconic acid copolymer, maleates, sulfonates and their copolymers, alkali metal gluconates.
- chelating agents are organic phosphonates such as 1-hydroxyethylidene-1,1-diphosphonic acid, amino tri(methylene phosphonic acid), hexamethylene diamine tetra(methylene phosphonic acid), diethylene triamine penta(methylene phosphonic acid), and 2-phosphonobutane-1,2,4-tricarboxylic acid and other commercially available organic phosphonates water conditioning agents. Most conventional agents appear to work since they are compatible in either the continuous phase or the droplet phase.
- a chelating agent is present in the composition concentrate in an amount of between 0.05 and 15 weight percent, more preferably 1 to 10 wt%, most preferably 3 to 8 wt%.
- Dequest® 2010 may be included in compositions of the invention as the sequestering or chelating agent.
- Dequest® 2010 is 1-Hydroxyethylidene -1,1,-diphosphonic acid, acts as a sequestrant in the present invention, and is a commercially available from ClearTech Industries, Inc. located in Saskatoon, Saskatchewan, Canada.
- compositions of the invention comprise between 0.01 to 10 weight percent sequestrant, between 0.5 to between 8 weight percent, and between 1 and 5 weight percent (60% active).
- Baypure® CX100 may be included in compositions of the invention as a chelating agent.
- Baypure® CX100 is a medium-strength complexing agent with low remobilization of heavy metals. It is effective at complexing iron, copper and calcium ions and is biodegradable. If Baypure® CX100 is included in compositions of the invention it is included in amount from 1 up to 30 weight percent, from 2 up to 20 weight percent, and from 3 up to 10 weight percent for a 34% actives solution of Baypure®.
- sequestrants may be included in the invention.
- composition of the invention does not generally include additional water. While it is recognized that certain ingredients contain some amount of water because they are provided as a solution in water, additional water is not generally added to compositions of the invention. This is important in particular to maintain the high viscosity required of compositions of the invention.
- Compositions of the invention can be formulated without any additional water or can be provided with a relatively small amount of water in order to reduce the expense of transporting the composition.
- the water of dilution that can be used to dilute the composition to form a use composition is preferably soft water. That is, it is preferable that water of dilution be substantially free of hardness. Water can be characterized as hard water when it includes at least 1 grain hardness.
- Detergents typically contain a number of conventional, important but minor ingredients. These can include optical brighteners, soil antiredeposition agents, antifoam agents, low foaming surfactants, defoaming surfactants, pigments and dyes, which are used in these formulas.
- the compositions can also include chlorine and oxygen bleaches, which are not currently used in these formulas. Such materials can be formulated with the other ingredients or added during cleaning operations.
- compositions of the invention optionally include a component to inhibit discoloration or browning of the formulation otherwise referred to as a color stabilizing agent.
- a color stabilizing agent is optional; however, due to the off-putting nature of discolored laundry detergent it is a desirable option to include.
- this color stabilizer is monoethanolamine.
- a color stabilizing agent comprises from 0.01 to 5 weight percent, from 0.05 to 3 weight percent, and from 0.10 to 2 weight percent.
- Brighteners are commonly added to laundry detergents to replace whitening agents removed during washing and to make the clothes appear cleaner.
- Optical brighteners are commonly dyes that absorb light in the ultraviolet and violet region (usually 340-370nm) of the electromagnetic spectrum, and re-emit light in the blue region (typically 420-470nm). These additives are often used to enhance the appearance of color of fabric, causing a perceived "whitening" effect, making materials look less yellow by increasing the overall amount of blue light reflected.
- Optical brighteners may or may not be a desirable addition to compositions of the invention. Whether or not it is desirable to include optical brighteners is dependent upon the user. For instance, a side effect of optical whitening is to make the treated fabrics more visible with night vision devices than non-treated ones. For military or other applications such an effect would likely be undesirable.
- optical brighteners examples include triazine-stilbenes (di-, tetra- or hexa-sulfonated), coumarins, imidazolines, diazoles, triazoles, benzoxazolines and biphenyl-stilbenes to name a few.
- a single optical brightener or combinations of optical brighteners may be useful in compositions of the invention.
- optical brighteners comprise from 0.1 to 5 weight percent, from 0.15 to 3 weight percent, and from 0.2 to 2 weight percent.
- Examples of commercially available optical brighteners suitable for use in compositions of the invention include but are not limited to DMS-X and CBS-X, a distyryl biphenyl derivative, both available from Vesta-Intracon BV.
- Compositions of the invention may further include antiredeposition agents.
- Antiredeposition agents may be made from complex cellulosic materials such as carboxymethylcellulose (CMC), or synthetic materials such as polyethylene glycol and polyacrylates. They aid in preventing loosened soil from redepositing onto cleaned fabrics. Polyphosphate builders also help in reducing redeposition.
- Colorants are optionally added to compositions of the invention. Colorants may be in the form of a pigment or dye and may be added to provide a certain color to the composition. Additionally, blue colorants may be added to provide a bluing that imparts a desirable blue/white color to white fabrics.
- Fragrances are optionally added to compositions of the invention. Fragrances generally provide three functions, regardless of the scent used. They cover the chemical odor of the detergent and the odor of soils in the washing solution and they impart a pleasant scent to fabrics, thus reinforcing the clean performance. Additionally, a fragrance may contribute to the character of the product. In an alternative embodiment, compositions of the invention may omit a fragrance in order to provide an unscented version thereby appealing to consumers who prefer low or no scent on laundry or to those whose skin is sensitive to fragrance ingredients.
- compositions of the invention Ingredient % by weight % by weight % by weight Sodium hydroxide (50%) 40-80 45-75 50-70 Fatty alcohol C13-C15 Ethoxylate (7EO) 4-20 9-15 10-14 Fatty alcohol C13-C15 Ethoxylate (3EO) 7-15 6-12 4-10 C10 Alcohol ethoxylate ___ _____ Fatty alcohol (C12-C14) EOPO __ ___ ___ Isotridecanol ethoxylate __ _____ Polyacrylic acid (20%) 25 20 15 Monoethanolamine 0.01-5 0.05-3 0.1-2.0 Alkyl Polyglucoside 0.1-7 0.5-5 1.0-3.0 Polyacrylate copolymer __ ___ _____ Acrylic Acid Polymer __ ____ _______ Hydroxyethylidene diphosphonic acid (60%) 0.1-7 0.5-5 1.0-3.0 Iminodisuccinate
- compositions of the invention are prepared by combining a nonionic surfactant, an alkyl polyglucoside composition, CMC and tall oil.
- the APG may be added at this time along with strong agitation.
- Any optical brighteners are added to the combination followed by addition of an aqueous base, the aqueous base comprising 50 wt. % active aqueous sodium hydroxide, to form an alkaline surfactant blend.
- Monoethanolamine is added to the combination followed by polyacrylic acid as the final ingredient.
- the final mixture is exposed to high shear to form a stable thickened emulsion characterized by a viscosity of greater than 250 Pa ⁇ s at 20 degrees C using Bohlin CVO rheometer with air bearing and thermostat.
- Measurement is taken using two parallel plates each having 20mm diameter with a distance of 2mm between the plates.
- the sample is confined in the gap between the two plates at a constant temperature of 20 degrees C.
- the measurement is performed in such way that the upper plate is rotating at a certain speed (shear rate) and the lower plate is fixed, thereby shearing the sample between the plates.
- the torque that is required to maintain a certain shear rate is measured.
- the shear stress on the sample is calculated from the torque and the viscosity results as the ratio of shear stress and shear rate.
- the present invention also includes methods of use. Such methods include contacting soiled laundry items with a wash liquor comprising a major proportion of water and 0.5 to 3.0 ppm of a liquid cleaner concentrate composition in the form of an aqueous emulsion having a continuous phase and a dispersed phase, the thickened emulsion having a stable viscosity and dispersed phase particle size, the composition comprising a phase stable thickened emulsion comprising a continuous phase; an effective soil removing amount comprising 15 to 50 wt % of a source of alkalinity; an effective soil removing amount comprising 10 to 30 wt % of a nonionic surfactant; an effective water conditioning or sequestering amount 0.1 to 10 wt % of a water conditioning or sequestering agent; an effective soil removing and emulsion stabilizing amount comprising up to 5 wt % of an alkyl polyglucoside surfactant; an effective thickening amount of polyacrylic acid comprising 5 to 20
- compositions were prepared according to the invention except that they lacked fatty acids. These comparative compositions were viscous fluids with viscosities of 10 Pas when taken at 0.2s -1 . Increasing the content of fatty acids from 0% to 1% resulted in a continuous increase of shear viscosity with the appearance changing from a flowing liquid to a solid gel or paste.
- compositions were prepared according to the invention except that they lacked polyacrylic acid. Without polyacrylic acid the composition appears as a viscous liquid with shear viscosity below 10 Pas (0.2s -1 ). With the concentration of polyacrylic acid between 5 and 8 weight percent, the composition turns into a paste resulting in viscosities in the range of 100-1000 Pas (0.2s -1 ).
- compositions were prepared according to the following tables. 1A *1 3A *1 5A 6A 8A Fatty alcohol C13-15 ethoxylate (7EO) 15% 15% 15% 15% 15% Fatty alcohol C13-15 ethoxylate (3EO) 4% 4% 4% 4% 4% 4% Alkyl Polyglycoside (50%) 2% 2% 2% 2% 2% 2% Carboxymethyl cellulose 2% 2% 2% 2% 2% 2% 2% 2% Tall Oil fatty acids 0% 0.4% 0.65% 0.75% 1% Optical Brightener DMS-X 0.5% 0.5% 0.5% 0.5% 0.5% 0.5% 0.5% 0.5% 0.5% Distyryl Biphenyl Derivative 0.25% 0.25% 0.25% 0.25% 0.25% Hydroxyethylidene Diphoyphonic Acid (60%) 2% 2% 2% 2% 2% 2% 2% 2% 2% 2% 2% 2% 2% Sodium Hydroxide Solution (50%) 61% 60.6% 60.35 % 60.25 % 60% Monoethanol
- Viscosity was measured using a parallel plate system with each plate having 20 mm diameter with a 2 mm gap distance between the plates. Measurements were taken at 20 degrees C. Each sample was confined in the gap between the two plates and the measurement was performed in such way that the upper plate was rotating at a certain speed (shear rate) and the lower plate was fixed, thereby shearing the sample between the plates. The torque that was required to maintain a certain shear rate was measured. The shear stress on the sample is calculated from the torque and the viscosity results as the ratio of shear stress and shear rate.
- compositions were prepared using Sokalan AT 10 from BASF, Carbopol EZ3 and EZ 4 from Noveon and Acusol 805S from Rohm & Haas but the resultant mixtures were not stable and separated into two viscous liquid phases.
- compositions were prepared according to the following table: Ingredient 1C *3 2C *3 3C *3 4C *3 Water 10.95% 10.95% 10.95% 10.95% KOH, 50% 25.00% 25.00% 25.00% 25.00% 25.00% DMS-X, Stilbene Disulfonic Acid 0.30% 0.30% 0.30% 0.30% CBS-X, Distyryl Biphenyl Derivative 0.10% 0.10% 0.10% 0.10% Hydroxyethylene Diphosphonic Acid (60%) 2.50% 2.50% 2.50% 2.50% 2.50% Sodium silicate (40%) 10.00% 10.00% 10.00% 10.00% Iminodisuccinate Sodium Salt (34%) 14.75% 14.75% 14.75% 14.75% Methyl gylcine diacetic acid, trisodium salt (40%) 7.50% 7.50% 7.50% 7.50% Polyacrylic Acid Copolymer 7.50% 7.50% 7.50% Silicone Emulsion 0.20% 0.20% 0.20% 0.20% 0.20% 0.20% Fatty alcohol eth
- FIG. 1 shows shear thinning of a sample 6A of the invention. As shear is increased, viscosity decreases by five orders of magnitude. As can be seen from the graph of Figure 1 , the viscosity varies over more than 5 orders of magnitude in a shear rate range between 0.01 and 500s -1 .
- compositions were prepared according to the following table: Ingredient % by weight Fatty alcohol C13-15 ethoxylate (7EO) 10-14% Fatty alcohol C13-15 ethoxylate (3EO) 5-9% Alkyl Polyglycoside (50%) 2% Carboxymethyl cellulose 0.5-2% Tall Oil fatty acids 0.25%-0.75% Optical Brightener DMS-X 0.5% Distyryl Biphenyl Derivative 0.25% Hydroxyethylidene Diphoyphonic Acid (60%) 2% Sodium Hydroxide Solution (50%) 40-60% Monoethanol amine 0.25% Polyacrylic acid (48%) 11.7-14.3%
- a composition of the invention was prepared according to the following table: Ingredient Manufacturer % by weight Lutensol AO7 BASF 15.00 Lutensol AO3 BASF 4.00 Glucopon 215 UP Cognis 2.00 CMC Hercules 2.00 Tall Oil Mosselman 0.50 DMS-X Ciba 1.00 CBS-X Hebei 0.25 Dequest 2010 Thermphos 2.00 NaOH (50%) BASF 60.00 Monethanolamine BASF 0.25 Accusol 445 Rohm & Haas 13.00
- the pH of a 1% solution of the above-identified formulation was in the range of 12.2 to 12.9.
- Standard test stains which are commercially available from WFK (Krefeld/Germany) were used for this Example.
- the test stains were produced in a standardized manner and were placed on test strips. These were included in a washing machine together with 6.5kg of polyester textiles. Each procedure was repeated 4 times in 4 different washing machines, the values in the tables below are the averages of the 4 results for each procedure.
- the above-prepared composition was included in a dosage of 1.5g/l along with 1ml/l of a bleaching agent (Ozonit super available from Ecolab, Inc.) was added in each test.
- the washing time was 10 minutes, temperature 70°C, bath ratio 1:5; soft water was used.
- the stain removal from the test strips was measured with an optical method, the light transmission at a fixed wave length is measured with the stain before and after washing. The results are the remission values shown in the tables.
- the tables below compare lab wash results of the thickened emulsion of the invention with a commercially available detergent.
- the top two tables show the results of wash performance with fat/pigment stains, the bottom table shows enzymatic stains.
- the results demonstrate that the thickened emulsion of the invention performed as well or better than the commercially available detergent in most situations.
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US11248192B2 (en) | 2019-01-22 | 2022-02-15 | Ecolab Usa Inc. | Polymer blend to stabilize highly alkaline laundry detergent |
WO2022120174A1 (en) * | 2020-12-04 | 2022-06-09 | Ecolab Usa Inc. | Improved stability and viscosity in high active high caustic laundry emulsion with low hlb surfactant |
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DE102012212726A1 (de) | 2012-07-19 | 2014-01-23 | Henkel Ag & Co. Kgaa | Stabiles, flüssiges Waschmittel mit vergrauungsinhibierender Leistung |
CN103060115A (zh) * | 2013-01-07 | 2013-04-24 | 北京洛娃日化有限公司 | 一种重油垢清洁剂凝胶 |
WO2014128922A1 (ja) * | 2013-02-22 | 2014-08-28 | 株式会社コーセー | 粘性洗浄剤組成物 |
DE102013210273A1 (de) * | 2013-06-03 | 2014-12-04 | Henkel Ag & Co. Kgaa | Wasch-, Reinigungs- oder Vorbehandlungsmittel mit erhöhter Reinigungskraft IV |
US10450538B2 (en) * | 2015-11-30 | 2019-10-22 | Henkel IP Holding GmbH | Detergent unit doses and methods of producing the same |
JP7133426B2 (ja) * | 2018-10-10 | 2022-09-08 | 日華化学株式会社 | ポリエステル衣料移染防止洗浄用組成物及びそれを用いる洗浄方法。 |
JP7271267B2 (ja) * | 2019-03-29 | 2023-05-11 | 株式会社Adeka | 硬質表面用乳化型洗浄剤組成物 |
CN118234839A (zh) * | 2021-11-15 | 2024-06-21 | 达尔格化学有限责任公司 | 浓缩的水溶性粉末洗涤剂 |
CN115926896B (zh) * | 2022-11-02 | 2024-05-14 | 合创(广州)科技研究有限公司 | 高粘度水溶性单位剂量洗涤剂组合物及其制备方法 |
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US11248192B2 (en) | 2019-01-22 | 2022-02-15 | Ecolab Usa Inc. | Polymer blend to stabilize highly alkaline laundry detergent |
US11773349B2 (en) | 2019-01-22 | 2023-10-03 | Ecolab Usa Inc. | Polymer blend to stabilize highly alkaline laundry detergent |
WO2022120174A1 (en) * | 2020-12-04 | 2022-06-09 | Ecolab Usa Inc. | Improved stability and viscosity in high active high caustic laundry emulsion with low hlb surfactant |
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MX2011006844A (es) | 2011-08-15 |
JP2012514061A (ja) | 2012-06-21 |
CA2746854A1 (en) | 2010-07-08 |
EP2379689A4 (en) | 2014-07-30 |
EP2379689A1 (en) | 2011-10-26 |
CA2746854C (en) | 2016-10-25 |
CN102264886A (zh) | 2011-11-30 |
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