EP1124927B1 - Verwendung von polymeren in stoffbehandlungsmitteln mit reduzierter gewebe-abreibung - Google Patents

Verwendung von polymeren in stoffbehandlungsmitteln mit reduzierter gewebe-abreibung Download PDF

Info

Publication number
EP1124927B1
EP1124927B1 EP99971446A EP99971446A EP1124927B1 EP 1124927 B1 EP1124927 B1 EP 1124927B1 EP 99971446 A EP99971446 A EP 99971446A EP 99971446 A EP99971446 A EP 99971446A EP 1124927 B1 EP1124927 B1 EP 1124927B1
Authority
EP
European Patent Office
Prior art keywords
weight
fabric
optionally
units
formula
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.)
Expired - Lifetime
Application number
EP99971446A
Other languages
English (en)
French (fr)
Other versions
EP1124927A1 (de
Inventor
Serge Gabriel Pierre Roger Cauwberghs
Raphael Angeline Alfons Ceulemans
Neil James Gordon
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
Publication of EP1124927A1 publication Critical patent/EP1124927A1/de
Application granted granted Critical
Publication of EP1124927B1 publication Critical patent/EP1124927B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • C11D3/3792—Amine oxide containing polymers
    • 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
    • C11D3/28—Heterocyclic compounds containing nitrogen in the ring
    • 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
    • C11D3/16—Organic compounds
    • C11D3/36—Organic compounds containing phosphorus
    • C11D3/365—Organic compounds containing phosphorus containing carboxyl groups

Definitions

  • the present invention relates to the use of one or more fabric abrasion reducing polymers as well as other ingredients in a fabric care composition for providing reduced fabric abrasion.
  • Short fibers are dislodged from woven and knit fabric/textile structures by the mechanical action of laundering. These dislodged fibers may form lint, fuzz or "pills" which are visible on the surface of fabrics and diminish the appearance of newness of the fabric. Such a problem of fabric abrasion is even more acute after multiwash cycles.
  • compositions which provide fabric with protection against damage done due to fabric abrasion There exists a long felt need for compositions which provide fabric with protection against damage done due to fabric abrasion. In addition, there is a long felt need to provide compositions which provide a remedy for fabric abrasion damage.
  • the present invention meets the aforementioned needs in that it has been surprisingly discovered that certain higher molecular weight polymers which comprise an amide unit, an N-oxide unit, or mixtures thereof, are useful for providing fabric abrasion reduction.
  • the polymers used according to the present invention herein described as "fabric abrasion reducing polymers", when applied to fabric provide a reduction in the amount of damage which is incurred by the fabric.
  • the fabric abrasion reducing polymers of the present invention comprise one or more units which in addition to fabric abrasion benefits, provides a dye transfer inhibition benefit. Therefore, the polymers of the present invention have a primary fabric abrasion benefit, and preferably a dye transfer inhibition benefit as well.
  • a first aspect of the present invention relates to the use of a polymer comprising:
  • the present invention further relates to said use, wherein the fabric care composition comprises:
  • the fabric care compositions are laundry detergent compositions, rinse-added fabric conditioning compositions, and dryer-added fabric conditioning compositions.
  • the present invention also relates to a method for providing reduced fabric abrasion to fabric, said method comprising the step of contacting said fabric with a composition comprising
  • compositions which when applied to fabric, reduce the fabric wear and enhance the fabric appearance are provided by the surprising discovery that certain polymers which comprise an amide or N-oxide functional unit have fabric abrasion reduction benefits. Surprisingly, it has also been discovered that theses units also provide a secondary benefit; dye transfer inhibition. Therefore the compositions of the present invention provide not only fabric damage amelioration but also fabric color fidelity benefits.
  • one or more fabric abrasion reducing polymers as described herein are used in the fabric care composition.
  • fabric care compositions is defined as "a composition which provides care to the fabric non-limiting examples of which include laundry detergent compositions, stand-alone compositions, detergent additives, fabric softening compositions inter alia rinse-added softening composition, dryer-added softening compositions".
  • Said compositions provide an efficient fabric abrasion reduction.
  • efficient fabric abrasion reduction is defined herein as "fabric which has been treated by the herein described compositions have an improved appearance relative to fabrics which have been un-treated by the herein disclosed compositions. The following describe the required elements of the present invention.
  • the fabric abrasion reducing polymer is used in the fabric care composition in an amount of from about 0.01%, preferably from about 0.1% to about 20%, preferably to about 10% by weight.
  • the prefered reduced abrasion polymers used in the present invention are water-soluble polymers.
  • water-soluble is defined as "a polymer which when dissolved in water at a level of 0.2% by weight, or less, at 25° C, forms a clear, isotropic liquid".
  • the fabric abrasion reducing polymers useful in the present invention have the formula: [-P(D) m -] n wherein the unit P is a polymer backbone which comprises units which are homopolymeric or copolymeric. D units arc defined herein below.
  • the term "homopolymeric” is defined as "a polymer backbone which is comprised of units having the same unit composition, i.e., formed from polymerization of the same monomer”.
  • copolymeric is defined as "a polymer backbone which is comprised of units having a different unit composition, i.e., formed from the polymerization of two or more monomers”.
  • P backbones preferably comprise units having the formula: -[CR 2 -CR 2 ]- or -[(CR 2 ) x -L]- wherein each R unit is independently hydrogen, C 1 -C 12 alkyl, C 6 -C 12 aryl, and D units as described herein below; preferably C 1 -C 4 alkyl.
  • Each L unit is independently selected from heteroatom-containing moieties, non-limiting examples of which are selected from the group consisting of: polysiloxane having the formula: wherein the index p is from 1 to about 6; units which have dye transfer inhibition activity: and mixtures thereof; wherein R 1 is hydrogen, C 1 -C 12 alkyl, C 6 -C 12 aryl, and mixtures thereof.
  • R 2 is C 1 -C 12 alkyl, C 1 -C 12 alkoxy, C 6 -C 12 aryloxy, and mixtures thereof; preferably methyl and methoxy.
  • R 3 is hydrogen C 1 -C 12 alkyl, C 6 -C 12 aryl, and mixtures thereof; preferably hydrogen or C 1 -C 4 alkyl, more preferably hydrogen.
  • R 4 is C 1 -C 12 alkyl, C 6 -C 12 aryl, and mixtures thereof.
  • the backbones of the fabric abrasion reducing polymers of the present invention comprise one or more D units which are units which comprise one or more units which provide a dye transfer inhibiting benefit.
  • the D unit can be part of the backbone itself as represented in the general formula: [-P(D) m -] n or the D unit may be incorporated into the backbone as a pendant group to a backbone unit having, for example, the formula:
  • the number of D units depends upon the formulation. For example, the number of D units will be adjusted to provide water solubility of the polymer as well as efficacy of any optional dye transfer inhibition while providing a polymer which has fabric abrasion reducing properties.
  • the molecular weight of the fabric abrasion reducing polymers used according to the present invention are from greater than 100,000 most preferably from 160,000 to about 6,000,000, preferably to about 2,000,000, more preferably to about 1,000,000, yet more preferably to about 500,000, most preferably to about 360,000 daltons. Therefore the value of the index n is selected to provide the indicated molecular weight, and providing for a water solubility of least 100 ppm, preferably at least about 300 ppm, and more preferably at least about 1,000 ppm in water at ambient temperature which is defined herein as 25°C.
  • Non-limiting examples of preferred D units are D units which comprise an amide moiety.
  • Examples of polymers wherein an amide unit is introduced into the polymer via a pendant group includes polyvinylpyrrolidone having the formula: polyvinyloxazolidone having the formula: polyvinylmethyloxazolidone having the formula: polyacrylamides and N-substituted polyacrylamides having the formula: wherein each R' is independently hydrogen, C 1 -C 6 alkyl, or both R' units can be taken together to form a ring comprising 4-6 carbon atoms; polymethacrylamides and N-substituted polymethacrylamides having the general formula: wherein each R' is independently hydrogen, C 1 -C 6 alkyl, or both R' units can be taken together to form a ring comprising 4-6 carbon atoms; poly(N-acrylylglycinamide) having the formula: wherein each R' is independently hydrogen, C 1 -C 6 alkyl, or both R' units can
  • the nitrogen of the dye transfer inhibiting moiety is incorporated into the polymer backbone is a poly(2-ethyl-2-oxazoline) having the formula: wherein the index n indicates the number of monomer residues present.
  • the fabric abrasion reducing polymer is a polyvinylpyrrolidone having a molecular weight of from 100,000 daltons to 360,000 daltons.
  • the fabric abrasion reducing polymers of the present invention can comprise any mixture of dye transfer inhibition units which provides the product with suitable properties.
  • the preferred polymers which comprise D units which are amide moieties are those which have the nitrogen atoms of the amide unit highly substituted so the nitrogen atoms are in effect shielded to a varying degree by the surrounding non-polar groups. This provides the polymers with an amphiphilic character.
  • Non-limiting examples include polyvinyl-pyrrolidones, polyvinyloxazolidones, N,N-disubstituted polyacrylamides, and N,N-disubstituted polymethacrylamides.
  • a detailed description of physico-chemical properties of some of these polymers are given in "Water-Soluble Synthetic Polymers: Properties and Behavior", Philip Molyneux, Vol. I, CRC Press, (1983) included herein by reference.
  • the amide containing polymers may be present partially hydrolyzed and/or crosslinked forms.
  • a preferred polymeric compound for the present invention is polyvinylpyrrolidone (PVP).
  • PVP polyvinylpyrrolidone
  • This polymer has an amphiphilic character with a highly polar amide group conferring hydrophilic and polar-attracting properties, and also has non-polar methylene and methine groups, in the backbone and/or the ring, conferring hydrophobic properties.
  • the rings may also provide planar alignment with the aromatic rings in the dye molecules.
  • PVP is readily soluble in aqueous and organic solvent systems.
  • PVP is available ex ISP, Wayne, New Jersey, and BASF Corp., Parsippany, New Jersey, as a powder or aqueous solutions in several viscosity grades, designated as, e.g., K-12, K-15, K-25, and K-30. These K-values indicate the viscosity average molecular weight, as shown below: PVP viscosity average molecular weight (in thousands of daltons) K-12 K-15 K-25 K-30 K-60 K-90 2.5 10 24 40 160 360 PVP K-12, K-15, and K-30 are also available ex Polysciences, Inc.
  • PVP K-15, K-25, and K-30 and poly(2-ethyl-2-oxazoline) are available ex Aldrich Chemical Co., Inc., Milwaukee, Wisconsin.
  • PVP K30 (40,000) through to K90 (360,000) are also commercially available ex BASF under the tradename Luviskol or commercially available ex ISP.
  • Still higher molecular PVP like PVP 1.3MM, commercially available ex Aldrich is also suitable for use herein.
  • PVP-type of material suitable for use in the present invention are polyvinylpyrrolidone-co-dimethylaminoethylmethacrylate, commercially available commercially ex ISP in a quaternised form under the tradename Gafquat® or commercially available ex Aldrich Chemical Co. having a molecular weight of approximately 1.0MM; polyvinylpyrrolidone-co-vinyl acetate, available ex BASF under the tradename Luviskol®, available in vinylpyrrolidone:vinylacetate ratios of from 3:7 to 7:3.
  • N-oxide units having the formula: wherein R 1 , R 2 , and R 3 can be any hydrocarbyl unit (for the purposes of the present invention the term "hydrocarbyl" does not include hydrogen atom alone).
  • the N-oxide unit may be part of a polymer, such as a polyamine, i.e., polyalkyleneamine backbone, or the N-oxide may be part of a pendant group attached to the polymer backbone.
  • An example of a polymer which comprises an the N-oxide unit as a part of the polymer backbone is polyethyleneimine N-oxide.
  • Non-limiting examples of groups which can comprise an N-oxide moiety include the N-oxides of certain heterocycles inter alia pyridine, pyrrole, imidazole, pyrazole, pyrazine, pyrimidine, pyridazine, piperidine, pyrrolidine, pyrrolidone, azolidine, morpholine.
  • a preferred polymer is poly(4-vinylpyriding N-oxide, PVNO).
  • the N-oxide unit may be pendant to the ring, for example, aniline oxide.
  • N-oxide comprising polymers of the present invention will preferably have a ration of N-oxidized amine nitrogen to non-oxidized amine nitrogen of from about 1:0 to about 1:2, preferably to about 1:1, more preferably to about 3:1.
  • the amount of N-oxide units can be adjusted by the formulator.
  • the formulator may co-polymerize N-oxide comprising monomers with non N-oxide comprising monomers to arrive at the desired ratio of N-oxide to non N-oxide amino units, or the formulator may control the oxidation level of the polymer during preparation.
  • the amine oxide unit of the polyamine N-oxides of the present invention have a Pk a less than or equal to 10, preferably less than or equal to 7, more preferably less than or equal to 6.
  • the average molecular weight of the N-oxide comprising polymers which provide a dye transfer inhibitor benefit to reduced fabric abrasion polymers is from
  • 100,000 daltons more preferably from about 160,000 daltons to about 6,000,000 daltons, preferably to about 2,000,000 daltons, more preferably to about 360,000 daltons.
  • a further example of polymers which are fabric abrasion reducing polymers which have dye transfer inhibition benefits are polymers which comprise both amide units and N-oxide units as described herein above.
  • Non-limiting examples include co-polymers of two monomers wherein the first monomer comprises an amide unit and the second monomer comprises an N-oxide unit.
  • oligomers or block polymers comprising these units can be taken together to form the mixed amide/N-oxide polymers.
  • the resulting polymers must retain the water solubility requirements described herein above.
  • the above described polymers of the invention it is most preferred that they have a molecular weight in the range as described herein above. This range is typically higher than the range for polymers which render only dye transfer inhibition benefits alone. Indeed, the higher molecular weight of the abrasion reducing polymers provides for reduction of fabric abrasion which typically occurs subsequent to treatment, for example during garment use, especially in a later washing procedure. Not to be bound by theory, it is believed that the high molecular weight enables the deposition of the polymer on the fabric surface and provides sufficient substantivity so that the polymer is capable of remaining on the fabric during subsequent use and subsequent laundering of the fabric.
  • the present invention relates to the use of :
  • compositions of the present invention optionally comprise from about 0.001%, preferably from about 0.5% to about 90%, preferably to about 50%, more preferably to about 10%, most preferably to about 5% by weight, of one or more dye fixing agents.
  • Dye fixing agents are well-known, commercially available materials which are designed to improve the appearance of dyed fabrics by minimizing the loss of dye from fabrics due to washing. Not included within this definition are components which can in some embodiments serve as fabric softener actives.
  • Cationic fixatives are available under various trade names from several suppliers. Representative examples include: CROSCOLOR PMF (July 1981, Code No. 7894) and CROSCOLOR NOFF (January 1988, Code No. 8544) ex Crosfield; INDOSOL E-50 (February 27, 1984, Ref. No. 6008.35.84; polyethyleneamine-based) ex Sandoz; SANDOFIX TPS, ex Sandoz, is a preferred dye fixative for use herein.
  • SANDOFIX SWE a cationic resinous compound ex Sandoz
  • REWIN SRF REWIN SRF-O
  • REWIN DWR ex CHT-Beitlich GMBH
  • Tinofix® ECO Tinofix® FRD
  • Solfin® ex Ciba-Geigy.
  • a preferred dye fixing agent for use in the compositions of the present invention is CARTAFIX CB® ex Clariant.
  • Dye fixing agents suitable for use in the present invention are ammonium compounds such as fatty acid-diamine condensates inter alia the hydrochloride, acetate, metosulphate and benzyl hydrochloride salts of diamine esters.
  • Non-limiting examples include oleyldiethyl aminoethylamide, oleylmethyl diethylenediamine methosulphate, monostearylethylene diaminotrimethylammonium methosulphate.
  • N-oxides of tertiary amines are suitable for use as dye fixatives in the compositions of the present invention.
  • compositions of the present invention optionally comprise from about 0.01%, preferably from about 0.05%, more preferably from about 0.5% to about 50%, preferably to about 25%, more preferably to about 10% by weight, most preferably to about 5% by weight, of one or more cellulose reactive dye fixing agents.
  • the cellulose reactive dye fixatives may be suitably combined with one or more dye fixatives described herein above in order to comprise a "dye fixative system”.
  • cellulose reactive dye fixing agent is defined herein as "a dye fixative agent which reacts with the cellulose fibers upon application of heat or upon a heat treatment either in situ or by the formulator".
  • the cellulose reactive dye fixing agents suitable for use in the present invention can be defined by the following test procedure.
  • All four swatches (the two control swatches and the two treated swatches, one of each which has been treated by the ironing calender) are washed separately in Launder-O-Meter pots under typical conditions with a commercial detergent used at the recommended dosage for 1 ⁇ 2 hour at 60°C, followed by a thorough rinsing of 4 times 200 ml of cold water and subsequently line dried.
  • DE values the computed color difference
  • ASTM D2244 the computed color difference
  • DE values relate to the magnitude and direction of the difference between two psychophysical color stimuli defined by tristimulus values, or by chromaticity coordinates and luminance factor, as computed by means of a specified set of color-difference equations defined in the CIE 1976 CIELAB opponent-color space, the Hunter opponent-color space, the Friele-Mac Adam-Chickering color space or any equivalent color space.
  • the lower the DE value for a sample the closer the sample is to the un-tested sample and the greater the color fastness benefit.
  • the candidate is a cellulose reactive dye fixing agent for the purposes of the invention.
  • cellulose reactive dye fixing agents are compounds which contain a cellulose reactive moiety
  • non limiting examples of these compounds include halogeno-triazines, vinyl sulphones, epichlorhydrine derivatives, hydroxyethylene urea derivatives, formaldehyde condensation products, polycarboxylates, glyoxal and glutaraldehyde derivatives, and mixtures thereof. Further examples can be found in “Textile Processing and Properties", Tyrone L. Vigo, at page 120 to 121, Elsevier (1997), which discloses specific electrophilic groups and their corresponding cellulose affinity.
  • Preferred hydroxyethylene urea derivatives include dimethyloldihydroxyethylene, urea, and dimethyl urea glyoxal.
  • Preferred formaldehyde condensation products include the condensation products derived from formaldehyde and a group selected from an amino-group, an imino-group, a phenol group, an urea group, a cyanamide group and an aromatic group.
  • Commercially available compounds among this class are Sandofix WE 56 ex Clariant, Zetex E ex Zeneca and Levogen BF ex Bayer.
  • Preferred polycarboxylates derivatives include butane tetracarboxilic acid derivatives, citric acid derivatives, polyacrylates and derivatives thereof.
  • a most preferred cellulosic reactive dye fixing agents is one of the hydroxyethylene urea derivatives class commercialized under the tradename of Indosol CR ex Clariant. Still other most preferred cellulosic reactive dye fixing agents are commercialized under the tradename Rewin DWR and Rewin WBS ex CHT R. Beitlich.
  • compositions of the present invention optionally comprise from about 0.01%, preferably from about 0.02%, more preferably from about 0.25% to about 15%, preferably to about 10%, more preferably to about 5% by weight, of a chlorine scavenger.
  • a chlorine scavenger In cases wherein the cation portion and the anion portion of the non-polymeric scavenger each react with chlorine, the amount of scavenger can be adjusted to fit the needs of the formulator.
  • Suitable chlorine scavengers include ammonium salts having the formula: [(R) 3 R 1 N] + X - wherein each R is independently hydrogen, C 1 -C 4 alkyl, C 1 -C 4 substituted alkyl, and mixtures thereof, preferably R is hydrogen or methyl, more preferably hydrogen.
  • R 1 is hydrogen C 1 -C 9 alkyl, C 1 -C 9 substituted alkyl, and mixtures thereof, preferably R is hydrogen.
  • X is a compatible anion, non-limiting examples include chloride, bromide, citrate, sulfate; preferably X is chloride.
  • Non-limiting examples of preferred chlorine scavengers include ammonium chloride, ammonium sulfate, and mixtures thereof; preferably ammonium chloride.
  • compositions of the present invention optionally comprise from about 0.005%, preferably from about 0.5%, more preferably from about 0.1% to about 1%, preferably to about 0.5%, more preferably to about 0.25%, most preferably to about 0.2% by weight, of one or more crystal growth inhibitors.
  • 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 microcrystals.
  • 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 HCl 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 HCl. 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, 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. 4,663,071, U.S. 3,923,679; U.S. 3,835,163; U.S. 4,158,635; U.S. 4,120,874 and U.S. 4,102,903.
  • 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.
  • 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.
  • 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).
  • a preferred is phosphonic acid is 2-phosphonobutane-1,2,4-tricarboxylic acid available as BAYHIBIT AM ® ex Bayer.
  • compositions of the present invention optionally comprise at least about 1%, preferably from about 10%, more preferably from about 20% to about 80%, more preferably to about 60%, most preferably to about 45% by weight, of the composition of one or more fabric softener actives.
  • the preferred fabric softening actives according to the present invention are amines having the formula: quaternary ammonium compounds having the formula: and mixtures thereof, wherein each R is independently C 1 -C 6 alkyl, C 1 -C 6 hydroxyalkyl, benzyl, and mixtures thereof; R 1 is preferably C 11 -C 22 linear alkyl, C 11 -C 22 branched alkyl, C 11 -C 22 linear alkenyl, C 11 -C 22 branched alkenyl, and mixtures thereof; Q is a carbonyl moiety independently selected from the units having the formula: wherein R 2 is hydrogen, C 1 -C 4 alkyl, preferably hydrogen; R 3 is C 1 -C 4 alkyl, preferably hydrogen or methyl; preferably Q has the formula: X is a softener compatible anion, preferably the anion of a strong acid, for example, chloride, bromide, methylsulfate, ethylsulfate, s
  • the anion can also, but less preferably, carry a double charge, in which case X (-) represents half a group.
  • the index m has a value of from 1 to 3; the index n has a value of from 1 to 4, preferably 2 or 3, more preferably 2.
  • One embodiment of the present invention provides for amines and quaternized amines having two or more different values for the index n per molecule, for example, a softener active prepared from the starting amine methyl(3-aminopropyl)(2-hydroxyethyl)amine.
  • More preferred softener actives according to the present invention have the formula: wherein the unit having the formula: is a fatty acyl moiety.
  • Suitable fatty acyl moieties for use in the softener actives of the present invention are derived from sources of triglycerides including tallow, vegetable oils and/or partially hydrogenated vegetable oils including inter alia canola oil, safflower oil, peanut oil, sunflower oil, corn oil, soybean oil, tall oil, rice bran oil.
  • DEQA's Diester Quaternary Ammonium Compounds
  • the formulator can choose any of the above mentioned sources of fatty acyl moieties, or alternatively, the formulator can mix sources of triglyceride to form a "customized blend".
  • the fatty acyl composition may vary, as in the case of vegetable oil, from crop to crop, or from variety of vegetable oil source to variety of vegetable oil source.
  • DEQA's which are prepared using fatty acids derived from natural sources are preferred.
  • a preferred embodiment of the present invention provides softener actives comprising R 1 units which have at least about 3%, preferably at least about 5%, more preferably at least about 10%, most preferably at least about 15% C 11 -C 22 alkenyl, including polyalkenyl (polyunsaturated) units inter alia oleic, linoleic, linolenic.
  • mixed chain fatty acyl units is defined as "a mixture of fatty acyl units comprising alkyl and alkenyl chains having from 10 carbons to 22 carbon atoms including the carbonyl carbon atom, and in the case of alkenyl chains, from one to three double bonds, preferably all double bonds in the cis configuration".
  • R 1 units of the present invention it is preferred that at least a substantial percentage of the fatty acyl groups are unsaturated, e.g., from about 25%, preferably from about 50% to about 70%, preferably to about 65%.
  • the total level of fabric softening active containing polyunsaturated fatty acyl groups can be from about 3%, preferably from about 5%, more preferably from about 10% to about 30%, preferably to about 25%, more preferably to about 18%.
  • cis and trans isomers can be used, preferably with a cis / trans ratio is of from 1:1, preferably at least 3:1, and more preferably from about 4:1 to about 50:1, more preferably about 20:1, however, the minimum being 1:1.
  • the level of unsaturation contained within the tallow, canola, or other fatty acyl unit chain can be measured by the Iodine Value (IV) of the corresponding fatty acid, which in the present case should preferably be in the range of from 5 to 100 with two categories of compounds being distinguished, having a IV below or above 25.
  • IV Iodine Value
  • a further preferred embodiment of the present invention comprises DEQA's wherein the average Iodine Value for R 1 is approximately 45.
  • the R 1 units suitable for use in the isotropic liquids present invention can be further characterized in that the Iodine Value (IV) of the parent fatty acid, said IV is preferably from about 10, more preferably from about 50, most preferably from about 70, to a value of about 140, preferably to about 130, more preferably to about 115.
  • formulators may wish to add an amount of fatty acyl units which have Iodine Values outside the range listed herein above. For example, "hardened stock" (IV less than or equal to about 10) may be combined with the source of fatty acid admixture to adjust the properties of the final softener active.
  • a prefered source of fatty acyl units especially fatty acyl units having branching, for example, "Guerbet branching", methyl, ethyl, etc. units substituted along the primary alkyl chain
  • synthetic sources of fatty acyl units are also suitable.
  • the formulator may with to add one or more fatty acyl units having a methyl branch at a "non-naturally occuring" position, for example, at the third carbon af a C 17 chain.
  • acyl units whihc are not found in significant (greater than about 0.1 %) quantities is common fats and oils which serve as feedstocks for the source of triglycerides described herein.” If the desired branched chain fatty acyl unit is unavailable from readily available natural feedstocks, therefore, synthetic fatty acid can be suitably admixed with other synthetic materials or with other natural triglyceride derived sources of acyl units.
  • N,N-di(tallowoyl-oxy-ethyl)-N,N-dimethyl ammonium chloride where the tallow chains are at least partially unsaturated and N,N-di(canoloyl-oxy-ethyl)-N,N-dimethyl ammonium chloride, N,N-di(tallowyl-oxy-ethyl)-N-methyl, N-(2-hydroxyethyl) ammonium methyl sulfate; N,N-di(canolyl-oxy-ethyl)-N-methyl, N-(2-hydroxyethyl) ammonium methyl sulfate; and mixtures thereof.
  • compositions of the present invention may also optionally comprise a principal solvent.
  • the level of principal solvent present in the compositions of the present invention is typically less than about 95%, preferably less than about 50%, more preferably less than about 25%, most preferably less than about 15% by weight.
  • Some embodiments of isotropic liquid embodiments of the present invention may comprise no principal solvent but may substitute instead a suitable nonionic surfactant.
  • the principal solvents of the present invention are primarily used to obtain liquid compositions having sufficient clarity and viscosity. Principal solvents must also be selected to minmize solvent odor impact in the composition. For example, isopropyl alcohol is not an effective principal solvent in that it does not serve to produce a composition having suitable viscosity. Isopropanol also fails as a suitable principal solvent because it has a relatively strong odor.
  • Principal solvents are also selected for their ability to provide stable compositions at low temperatures, preferably compositions comprising suitable principal solvents are clear down to about 4° C and have the ability to fully recover their clarity if stored as low as about 7° C.
  • the principal solvents according to the present invention are selected base upon their octanol/water partition coefficient (P).
  • the octanol/water partition coefficient is a measure of the ratio of the concentrations of a particular principal solvent in octanol and water at equilibrium.
  • the partition coefficients are conveniently expressed and reported as their logarithm to the base 10; logP.
  • logP logP
  • ClogP The "calculated logP” (ClogP) is determined by the fragment approach of Hansch and Leo (cf., A. Leo, in Comprehensive Medicinal Chemistry, Vol. 4, C. Hansch, P. G. Sammens, J. B. Taylor and C. A. Ransden, Eds., p. 295, Pergamon Press, 1990, incorporated herein by reference). The fragment approach is based on the chemical structure of each HR species, and takes into account the numbers and types of atoms, the atom connectivity, and chemical bonding.
  • ClogP values are the most reliable and widely used estimates for octanol water partitioning. It will be understood by those skilled in the art that experimental log P values could also be used. Experimental log P values represent a less preferred embodiment of the invention. Where experimental log P values are used, the one hour log P values are preferred. Other methods that can be used to compute ClogP include, e.g., Crippen's fragmentation method as disclosed in J. Chem. Inf. Comput. Sci., 27a, 21 (1987); Viswanadhan's fragmentation method as disclosed in J. Chem. Inf. Comput. Sci., 29, 163 (1989); and Broto's method as disclosed in Eur. J. Med. Chem. - Chim. Theor. , 19, 71 (1984).
  • the principal solvents suitable for use in the present invention are selected from those having a ClogP of from about 0.15 to about 1, preferably from about 0.15 to about 0.64, more preferably from about 0.25 to about 0.62, most preferably form about 0.4 to about 0.6.
  • the principal solvent is at least to some degree an asymmetric molecule, preferably having a melting, or solidification point which allows the principal solvent to be liquid at or near room temperature.
  • Low molecular weight principal solvents may be desirable for some embodiments. More preferred molecules are highly asymmetrical.
  • 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, 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 1 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.
  • any suitable clay/soil dispersent or anti-redepostion agent can be used in the laundry compositions of the present invention.
  • the fabric softening embodiments of the compositions of the present invention may also optionally, but preferably comprise, one or more electrolytes for control of phase stability, viscosity, and/or clarity.
  • electrolytes inter alia calcium chloride, magnesium chloride may be key to insuring initial product clarity and low viscosity, or may affect the dilution viscosity of liquid embodiments, especially isotropic liquid embodiments.
  • the formulator must insure proper dilution viscosity, includes the following example.
  • Isotropic or non-isotropic liquid fabric softener compositions can be introduced into the rinse phase of laundry operations via an article of manufacture designed to dispense a measured amount of said composition.
  • the article of manufacture is a dispenser which delivers the softener active only during the rinse cycle.
  • These dispensers are typically designed to allow an amount of water equal to the volume of softener composition to enter into the dispenser to insure complete delivery of the softener composition.
  • An electrolyte may be added to the compositions of the present invention to insure phase stability and prevent the diluted softener composition from "gelling out” or from undergoing an undesirable or unacceptable viscosity increase. Prevention of gelling or formation of a "swelled", high viscosity solution insures thorough delivery of the softener composition.
  • the level of electrolyte is also influenced by other factors inter alia the type of fabric softener active, the amount of principal solvent, and the level and type of nonionic surfactant.
  • triethanol amine derived ester quaternary amines suitable for use as softener actives according to the present invention are typically manufactured in such a way as to yield a distribution of mono-, di-, and tri- esterified quaternary ammonium compounds and amine precursors. Therefore, as in this example, the variability in the distribution of mono-, di-, and tri- esters and amines may predicate a different level of electrolyte.
  • the formulator must consider all of the ingredients, namely, softener active, nonionic surfactant, and in the case of isotropic liquids, the principal solvent type and level, as well as level and identity of adjunct ingredients before selecting the type and/or level of electrolyte.
  • ionizable salts can be used.
  • suitable salts are the halides of the Group IA and ILA metals of the Periodic Table of the elements, e.g., calcium chloride, sodium chloride, potassium bromide, and lithium chloride.
  • the ionizable salts are particularly useful during the process of mixing the ingredients to make the compositions herein, and later to obtain the desired viscosity.
  • the amount of ionizable salts used depends on the amount of active ingredients used in the compositions and can be adjusted according to the desires of the formulator. Typical levels of salts used to control the composition viscosity are from about 20 to about 10,000 parts per million (ppm), preferably from about 20 to about 5,000 ppm, of the composition.
  • Alkylene polyammonium salts can be incorporated into the composition to give viscosity control in addition to or in place of the water-soluble, ionizable salts above, In addition, these agents can act as scavengers, forming ion pairs with anionic detergent carried over from the main wash, in the rinse, and on the fabrics, and can improve softness performance. These agents can stabilized the viscosity over a broader range of temperature, especially at low temperatures, compared to the inorganic electrolytes.
  • Specific examples of alkylene polyammonium salts include L-lysine, monohydrochloride and 1,5-diammonium 2-methyl pentane dihydrochloride.
  • compositions and processes herein can optionally employ one or more enzymes inter alia lipases, proteases, cellulase, amylases, mannanases, xyloglucanases, and peroxidases.
  • a preferred enzyme for use herein is cellulase enzyme.
  • Cellulases usable for use in the fabric enhancement compositions of the present invention include both bacterial and fungal types which preferably exhibit an optimal performance at a pH of from 5 to 9.5. U.S.
  • compositions may comprise up to 5 mg by weight, more typically 0.01 mg to 3 mg, of active enzyme per gram of the composition. Stated otherwise, the compositions herein will typically comprise from 0.001%, preferably from 0.01% to 5%, preferably to 1% by weight, of a commercial enzyme preparation. In the particular cases where activity of the enzyme preparation can be defined otherwise such as with cellulases, corresponding activity units are preferred (e.g. CEVU or cellulase Equivalent Viscosity Units).
  • compositions of the present invention can contain cellulase enzymes at a level equivalent to an activity from 0.5 to 1000 CEVU/gram of composition.
  • Cellulase enzyme preparations used for the purpose of formulating the compositions of this invention typically have an activity comprised between 1,000 and 10,000 CEVU/gram in liquid form, around 1,000 CEVU/gram in solid form.
  • compositions or the present invention may optionally comprise one or more cationic charge boosters, especially to the rinse-added fabric softening embodiments of the present invention.
  • ethanol is used to prepare many of the below listed ingredients and is therefore a source of solvent into the final product formulation.
  • the formulator is not limited to ethanol, but instead can add other solvents inter alia hexyleneglycol to aid in formulation of the final composition. This is especially true in clear, translucent, isotropic compositions.
  • An optional composition of the present invention comprises at least about 0.2%, preferably from about 0.2% to about 10%, more preferably from about 0.2% to about 5% by weight, of a cationic charge booster having the formula: wherein R 1 , R 2 , R 3 , and R 4 are each independently C 1 -C 22 alkyl, C 3 -C 22 alkenyl, R 5 -Q-(CH 2 ) m -, wherein R 5 is C 1 -C 22 alkyl, and mixtures thereof, m is from 1 to about 6; X is an anion.
  • R 1 is C 6 -C 22 alkyl, C 6 -C 22 alkenyl, and mixtures thereof, more preferably C 11 -C 18 alkyl, C 11 -C 18 alkenyl, and mixtures thereof;
  • R 2 , R 3 , and R 4 are each preferably C 1 -C 4 alkyl, more preferably each R 2 , R 3 , and R 4 are methyl.
  • R 1 may similarly choose R 1 to be a R 5 -Q-(CH 2 ) m - moiety wherein R 5 is an alkyl or alkenyl moiety having from 1 to 22 carbon atoms, preferably the alkyl or alkenyl moiety when taken together with the Q unit is an acyl unit derived preferably derived from a source of triglyceride selected from the group consisting of tallow, partially hydrogenated tallow, lard, partially hydrogenated lard, vegetable oils and/or partially hydrogenated vegetable oils, such as, canola oil, safflower oil, peanut oil, sunflower oil, corn oil, soybean oil, tall oil, rice bran oil, etc. and mixtures thereof.
  • R 5 is an alkyl or alkenyl moiety having from 1 to 22 carbon atoms, preferably the alkyl or alkenyl moiety when taken together with the Q unit is an acyl unit derived preferably derived from a source of triglyceride selected from the group consisting
  • An example of a fabric softener cationic booster comprising a R 5 -Q-(CH 2 ) m - moiety has the formula: wherein R 5 -Q- is an oleoyl units and m is equal to 2.
  • X is a softener compatible anion, preferably the anion of a strong acid, for example, chloride, bromide, methylsulfate, ethylsulfate, sulfate, nitrate and mixtures thereof, more preferably chloride and methyl sulfate.
  • a strong acid for example, chloride, bromide, methylsulfate, ethylsulfate, sulfate, nitrate and mixtures thereof, more preferably chloride and methyl sulfate.
  • a preferred embodiment of the present invention contains at least about 0.2%, preferably from about 0.2% to about 5%, more preferably from about 0.2% to about 2% by weight, of one or more polyvinyl amines having the formula wherein y is from about 3 to about 10,000, preferably from about 10 to about 5,000, more preferably from about 20 to about 500.
  • Polyvinyl amines suitable for use in the present invention are available from BASF.
  • one or more of the polyvinyl amine backbone -NH 2 unit hydrogens can be substituted by an alkyleneoxy unit having the formula: -(R 1 O) x R 2 wherein R 1 is C 2 -C 4 alkylene, R 2 is hydrogen, C 1 -C 4 alkyl, and mixtures thereof; x is from 1 to 50.
  • the polyvinyl amine is reacted first with a substrate which places a 2-propyleneoxy unit directly on the nitrogen followed by reaction of one or more moles of ethylene oxide to form a unit having the general formula: wherein x has the value of from 1 to about 50.
  • Substitutions such as the above are represented by the abbreviated formula PO-EO x -.
  • more than one propyleneoxy unit can be incorporated into the alkyleneoxy substituent.
  • Polyvinyl amines are especially preferred for use as cationic charge booster in liquid fabric softening compositions since the greater number of amine moieties per unit weight provides substantial charge density.
  • the cationic charge is generated in situ and the level of cationic charge can be adjusted by the formulator.
  • a preferred composition of the present invention comprises at least about 0.2%, preferably from about 0.2% to about 10%, more preferably from about 0.2% to about 5% by weight, of a cationic charge booster having the formula: wherein R is substituted or unsubstituted C 2 -C 12 alkylene, substituted or unsubstituted C 2 -C 12 hydroxyalkylene; each R 1 is independently C 1 -C 4 alkyl, each R 2 is independently C 1 -C 22 alkyl, C 3 -C 22 alkenyl, R 5 -Q-(CH 2 ) m - , wherein R 5 is C 1 -C 22 alkyl, C 3 -C 22 alkenyl, and mixtures thereof; m is from 1 to about 6; Q is a carbonyl unit as defined hereinabove; and mixtures thereof; X is an anion.
  • R is ethylene;
  • R 1 is methyl or ethyl, more preferably methyl;
  • at least one R 2 is preferably C 1 -C 4 alkyl, more preferably methyl.
  • at least one R 2 is C 11 -C 22 alkyl, C 11 -C 22 alkenyl, and mixtures thereof.
  • the formulator may similarly choose R 2 to be a R 5 -Q-(CH 2 ) m - moiety wherein R 5 is an alkyl moiety having from 1 to 22 carbon atoms, preferably the alkyl moiety when taken together with the Q unit is an acyl unit derived preferably derived from a source of triglyceride selected from the group consisting of tallow, partially hydrogenated tallow, lard, partially hydrogenated lard, vegetable oils and/or partially hydrogenated vegetable oils, such as, canola oil, safflower oil, peanut oil, sunflower oil, corn oil, soybean oil, tall oil, rice bran oil, etc. and mixtures thereof.
  • An example of a fabric softener cationic booster comprising a R 5 -Q-(CH 2 ) m - moiety has the formula: where in R 1 is methyl, one R 2 units is methyl and the other R 2 unit is R 5 -Q-(CH 2 ) m -wherein R 5 -Q- is an oleoyl unit and m is equal to 2.
  • X is a softener compatible anion, preferably the anion of a strong acid, for example, chloride, bromide, methylsulfate, ethylsulfate, sulfate, nitrate and mixtures thereof, more preferably chloride and methyl sulfate.
  • a strong acid for example, chloride, bromide, methylsulfate, ethylsulfate, sulfate, nitrate and mixtures thereof, more preferably chloride and methyl sulfate.
  • compositions containing both saturated and unsaturated diester quaternary ammonium compounds can be prepared that are stable without the addition of concentration aids.
  • the compositions of the present invention may require organic and/or inorganic concentration aids to go to even higher concentrations and/or to meet higher stability standards depending on the other ingredients.
  • concentration aids which typically can be viscosity modifiers may be needed, or preferred, for ensuring stability under extreme conditions when particular softener active levels are used.
  • the surfactant concentration aids are typically selected from the group consisting of (1) single long chain alkyl cationic surfactants; (2) nonionic surfactants; (3) amine oxides; (4) fatty acids; and (5) mixtures thereof. These aids are described in P&G Copending Application Serial No. 08/461,207, filed June 5, 1995, Wahl et al., specifically on page 14, line 12 to page 20, line 12.
  • Preferred dispersibility aids are GENAMINE ® and GENAPOL ® ex Clariant.
  • a preferred embodiment comprises both a cocoyl ethoxylated amine and a cocoyl ethoxylated alcohol, wherein the ethoxylation is approximately 10, each of which are available as GENAMINE ® and GENAPOL ® .
  • a preferred example of the use of this admixture is a composition which compries, for example, 0.2% GENAMINE ® and 0.1 % GENAPOL ® .
  • the total level is from 0.1%, preferably from 0.3%, more preferably from 3%, even more preferably from 4%, and most preferably from 5% to 25%, preferably to 17%, more preferably to 15%, most preferably to 13% by weight, of the composition.
  • These materials can either be added as part of the active softener raw material, e.g., the mono-long chain alkyl cationic surfactant and/or the fatty acid which are reactants used to form the fabric softener active as discussed hereinbefore, or added as a separate component.
  • the total level of dispersibility aid includes any amount that may be present as part of the softener active.
  • certain soil release agents provide not only the below described soil release properties but are added for their suitability in maintaining proper viscosity, especially in the dispersed phase, non-isotropic compositions.
  • Polymeric soil release agents are characterized by having both hydrophilic segments, to hydrophilize the surface of hydrophobic fibers, such as polyester and nylon, and hydrophobic segments, to deposit upon hydrophobic fibers and remain adhered thereto through completion of the rinsing cycle and, thus, serve as an anchor for the hydrophilic segments. This can enable stains occurring subsequent to treatment with the soil release agent to be more easily cleaned in later washing procedures.
  • soil release agents will generally comprise from about 0.01% to about 10.0%, by weight, of the detergent compositions herein, typically from about 0.1% to about 5%, preferably from about 0.2% to about 3.0%.
  • compositions optionally comprise from about 0.01%, preferably from about 0.75%, more preferably from 10%, most preferably from about 15% to about 50%, preferably to about 35%, more preferably to about 30%, most preferably to about 5% by weight, of one or more linear or cyclic polyamines which provide bleach protection.
  • the bleach protection polyamines of the present invention have the formula: wherein R is 1,2-propylene, 1,3-propylene, and mixtures thereof; preferably 1,3-propylene.
  • Each R 1 is independently hydrogen, methyl, ethyl, or an alkyleneoxy unit having the formula: -(R 3 O)-R 4 wherein R 3 is ethylene, 1,2-propylene, 1,2-butylene, or mixtures thereof; preferably R 3 is ethylene or 1,2-propylene, more preferably 1,2-propylene.
  • R 4 is hydrogen, C 1 -C 4 alkyl, and mixtures thereof; preferably hydrogen.
  • R 1 may comprise any mixture of alkyleneoxy units.
  • R 2 is hydrogen, R 1 , -RN(R 1 ) 2 , and mixtures thereof; preferably at least one R 2 is hydrogen when n is equal to 2.
  • the integer n is 1 or 2.
  • each R 1 and R 2 will be independently selected from methyl or ethyl.
  • a prefered bleach protection linear polyamine has a backbone wherein R is 1,3-propylene, R 2 is hydrogen, or alkoxy, and n is equal to 2 is N,N'-bis(3-aminopropyl)-1,3-propylenediamine (TPTA).
  • TPTA N,N'-bis(3-aminopropyl)-1,3-propylenediamine
  • polyamines which comprise alkylated polyamines are preferred, for example, tetramethyl dipropylenetriamine, permethylated dipropylenetriamine, mono-methylated dipropylenetriamine.
  • the bleach protection cyclic polyamines comprise polyamine backbones having the formula: R-L-R wherein L is a linking unit, said linking unit comprising a ring having at least 2 nitrogen atoms; R is hydrogen, -(CH 2 ) k N(R 1 ) 2 , and mixtures thereof; wherein each index k independently has the value from 2 to 4, preferably 3.
  • L is a linking unit, said linking unit comprising a ring having at least 2 nitrogen atoms
  • R is hydrogen, -(CH 2 ) k N(R 1 ) 2 , and mixtures thereof; wherein each index k independently has the value from 2 to 4, preferably 3.
  • the backbone of the cyclic amines including R units is 200 daltons or less.
  • Each R 1 is independently hydrogen, C 1 -C 2 alkyl, or an alkyleneoxy unit having the formula: -(R 3 O)- R 4 wherein R 3 is ethylene, 1,2 propylene, 1,2-butylene, or mixtures thereof; preferably R 3 is ethylene or 1,2-propylene, more preferably 1,2-propylene.
  • R 4 is hydrogen, C 1 -C 4 alkyl, and mixtures thereof; preferably hydrogen.
  • R 1 may comprise any mixture of alkyleneoxy units.
  • Preferred polyamines have the formula: (R 1 ) 2 N-(CH 2 ) k -L-(CH 2 ) k -N(R 1 ) 2 wherein the indices k each have the same value and each R 1 is the same unit.
  • Examples of carbonyl containing rings which comprise L units are 1,4-diketopiperizines.
  • a preferred backbone of the chlorine scavenging polyamines, prior to modification, has the formula: wherein each R unit is -(CH 2 ) 3 NH 2 and each R 5 unit is hydrogen.
  • the cyclic units may be substituted on only one ring nitrogen as in the case wherein one R unit is hydrogen, and the other R unit is -(CH 2 ) k NH 2 , for example, the piperazine having the formula:
  • the backbones of the cyclic polyamines preferably comprise at least one 1,3-propylene unit, more preferably at least two 1,3-propylene units.
  • the fabric enhancement compositions may optionally comprise from about 0.5%, preferably from about 1% to about 10%, preferably to about 5% by weight, of one or more cationic nitrogen containing compound, preferably a cationic surfactant having the formula: wherein R is C 10 -C 18 alkyl, each R 1 is independently C 1 -C 4 alkyl, X is a water soluble anion; preferably R is C 12 -C 14 , preferably R 1 is methyl.
  • Preferred X is halogen, more preferably chlorine.
  • cationic nitrogen compounds suitable for use in the fabric care compositions are Non-limiting examples of preferred cationic nitrogen compounds are N,N-dimethyl-(2-hydroxyethyl)-N-dodecyl ammonium bromide, N,N-dimethyl-(2-hydroxyethyl)-N-tetradecyl ammonium bromide. Suitable cationic nitrogen compounds are available ex Akzo under the tradenames Ethomeen T/15 ® , Secomine TA15 ® , and Ethoduomeen T/20 ® .
  • the present invention relates to a pre-soak or rinse-added composition
  • a pre-soak or rinse-added composition comprising:
  • the present invention relates to a pre-soak or rinse-added composition as above, further comprising a dispersibility aid system, said system comprising:
  • the present invention further relates to a method for providing protection and enhancement of fabric, said method comprising the step of contacting a fabric with a composition comprising:
  • contacting is defined as "intimate contact of a fabric with an aqueous solution of the hereinabove described composition which comprises a fabric abrasion reducing polymer.”
  • 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.
  • Laundering is a preferred process. Temperatures for laundering can take place at a variety of temperatures, however, laundering typically occurs at a temperature less than about 30° C, preferably from about 5° C to about 25° C.
  • Dye fixing agent ex Clariant under the tradename Cartafix CB ® .
  • PEI 1200 E4 according to U.S. 5,565,145 Watson et al., issued October 15, 1996.
  • PEI 1200 E1 according to U.S. 5,565,145 Watson et al., issued October 15, 1996.
  • 2-Phosphonobutane-1,2,4-tricarboxylic acid ex Bayer.
  • PEI 1200 E4 according to U.S. 5,565,145 Watson et al., issued October 15, 1996. 7.
  • Cellulose reactive dye fixing agent ex Clariant under the tradename Indosol CR ® .
  • Cellulose reactive dye fixing agent ex CHT R. Beitlich under the tradename Rewin WBS ® .
  • compositions which are suitable for delivery via a substrate dryer sheet.
  • TABLE VI weight % Ingredients 31 32 33 34 35 36 Polymer 1 20.0 30.0 10.0 5.0 7.5 15.0 Softener active 2 40.0 25.0 -- -- -- -- -- Softener active 3 -- -- 20.0 -- -- -- Softener active 4 -- -- -- 20.0 12.0 60.0 Softener active 5 30.0 30.0 20.0 30.0 20.0 -- Glycosperse S-20 6 -- -- 10.0 -- -- -- -- Glycerol monostearate -- -- -- 20.0 10.0 -- Clay 4.0 4.0 3.0 4.0 4.0 -- Perfume 0.7 1.1 0.7 1.6 2.6 1.4 Polyalkyleneimine 7 -- 5.0 -- -- -- -- Polyalkyleneimine 8 -- -- -- 4.0 2.2 -- -- Polyalkyleneimine 9 2.0 -- -- -- 5.0 7.0 Dye fixative 10 2.0 5.0 4.0 2.2 5.0 3.0 HEDP 11 0.2 -- 0.5 -- -- 0.7 Glycolic acid -- 0.2 -- 0.2 -- Polycar
  • PEI 1800 E1 according to U.S. 5,565,145 Watson et al., issued October 15, 1996. 8.
  • PEI 1200 E4 according to U.S. 5,565,145 Watson et al., issued October 15, 1996.
  • PEI 1800 E4 according to U.S. 5,565,145 Watson et al., issued October 15, 1996.
  • Cellulose reactive dye fixing agent ex Clariant under the tradename Indosol CR ® .
  • 1,1-Hydroxyethane diphosphonic acid 11.
  • Polycarboxylic compound ex BASF under the tradename Sokalan CP 10 ® .
  • pre-soak fabric conditioning and/or fabric enhancement compositions which can also be suitably used in the laundry rinse cycle.
  • the following provide fabric abrasion protection for fabric treated with said compositions.
  • Dye fixative ex Clariant under the tradename Cartafix CB ® .
  • Dye fixing agent ex Clariant under the tradename Cartafix CB ® .
  • 2-Phosphonobutane-1,2,4-tricarboxylic acid ex Bayer.
  • Dye fixing agent ex Clariant under the tradename Cartafix CB ® .
  • 2-Phosphonobutane-1,2,4-tricarboxylic acid ex Bayer.
  • N,N'-bis(3-aminopropyl)-1,4-piperazine 4. 1,1-N-dimethyl-5-N'-methyl-9,9-N"-dimethyl dipropylenetriamine. 5. 2-Phosphonobutane-1,2,4-tricarboxylic acid ex Bayer.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Claims (10)

  1. Verwendung eines Polymers, umfassend:
    (i) mindestens eine Monomereinheit, die eine Amideinheit umfasst; oder
    (ii) mindestens eine Monomereinheit, die eine N-Oxid-Einheit umfasst; oder
    (iii) Mischungen davon; und
    mit einem Molekulargewicht von mehr als 0,166 ag (100.000 Dalton) als stoffabriebverringerndes Polymer in einer Menge von 0,01 Gew.-% bis 20 Gew.-%, wobei der Rest Träger und Zusatzbestandteile sind, in einer Stoffpflegezusammensetzung für verringerten Stoffabrieb.
  2. Verwendung nach Anspruch 1, wobei das Stoffabriebpolymer eine oder mehrere Monomereinheiten umfasst, ausgewählt aus der Gruppe bestehend aus:
    a) einem Polyvinylpyrrolidon mit der Formel:
    Figure imgb0044
    b) einem Polyvinyloxazolidon mit der Formel:
    Figure imgb0045
    c) einem Polyvinylmethyloxazolidon mit der Formel:
    Figure imgb0046
    d) Polyacrylamiden und N-substituierten Polyacrylamiden mit der Formel:
    Figure imgb0047
     worin jedes R' unabhängig Wasserstoff, C1-C6-Alkyl ist oder beide R'-Einheiten zusammengefasst werden können, um einen Ring zu bilden, der 4-6 Kohlenstoffatome umfasst;
    e) Polymethacrylamiden und N-substituierten Polymethacrylamiden mit der allgemeinen Formel:
    Figure imgb0048
     worin jedes R' unabhängig Wasserstoff, C1-C6-Alkyl ist oder beide R'-Einheiten zusammengefasst werden können, um einen Ring zu bilden, der 4-6 Kohlenstoffatome umfasst;
    f) Poly(N-acrylylglycinamid) mit der Formel:
    Figure imgb0049
     worin jedes R' unabhängig Wasserstoff, C1-C6-Alkyl ist oder beide R'-Einheiten zusammengefasst werden können, um einen Ring zu bilden, der 4-6 Kohlenstoffatome umfasst;
    g) Poly(N-methacrylylglycinamid) mit der Formel:
    Figure imgb0050
     worin jedes R' unabhängig Wasserstoff, C1-C6-Alkyl ist oder beide R'-Einheiten zusammengefasst werden können, um einen Ring zu bilden, der 4-6 Kohlenstoffatome umfasst;
    h) Polyvinylurethane mit der Formel:
    Figure imgb0051
     worin jedes R' unabhängig Wasserstoff, C1-C6-Alkyl ist oder beide R'-Einheiten zusammengefasst werden können, um einen Ring zu bilden, der 4-6 Kohlenstoffatome umfasst.
    i) und Mischungen davon.
  3. Verwendung nach einem der Ansprüche 1 oder 2, wobei das stoffabriebverringemde Polymer außerdem eine farbstoffübertragungshemmende Einheit ist, die eine oder mehrere Poly(2-ethyl-2-oxazolin)-Monomereinheiten mit der folgenden Formel umfasst:
    Figure imgb0052
     worin der Index n für ein Molekulargewicht von mehr als 0,166 ag (100.000 Dalton) sorgt.
  4. Verwendung nach einem der Ansprüche 1-3, wobei das stoffabriebverringernde Polymer ein Polyvinylpyrrolidon mit einem Molekulargewicht von 0,166 ag (100.000 Dalton) bis 0,598 ag (360.000 Dalton) ist.
  5. Verwendung nach einem der Ansprüche 1-4, wobei die Zusammensetzung ferner von 0,001 Gew.-% bis 50 Gew.-% ein Farbstofffixiermittel umfasst.
  6. Verwendung nach einem der Ansprüche 1-5, wobei die Zusammensetzung ferner von 0,01 Gew.-% bis 50 Gew.-% ein Bleichschutz-Polyamin umfasst, ausgewählt aus der Gruppe bestehend aus 1,4-Bis-(3-Aminopropyl)piperazin, 1,1-N-Dimethyl-5-N'-methyl-9,9-N"-dimethyldipropylentriamin, 1,1-N-Dimethyl-9,9-N"-dimethyldipropylentriamin, N,N'-bis(3-Aminopropyl)-1,3-propylendiamin und Mischungen davon.
  7. Verwendung nach Anspruch 1, wobei die Stoffpflegezusammensetzung ferner Folgendes umfasst:
    a) wahlweise von 1 Gew.-% an einen Gewebeweichmacher;
    b) wahlweise zu weniger als 15 Gew.-% ein Hauptlösemittel, wobei das Hauptlösemittel einen ClogP-Wert von 0,15 bis 1 aufweist;
    c) wahlweise von 0,001 Gew.-% bis 90 Gew.-% ein oder mehrere Farbstofffixiermittel;
    d) wahlweise von 0,01 Gew.-% bis 50 Gew.-% ein oder mehrere cellulosereaktive Farbstofffixiermittel;
    e) wahlweise von 0,01 Gew.-% bis 15 Gew.-% einen Chlorfänger;
    f) wahlweise von 0,005 Gew.-% bis 1 Gew.-% einen oder mehrere Kristallwachstumsinhibitoren;
    g) wahlweise von 1 Gew.-% bis 12 Gew.-% einen oder mehrere flüssige Träger;
    h) wahlweise von 0,001 Gew.-% bis 1 Gew.-% ein Enzym;
    i) wahlweise von 0,01 Gew.-% bis 8 Gew.-% eine Polyolefinemulsion oder -suspension;
    j) wahlweise von 0,01 Gew.-% bis 0,2 Gew.-% ein Stabilisierungsmittel;
    k) wahlweise von 0,5 Gew.-% bis 5 Gew.-% ein kationisches Tensid; und
    l) von 0,01 Gew.-% an ein oder mehrere lineare oder cyclische Polyamine, die für Bleichschutz sorgen.
  8. Verwendung nach Anspruch 1, wobei die Stoffpflegezusammensetzung eine Voreinweichzusammensetzung oder eine der Spülung zugegebene Zusammensetzung ist, umfassend:
    a) von 3 Gew.-% bis 4 Gew.-% ein stoffabriebverringerndes Polyvinylpyrrolidon-Polymer mit einem Molekulargewicht von 0,266 ag (160.000 Dalton);
    b) von 2 Gew.-% bis 3 Gew.-% ein nicht cellulosereaktives Farbstofffixiermittel;
    c) von 15 Gew.-% bis 20 Gew.-% 1,4-Bis-(3-Aminopropyl)piperazin;
    d) von 0,5 bis 1,5 Gew.-% 2-Phosphonobutan-1,2,4-tricarbonsäure; und
    e) zu übrigen Teilen Träger und Zusatzbestandteile.
  9. Verwendung nach Anspruch 8, wobei die Zusammensetzung ferner ein Dispergierbarkeitsunterstützungssystem umfasst, wobei das System Folgendes umfasst:
    i) 0,2 % ethoxyliertes Cocoylamin mit durchschnittlich 10 Ethoxyeinheiten; und
    ii) 0,1 % ethoxylierten Cocoylalkohol mit durchschnittlich 10 Ethoxyeinheiten.
  10. Verfahren zum Versehen von Stoff mit weniger Abriebschäden, umfassend den Schritt des Kontaktierens eines Stoffs mit einer Zusammensetzung, umfassend:
    a) von 0,01 Gew.-% bis 20 Gew.-% ein stoffabriebverringerndes Polymer, wobei das Stoffabriebpolymer Folgendes umfasst:
    (i) mindestens eine Monomereinheit, die eine Amideinheit umfasst;
    (ii) mindestens eine Monomereinheit, die eine N-Oxid-Einheit umfasst;
    (iii) oder Mischungen davon;
    b) wahlweise einen oder mehrere Stoffverbesserungsbestandteile; und
    c) zu übrigen Teilen Träger und Zusatzbestandteile;
    mit der Maßgabe, dass das Molekulargewicht des stoffabriebverringernden Polymers größer als 0,166 ag (100.000 Dalton) ist.
EP99971446A 1998-11-02 1999-10-22 Verwendung von polymeren in stoffbehandlungsmitteln mit reduzierter gewebe-abreibung Expired - Lifetime EP1124927B1 (de)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
US10675998P 1998-11-02 1998-11-02
US106759P 1998-11-02
US11031098P 1998-11-30 1998-11-30
US110310P 1998-11-30
PCT/US1999/024941 WO2000026331A1 (en) 1998-11-02 1999-10-22 Fabric care compositions having reduced fabric abrasion

Publications (2)

Publication Number Publication Date
EP1124927A1 EP1124927A1 (de) 2001-08-22
EP1124927B1 true EP1124927B1 (de) 2007-01-24

Family

ID=26804003

Family Applications (1)

Application Number Title Priority Date Filing Date
EP99971446A Expired - Lifetime EP1124927B1 (de) 1998-11-02 1999-10-22 Verwendung von polymeren in stoffbehandlungsmitteln mit reduzierter gewebe-abreibung

Country Status (10)

Country Link
EP (1) EP1124927B1 (de)
JP (1) JP4509384B2 (de)
CN (1) CN100463956C (de)
AT (1) ATE352605T1 (de)
AU (1) AU1228300A (de)
BR (1) BR9914980B1 (de)
CA (1) CA2347809C (de)
DE (1) DE69935001T2 (de)
ES (1) ES2281208T3 (de)
WO (1) WO2000026331A1 (de)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5670815B2 (ja) * 2011-04-21 2015-02-18 花王株式会社 衣料用処理剤組成物

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0919610A1 (de) * 1997-10-31 1999-06-02 The Procter & Gamble Company Saure flüssige Zusammensetzungen zum Entfernen von Kesselstein verpackt in einem Sprühspender
EP0957156A1 (de) * 1998-05-15 1999-11-17 The Procter & Gamble Company Flüssige, saure Reinigungszusammensetzung für harte Oberflächen
WO1999061569A1 (en) * 1998-05-22 1999-12-02 The Procter & Gamble Company Acidic cleaning compositions with c10 alkyl sulfate detergent surfactant
EP0982394A1 (de) * 1998-08-27 2000-03-01 The Procter & Gamble Company Flüssige neutrales oder alkalisches Reinigungsmittel für harte Oberflächen

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE785653A (de) * 1971-07-02 1973-01-02 Procter & Gamble Europ
US4126563A (en) * 1974-07-08 1978-11-21 Graham Barker Composition for treating fabrics, method for making and using the same
DE69117490T2 (de) * 1991-04-12 1996-09-26 Procter & Gamble Polyvinylpyrrolidon enthaltendes Kompaktwaschmittel
GB9317803D0 (en) * 1993-08-27 1993-10-13 Cussons Int Ltd Laundry detergent composition
US5451341A (en) * 1993-09-10 1995-09-19 The Procter & Gamble Company Soil release polymer in detergent compositions containing dye transfer inhibiting agents to improve cleaning performance
EP0778342A1 (de) * 1995-12-06 1997-06-11 The Procter & Gamble Company Waschmittelzusammensetzungen
ZA974226B (en) * 1996-05-17 1998-12-28 Procter & Gamble Detergent composition
CA2342902C (en) * 1998-09-15 2006-08-01 The Procter & Gamble Company Rinse-added fabric care compositions comprising low molecular weight linear and cyclic polyamines

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0919610A1 (de) * 1997-10-31 1999-06-02 The Procter & Gamble Company Saure flüssige Zusammensetzungen zum Entfernen von Kesselstein verpackt in einem Sprühspender
EP0957156A1 (de) * 1998-05-15 1999-11-17 The Procter & Gamble Company Flüssige, saure Reinigungszusammensetzung für harte Oberflächen
WO1999061569A1 (en) * 1998-05-22 1999-12-02 The Procter & Gamble Company Acidic cleaning compositions with c10 alkyl sulfate detergent surfactant
EP0982394A1 (de) * 1998-08-27 2000-03-01 The Procter & Gamble Company Flüssige neutrales oder alkalisches Reinigungsmittel für harte Oberflächen

Also Published As

Publication number Publication date
ATE352605T1 (de) 2007-02-15
CN100463956C (zh) 2009-02-25
ES2281208T3 (es) 2007-09-16
BR9914980B1 (pt) 2009-01-13
BR9914980A (pt) 2001-08-14
AU1228300A (en) 2000-05-22
JP2002528663A (ja) 2002-09-03
CA2347809A1 (en) 2000-05-11
CA2347809C (en) 2007-04-24
DE69935001T2 (de) 2007-08-30
JP4509384B2 (ja) 2010-07-21
EP1124927A1 (de) 2001-08-22
DE69935001D1 (de) 2007-03-15
CN1325433A (zh) 2001-12-05
WO2000026331A1 (en) 2000-05-11

Similar Documents

Publication Publication Date Title
US6551986B1 (en) Fabric enhancement compositions
EP1163319B1 (de) Wäschewaschmittelzusammensetzungen enthaltend bestimmten kationisch geladenen farbstofferhaltenden polymer
US6642200B1 (en) Fabric maintenance compositions comprising certain cationically charged fabric maintenance polymers
EP1114134B1 (de) Wäschenachspülzusätze enthaltend lineare polyamine mit niedrigem molekulargewicht
US20020137653A1 (en) Fabric care compositions
EP1240382A1 (de) Zusammensetzungen zur verhinderung der abrasiven entfärbung von denim-gewebe
US6794355B1 (en) Fabric care composition having reduced fabric abrasion
EP1124927B1 (de) Verwendung von polymeren in stoffbehandlungsmitteln mit reduzierter gewebe-abreibung
CA2359438A1 (en) Fabric enhancement compositions
US6750189B1 (en) Fabric enhancement compositions
EP1106676B1 (de) Verfahren zum Schaffen von Tragekomfort
CA2359457A1 (en) Fabric enhancement compositions containing amino acid based polymers
WO2000049123A1 (en) Fabric enhancement compositions comprising high molecular weight polyamines
EP1238138A1 (de) Nichtreaktives gewebeveredlungsmittel
US20030216094A1 (en) Method for providing in-wear comfort
CA2388836A1 (en) Fabric enhancement treatment
MXPA01008389A (en) Fabric enhancement compositions

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20010523

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

AX Request for extension of the european patent

Free format text: AL;LT;LV;MK;RO;SI

17Q First examination report despatched

Effective date: 20030718

RTI1 Title (correction)

Free format text: USE OF POLYMERS IN FABRIC CARE COMPOSITIONS HAVING REDUCED FABRIC ABRASION

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20070124

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20070124

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20070124

Ref country code: CH

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20070124

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20070124

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REF Corresponds to:

Ref document number: 69935001

Country of ref document: DE

Date of ref document: 20070315

Kind code of ref document: P

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20070424

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20070625

ET Fr: translation filed
REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2281208

Country of ref document: ES

Kind code of ref document: T3

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20071025

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20070124

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20070425

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20071031

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20071022

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20070124

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20071022

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20101004

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20100923

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20100912

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20101029

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20101021

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20101019

Year of fee payment: 12

REG Reference to a national code

Ref country code: NL

Ref legal event code: V1

Effective date: 20120501

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20111022

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20120629

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20120501

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20120501

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 69935001

Country of ref document: DE

Effective date: 20120501

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20111102

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20111022

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20111022

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20130417

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20111023