EP1085079A1 - Treatment compositions for fabrics - Google Patents

Treatment compositions for fabrics Download PDF

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Publication number
EP1085079A1
EP1085079A1 EP99870190A EP99870190A EP1085079A1 EP 1085079 A1 EP1085079 A1 EP 1085079A1 EP 99870190 A EP99870190 A EP 99870190A EP 99870190 A EP99870190 A EP 99870190A EP 1085079 A1 EP1085079 A1 EP 1085079A1
Authority
EP
European Patent Office
Prior art keywords
composition
fabrics
acid
compounds
mixtures
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.)
Withdrawn
Application number
EP99870190A
Other languages
German (de)
English (en)
French (fr)
Inventor
Jean-Luc Philippe Bettiol
Bernard Charlier
Nancy Van Damme
Bruno Albert Jean Hubesch
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Procter and Gamble Co
Original Assignee
Procter and Gamble Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to EP99870190A priority Critical patent/EP1085079A1/en
Priority to CZ2002858A priority patent/CZ2002858A3/cs
Priority to CN00815936A priority patent/CN1391603A/zh
Priority to ARP000104930A priority patent/AR031225A1/es
Priority to CNA2009100033108A priority patent/CN101475887A/zh
Priority to EG20001208A priority patent/EG22865A/xx
Priority to HU0202675A priority patent/HUP0202675A3/hu
Priority to TR2002/00709T priority patent/TR200200709T2/xx
Priority to AU75923/00A priority patent/AU7592300A/en
Priority to EP00965159A priority patent/EP1214391A1/en
Priority to PCT/US2000/025685 priority patent/WO2001021747A1/en
Priority to KR1020027003635A priority patent/KR20020033183A/ko
Priority to BR0014100-3A priority patent/BR0014100A/pt
Priority to JP2001525309A priority patent/JP2003510410A/ja
Publication of EP1085079A1 publication Critical patent/EP1085079A1/en
Priority to MA26560A priority patent/MA25494A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/373—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
    • 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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/001—Softening 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
    • C11D1/38—Cationic compounds
    • C11D1/62—Quaternary ammonium 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
    • C11D1/667—Neutral esters, e.g. sorbitan esters
    • 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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0026—Low foaming or foam regulating 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
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/30—Amines; Substituted amines ; Quaternized amines
    • 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
    • C11D3/48—Medical, disinfecting agents, disinfecting, antibacterial, germicidal or antimicrobial 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
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/12—Soft surfaces, e.g. textile

Definitions

  • the present invention relates to treatment composition for fabrics, in particular the hand rinsing of fabrics as well as the rinsing of fabrics in top loaded non automatic washing machines which have been laundered with a detergent composition, especially a high suds composition.
  • the trends for washing is by using a washing machine whereby the laundry detergent and the softening composition are dispensed from the washing machine via two separate compartments, thereby ensuring the automated release of the detergent at the beginning of the washing process and the release of the softening composition in the rinse process, usually the last rinse process.
  • the washing in non automatic top loaded washing machines is operated by placing the fabric with detergent in the cubicle containing water and agitation, removing the fabrics from the cubicle containing the detergent liquor, placing the fabric in the spinning cubicle for spinning step, empty the detergent liquor from the other cubicle and replace it by fresh water and then put back the spinned fabrics for rinsing, the rinsing step of spinning, rinsing, and spinning being often reiterated several time to obtain acceptable rinsed fabrics.
  • hand-washing treatment of fabric in general, is not constrained to any particular geographical region. Although certain areas having limited access to modern appliances have a higher prevalence of laundering treatment by hand, the need to hand-wash, including rinsing, at least certain items of clothing appears universal. Hence, even with modern washing machine having the rinsing step, there are still many garments, especially those manufactured from "fine fabric” material (i.e. silk) or those which comprise “soft woven” material (i.e. woolen knitted sweaters) are commonly “laundered by hand", for example, "delicate” or "personal” items typically require hand-washing. Hand laundering treatment typically limits the temperature at which the fabric is washed, usually within a range tolerable to the person washing the garment.
  • a unique aspect of washing-by-hand, and/or washing in non automatic top loaded washing machine is the high detergent to water ratio and/or the high soil to water ratio (high soil loading).
  • fabric treated with such detergent usually become saturated with residual detergent and/or dirt and particulate matter upon transfer to the rinse step.
  • this problem of saturation is even more acute with manual washing and/or washing in non automatic top loaded washing machine, as it is due to the poor efficiency of the spinning and/or wringing in between the wash and the rinse steps.
  • Conventional rinsing step involves the step of contacting the laundered fabric with water so as to remove the soiled laundry liquor but the suds as well.
  • the clarity of the rinse water is an important factor for the consumer. Indeed, it is often perceived by the consumers as a signal of a thoroughly completed rinse. In other words, the more turbid the rinse water is, the more rinses are performed by the consumer, i.e. until a clear rinse solution is obtained. In the end, more water than is necessary is used to complete the rinse, particularly when a significant amount of residual detergent and soil are carried over the wash steps.
  • a fabric rinse treatment composition that has a clarity value upon dilution of less than a 0.04 % by weight of a dimethyl bis(steroyl oxyethyl) ammonium chloride aqueous solution and a suds reduction value of at least about 50% fulfill such a need.
  • the invention composition gives a reduced re-soiling of the fabrics during the rinsing steps.
  • the re-soiling is believed to arise from the excess of soil which is carried over from the wash to the rinse steps and/or of the use of water contaminated with heavy metal ion.
  • this composition has also been found effective in the pre-treatment or soaking of fabric to improve the cleaning end result benefits of the wash process. Not to be bound by theory, it is believed that the mechanism behind the improved cleaning benefit lies in the composition weakening the link between the residual soil present on the fabric and the cellulose fabric fiber, thereby enabling an easier removal in the subsequent wash process.
  • This additional advantage of the invention composition is particularly beneficial when water contaminated with heavy metal ions is used. Indeed, water contaminated with heavy metal ions is often the cause of re-soiling on fabrics upon treatment. Accordingly, it is an advantage of the invention to provide a pre-treatment composition and/or soaking composition which reduces or even prevents the resoiling of the fabric.
  • a fabric treatment composition comprising a suds suppressing system, characterised in that the composition which has a clarity value upon a 0.2% dilution of less than a 0.04% by weight of a dimethyl bis(steroyl oxyethyl) ammonium chloride aqueous solution and a suds reduction value of at least about 50%.
  • a method for rinsing fabrics which comprises the steps of contacting the fabrics, previously contacted with an aqueous detergent liquor, with a composition of the invention.
  • a method for pre-treating the fabrics which comprises the steps of applying in neat form the composition to the fabrics, and subsequently rinse or wash and rinse it.
  • a method for soaking the fabrics which comprises the step of contacting the fabrics with a composition of the invention, in its diluted form, before the fabrics are rinsed or washed and rinsed.
  • composition has a has a clarity value upon a 0.2% dilution of less than a 0.04% by weight of a dimethyl bis(steroyl oxyethyl) ammonium chloride aqueous solution.
  • the clarity of the treatment composition is one essential feature of the invention. Clarity is defined according to the following test method:
  • a reference composition is made containing 0.04% by weight of a C11-C22 diakylester quaternary ammonium compound, in particular, the dimethyl bis(steroyl oxyethyl) ammonium chloride, in deionised water at 70°C.
  • a C11-C22 diakylester quaternary ammonium compound in particular, the dimethyl bis(steroyl oxyethyl) ammonium chloride
  • test composition is then prepared by dilution of the composition to obtain a 0.2% diluted composition, using deionised water at the temperature required to solubilize or disperse all the actives.
  • the two compositions are subsequently evaluated for their clarity properties using a KONTRON Instrument Uvikon 933 set up on the following parameters: Wavelength range (nm) 350-700 Scan Speed (nm/min) 500 Data Interval (nm) 1.0 Cycles (min) 1*00 Lamp change (nm) 340 Bandwith (nm) 2.0
  • Tested composition at 0.2% which have an intensity below or equal to that of the reference composition at 0.04% are suitable for the present invention provided they also meet the suds suppressing Test.
  • the suds reduction property of the hand treatment is another essential feature of the invention. Suds reduction is defined according to the following test method:
  • foam in the reference beaker remains at about 3cm.
  • Suitable compositions are those that have a suds reduction over the reference of about at least 50%, preferably of at least 80% and most preferably of at least 99%. 99% is where all the foam disappeared apart from the optional presence of a white film that may partially cover the surface of the solution.
  • the reduction of the suds is achieved by use of a suds suppressing system.
  • the suds suppressing system is preferably present at a level of from 0.01% to 99%, more preferably from 0.05% to 50%, most preferably from 0.1% to 5% by weight of the composition.
  • Such suds suppressing systems are even more desired components of the compositions of the invention when the detergent liquor is made of detergent which comprises a surfactant system that comprises high foaming surfactant, such as the conventional C 11 -C 18 alkyl benzene sulfonates ("LAS").
  • suds suppressors A wide variety of materials may be used as suds suppressors, and suds suppressors are well known to those skilled in the art. See, for example, Kirk Othmer Encyclopedia of Chemical Technology, Third Edition, Volume 7, pages 430-447 (John Wiley & Sons, Inc., 1979).
  • Suitable suds suppressing systems for use herein may comprise essentially any known antifoam compound, including, for example silicone antifoam compounds, alcohol antifoam compounds like 2-alkyl alcanol antifoam compounds, fatty acids, and paraffin antifoam compounds, and mixtures thereof.
  • antifoam compound any compound or mixtures of compounds which act such as to depress the foaming or sudsing produced by a solution of a detergent composition, particularly in the presence of agitation of that solution.
  • silicone antifoam compounds defined herein as any antifoam compound including a silicone component.
  • silicone antifoam compounds also typically contain a silica component.
  • Silicone suds suppressors are well known in the art and are, for example, disclosed in U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo et al and European Patent Application No. 89307851.9, published February 7, 1990, by Starch, M. S.
  • Other silicone suds suppressors are disclosed in U.S. Patent 3,455,839 which relates to compositions and processes for defoaming aqueous solutions by incorporating therein small amounts of polydimethylsiloxane fluids. Mixtures of silicone and silanated silica are described, for instance, in German Patent Application DOS 2,124,526. Silicone defoamers and suds controlling agents in granular detergent compositions are disclosed in U.S.
  • Patent 3,933,672 Bartolotta et al, and in U.S. Patent 4,652,392, Baginski et al, issued March 24, 1987.
  • suitable silicone antifoam compounds are the combinations of polyorganosiloxane with silica particles commercially available under the tradename DC 2-3565 or DC 2-3000 from Dow Corning.
  • Suitable antifoam compounds include the monocarboxylic fatty acids and soluble salts thereof. These materials are described in US Patent 2,954,347, issued September 27, 1960 to Wayne St. John.
  • the monocarboxylic fatty acids, and salts thereof, for use as suds suppressing system typically have hydrocarbyl chains of 10 to about 24 carbon atoms, preferably 12 to 18 carbon atoms like the tallow amphopolycarboxyglycinate commercially available under the tradename TAPAC.
  • Suitable salts include the alkali metal salts such as sodium, potassium, and lithium salts, and ammonium and alkanolammonium salts.
  • Suitable antifoam compounds include, for example, high molecular weight hydrocarbons such as paraffin, light petroleum odorless hydrocarbons, fatty esters (e.g. fatty acid triglycerides, glyceryl derivatives, polysorbates), fatty acid esters of monovalent alcohols, aliphatic C 18 -C 40 ketones (e.g.
  • N-alkylated amino triazines such as tri- to hexa-alkylmelamines or di- to tetra alkyldiamine chlortriazines formed as products of cyanuric chloride with two or three moles of a primary or secondary amine containing 1 to 24 carbon atoms, propylene oxide, bis stearic acid amide and monostearyl phosphates such as monostearyl alcohol phosphate ester and monostearyl di-alkali metal (e.g., K, Na, and Li) phosphates and phosphate esters, quaternary ammonium compounds, di-alkyl quaternary compounds, poly fuctionalised quaternary compounds, and nonionic polyhydroxyl derivatives.
  • N-alkylated amino triazines such as tri- to hexa-alkylmelamines or di- to tetra alkyldiamine chlortriazines formed as products of cyanuric chloride with two or three moles
  • the hydrocarbons such as paraffin and haloparaffin
  • the liquid hydrocarbons will be liquid at room temperature and atmospheric pressure, and will have a pour point in the range of about -40°C and about 5°C, and a minimum boiling point not less than 110°C (atmospheric pressure). It is also known to utilize waxy hydrocarbons, preferably having a melting point below about 100°C.
  • Hydrocarbon suds suppressors are described, for example, in U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo et al.
  • the hydrocarbons thus, include aliphatic, alicyclic, aromatic, and heterocyclic saturated or unsaturated hydrocarbons having from about 12 to about 70 carbon atoms.
  • the term "paraffin", as used in this suds suppressor discussion, is intended to include mixtures of true paraffins and cyclic hydrocarbons.
  • Copolymers of ethylene oxide and propylene oxide particularly the mixed ethoxylated/propoxylated fatty alcohols with an alkyl chain length of from 10 to 16 carbon atoms, a degree of ethoxylation of from 3 to 30 and a degree of propoxylation of from 1 to 10, are also suitable antifoam compounds for use herein.
  • suds suppressors useful herein comprise the secondary alcohols (e.g., 2-alkyl alkanols as described in DE 40 21 265) and mixtures of such alcohols with silicone oils, such as the silicones disclosed in U.S. 4,798,679, 4,075,118 and EP 150,872.
  • the secondary alcohols include the C 6 -C 16 alkyl alcohols having a C 1 -C 16 chain like the 2-Hexyldecanol commercially available under the tradename ISOFOL16, 2-Octyldodecanol commercially available under the tradename ISOFOL20, and 2-butyl octanol, which is available under the trademark ISOFOL 12 from Condea.
  • a preferred alcohol is 2-butyl octanol, which is available from Condea under the trademark ISOFOL 12.
  • Mixtures of secondary alcohols are available under the trademark ISALCHEM 123 from Enichem.
  • Mixed suds suppressors typically comprise mixtures of alcohol silicone at a weight ratio of 1:5 to 5:1.
  • Suitable antifoams described in the literature such as in Hand Book of food additives, ISBN 0-566-07592-X, p804, are selected from dimethicone, poloxamer, polypropyleneglycol, tallow derivatives, and mixtures thereof.
  • the composition is substantially free (i.e. less than 1.5% by weight of the composition) and preferably free of quaternary ammonium compounds having di-long chain such as ditallow dimethyl ammonium chloride (DTDMAC), C11-C22 diakylester quaternary ammonium compound, in particular, the dimethyl bis(steroyl oxyethyl) ammonium chloride or the 1,2-di(tallowyloxy-oxo)-3-N,N,N-trimethylammoniopropane chloride, so that the clarity rinse solution is not affected. Indeed, although they have effective suds suppressing properties, their water-insoluble properties renders the solution cloudy, and even turbid.
  • DTDMAC ditallow dimethyl ammonium chloride
  • C11-C22 diakylester quaternary ammonium compound in particular, the dimethyl bis(steroyl oxyethyl) ammonium chloride or the 1,2-di(tallowyloxy-oxo)-3-N,N
  • Preferred among the suds suppressing systems described above are the silicone antifoam, in particular the the combinations of polyorganosiloxane with silica particles.
  • compositions according to the invention have a pH as a 0.2% solution in distilled water at 20°C of less than 7, preferably from 3 to 6.5, most preferably from 4 to 6.5.
  • This acid pH range is desirable for the invention compositions as it enables the rejuvenation of the smoothness of the fabric as well as a stain removal performance, in particular of bleachable stains.
  • the pH of the compositions may be adjusted by the use of various pH acidification agents.
  • Preferred acidification agents include inorganic and organic acids including, for example, carboxylate acids, such as citric and succinic acids, polycarboxylate acids, such as polyacrylic acid, and also acetic acid, boric acid, malonic acid, adipic acid, fumaric acid, lactic acid, glycolic acid, tartaric acid, tartronic acid, maleic acid, their derivatives and any mixtures of the foregoing.
  • Citric acid is a useful pH acidification agent herein.
  • a highly preferred acidification acid is citric acid which has the advantage of providing a rejuvenation of the natural smoothness of the fabric.
  • a typical amount of acidifying agent is of from 0.1% to 50%, preferably from 0.5 to 10% by weight of the composition.
  • a pH buffering component is another preferred component for the compositions of the invention.
  • the pH buffering component ensures that the pH of the composition is buffered to a pH value ranging from 3.0 to 7, and preferably from 4 to 6 after the composition has been diluted into 1 to 10000 times, preferably 1 to 5000, most preferably 300 to 600 its weight of water.
  • Suitable pH buffering components for use herein are selected from the group consisting of alkali metal salts of carbonates, preferably sodium bicarbonate, polycarbonates, sesquicarbonates, silicates, polysilicates, borates, metaborates, phosphates, preferably sodium phosphate such as sodium hydrogenophosphate, polyphosphate like sodium tripolyphosphate, alluminates, and mixtures thereof, and preferably are selected from alkali metal salts of carbonates, phosphates, and mixtures thereof.
  • Optimum buffering system are characterised by good solubility, even in very hard water conditions (e.g. 30gpg).
  • One less preferred buffering system is sodium tripolyphosphate (STPP) at a high level, i.e.
  • the treatment compositions herein will contain an amount of pH buffering component of from 0.1% to 50% by weight, preferably from 0.2% to 20% by weight, and more preferably in an amount of from 0.4% to 10% by weight of the composition.
  • compositions of the present invention optionally comprise from about 0.005 to about 5%, more preferably from about 0.1% to about 1%,
  • Crystal Growth Inhibition Test is used to determine the suitability of a material for use as a crystal growth inhibitor.
  • the suitability of a material to serve as a crystal growth inhibitor according to the present invention can be determined by evaluating in vitro the growth rate of certain inorganic micro-crystals.
  • the procedure of Nancollas et al., described in "Calcium Phosphate Nucleation and Growth in Solution", Prog. Crystal Growth Charact., Vol 3, 77-102, (1980), incorporated herein by reference, is a method which is suitable for evaluating compounds for their crystal growth inhibition.
  • the graph below serves as an example of a plot indicating the time delay (t-lag) in crystal formation afforded by a hypothetical crystal growth inhibitor.
  • the observed t-lag provides a measure of the compound's efficiency with respect to delaying the growth of calcium phosphate crystal. The greater the t-lag, the more efficient the crystal growth inhibitor.
  • the hydroxyapatite slurry can be prepared by digesting Bio-Gel® HTP hydroxyapatite powder (100 g) in 1 L of distilled water the pH of which is adjusted to 2.5 by the addition of sufficient 6N HCI and subsequently heating the solution until all of the hydroxyapatite is dissolved (heating for several days may be necessary). The temperature of the solution is then maintained at about 22° C while the pH is adjusted to 12 by the addition of a solution of 50% aqueous KOH. Once again the solution is heated and the resulting slurry is allowed to settle for two days before the supernatant is removed. 1.5 L of distilled water is added, the solution stirred, then after settling again for 2 days the supernatant is removed. This rinsing procedure is repeated six more time after which the pH of the solution is adjusted to neutrality using 2N HCI. The resulting slurry can be stored at 37°C for eleven months.
  • Crystal growth inhibitors which are suitable for use in the present invention have a t-lag of at least 10 minutes, preferably at least 20 minutes, more preferably at least 50 minutes, at a concentration of 1 x 10 -6 M.
  • Crystal growth inhibitors are differentiated form chelating agents by the fact that crystal growth inhibitors have a low binding affinity of heavy metal ions, i.e., copper.
  • crystal growth inhibitors have an affinity for copper ions in a solution of 0.1 ionic strength when measured at 25° C, of less than 15, preferably less than 12.
  • the preferred crystal growth inhibitors of the present invention are selected from the group consisting of carboxylic compounds, organic diphosphonic acids, organic monophosphonic acids, and mixtures thereof.
  • the following are non-limiting examples of preferred crystal growth inhibitors.
  • Non-limiting examples of carboxylic compounds which serve as crystal growth inhibitors include glycolic acid, phytic acid, polycarboxylic acids, polymers and co-polymers of carboxylic acids and polycarboxylic acids, and mixtures thereof.
  • the inhibitors may be in the acid or salt form.
  • the polycarboxylic acids comprise materials having at least two carboxylic acid radicals which are separated by not more than two carbon atoms (e.g., methylene units).
  • the preferred salt forms include alkali metals; lithium, sodium, and potassium; and alkanolammonium.
  • the polycarboxylates suitable for use in the present invention are further disclosed in U.S. 3,128,287, U.S. 3,635,830, U.S.
  • polycarboxylates include ether hydroxypolycarboxylates, polyacrylate polymers, copolymers of maleic anhydride and the ethylene ether or vinyl methyl ethers of acrylic acid. Copolymers of 1,3,5-trihydroxybenzene, 2, 4, 6-trisulphonic acid, and carboxymethyloxysuccinic acid are also useful.
  • Alkali metal salts of polyacetic acids for example, ethylenediamine tetraacetic acid and nitrilotriacetic acid
  • the alkali metal salts of polycarboxylates for example, mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, are suitable for use in the present invention as crystal growth inhibitors.
  • the polymers and copolymers which are useful as crystal growth inhibitors have a molecular weight which is preferably greater than about 500 daltons to about 100,000 daltons, more preferably to about 50,000 daltons.
  • Examples of commercially available materials for use as crystal growth inhibitors include, polyacrylate polymers Good-Rite® ex BF Goodrich, Acrysol® ex Rohm & Haas, Sokalan® ex BASF, and Norasol® ex Norso Haas.
  • Preferred are the Norasol® polyacrylate polymers, more preferred are Norasol ® 410N (MW 10,000) and Norasol® 440N (MW 4000) which is an amino phosphonic acid modified polyacrylate polymer, and also more preferred is the acid form of this modified polymer sold as Norasol® QR 784 (MW 4000) ex Norso-Haas.
  • Polycarboxylate crystal growth inhibitors include citrates, e.g., citric acid and soluble salts thereof (particularly sodium salt), 3,3-dicarboxy-4-oxa-1,6-hexanedioates and related compounds further disclosed in U.S. 4,566,984 incorporated herein by reference, C 5 -C 20 alkyl, C 5 -C 20 alkenyl succinic acid and salts thereof, of which dodecenyl succinate, lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenylsuccinate, 2-pentadecenyl succinate, are non-limiting examples.
  • Other suitable polycarboxylates are disclosed in U.S. 4,144,226, U.S. 3,308,067 and U.S. 3,723,322, all of which are incorporated herein by reference.
  • Organic diphosphonic acid are also suitable for use as crystal growth inhibitors.
  • organic diphosphonic acid is defined as "an organo-diphosphonic acid or salt which does not comprise a nitrogen atom”.
  • Preferred organic diphosphonic acids include C 1 -C 4 diphosphonic acid, preferably C 2 diphosphonic acid selected from the group consisting of ethylene diphosphonic acid, ⁇ -hydroxy-2 phenyl ethyl diphosphonic acid, methylene diphosphonic acid, vinylidene-1,1-diphosphonic acid , 1,2-dihydroxyethane-1,1-diphosphonic acid, hydroxy-ethane 1,1 diphosphonic acid, the salts thereof, and mixtures thereof. More preferred is hydroxyethane-1,1-diphosphonic acid (HEDP).
  • HEDP hydroxyethane-1,1-diphosphonic acid
  • Organic monophosphonic acid is also suitable for use herein as a CGI.
  • organo monophosphonic acid it is meant herein an organo monophosphonic acid which does not contain nitrogen as part of its chemical structure. This definition therefore excludes the organo aminophosphonates, which however may be included in compositions of the invention as heavy metal ion sequestrants.
  • the organo monophosphonic acid component may be present in its acid form or in the form of one of its salts or complexes with a suitable counter cation.
  • any salts/complexes are water soluble, with the alkali metal and alkaline earth metal salts/complexes being especially preferred.
  • a prefered organo monophosphonic acid is 2-phosphonobutane-1,2,4-tricarboxylic acid commercially available from Bayer under the tradename of Bayhibit.
  • Heavy metal ion (HMI) sequestrants are useful components herein for optimum whiteness and HMI control.
  • Heavy metal ion sequestrants are preferably present at a level of from 0.005% to 20%, more preferably from 0.1% to 10%, most preferably from 0.2% to 5% by weight of the compositions.
  • Heavy metal ion sequestrants which are acidic in nature, having for example phosphonic acid or carboxylic acid functionalities, may be present either in their acid form or as a complex/salt with a suitable counter cation such as an alkali or alkaline metal ion, ammonium, or substituted ammonium ion, or any mixtures thereof.
  • a suitable counter cation such as an alkali or alkaline metal ion, ammonium, or substituted ammonium ion, or any mixtures thereof.
  • any salts/complexes are water soluble.
  • the molar ratio of said counter cation to the heavy metal ion sequestrant is preferably at least 1:1.
  • Suitable heavy metal ion sequestrants for use herein include the organo aminophosphonates, such as the amino alkylene poly (alkylene phosphonates) and nitrilo trimethylene phosphonates.
  • organo aminophosphonates are diethylene triamine penta (methylene phosphonate) and hexamethylene diamine tetra (methylene phosphonate).
  • Suitable heavy metal ion sequestrants for use herein include nitrilotriacetic acid and polyaminocarboxylic acids such as ethylenediaminotetracetic acid, ethylenetriamine pentacetic acid, or ethylenediamine disuccinic acid.
  • ethylenediamine-N,N'-disuccinic acid EDDS
  • heavy metal ion sequestrants for use herein are iminodiacetic acid derivatives such as 2-hydroxyethyl diacetic acid or glyceryl imino diacetic acid, described in EPA 317 542 and EPA 399 133.
  • composition of the invention optionally comprises a hydrophobic dispersant.
  • the hydrophobic dispersant is suitable herein for giving optimised stain removal benefit on clay.
  • a preferred composition of the present invention comprises from about 0.1%, preferably from about 5%, more preferably form about 10% to about 80%, preferably to about 50%, more preferably to about 25% by weight, of a hydrophobic polyamine dispersant having the formula: wherein R, R 1 and B are suitably described in U.S. 5,565,145 Watson et al., issued October 15, 1996 incorporated herein by reference, and w, x, and y have values which provide for a backbone prior to substitution of preferably at least about 1200 daltons, more preferably 1800 daltons.
  • R 1 units are preferably alkyleneoxy units having the formula: -(CH 2 CHR'O) m (CH 2 CH 2 O) n H wherein R' is methyl or ethyl, m and n are preferably from about 0 to about 50, provided the average value of alkoxylation provided by m + n is at least about 0.5.
  • polyamine dispersants suitable for use in the present invention is found in U.S. 4,891,160; U.S.4,597,898; EP 111,965; EP 111,984; EP 112,592; U.S. 4,548,744; and U.S. 5,565,145; all of which are included herein by reference.
  • any suitable clay/soil dispersant or antiredeposition agent can be used in the compositions of the present invention.
  • amino-functional polymer suitable for use herein are poly(ethyleneimine) with a MW 1200, hydroxyethylated poly(ethyleneimine) from Polysciences, with a MW 2000, and 80% hydroxyethylated poly(ethyleneimine) from Aldrich.
  • Preferred polyamines are the poly(ethyleneimine) with a MW 1200, 1800, and ethoxylated with 1, 2, 3, or 7 moles of ethylene oxide.
  • Typical levels of stabilising agents are of from 0.01% to 20%, preferably from 0.5% to 8%,more preferably from 0.1% to 6% by weight of the composition.
  • Suitable stabilising agents to be used herein include synthetic and natural occurring polymers.
  • Suitable stabilising agents for used herein include xanthan gum or derivatives thereof, alginate or a derivative thereof, polysaccharide polymers such as substituted cellulose materials like ethoxylated cellulose, carboxymethylcellulose, hydroxymethylcellulose, hydroxypropyl cellulose, hydroxyethyl cellulose and mixtures thereof.
  • Preferred stabilising agents for use in the compositions of the invention are xanthan gum or derivatives thereof sold by the Kelco Division of Merck under the tradenames KELTROL®, KELZAN AR®, KELZAN D35®, KELZAN S®, KELZAN XZ® and the like.
  • Polymeric soil release agents are also useful in the present invention as stabilising agents. These include cellulosic derivatives such as hydroxyether cellulosic polymers, ethoxylated cellulose, carboxymethylcellulose, hydroxymethylcellulose, hydroxypropyl cellulose, hydroxyethyl cellulose, and the like. Such agents are commercially available and include hydroxyethers of cellulose such as METHOCEL (Dow). Cellulosic soil release agents for use herein also include those selected from the group consisting of C1-C4 alkyl and C4 hydroxyalkyl cellulose; see U.S. Patent 4,000,093, issued December 28,1976 to Nicol, et al.
  • antimicrobial preservative can be added to the composition of the present invention, especially if the stabilising agent is made of cellulose.
  • the cellulose materials can make a prime breeding ground for certain microorganisms, especially when in aqueous compositions. This drawback can lead to the problem of storage stability of the solutions for any significant length of time. Contamination by certain microorganisms with subsequent microbial growth can result in an unsightly and/or malodorous solution. Because microbial growth in solutions is highly objectionable when it occurs, it is highly preferable to include an antimicrobial preservative, which is effective for inhibiting and/or regulating microbial growth in order to increase storage stability of the composition.
  • a broad spectrum preservative e.g., one that is effective on both bacteria (both gram positive and gram negative) and fungi.
  • a limited spectrum preservative e.g., one that is only effective on a single group of microorganisms, e.g., fungi, can be used in combination with a broad spectrum preservative or other limited spectrum preservatives with complimentary and/or supplementary activity.
  • a mixture of broad spectrum preservatives can also be used.
  • aminocarboxylate chelators such as those described hereinbefore, can be used alone or as potentiators in conjunction with other preservatives.
  • chelators which include, e.g., ethylenediaminetetraacetic acid (EDTA), hydroxyethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, and other aminocarboxylate chelators, and mixtures thereof, and their salts, and mixtures thereof, can increase preservative effectiveness against Gram-negative bacteria, especially Pseudomonas species.
  • EDTA ethylenediaminetetraacetic acid
  • hydroxyethylenediaminetriacetic acid hydroxyethylenediaminetriacetic acid
  • diethylenetriaminepentaacetic acid diethylenetriaminepentaacetic acid
  • other aminocarboxylate chelators and mixtures thereof, and their salts, and mixtures thereof, can increase preservative effectiveness against Gram-negative bacteria, especially Pseudomonas species.
  • Antimicrobial preservatives useful in the present invention include biocidal compounds, i.e., substances that kill microorganisms, or biostatic compounds, i.e., substances that inhibit and/or regulate the growth of microorganisms.
  • biocidal compounds i.e., substances that kill microorganisms
  • biostatic compounds i.e., substances that inhibit and/or regulate the growth of microorganisms.
  • Well known preservatives such as short chain alkyl esters of p-hydroxybenzoic acid, commonly known as parabens; N-(4-chlorophenyl)-N'-(3,4-dichlorophenyl) urea, also known as 3,4,4'-trichlorocarbanilide or triclocarban; 2,4,4'-trichloro-2'-hydroxy diphenyl ether, commonly known as triclosan are useful preservative in the present invention.
  • Still other preferred preservatives are the water-soluble preservatives, i.e. those that have a solubility in water of at least about 0.3 g per 100 ml of water, i.e., greater than about 0.3% at room temperature, preferably greater than about 0.5% at room temperature.
  • the preservative in the present invention is included at an effective amount.
  • effective amount means a level sufficient to prevent spoilage, or prevent growth of inadvertently added microorganisms, for a specific period of time.
  • the preservative is not being used to kill microorganisms on the surface onto which the composition is deposited in order to eliminate odors produced by microorganisms. Instead, it is preferably being used to prevent spoilage of the solution in order to increase the shelf-life of the composition.
  • Preferred levels of preservative are from about 0.0001% to about 0.5%, more preferably from about 0.0002% to about 0.2%, most preferably from about 0.0003% to about 0.1%, by weight of the usage composition.
  • the preservative can be any organic preservative material which will not cause damage to fabric appearance, e.g., discoloration, coloration, bleaching.
  • Preferred water-soluble preservatives include organic sulfur compounds, halogenated compounds, cyclic organic nitrogen compounds, low molecular weight aldehydes, quaternary ammonium compounds, dehydroacetic acid, phenyl and phenolic compounds, and mixtures thereof.
  • Non-limiting examples of preferred water-soluble preservatives for use in the present invention can be found in U.S. Patent 5,714,137, incorporated hereinbefore by reference, as well as co-pending application PCT/US 98/12154 pages 29 to 36.
  • Preferred water-soluble preservatives for use in the present invention are organic sulfur compounds.
  • organic sulfur compounds suitable for use in the present invention are:
  • a preferred preservative is an antimicrobial, organic preservative containing 3-isothiazolone groups. This class of compounds is disclosed in U.S. Pat. No. 4,265,899, Lewis et al., issued May 5, 1981, and incorporated herein by reference.
  • a preferred preservative is a water-soluble mixture of 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one, more preferably a mixture of about 77% 5-chloro-2-methyl-4-isothiazolin-3-one and about 23% 2-methyl-4-isothiazolin-3-one, a broad spectrum preservative available as a 1.5% aqueous solution under the trade name Kathon® CG by Rohm and Haas Company.
  • Kathon® When Kathon® is used as the preservative in the present invention it is present at a level of from about 0.0001% to about 0.01%, preferably from about 0.0002% to about 0.005%, more preferably from about 0.0003% to about 0.003%, most preferably from about 0.0004% to about 0.002%, by weight of the composition.
  • isothiazolins include 1,2-benzisothiazolin-3-one, available under the trade name Proxel® products; and 2-methyl-4,5-trimethylene-4-isothiazolin-3-one, available under the trade name Promexal®. Both Proxel and Promexal are available from Zeneca. They have stability over a wide pH range (i.e., 4-12). Neither contain active halogen and are not formaldehyde releasing preservatives.
  • Proxel and Promexal are effective against typical Gram negative and positive bacteria, fungi and yeasts when used at a level from about 0.001% to about 0.5%, preferably from about 0.005% to about 0.05%, and most preferably from about 0.01% to about 0.02% by weight of the usage composition.
  • Another preferred organic sulfur preservative is sodium pyrithione, with water solubility of about 50%.
  • sodium pyrithione is typically present at a level of from about 0.0001% to about 0.01%, preferably from about 0.0002% to about 0.005%, more preferably from about 0.0003% to about 0.003%, by weight of the usage composition.
  • Mixtures of the preferred organic sulfur compounds can also be used as the preservative in the present invention.
  • composition of the invention may also comprises antimicrobial actives. These are useful in providing protection against organisms that become attached to the treated material.
  • compositions of the present invention containing, antimicrobial materials, e.g., antibacterial halogenated compounds, quaternary compounds, and phenolic compounds, and preferably quaternary compounds .
  • antimicrobial materials e.g., antibacterial halogenated compounds, quaternary compounds, and phenolic compounds, and preferably quaternary compounds .
  • a typical disclosure of these antimicrobial can be found in co-pending application PCT/US 98/12154 pages 17 to 20.
  • quaternary compounds can also be used as antimicrobial actives, in conjunction with the preferred surfactants, for compositions of the present invention that do not contain cyclodextrin.
  • useful quaternary compounds include: (1) benzalkonium chlorides and/or substituted benzalkonium chlorides such as commercially available Barquat® (available from Lonza), Maquat® (available from Mason), Variquat® (available from Witco/Sherex), and Hyamine® (available from Lonza); (2) di(C 6 -C 14 )alkyl di short chain (C 1-4 alkyl and/or hydroxyalkyl) quaternary such as Bardac® products of Lonza, (3) N-(3-chloroallyl) hexaminium chlorides such as Dowicide® and Dowicil® available from Dow; (4) benzethonium chloride such as Hyamine® 1622 from Rohm & Haas; (5) methylbenzethonium chloride represented by
  • dialkyl quaternary compounds examples include di(C 8 -C 12 )dialkyl dimethyl ammonium chloride, such as didecyldimethylammonium chloride (Bardac 22), and dioctyldimethylammonium chloride (Bardac 2050).
  • Typical concentrations for biocidal effectiveness of these quaternary compounds range from about 0.001% to about 0.8%, preferably from about 0.005% to about 0.3%, more preferably from about 0.01% to about 0.2%, and even more preferably from about 0.03% to about 0.1%, by weight of the usage composition.
  • the liquid carrier employed in the instant compositions is preferably at least primarily water due to its low cost, relative availability, safety, and environmental compatibility.
  • the level of water in the liquid carrier is preferably at least about 50%, most preferably at least about 60%, by weight of the carrier.
  • Mixtures of water and low molecular weight, e.g., ⁇ about 200, organic solvent, e.g., lower alcohols such as ethanol, propanol, isopropanol or butanol are useful as the carrier liquid.
  • Low molecular weight alcohols include monohydric, dihydric (glycol, etc.) trihydric (glycerol, etc.), and higher polyhydric (polyols) alcohols.
  • the present invention composition can include optional components conventionally used in textile treatment compositions, for example: brighteners, photoactivated bleaching agents such as the sulfonated zinc and/or aluminum phthalocyanines, perfumes, chlorine scavengers, colorants; surfactants; anti-shrinkage agents; fabric crisping agents; spotting agents; germicides; fungicides; anti-oxidants such as butylated hydroxy toluene, anti-corrosion agents, and mixtures thereof.
  • brighteners photoactivated bleaching agents such as the sulfonated zinc and/or aluminum phthalocyanines, perfumes, chlorine scavengers, colorants; surfactants; anti-shrinkage agents; fabric crisping agents; spotting agents; germicides; fungicides; anti-oxidants such as butylated hydroxy toluene, anti-corrosion agents, and mixtures thereof.
  • photoactivated bleaching agents such as the sulfonated zinc and/or aluminum phthalo
  • composition of the invention may take a variety of physical form including liquid, liquid-gel, paste-like, foam in either aqueous or non-aqueous form, powder like granular and tablet forms.
  • a preferred form of the composition is a liquid form.
  • the composition When in a liquid form, the composition may also be dispensed by a dispensing means such as a spray dispenser, or aerosol dispenser.
  • a dispensing means such as a spray dispenser, or aerosol dispenser.
  • the present invention also relates to such compositions incorporated into a spray dispenser to create an article of manufacture that can facilitate treatment of fabric articles and/or surfaces with the compositions according to the invention at a level that is effective.
  • the spray dispenser comprises manually activated and non-manual powered (operated) spray means and a container containing the treating composition. Typical disclosure of such spray dispenser can be found in WO 96/04940 page 19 line 21 to page 22 line 27.
  • a composition as defined herein is first diluted in an aqueous bath. Subsequently, the fabric which have been washed with a detergent liquor are contacted with the diluted composition. Of course, the composition may also incorporated into the aqueous bath once the fabrics have been immersed therein. Following that step, the fabrics are rinsed according to the conventional process of agitation whereby the suds collapse, and optionally further rinsing with water. The fabric can then be optionally wringed for drying. Accordingly, there is provided a method for rinsing fabrics, which comprises the steps of contacting fabrics, previously contacted with a detergent liquor, with a composition of the invention.
  • this rinse process may be performed in a non-automated washing machine, whereby the laundered fabrics are removed from the detergent liquor, wringed while the detergent liquor is removed from the drum and replaced by fresh water.
  • the composition of the invention is added to the water and the fabrics are then rinsed according to the conventional rinsing habit.
  • composition of the invention were also suitable for pre-treatment process and/or soaking processes.
  • use of the composition has been found very effective on collar and socks which conventionally are the items and/or locations which are the most difficult to clean.
  • pretreatment mode where a composition, as defined herein, is applied neat onto said fabrics before the fabrics are rinsed, or washed then rinsed, or in a "soaking mode” where a composition, as defined herein, is first diluted in an aqueous bath and the fabrics are immersed and soaked in the bath, before they are rinsed. It is also essential in both cases, that the fabrics be rinsed after they have been contacted with said composition, before said composition has completely dried off.
  • compositions according to the present invention may be used in neat or diluted form. However the compositions herein are typically used in diluted form in a laundry operation. By “in diluted form”, it is meant herein that the compositions for the treating of fabrics according to the present invention may be diluted by the user, preferably with water. Such dilution may occur for instance in hand laundry applications as well as by other means such as in a washing machine, preferably non auto top loaded washing machine. Said compositions can be diluted up to 1 to 10000 times, preferably 1 to 5000, most preferably 300 to 600 times.
  • Typical rinse dilutions are of 500 times (20 ml in 10liters) for a dilution in a basin (hand-rinsing), of 390 for a dilution in a non automatic washing machine (90ml in 35 liters), of 342 for a dilution with a current fabric softener composition in western Europe washing machine (38 ml in 12 liters), and of 555 for a dilution with a current fabric softener composition in western Europe hand rinsing.
  • the process of soaking the fabrics according to the present invention comprises the steps of first contacting said fabrics with a composition according to the present invention, in its diluted form, then allowing said fabrics to remain in contact with said composition, for a period of time sufficient to treat said fabrics, typically 1 minute to24 hours, preferably 1 to 60 minutes, more preferably 1 to 5 minutes, then complete the rinsing of said fabrics as done usually (agitation, optional rinse, and wringing).
  • said fabrics are to be washed, i.e., with a conventional detergent composition preferably comprising at least one surface active agent, said washing may be subsequently followed by a rinse step comprising a composition of the invention.
  • said process according to the present invention allows cleaning of fabrics and optionally washing of fabrics with a detergent composition preferably comprising at least one surface active agent before the optional step of contacting said fabrics with said composition in the rinse step.
  • the process of pre-treating fabrics comprises the step of contacting fabrics with a composition according to the present invention, in its neat form and allowing said fabrics to remain in contact with said composition for a period of time sufficient to clean said fabrics, typically 5 seconds to 30 minutes, preferably 1 minute to 10 minutes and then rinsing said fabrics with water. If said fabrics are to be washed, i.e., with a conventional detergent composition comprising at least one surface active agent, said washing may be conducted before or after that said fabrics have been pre-treated.
  • the present invention provides compositions that may be applied neat onto a fabric; the present compositions being safe to colors and fabrics per se.
  • the pre-treatment operation may also be followed by the diluted washing process as described herein before either in bucket (hand operation) or in a washing machine.
  • contacting is defined as "intimate contact of a fabric with an aqueous solution of the hereinabove described composition which comprises a suds suppressing system.” Contacting typically occurs by soaking, washing, rinsing, spraying the composition onto fabric, but can also include contact of a substrate inter alia a material onto which the composition has been absorbed, with the fabric. Hand treatment is a preferred process. Temperatures for treatment can take place at a variety of temperatures, however, treatment typically occurs at a temperature less than about 30° C, preferably from about 5° C to about 25° C.
  • the abbreviated component identifications have the following meanings: Suds Sup 35 Silicone 3565 commercially available from Dow Corning Suds Sup 23 Silicone 2-3000 commercially available from Dow Corning Suds Sup Iso 2-Butyloctanol commercially available under the tradename ISOFOL12 from Condea Gum A CarboMethoxyCellulose commercially available from Fluka Gum B Xanthan Gum commercially available from Aldrich Antibacterial Triclosan commercially available from Aldrich Acidifying A Citric Acid Acidifying B Maleic Acid Buffering A Sodium Hydrogenophosphate Buffering B Sodium tripolyphosphate Chelant Diethyleneaminepentamethylphosphonic acid Ca Inhibitor. Hydroxyethyldiphosphonic acid Polymer Polyethylene imine ethoxylated with 7 moles of ethylene oxide(MW 1800, at 50% active) Photobleach Zinc phthalocyanine

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EP99870190A 1999-09-20 1999-09-20 Treatment compositions for fabrics Withdrawn EP1085079A1 (en)

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Application Number Priority Date Filing Date Title
EP99870190A EP1085079A1 (en) 1999-09-20 1999-09-20 Treatment compositions for fabrics
TR2002/00709T TR200200709T2 (tr) 1999-09-20 2000-09-20 Çamaşırlar için işlem bileşimleri
AU75923/00A AU7592300A (en) 1999-09-20 2000-09-20 Treatment compositions for fabrics
ARP000104930A AR031225A1 (es) 1999-09-20 2000-09-20 Composicion para tratamiento de telas que comprende supresion de espuma y metodos para enjuagar, pretratar o remojar telas con la misma
CNA2009100033108A CN101475887A (zh) 1999-09-20 2000-09-20 手洗织物处理组合物
EG20001208A EG22865A (en) 1999-09-20 2000-09-20 Treatment compositions for fabrics
HU0202675A HUP0202675A3 (en) 1999-09-20 2000-09-20 Treatment compositions for fabrics
CZ2002858A CZ2002858A3 (cs) 1999-09-20 2000-09-20 Směsi pro ošetření látek při ručním namáčení, máchání a praní
CN00815936A CN1391603A (zh) 1999-09-20 2000-09-20 用于织物处理的组合物
EP00965159A EP1214391A1 (en) 1999-09-20 2000-09-20 Treatment compositions for fabrics
PCT/US2000/025685 WO2001021747A1 (en) 1999-09-20 2000-09-20 Treatment compositions for fabrics
KR1020027003635A KR20020033183A (ko) 1999-09-20 2000-09-20 직물 처리 조성물
BR0014100-3A BR0014100A (pt) 1999-09-20 2000-09-20 Composições de tratamento para tecidos
JP2001525309A JP2003510410A (ja) 1999-09-20 2000-09-20 布地処理用組成物
MA26560A MA25494A1 (fr) 1999-09-20 2002-03-18 Compositions de traitement pour tissus

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WO2008147934A2 (en) * 2007-05-25 2008-12-04 Healthpro Brands Inc. Microorganism reduction methods and compositions for food with controlled foam generation
CN102057032A (zh) * 2008-06-06 2011-05-11 宝洁公司 织物手工洗涤体系
WO2009148801A1 (en) * 2008-06-06 2009-12-10 The Procter & Gamble Company Hand fabric laundering method
WO2012041658A1 (en) 2010-09-28 2012-04-05 Unilever Nv Aqueous rinse treatment compositions
KR101374677B1 (ko) * 2013-06-10 2014-03-17 주식회사 비앤피 환경친화성 섬유유연제 조성물
EP3390600B1 (en) * 2015-12-15 2019-05-08 Unilever Plc. Fabric conditioning composition
KR102178136B1 (ko) * 2018-11-09 2020-11-12 김대송 액체 세정 조성물
CN110331056A (zh) * 2019-05-10 2019-10-15 湖北文理学院 一种洗衣液用复合消泡剂及其制备方法
CN110295482A (zh) * 2019-08-05 2019-10-01 陶从丰 一种洗衣方法
CN110314418A (zh) * 2019-08-05 2019-10-11 陶从丰 消泡组合物
WO2022087765A1 (en) * 2020-10-26 2022-05-05 Dow Global Technologies Llc Industrial and institutional cleaning foam control agent

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EP0354016A2 (en) * 1988-08-04 1990-02-07 Dow Corning Corporation Dispersible silicone antifoam formulations
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EP0354016A2 (en) * 1988-08-04 1990-02-07 Dow Corning Corporation Dispersible silicone antifoam formulations
WO1998027189A1 (en) * 1996-12-17 1998-06-25 Colgate-Palmolive Company Mildly acidic laundry detergent composition
EP0908511A1 (en) * 1997-10-08 1999-04-14 The Procter & Gamble Company Liquid multipurpose-cleaning compositions with effective foam control
EP0927567A1 (en) * 1997-12-11 1999-07-07 OSi Specialties, Inc. Aqueous foam quenching compositions

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TR200200709T2 (tr) 2002-08-21
CN101475887A (zh) 2009-07-08
KR20020033183A (ko) 2002-05-04
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WO2001021747A1 (en) 2001-03-29
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