EP0786514A2 - Compositions de prétraitement - Google Patents

Compositions de prétraitement Download PDF

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Publication number
EP0786514A2
EP0786514A2 EP97200112A EP97200112A EP0786514A2 EP 0786514 A2 EP0786514 A2 EP 0786514A2 EP 97200112 A EP97200112 A EP 97200112A EP 97200112 A EP97200112 A EP 97200112A EP 0786514 A2 EP0786514 A2 EP 0786514A2
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EP
European Patent Office
Prior art keywords
group
polymer
weight
composition
hydrophilic
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
EP97200112A
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German (de)
English (en)
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EP0786514A3 (fr
EP0786514B1 (fr
Inventor
Barbara Helen Bory
Walter Joseph Lunsmann
Dennis Stephen Murphy
Tamara Padron
Lucia Victoria Salas
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Unilever PLC
Unilever NV
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Unilever PLC
Unilever NV
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Priority claimed from US08/591,790 external-priority patent/US5820637A/en
Priority claimed from US08/591,750 external-priority patent/US5747442A/en
Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Publication of EP0786514A2 publication Critical patent/EP0786514A2/fr
Publication of EP0786514A3 publication Critical patent/EP0786514A3/fr
Application granted granted Critical
Publication of EP0786514B1 publication Critical patent/EP0786514B1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • 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
    • C11D3/16—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
    • 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
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C11D3/3773—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines 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
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols

Definitions

  • This invention relates to a laundry pretreatment composition in either a liquid, gel or stick form which contains a hydrophobically modified polar polymer and nonionic surfactants. These can be used to effect or enhance stain removal in lieu of or in advance of, the main wash.
  • the liquid and gel compositions may also be used as laundry additives to boost whitening effects and improve stain removal in the wash.
  • Prewash stain remover compositions for the laundry have been in use for many years. Recently developed pretreater compositions available in liquid, spray and gel forms are usually based on nonionic surfactants. The consumer applies the stain remover to the soiled portions of the garments before washing with a laundry detergent. The ingredients in the prewash stain remover or in-wash whitener/stain remover work to remove stains, but either high levels of costly ingredients are required or a plateau in stain removal is observed with increasing concentration of the ingredient.
  • a convenient application method for a pretreatment composition is by the stick form. So-called stick forms essentially comprise the composition in the form of a block (often bar-or-stick shaped or cylindrical in shape), which block is solid or else has the consistency of soap or hard wax.
  • stick As used herein, the terms "stick”, “stick form”, stick composition” etc. are to be construed as referring to pretreatment compositions having such a physical consistency. Stick compositions are conveniently sold often in a dispensing holder. It is difficult to produce stick forms which have optimal hardness to effectively deliver the pretreater compositions.
  • Stick form versions of such pretreaters are generally aqueous based rather than solvent based and contain both nonionic surfactants and anionic soaps such aqueous based systems, while exhibiting proper hardness characteristics, often compromise cleaning performance (see U. S. No. 5,147,576 owned by S.C. Johnson.)
  • hydrophobically modified polar polymers helps to significantly enhance the stain removal performance of the prewash stain remover. Similar compositions may also be used as in wash laundry additives to boost whitening effects and improve stain removal. It has also now been found that such formulations containing hydrophobically modified polar polymers when used in conjunction with a detergent significantly boosts whitening and improve stain removal.
  • the polymers of the Montague reference comprise a hydrophilic backbone which is generally a linear branched or highly cross-linked molecular composition containing one or more types of hydrophilic monomer units; and hydrophobic side chains, for example, selected from the group consisting of siloxanes, saturated or unsaturated alkyl and hydrophobic alkoxy groups, aryl and alkylarlyl groups, and mixtures thereof.
  • compositions which are designed for direct application to stains or for boosting the performance of detergents, respectively, and require compositions which are significantly different from detergents.
  • These compositions are preferably based on nonionic aqueous solutions.
  • Another object of the invention is to provide an aqueous nonionic based composition which boosts the fluorescer whitening of detergents without added fluorescer and improves stain removal.
  • Another object of the invention is to provide a stick pretreater composition which has an effective hardness profile, is shelf stable and which is free of chelating agents yet does not compromise cleaning performance.
  • a first aspect of the present invention now provides a pretreatment composition comprising
  • Liquid, paste and gel compositions of the invention achieve the aforementioned and other objects of the invention by virtue of containing from about 0.1 to about 20%, more preferably 10% by wt of a hydrophobically modified polar polymer which has a hydrophilic backbone (hydrophilic backbone made of one monomer only, e.g., acrylate) wherein there is a critical molar ratio of hydrophilic groups (e.g., the backbone) to hydrophobic “anchors" attached (“tail”) to the backbone and about 0.1 to about 20% of a nonionic surfactant.
  • hydrophilic backbone hydrophilic backbone made of one monomer only, e.g., acrylate
  • tail hydrophobic “anchors” attached
  • a second aspect of the present invention provides an aqueous pretreatment composition, preferably in liquid, paste or gel form which comprise from 0.1 to 20% by weight of nonionic surfactant, from 0 to 5% by weight of anionic soap and from 0.1 to 10% by weight of polymer having:-
  • Stick compositions of the invention achieve the aforementioned and other objects by virtue of containing from about 0.1 to about 10% by wt. of a hydrophobically modified polar polymer which has a hydrophilic backbone (hydrophilic backbone made of one monomer only, e.g., acrylate) wherein there is a critical molar ratio of hydrophilic groups (e.g., the backbone) to hydrophobic "anchors" attached (“tail”) to the backbone, and about 30 wt. % to about 80 wt. % of a nonionic surfactant, and from about 5 wt. % to about 20 wt. % of an anionic soap.
  • a hydrophobically modified polar polymer which has a hydrophilic backbone (hydrophilic backbone made of one monomer only, e.g., acrylate) wherein there is a critical molar ratio of hydrophilic groups (e.g., the backbone) to hydrophobic “anchors" attached (“
  • a third aspect of the present invention provides a stick pretreatment composition
  • a stick pretreatment composition comprising from 30% to 80% by weight of nonionic surfactant, from 1 to 20% by weight of anionic soap and from 0. 1 to 10% by weight of a polymer having:
  • Enzymes and an enzyme stabilising system are optionally incorporated into the composition for improved cleaning.
  • compositions of the invention provide improved stain removal by the pretreater composition prior to the laundry wash. When used as an in wash additive, they also provide enhanced fluorescer effectiveness and stain removal.
  • the present invention relates to compositions which may be used as either pretreaters in liquid, gel or spray form or in-wash laundry additives. It is understood that the terms “in-wash” or “in-wash laundry booster” are interchangeable with the terms “laundry additive” or. "in-wash laundry additive”.
  • the present invention also relates to compositions which may be used a pretreaters in stick form.
  • compositions are based on nonionic surfactants and are preferably substantially free of synthetic (non-soap) anionic surfactants. They also contain specific polymers which have a critical molar ratio of a number of hydrophilic "backbone” groups (single monomer hydrophilic backbone) to a number of hydrophobic "anchor” or tail group.
  • compositions have better stain removal efficacy compared to compositions which do not contain the polymers.
  • the polymer of the invention is one which, as noted above, has previously been used in structured (i.e., lamellar) compositions such as those described in U.S. Patent No. 5,147,576 to Montague et al., hereby incorporated by reference into the subject application.
  • the polymer comprises a "backbone” component which is a monomer (single monomer) as discussed below and a “tail” portion which is a second monomer which is hydrophobic in nature (e.g., lauryl methacrylate or styrene).
  • the hydrophilic backbone generally is a linear, branched or highly cross-linked molecular composition containing one type of relatively hydrophobic monomer unit wherein the monomer is preferably sufficiently soluble to form at least a 1% by weight solution when dissolved in water.
  • the only limitation to the structure of the hydrophilic backbone is that a polymer corresponding to the hydrophilic backbone made from the backbone monomeric constituents is relatively water soluble (solubility in water at ambient temperature and at pH of 3.0 to 12.5 is preferably more than 1 g/l).
  • the hydrophilic backbone is also preferably predominantly linear, e.g., the main chain of backbone constitutes at least 50% by weight, preferably more than 75%, most preferably more than 90% by weight.
  • the hydrophilic backbone is composed of one monomer unit selected from a variety of units available for polymer preparation and linked by any chemical links including:
  • the "tail” group comprises a monomer unit comprising hydrophobic side chains which are incorporated in the “tail” monomer.
  • the polymer is made by copolymerizing hydrophobic monomers (tail group comprising hydrophobic groups) and the hydrophilic monomer making up the backbone.
  • the hydrophobic side chains preferably include those which when isolated from their linkage are relatively water insoluble, i.e., preferably less than 1 g/l, more preferred less than 0.5 g/l, most preferred less than 0. g/l of the hydrophobic monomers, will dissolve in water at ambient temperature at pH of 3.0 to 12.5.
  • the hydrophobic moieties are selected from siloxanes, saturated and unsaturated alkyl chains, e.g., having from 5 to 24 carbons, preferably 6 to 18, most preferred 8 to 16 carbons, and are optionally bonded to hydrophilic backbone via an alkoxylene or polyalkoxylene linkage, for example a polyethoxy, polypropoxy, or butyloxy (or mixtures of the same) linkage having from 1 to 50 alkoxylene groups.
  • the hydrophobic side chain can be composed of relatively hydrophobic alkoxy groups, for example, butylene oxide and/or propylene oxide, in the absence of alkyl or alkenyl groups.
  • Monomer units which make up the hydrophilic backbone include:
  • Monomeric units comprising both the hydrophilic backbone and hydrophobic side chain may be substituted with groups such as amino, amine, amide, sulphonate, sulphate, phosphonate, phosphate, hydroxy, carboxyl and oxide groups.
  • the hydrophilic backbone is composed of one unit.
  • the backbone may also contain small amounts of relatively hydrophilic units such as those derived from polymers having a solubility of less than 1 g/l in water provided the overall solubility of the polymer meets the requirements discussed above. Examples include polyvinyl acetate or polymethyl methacrylate.
  • the group such as, group (defined by z) can be substituted with benzene, for example styrene.
  • the present invention is direct to the observation that, when polymers such as those described above (known as deflocculating or decoupling polymers in the "structured liquid” art) are used in pretreater or laundry additive booster formulations they provide enhanced stain removal and, when used in the wash with a detergent containing fluorescer, they enhance the fluorescer whitening.
  • polymers such as those described above (known as deflocculating or decoupling polymers in the "structured liquid” art) are used in pretreater or laundry additive booster formulations they provide enhanced stain removal and, when used in the wash with a detergent containing fluorescer, they enhance the fluorescer whitening.
  • the polymer should be used in an amount comprising 0.01 to 10% by wt., preferably 0.1% to 5% by wt. of the composition.
  • nonionic surfactants useful in the present invention are those compounds produced by the condensation of alkylene oxide groups with an organic hydrophobic material which may be aliphatic or alkyl or aromatic in nature.
  • the link 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.
  • Illustrative, but not limiting examples, of various suitable non-ionic surfactant types are:
  • Examples of commercially available materials from Henkel Techandit GmbH Aktien of Dusseldorf, Germany include APG ® 300, 325 and 350 with R 4 being C 9 -C 11 , n is 0 and p is 1.3, 1.6 and 1.8-2.2 respectively; APG ® 500 and 550 with R 4 is C 12 -C 13 , n is 0 and p is 1.3 and 1.8-2.2, respectively; and APG ® 600 with R 4 being C 12 -C 14 , n is 0 and p is 1.3. Particularly preferred is APG ® 600.
  • the nonionic surfactant which are most preferred are the polyoxyalkylene condensates of paragraphs "(a)" and "(b)” and the alkyl glycosides. Most preferred are the polyoxyalkylene condensates.
  • the nonionic is used in an amount of about 0.1 to about 20 wt. % in liquid, paste or gel products and from about 30 to about 80 wt.%, preferably up to 60, more preferably up to 40wt.% in stick products..
  • polycarboxylates e.g. copolymers of acrylate/maleate commercially available as Sokolan ® copolymers supplied by BASF
  • polyoxyalkylene copolymers e.g. Pluronic Series supplied by BASF
  • carboxymethylcelluloses e.g. CMC Series supplied by Union Carbide
  • methylcellulose e.g. Methocel from Dow Chemical
  • ethoxylated polyamines e.g. ethoxylated tetra ethylene pentamine from Shell Chemical Co.
  • polycarboxylate polymers Especially preferred are the polycarboxylate polymers.
  • the polymers should be incorporated in the formulations of the invention in an amount of up to about 5 wt. %, preferably 0.1 wt. % to 3 wt. %, most preferably 0.5 wt. % to 1 wt. %.
  • the pretreater formulations of the invention are preferably substantially free of synthetic (non-soap) anionic surfactants. It is possible, however, to add less from about 5 wt. %, preferably less than 3 wt. % of an anionic soap to liquid, paste or gel compositions according to the invention, particularly for some in-wash formulations intended to boost whitening of fabrics.
  • Compositions according to the present invention which are in stick form contain from about 1wt.% to about 20wt.% of anionic soap.
  • soap is used herein in its popular sense, i.e., the alkali metal or alkanol ammonium salts of aliphatic alkane- or alkene monocarboxylic acids.
  • Sodium, potassium, mono-, dipand tri-ethanol ammonium cations, or combinations thereof, are suitable for purposes of this invention.
  • sodium soaps are used in the compositions of this invention, but from about 1% to about 25% of the soap may be potassium soaps.
  • the soaps useful herein are the well known alkali metal salts of natural or synthetic aliphatic (alkanoic or alkanoic) acids having about 8 to 22 carbons, preferably about 12 to about 18 carbon atoms.
  • alkali metal carboxylates of acrylic hydrocarbons having about 12 to about 22 carbon atoms may be described as alkali metal carboxylates of acrylic hydrocarbons having about 12 to about 22 carbon atoms. They also include soaps derived from natural carboxylic acids such as "coconut” fatty acids (derived from coconut oil) which contain an average of about 12 carbon atoms, "tallow” fatty acids (derived from tallow-class fats) which contain an average of about 18 carbon atoms, palmitic acid, myristic acid, stearic acid and lauric acid. The soaps preferably contain saturated or partially saturated fatty acids. Excessive unsaturation should be avoided.
  • Typical stick form stain remover compositions according to the present invention will comprise about 1-20 wt. %, preferably 5-15 wt. % of normally distributed stearic soap (nominally >95% C 18 H 36 O 2 ) as the gelling agent.
  • the current invention preferably uses blends of saturated soaps (carbon chain lengths of C 8 -C 18 ) as the coagel structurant which solidifies the stain treatment sticks.
  • the coagel structuring is used in the margarine industry to solidify oil and water mixtures.
  • a coagel solid relies on the structuring of alternating water and oil bi-layer lamellar sheets to form a macroscopically solid phase.
  • blend of saturated soaps modifies the surfactant and oil interface in order to form the bi-layer lamellar sheets necessary for the coagel structuring.
  • blends of soaps neutralized (in-situ) from the following table: As % of Total Fatty Acid in Formulation Caprylic C 8 H 16 O 2 Capric C 10 H 20 O 2 Lauric C 12 H 24 O Myristic C 14 H 28 O 2 Palmitic C 16 H 32 O 2 Stearic C 18 H 36 O 2 Unsaturated Preferred Range 0-6.0 0-5.0 5.0-40.0 0-18.0 10.0-60.0 5.0-60.0 0-5.0 Most Preferred Range 3.5-5.5 3.0-4.8 24.5-37.5 10.8-15.2 17.5-29.5 15.2-26.0 0-2.8 Example 1 0 0 0 0 0-5 95-100 0-2.0 1 as described in U.S. Patent No. 5,147,576.
  • the novel benefits of the current invention which uses a blend of saturated soap
  • Formulations containing the preferred blend of saturated soaps may or may not also contain the hydrophobically modified polar polymer of the invention.
  • Synthetic anionic surfactants are preferably substantially or completely excluded from compositions according to the present invention. If present at all, then they are only included in minor amounts such as less than 10%, preferably less than 5%, more preferably less than 2%, still more preferably less than 1%, especially less than 0.5%, e.g. less than 0.1% by weight of the total composition. If present, such anionic surfactants may be chosen from any of those known in the art of formulating detergent compositions, such as the usual linear alkyl benzene sulphonates, primary alkyl sulphates, alkyl ether sulphates etc. Though, most preferred of all is total exclusion of synthetic anionic surfactants.
  • Enzymes may optionally be included in the pretreater or in wash formulations to enhance the removal of soils from fabrics. If present, the enzymes are in an amount of from about 0 to 10 weight %, preferably 1 to about 5 wt. %.
  • Such enzymes include proteases (e.g. Alcalase ® , Savinase ® and Esperase ® from Novo Industries A/S), amylases (e.g. Termamyl ® from Novo Industries A/S), lipolases (e.g. Lipolase ® from Novo Industries A/S) and cellulases, (e.g. Celluzyme ® from Novo Industries A/S).
  • Stabilizers or stabilizer systems may be used in conjunction with enzymes and generally comprise from about 1 to 15% by weight of the composition.
  • the enzyme stabilization system may comprise calcium ion; boric acid, propylene glycol and/or short chain carboxylic acids.
  • the composition preferably contains from about 0.01 to about 50, preferably from about 0.1 to about 30, more preferably from about I to about 20 millimoles of calcium ion per litre.
  • the level of calcium ion should be selected so that there is always some minimum level available for the enzyme after allowing for complexation with builders, etc., in the composition.
  • Any water-soluble calcium salt can be used as the source of calcium ion, including calcium chloride, calcium formate, calcium acetate and calcium propionate.
  • a small amount of calcium ion generally from about 0.05 to about 2.5 millimoles per litre, is often also present in the composition due to calcium in the enzyme slurry and formula water.
  • Another enzyme stabilizer which may be used is propionic acid or a propionic acid salt capable of forming propionic acid. When used, this stabilizer may be used in an amount from about 0.1% to about 15% by weight of the composition.
  • polyols containing only carbon, hydrogen and oxygen atoms are preferred. They preferably contain from 2 to 6 carbon atoms and from 2 to 6 hydroxy groups. Examples include propylene glycol (especially 1,2 propanediol which is preferred), ethylene glycol, glycerol, sorbitol, mannitol and glucose.
  • the polyol generally represents from about 0.5% to about 15%, preferably from about 1.0% to about 8% by weight of the composition.
  • the composition herein may also optionally contain from about 0.25% to about 5%, most preferably from about 0.5% to about 3% by weight of boric acid.
  • the boric acid may be, but is preferably not, formed by a compound capable of forming boric acid in the composition. Boric acid is preferred, although other compounds such as boric oxide, borax and other alkali metal borates (e.g. sodium ortho-, meta- and pyroborate and sodium pentaborate) are suitable. Substituted boric acids (e.g., phenylboronic acid, butane boronic acid and a p-bromo phenylboronic acid) can also be used in place of boric acid.
  • One especially preferred stabilization system is a polyol in combination with boric acid.
  • the weight ratio of polyol to boric acid added is at least 1, more preferably at least about 1.3.
  • compositions of the invention may be prepared in any form known in the art such as liquid, (including in spray form), paste or gel. Those compositions should be prepared by conventional formulation methods such as those described in U.S. 5,186,856, particularly directed to an aqueous form, herein incorporated by reference.
  • aqueous liquid, paste or gel formulations are prepared by mixing the nonionic and selected polymers together and heating the mixture to a temperature of up to 160°F. The mixture is then cooled and the enzymes and enzyme stabilising system may be added. Optional ingredients, such as preservatives, dyes and perfumes are added to the cooled mixtures. The compositions are then packaged and stored.
  • formulations of the invention which are in stick forms are prepared as follows, but may be prepared in any form known in the art for stick forms.
  • the fatty acid(s) used are typically neutralized to soap in-situ.
  • the nonionic surfactant, the blend of fatty acid(s) and the polyols such as sorbital, glycerol, propylene glycol are heated to about 70°C to form a homogeneous melt mixture.
  • Water and neutralizing base typically caustic
  • the polymer is then added and mixed until the mixture is homogeneous.
  • the homogenous mixture is than cooled to just above the mixtures dropping point. Any heat labile additional ingredients (i.e., enzymes, fragrance, preservatives) are then added.
  • the composition is then packaged, cooled and stored.
  • the initial melt mixture can be added to a premixed mixture of water, caustic and polymer to perform the in-situ neutralization.
  • Thickeners may be incorporated into the formulations of the invention-particularly to import viscosity to liquid or to produce gel or paste consistency.
  • Such thickeners include, but are not limited to natural thickeners such as xanthan gums and other conventional polymeric thickeners as known in the art.
  • the thickeners may comprise up to 5% of the formulation. Preferably, 0.1 wt. % to 3 wt. %, most preferably 0.3 wt. % to 1 wt. %.
  • an antifoam agent may be incorporated into formulations according to the invention in an amount of up to 2 wt. %, preferably 0.05 to 1 wt. %, to reduce the level of air entrapped in the solidified sticks.
  • Suitable antifoams include mono- and distearyl acid phosphate, silicone oil, silicon emulsion, silicon compounds and mineral oil.
  • silicon emulsions are used.
  • One or more optional additives may be included in the formulations including perfumes, dyes, pigment, opacifiers, germicides, optical brighteners, anticorrosional agents and preservatives.
  • Each additive incorporated in the composition should be present in an amount of up to about 0.5% by wt.
  • a aqueous pretreater formulation according to the invention was prepared as Sample A below.
  • an aqueous pretreater formulation without the selected hydrophobically modified polymer was prepared as Sample B.
  • Table 1 Samples Ingredient A B boric acid 1.4 1.4 propylene glycol 3.0 3.0 alcohol ethoxylate 2 4.7 4.7 Narlex ® DC-1 3 0.5 0 enzyme 0.7 0.7 xanthan gum 0.3 0.3 preservative .003 .003 deionized water to 100% 2 a nonionic surfactant having 12-15 carbon atoms in the hydrophobic group and 9 EOs and supplied as Neodol 25-9 by Shell Chemical Co. 3 a copolymer of acrylic acid and lauryl methacrylic acid supplied by National Starch and Chemical Co.
  • the liquid composition of the invention was made by charging a vessel with water and heating to 160°F, adding the boric acid and stirring the liquid until a clear solution was obtained. The surfactant was then added, and the heater turned off. The polymer of Sample A was then added when the solution temperature was between 120-150°F. The enzymes were added when the solution temperature was below 120°F, then preservative was added. The pH of the formulation was then adjusted to 7.0 ( ⁇ 0.5).
  • Cloths 1 and 2 were obtained from Textile Innovators (Windsor, North Carolina), and the polyester cloth 3 was obtained from Test Fabrics (Middlesex, New Jersey). Prior to staining the cloths were prewashed five times with a fluorescer free detergent at 130°F (and dried) to remove spinning oils and increase the absorbency of the cloth. Swatches were cut to 4-3/4" x 8-3/4", and a 2" diameter circle inscribed in the middle.
  • Stain removal was measured by reflectometry and colour change using a Pacific Scientific Colorgard System model 5 colorimeter.
  • Sample C did not contain the hydrophobically modified polymer while Sample D contained Narlex ® DC-1, a copolymer of acrylic acid and lauryl methacrylic acid supplied by National Starch and Chemical Co.
  • a gel form of the inventive formulation incorporating a styrene containing acrylic acid copolymer was prepared as described in Example 1 and presented in Table 6 below: Table 6 Ingredient % Active boric acid 1.4 propylene glycol 3.0 alcohol ethoxylate 14 enzyme 1.5 xanthan gum 0.7 ALCO EXP 2499 6 0.5 Deionized water to 100% 6 a styrene containing acrylic acid copolymer supplied by Alco under the Series H100.
  • aqueous composition incorporating a styrene containing acrylic acid copolymer was prepared as described in Example 1 having the formula described in Table 7: Table 7 Ingredient % Active boric acid 1.4 propylene glycol 3.0 alcohol ethoxylate 7 4.7 enzyme 0.7 xanthan gum 0.3 ALCO EXP 2499 8 0.5 Deionized water to 100% 7 a nonionic surfactant supplied by Shell as Neodol 25-9. 8 a styrene containing acrylic acid copolymer supplied by Alco under the Series H100.
  • Example 1 The following laundry additive compositions were prepared as described in Example 1: Table 8 E F boric acid 1.4 1.4 propylene glycol 4.0 4.0 alcohol ethoxylate 9 2.0 2.0 enzyme 0.7 0.7 xanthan gum 0.3 0.3 Narlex DC-1 10 1.0 1.0 monoethanolamine - 0.4 coconut fatty acid - 2.0 deionized water to 100% 9 a nonionic surfactant supplied by Shell as Neodol 25-9. 10 a styrene containing acrylic acid copolymer supplied by Alco under the Series H100.
  • Samples of composition E were prepared as described in Example 1.
  • Samples of composition F were prepared by adding the monoethanolamine and coconut fatty acid to the alcohol ethoxylate (as described in Example 1), adding the monoethanolamine first followed by the fatty acid.
  • the fluorescent whitening of the inventive compositions used as laundry additives with a commercial detergent containing fluorescer whitening agents versus the detergent alone was evaluated on soiled cloths.
  • Soil cloths were obtained from EMPA, St. Gallen, Switzerland.
  • EMPA 112 is composed of cocoa, milk and sugar on cotton.
  • EMPA 116 is composed of blood, milk, and indian ink on cotton.
  • EMPA 117 has the same soil as EMPA 116 but it is on polyester/cotton.
  • VCD is composed of vacuum cleaner dust on polyester/cotton.
  • AS-10 is composed of milk powder, ground nut oil, carboxymethylcarubin and small levels of dyes on cotton.
  • inventive formulations increase the fluorescent whitening of the detergent significantly.
  • the boost in fluorescent whitening due to the inventive formulations is unexpected because these do not contain fluorescer.
  • a stick formulation according to the invention was prepared as Sample G below.
  • an aqueous pretreater formulation without the selected hydrophobically modified polymer was prepared as Sample H.
  • Table 10 Samples Ingredient G H propylene glycol 11.0 11.0 alcohol ethoxylate 11 57.9 57.9 Narlex ® DC- 1 12 0.3 0 stearic acid 13 4.4 4.4 coconut fatty acid 14 7.9 7.9 sodium hydroxide 2.1 2.1 deionized water to 100% 11 a nonionic surfactant having 12-15 carbon atoms in the hydrophobic group and 9 EOs and supplied as Neodol 25-9 by Shell Chemical Co. 12 a copolymer of acrylic acid and lauryl methacrylic acid supplied by National Starch and Chemical Co. 13 stearic acid containing a mixture of C 12-18 saturated fatty acids supplied as Emersol 132 by Henkle. 14 partially hydrogenated coconut fatty acid C 8 -C 22 saturated fatty acids supplied by Henkle.
  • the nonionic surfactant, the anionic surfactant, the polymer and the propylene glycol were added together in a mixture with low to medium agitation.
  • the batch was heated up 40°C.
  • the fatty acid was then added and heating was continued until the batch reached 55°C. Once the fatty acid was completely melted, the water was added with heating to maintain the batch at 50-55°C. Once the batch was homogeneous, the sodium hydroxide was added.
  • the batch was then mixed for 45 minutes to ensure full neutralization of the fatty acid.
  • the batch was then cooled to 50°C.
  • the batch was then placed in a package and allowed to air cool with chilling.
  • test cloths used to evaluate the compositions were:
  • Cloths 1 and 2 were obtained from Textile Innovators (Windsor, North Carolina), and the polyester cloth 3 was obtained from Test Fabrics (Middlesex, New Jersey). Prior to staining, the cloths were prewashed 5 times in Dye Free Liquid "all" at 130°F (and dried) to remove spinning oils and increase the absorbency of the cloth. Swatches were cut to 4-3/4" x 8-3/4", and a 2" diameter circle inscribed in the middle.
  • the stain cloth were pretreated (by rubbing) with the stick.
  • Application of the stick is done using minimal force, allowing the natural gliding tendency of the stick to drive the movement.
  • the stained and treated clothes were allowed to sit for 5 minutes before washing.
  • the washes were done using the recommended dosages of a laundry liquid detergent in warm, 95°F water and rinsed in cold water.
  • the cloths were then placed in a static dryer until dry. Four replicates of each stain with each cloth were performed.
  • Stain removal was measured by reflectometry and color change using a Pacific Scientific Colorgard System model 5 colorimeter.
  • Stick forms of the inventive formulation incorporating a styrene containing acrylic acid copolymer were prepared as described in Example 8 and presented in Table 13 below: Table 13 Ingredient % Active propylene glycol 11.0 alcohol ethoxylate 15 57.9 ALCO EXP 2499 16 0.5 stearic acid 17 4.4 coconut fatty acid 18 7.9 sodium hydroxide 2.1 deionized water to 100% 15 a nonionic surfactant supplied by Shell as Neodol 25-9. 16 a styrene containing acrylic acid copolymer supplied by Alco under the Series H100. 17 stearic acid containing a mixture of C 2-18 saturated fatty acids supplied as Emersol 132 by Henkle. 18 partially hydrogenated coconut fatty acid C 8 -C 22 saturated fatty acids supplied by Henkle.

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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)
  • Dispersion Chemistry (AREA)
  • Detergent Compositions (AREA)
EP97200112A 1996-01-25 1997-01-16 Compositions de prétraitement en stick Expired - Lifetime EP0786514B1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US08/591,790 US5820637A (en) 1996-01-25 1996-01-25 Method of pretreating stained fabrics with pretreater or laundry additive compositions containing hydrophobically modified polar polymers
US591790 1996-01-25
US591750 1996-01-25
US08/591,750 US5747442A (en) 1996-01-25 1996-01-25 Stick pretreater compositions containing hydrophobically modified polar polymers

Publications (3)

Publication Number Publication Date
EP0786514A2 true EP0786514A2 (fr) 1997-07-30
EP0786514A3 EP0786514A3 (fr) 1999-08-18
EP0786514B1 EP0786514B1 (fr) 2004-07-14

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Family Applications (1)

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EP97200112A Expired - Lifetime EP0786514B1 (fr) 1996-01-25 1997-01-16 Compositions de prétraitement en stick

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EP (1) EP0786514B1 (fr)
CA (1) CA2195510C (fr)
DE (1) DE69729815T2 (fr)
ES (1) ES2221012T3 (fr)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19750385A1 (de) * 1997-11-13 1999-05-20 Uhu Gmbh Reinigungszusammensetzung auf der Basis einer Waschpaste
EP0995791A1 (fr) * 1998-10-22 2000-04-26 Rohm And Haas Company Compositions polymériques et méthode favorisant l'élimination des salissures du linge au moyen desdites compositions polymériques
WO2001030955A1 (fr) * 1999-10-22 2001-05-03 The Procter & Gamble Company Compositions destinees au traitement des chaussures et procedes et articles dans lesquels ces compositions sont utilisees
US6447803B1 (en) 1998-08-14 2002-09-10 National Starch And Chemical Investment Holding Corporation Thickener-rheology modifier system for personal care compositions
US6861396B2 (en) 2000-10-20 2005-03-01 The Procter & Gamble Company Compositions for pre-treating shoes and methods and articles employing same
KR100485941B1 (ko) * 2002-08-06 2005-05-03 (주) 청도정밀화학 폴리 카본산계 고성능 콘크리트 분산제의 새로운 조성물
WO2006130442A1 (fr) * 2005-05-31 2006-12-07 The Procter & Gamble Company Composition detergente
WO2006130575A3 (fr) * 2005-05-31 2007-06-21 Procter & Gamble Compositions detergentes renfermant un polymere et leur utilisation
US8143209B2 (en) 2006-05-31 2012-03-27 The Procter & Gamble Company Cleaning compositions with amphiphilic graft polymers based on polyalkylene oxides and vinyl esters
US8859484B2 (en) 2012-03-09 2014-10-14 The Procter & Gamble Company Detergent compositions comprising graft polymers having broad polarity distributions
DE102013106363B3 (de) * 2013-06-18 2014-12-11 Geting Solutions Gmbh Mittel zur Entfernung von Flecken und Ablagerungen

Citations (3)

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US5147576A (en) 1988-06-13 1992-09-15 Lever Brothers Company, Division Of Conopco, Inc. Liquid detergent composition in the form of lamellar droplets containing a deflocculating polymer
US5186856A (en) 1992-06-02 1993-02-16 Basf Corp. Aqueous prewash stain remover compositions with efficacy on tenacious oily stains
US5308530A (en) 1990-11-21 1994-05-03 Lever Brothers Company, Division Of Conopco, Inc. Detergent compositions containing polycarboxylates and calcium-sensitive enzymes

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GB8626080D0 (en) * 1986-10-31 1986-12-03 Unilever Plc Detergent composition
US4797223A (en) * 1988-01-11 1989-01-10 Rohm And Haas Company Water soluble polymers for detergent compositions
ES2060811T3 (es) * 1988-09-01 1994-12-01 Ciba Geigy Ag Humectante y detergente acuoso resistente al agua dura, su preparacion y empleo en el pretratamiento textil.
US4946627A (en) * 1989-07-19 1990-08-07 National Starch And Chemical Investment Holding Corporation Hydrophobically modified polycarboxylate polymers utilized as detergent builders
CA2055432A1 (fr) * 1990-02-28 1991-08-29 Dale M. Pickelman Compositions nettoyantes a base de polymeres ionisables, et methodes pour l'enlevement des taches
US5380447A (en) * 1993-07-12 1995-01-10 Rohm And Haas Company Process and fabric finishing compositions for preventing the deposition of dye in fabric finishing processes
BR9507646A (pt) * 1994-05-13 1997-09-09 Unilever Nv Composiçao detergente liquida
ES2186719T3 (es) * 1994-05-17 2003-05-16 Johnson & Son Inc S C Pre-desmanchantes de lavanderia con espesante polimero asociativo.

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5147576A (en) 1988-06-13 1992-09-15 Lever Brothers Company, Division Of Conopco, Inc. Liquid detergent composition in the form of lamellar droplets containing a deflocculating polymer
US5308530A (en) 1990-11-21 1994-05-03 Lever Brothers Company, Division Of Conopco, Inc. Detergent compositions containing polycarboxylates and calcium-sensitive enzymes
US5186856A (en) 1992-06-02 1993-02-16 Basf Corp. Aqueous prewash stain remover compositions with efficacy on tenacious oily stains

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19750385A1 (de) * 1997-11-13 1999-05-20 Uhu Gmbh Reinigungszusammensetzung auf der Basis einer Waschpaste
US7105153B2 (en) 1998-08-14 2006-09-12 National Starch And Chemical Investment Holding Corporation Thickener-rheology modifier system for personal care compositions
US6447803B1 (en) 1998-08-14 2002-09-10 National Starch And Chemical Investment Holding Corporation Thickener-rheology modifier system for personal care compositions
EP0995791A1 (fr) * 1998-10-22 2000-04-26 Rohm And Haas Company Compositions polymériques et méthode favorisant l'élimination des salissures du linge au moyen desdites compositions polymériques
US6451756B2 (en) 1998-10-22 2002-09-17 Jan Edward Shulman Method of promoting soil release from fabrics
WO2001030955A1 (fr) * 1999-10-22 2001-05-03 The Procter & Gamble Company Compositions destinees au traitement des chaussures et procedes et articles dans lesquels ces compositions sont utilisees
US6750188B2 (en) 1999-10-22 2004-06-15 The Procter & Gamble Company Compositions for treating shoes and methods and articles employing same
US6866888B2 (en) 1999-10-22 2005-03-15 The Procter & Gamble Company Compositions for treating shoes and methods and articles employing same
US6861396B2 (en) 2000-10-20 2005-03-01 The Procter & Gamble Company Compositions for pre-treating shoes and methods and articles employing same
KR100485941B1 (ko) * 2002-08-06 2005-05-03 (주) 청도정밀화학 폴리 카본산계 고성능 콘크리트 분산제의 새로운 조성물
WO2006130442A1 (fr) * 2005-05-31 2006-12-07 The Procter & Gamble Company Composition detergente
WO2006130575A3 (fr) * 2005-05-31 2007-06-21 Procter & Gamble Compositions detergentes renfermant un polymere et leur utilisation
US8143209B2 (en) 2006-05-31 2012-03-27 The Procter & Gamble Company Cleaning compositions with amphiphilic graft polymers based on polyalkylene oxides and vinyl esters
US8859484B2 (en) 2012-03-09 2014-10-14 The Procter & Gamble Company Detergent compositions comprising graft polymers having broad polarity distributions
DE102013106363B3 (de) * 2013-06-18 2014-12-11 Geting Solutions Gmbh Mittel zur Entfernung von Flecken und Ablagerungen
US10047322B2 (en) 2013-06-18 2018-08-14 Buck Service Gmbh Agent for removing stains and deposits comprising an alkylene styrene copolymer

Also Published As

Publication number Publication date
CA2195510A1 (fr) 1997-07-26
CA2195510C (fr) 2006-08-29
EP0786514A3 (fr) 1999-08-18
DE69729815T2 (de) 2004-12-02
DE69729815D1 (de) 2004-08-19
EP0786514B1 (fr) 2004-07-14
ES2221012T3 (es) 2004-12-16

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