WO2000049122A1 - Compositions d'amelioration de l'aspect des textiles - Google Patents

Compositions d'amelioration de l'aspect des textiles Download PDF

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Publication number
WO2000049122A1
WO2000049122A1 PCT/US2000/003933 US0003933W WO0049122A1 WO 2000049122 A1 WO2000049122 A1 WO 2000049122A1 US 0003933 W US0003933 W US 0003933W WO 0049122 A1 WO0049122 A1 WO 0049122A1
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WIPO (PCT)
Prior art keywords
weight
unit
optionally
units
fabric
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PCT/US2000/003933
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English (en)
Inventor
Janet Sue Littig
Dieter Boeckh
Oliver Borzyk
Michael Ehle
Frederick Anthony Hartman
John Cort Severns
Shulin Zhang
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The Procter & Gamble Company
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Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to BR0008373-9A priority Critical patent/BR0008373A/pt
Priority to US09/890,676 priority patent/US6551986B1/en
Priority to JP2000599850A priority patent/JP2002537491A/ja
Priority to EP00908660A priority patent/EP1153117A1/fr
Priority to CA002359438A priority patent/CA2359438A1/fr
Priority to AU29962/00A priority patent/AU2996200A/en
Publication of WO2000049122A1 publication Critical patent/WO2000049122A1/fr

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    • 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
    • C11D3/3723—Polyamines or polyalkyleneimines
    • 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
    • C11D3/3719—Polyamides or polyimides
    • 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
    • C11D3/3788—Graft 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
    • C11D3/37—Polymers
    • C11D3/3792—Amine oxide containing polymers

Definitions

  • the present application relates to rinse-added fabric care compositions which comprise one or more crosslmked and/or grafted polya ines which provide enhanced fabric appearance benefits
  • the crosslmked and/or grafted polyam es of the present invention which mitigate fabric damage and improve fabric appearance may be combined with fabric softener actives compositions which mitigate fabric damage.
  • 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 dimmish the appearance of newness of the fabric Such a problem of fabric abrasion is even more acute after multiwash cycles.
  • compositions which provide fab ⁇ c with protection against damage done due to fabric abrasion there exists a long felt need for compositions which provide fab ⁇ c with protection against damage done due to fabric abrasion
  • compositions which provide a remedy for fabric abrasion damage SUMMARY OF THE INVENTION
  • high molecular weight modified polyamine compounds preferably compounds formed by the reaction of grafted or ungrafted and/or modified or unmodified polyammes with a crosslinking agent wherem said modified polyamine compounds have a molecular weight of from about 1,000 daltons, preferably from about 10,000 daltons to about 10 million daltons, preferably to about 2.5 million daltons, are suitable for use in ⁇ nse-added fabric care compositions wherein said modified polyammes comprise a fabric enhancement system which provides fabric appearance benefits inter aha mitigation of fabric dye damage via bleaching agents, prevention of fabric mechanical damage.
  • a first aspect of the present invention relates to rmse-added fab ⁇ c enhancement or fabric caie compositions comprising: a) from about 0.01% by weight, of a fabric enhancement system, said fabric enhancement system comprising one or more modified polyamine compounds, said modified polyamine compounds are selected from: i) (PA) W (T) > ii) (PA) W (L) Z ; in) [(PA) w (T) y [L] z ; and IV) mixtures thereof; where PA is a grafted or non-grafted, modified or unmodified polyamine backbone unit, T is an amide-formmg polycarboxylic acid crosslinking unit, and L is a non-amide forming crosslinking unit; provided that for compounds of type (I) and (in) the indices w and x have values such that the ratio of w to x is from 0.8 : 1 to 1.5 : 1 , for compounds of type (n) the indices w and z have values such that
  • a second aspect of the present invention relates to fabric care compositions comprising a) from about 0.01%, preferably from about 0.1% to about 20%, preferably to about
  • a modified polyamine compound according to the present invention 10% by weight, of a modified polyamine compound according to the present invention; b) optionally from about 0.01% by weight, of a fabric abrasion polymer comprising:
  • 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 which comprises from about 0.01% by weight, of the herein desc ⁇ bed modified polyamine fabric enhancement system.
  • a further aspect of the present invention provides a method for enhancing the color fidelity of fabric while reducing the damage to fabric due to the interaction of laundry adjunct ingredients and damage due to mechanical wear.
  • This method comprises the step of contacting an article of fabric with the compositions of the present invention in an aqueous solution.
  • the present invention further provides laundry pre-soak compositions which are used to pre-treat fabric which have not been previously treated with a composition of the present invention.
  • the disclosed pre-treatment compositions provide fab ⁇ c and fab ⁇ c color protection though the wash to the treated articles.
  • the present invention relates to fabric enhancement compositions which comprise from about 0.01%, preferably from about 0.1%, more preferably from 0.25%, most preferably from about 0.5%o to about 20%, preferably to about 10%, more preferably to about 5% by weight, of a fabric enhancement system
  • Said fabric enhancement system is comprised of one or more modified polyamine compounds.
  • the fabric care and/or fabric enhancement compositions may take any form, for example, solids (i.e., powders, granules, extrudates), gels, thixotropic liquids, liquids (i.e., dispersions, lsotropic solutions), preferably the nnse-added fabric conditioning compositions take the form of liquid dispersions or lsotropic liquids.
  • the terms "fabric enhancement” and “fabric care” are used interchangeable throughout the present specification and stand equally well for one another. Fabric enhancement/fabric care is achieved when the properties inter aha color, fiber integrity of the garment are conserved.
  • An additional benefit realized by the use of the compositions of the present invention is a reversion of much of the damage which has occurred to fabric which has never been treated with the herein described fabric enhancement compositions.
  • the fabric enhancement system of the present invention is comprised of one or more modified polyammes according to the present invention.
  • the modified polyammes of the present invention which comprise the fabric enhancement system may be formulated as an admixture wherein a proportional amount of two or more compounds are combined to make up the fabric enhancement system.
  • the formulator may adjust the reaction conditions which form the modified polyammes of the present invention m order to create an admixture of suitable ingredients inter aha an admixture of polyamine fragments and/or partially crosslmked modified polyammes.
  • the compounds which comp ⁇ se the fab ⁇ c enhancement compositions of the present invention have the formula: i) (PA) W (T) X,
  • PA PA W (L) Z ; in) [(PA) w (T) ] y [L] z ; wherein PA is a grafted or non-grafted, modified or unmodified polyamine backbone unit, T is an amide-forming polycarboxylic acid crosslinking unit, and L is a non-amide forming crosslinking unit.
  • T is an amide-forming polycarboxylic acid crosslinking unit
  • L is a non-amide forming crosslinking unit.
  • the relative amounts of PA units and T units which are present are such that the molar ratio of PA units to T units is from 0.8 : 1 to 1.5 : 1.
  • the relative amounts of PA units and L units which are present are such that the (PA) W (L) Z comprises from about 0.05, preferably from about 0.3 to 2 parts by weight of said L units. Therefore, 1 part of a grafted or non-grafted, modified or unmodified polyamine backbone unit may be combined with from about 0.05, preferably from about 0.3 parts by weight of an L unit to about 2 parts by weight of an L unit to form a suitable modified polyamine compound.
  • crosslmked polyammes having the formula (PA) w (T) ⁇ may be combined with from about 0.05, preferably from about 0.3 parts by weight of an L unit to about 2 parts by weight of an L unit to form a suitable modified polyamine compound having the formula [(PA) w (T) x ] y [L] z .
  • the modified polyamine compounds of the present invention comprise a Polyamine
  • PA unit which can be optionally, but preferably grafted.
  • PA unit which can be optionally, but preferably grafted.
  • a preferred PA unit according to the present invention are polyalkyleneimines and polyalkyleneamines having the general formula:
  • R is C 2 -C u linear alkylene, C 3 -C 12 branched alkylene, and mixtures thereof; preferably R is ethylene, 1,3-propylene, and 1 ,6-hexylene, more preferred is ethylene.
  • w 8
  • x 0
  • y 7
  • the index w typically has the value of y + 1.
  • the simplest of the low molecular weight polyammes of this type is ethylene diam e which may be present up to about 10% by weight of the PA unit mixture.
  • Non-limiting examples of low molecular weight polyalkyleneimme PA units include diethylene t ⁇ amme, t ⁇ ethylene tetramme, tetraethylene pentamme, dipropylene t ⁇ amme, t ⁇ propylene tetramme, and dihexamethylene t ⁇ amme PA units may be used as crude products or mixtures, and if desired by the formulator, these PA units may be used in the presence of small amounts of diammes as described herein above, wherem the amount of diammes, inter aha, ethylene diamme, hexamethylene diamme may be present up to about 10% by weight, of the PA unit mixture.
  • R is C 2 -C 4 linear alkylene, C 3 -C 4 branched alkylene, and mixtures thereof; preferably R is ethylene, 1,3-propylene, and mixtures thereof, more preferred is ethylene wherem said polyammes are polyethyleneimmes (PEI's).
  • PEI's polyethyleneimmes
  • the indices w, x, and y are such that the molecular weight of said polyammes is from about 600 daltons to about 50,000 daltons
  • the indices w, x, and y will indicate not only the molecular weight of the polyalkyleneimines but also the degree of branching present in the PA unit backbone High Molecular Weight Polyalkyleneimines
  • R is C 2 -C 3 linear alkylene, preferably R is ethylene.
  • the indices w, x, and y are such that the molecular weight of said polyamines is from about 50,000 daltons to about 1,000,000 (1 million) daltons.
  • the indices w, x, and y will indicate not only the molecular weight of the polyalkyleneimines but also the degree of branching present in the PA unit backbone.
  • Co-polvmeric Polyamines Another example of a preferred PA unit according to the present invention are the polyvinyl amine homo-polymers or co-polymers having the formula:
  • V is a co-monomer, non-limiting examples of which include vinyl amides, vinyl pyrrolidone, vinyl imidazole, vinyl esters, vinyl alcohols, and mixtures thereof, all of which can be taken together or in combination with polyvinyl amine to form suitable co-polymerization products suitable for use in the fabric enhancement systems of the present invention.
  • the indices m and n are such that the copolymers comprise at least 10%, more preferably at least about 30% of units derived from vinyl amine and wherein further the molecular weight of said copolymers if from about 500 daltons, preferably from about 5,000 daltons to about 50,000 daltons, preferably to about 20,000 daltons.
  • the PA units of the present invention are modified either before or after reaction with a T unit or L unit crosslinking agent.
  • the two preferred types of modifications are grafting and capping.
  • the PA units of the present invention are grafted, that is the PA unit is further reacted with a reagent which elongates said PA unit chain, preferably by reaction of the nitrogens of the PA backbone unit with one or more equivalents of aziridine (ethyleneimine), caprolactam, and mixtures thereof. Grafting units, in contrast to the "capping" units described herein below, can further react on themselves to provide PA unit chain propagation.
  • An example of a preferred grafted PA unit of the present invention has the formula: G B
  • R, B, w, x, and y are the same as defined herein above and G is hydrogen or an extension of the PA unit backbone by grafting.
  • preferred grafting agents are aziridine (ethyleneimine), caprolactam, and mixtures thereof.
  • a preferred grafting agent is aziridine wherein the backbone is extended by units having the formula:
  • B' is a continuation by branching wherein the graft does not exceed about 12 units, preferably -CH 2 CH 2 NH 2 and the value of the indices p + q have the value from 0, preferably from about 1, more preferably from about 2 to about 7, preferably to about 5.
  • Another preferred grafting unit is caprolactam.
  • the PA units of the present invention can be grafted prior to or after crosslinking with one or more T units described herein below, preferably the grafting is accomplished after crosslinking with said T unit.
  • This allows the formulator to take advantage of the differential reactivity between the primary and secondary amino units of the PA unit backbone thereby allowing the formulator to controllably link said PA units and to also control the amount of subsequent branching which results from the grafting step.
  • PA unit modification is the presence of "capping" units.
  • a PA unit is reacted with an amount of a monocarboxylic acid, non-limiting examples of which are C C 22 linear or branched alkyl, preferably C 10 -C 18 linear alkyl inter alia lauric acid, myristic acid.
  • the amount of capping unit which is reacted with the PA unit is an amount which is sufficient to achieve the desired properties of the formula.
  • the amount of capping unit used is not sufficient to abate any further crosslinking or grafting which the formulator may choose to perform.
  • T crosslinking units are preferably carbonyl comprising polyamido forming units.
  • the T units are taken together with PA units to form crosslinked modified polyamine compounds having the formula (PA) W (T) X or [(PA) w (T) x ] y [L] 2 .
  • a preferred embodiment of the present invention includes crosslinked PA units wherein a T unit provides crosslinking between two or more PA units to form a (PA) W (T) X polyamido crosslinked section.
  • a preferred crosslinking T unit has the general formula: wherein R 1 is methylene, phenylene, and mixtures thereof; preferably methylene.
  • the index k has the value from 2 to about 8, preferably to about 4. Preferred values of k are 2, 3, and 4.
  • R 2 is - NH- thereby forming a urethane amide linkage when said R 2 comprising T units react with the backbone nitrogens of the PA units.
  • the value of the index j is independently 0 or 1.
  • R 2 units can result, for example, from the use of dnsocyanates as crosslinking agents.
  • dibasic acids which are used as a source for T units in the above formula include succmic acid, maleic acid, adipic acid, gluta ⁇ c acid, suberic acid, sebacic acid, and terephthalic acid.
  • the formulator is not limited to crosslinking T units de ⁇ vmg from dibasic acids, for example, t ⁇ basic crosslinking T units, inter aha, citrate, may be used to link the PA units of the present invention.
  • Examples of (PA) W (T) compounds according to the present invention are obtained by condensation of dicarboxyhc acids wter alia succmic acid, maleic acid, adipic acid, terephthalic acid, with polyalkylene polyammes inter alia diethylenet ⁇ amme, t ⁇ ethylenetetramine, dipropylenet ⁇ amme, t ⁇ propylenetetramine wherem the ratio of the dicarboxyhc acid to polyalkyleneamme is from 1 :0.8 to 1:1.5 moles, preferably a ratio of from 1 :0.9 to 1 : 1.2 moles wherein the resulting crosslmked material has a viscosity in a 50% by weight, aqueous solution of more than 100 centipoise at 25 °C.
  • Non-amide Forming L Crosslinking Units Non-amide Forming L Crosslinking Units
  • polyamines of the present invention are (PA).. (T) units which are further crosslinked by L units to form polyamido ammes having the formula [(PA) w (T)J j [L] . or are reacted with PA units to form non-amide polyam es having the formula (PA) W (L) Z .
  • the L units of the present invention are any unit which suitably crosslinks PA units or
  • Preferred L linking units comprise units which are derived from the use of epihalohydrms, preferably epichlorohyd ⁇ n, as a crosslinking agent.
  • the epihalohydrms can be used directly with the PA units or suitably combined with other crosslinking adjuncts non- hmitmg examples of which include alkyl eneglycols, and polyalkylene polyglycols inter aha ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol- 1 ,6-glycerol, oligoglycerol, pentaeryth ⁇ tes, polyols which are obtained by the reduction of carbohydrates (sorbitol, mannitol), monosaccha ⁇ des, disaccha ⁇ des, oligosaccha ⁇ des, polysaccha ⁇ des, polyvinyl alcohols, and mixtures thereof.
  • hydrocarbyl units are polyalkylene units have the formula:
  • Hydrocarbyl L units may be derived from hydrocarbons having two units which are capable of reacting with the nitrogen of the PA units.
  • Non-limiting examples of precursors which result in the formation of hydrocarbyl L units include 1,6-dibromohexane, 1,8- ditosyloctane, and 1 ,14-dichlorotetradecane.
  • non-amide forming crosslinking L units are the units which derive from crosslinking units wherein epihalohydrin is used as the connecting unit.
  • epihalohydrin is used as the connecting unit.
  • 1,12-dihydroxydodecane is reacted with epichlorohydrin to form the bis-epoxide non- amide forming L unit precursor having the formula:
  • crosslinking unit precursor may be formed in situ by reaction of 1,12-dihydroxydodecane or other suitable precursor unit with epihalohydrin in the presence of grafted or ungrafted PA units or (PA) W (T) X units.
  • Other crosslinking L units which utilize one or more epihalohydrin connecting units include polyalkyleneoxy L units having the formula: CH 2 — CH— CH 2 — O ⁇ O ⁇ R ⁇ y — CH 2 — CH— CH 2 —
  • Another preferred unit which can comprise an L unit and which can be suitably combined with epihalohydrin connecting units include polyhydroxy units having the formula:
  • the formulator may also combine units to form hybrid L crosslinking units, for example, units having the formula:
  • indexes w and y are each independently from 1 to 50, z is units are present in a sufficient to suitably connect the polyhydroxy units and the polyalkyleneoxy units into the backbone without the formation of ether linkages.
  • L linking group which comprises both a polyalkyleneoxy and a polyhydroxy unit.
  • a further example of a preferred crosslinking L units are units which comprises at least two aziridine groups as connecting groups, for example an L unit having the formula:
  • the polyamines of the present invention may have varying final compositions, for example, (PA) tt (T) , [(PA) W (T) ]. [L] z , [(PA)] L] Z , and mixtures thereof, wherem each PA unit may be grafted or ungrafted.
  • the indices w and x have values such that the ratio of w to x is from 0.8 : 1 to 1.5 : 1; y and z have values such that said polyamido compound comprises from about 0.05, preferably to about 0.3 to 2 parts by weight of said L unit.
  • the index y is equal to 1 and z is equal to 0.
  • the indices w and y are equal to 1 and x is equal to 0.
  • the indices w and y are equal to 1 and x is equal to 0.
  • An preferred embodiment of the present invention which comprises PA units, T units, and L units includes the reaction product of: a) 1 part by weight, of a polyamine obtained by condensation of 1 mole of a dicarboxyhc acid with a polyalkylene polyamine (i.e., diethylenet ⁇ amme) to the extent wherein at least about 10% of the -NH backbone hydrogens are unmodified by reaction with said dicarboxyhc acid, then optionally reacting the obtained polyamine condensation product with up to 12 ethyleneimme units (i.e., grafting of the backbone using aziridine) per basic nitrogen atom; and b) further reacting the product obtained in (a) with from 0.05, preferably from about
  • a preferred embodiment of the present invention are the water-soluble condensation products which can be obtained by the reaction of: a) polyalkyleneimines and polyalkyleneimines grafted with ethyleneimmes, and mixtures thereof; with b) at least bifunctional halogen-free cross-linking agents, said agents selected from the group consisting of: l) ethylene carbonate, propylene carbonate, urea, and mixtures thereof, n) mono-carboxyhc acids comprising one olefin moiety inter aha acrylic acid, methacryhc acid, crotomc acid; and the esters, amides, and anhydrides thereof; polycarboxylic acids inter aha oxalic acid, succmic acid, tarta ⁇ c acid, ltacomc acid, maleic acid; and the esters, amides, and anhydrides thereof; m) reaction products of polyetherdiamines, alkylenediam es, polyalkylene- diammes, and mixtures thereof
  • the (PA) W (T) X polyamine compound may be partially amidated ("capped" as described herein above) by treatment with a mono carboxylic acid or the esters of mono carboxylic acids.
  • the formulator may vary the degree to which the backbone nitrogens are amidated according to the desired properties of the final Fabric Enhancement Polymer.
  • suitable mono- carboxylic acids include formic acid, acetic acid, propionic acid, benzoic acid, salicylic acid, lauric acid, palmitic acid, stearic acid, oleic acid, linoleic acid, behenic acid, and mixtures thereof.
  • the high molecular weight modified polyamine condensation products of the present invention are preferably formed from the reaction of one or more grafted, cross-linked polyethyleneimmes and one or more polyethylene and/or polypropylene glycol copolymers, wherein the resulting crosslinked modified polyamines (resins) have a final viscosity of more than or equal to 300 mPa-sec, preferably from 400 to 2,500 mPa-sec. when measured at 20° C in a 20% aqueous solution.
  • the modified polyamine compounds of the present invention are suitably described in U.S. 3,642,572 Eadres et al., issued February 15, 1972, U.S. 4,144,123 Scharf et al, issued March 13, 1979 and U.S. 4,371,674
  • the present invention relates to fabric care compositions which comprise: a) from about 0.01%, preferably from about 0.1% to about 20%, preferably to about 10% by weight, of a fabric enhancement system according to the present invention; b) optionally from about 0.01% by weight, of a fabric abrasion polymer comprising: i) at least one monomeric unit comprising an amide moiety; ii) at least one monomeric unit comprising an N-oxide moiety; iii) and mixtures thereof; c) optionally from about 1%, preferably from about 10%, more preferably from about 20% to about 80%, preferably to about 60%, more preferably to about 45% by weight, of a fabric softening active; d) optionally less than about 15% by weight, of a principal solvent, preferably said principal solvent has a ClogP of from about 0.15 to about 1; e) optionally from about 0.001% to about 90% by weight, of one or more dye fixing agents; g) optionally from about
  • One aspect of the fabric enhancement systems of the present invention is the combination of the enhancement system and a catiomc fabric softening active.
  • a preferred embodiment of the present invention provides for rinse-added compositions which comp ⁇ se. a) from about 0.01% by weight, of a fabric enhancement system, said fabric enhancement system comprising one or more modified polyamine compounds, said modified polyamine compounds are selected from: i) (PA) W (T) X, n) (PA) W (L) Z ; in) [(PA) w (T) y [L] z ; and
  • PA is a grafted or non-grafted, modified or unmodified polyamine backbone unit
  • T is an amide-formmg polycarboxylic acid crosslinking unit
  • L is a non-amide forming crosslinking unit
  • the indices w and x have values such that the ratio of w to x is from 0.8 : 1 to 1.5 : 1
  • the indices w and z have values such that said modified polyamine compound comprises from about 0.05, preferably from about 0.3 to 2 parts by weight of said L unit
  • the indices y and z have values such that said modified polyamine compound comprises from about 0.05, preferably from about 0.3 to 2 parts by weight of said L unit
  • the balance carriers and adjunct ingredients are examples of the balance carriers and adjunct ingredients.
  • the term "effective amount" of a fabric softener active may vary depending upon the execution of the fab ⁇ c softener formulation. Certain embodiments may comp ⁇ se from 6% to about 9%, preferably about 8% by weight, of a fabric softener active, while isotropic liquid embodiments may comp ⁇ se from about 28% to bout 45% by weight of a catiomc softener active. Other embodiments may comprise amounts between the two ranges.
  • the fabric care compositions of the present invention comprise one or more modified polyamine compounds as described herein.
  • fabric care compositions is defined as "a composition which provides care to the fab ⁇ c non- hmitmg examples of which include stand-alone compositions, detergent additives, fabric softening compositions z «ter alia ⁇ nse-added softening composition, dryer-added softening compositions”.
  • the compositions of the present invention provide an efficient fabric abrasion reduction.
  • the term “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 are non-limiting examples of ingredients which can be combined with the modified polyamine compounds of the present invention. Fabric Abrasion Reducing Polymers
  • compositions of the present invention comprise from about 0.01%, preferably from about 0.1% to about 20%, preferably to about 10% by weight, of a fabric abrasion reducing polymer.
  • the prefered reduced abrasion polymers of the present invention are water-soluble polymers.
  • water-soluble is defined as "a polymer which when dissolved m 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:
  • unit P is a polymer backbone which comprises units which are homopolymeric or copolymeric.
  • D units are defined herein below.
  • 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:
  • each R unit is independently hydrogen, C,-C 12 alkyl, C 6 -C I2 aryl, and D units as described herein below; preferably C,-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:
  • index p is from 1 to about 6; units which have dye transfer inhibition activity: R* O O
  • R 1 is hydrogen, C,-C 12 alkyl, C 6 -C 12 aryl, and mixtures thereof.
  • R 2 is C,-C 12 alkyl, C r C 12 alkoxy, C 6 -C 12 aryloxy, and mixtures thereof, preferably methyl and methoxy.
  • R 3 is hydrogen C,-C ⁇ 2 alkyl, -C 12 aryl, and mixtures thereof; preferably hydrogen or C C 4 alkyl, more preferably hydrogen.
  • R 4 is C r C 12 alkyl, C 6 -C, 2 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 - 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 dye transfer inhibition while providing a polymer which has fabric abrasion reducing properties.
  • the molecular weight of the fabric abrasion reducing polymers of the present invention aie from about 500, preferably from about 1,000, more preferably from about 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.
  • 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-hmitmg examples of preferred D units are D units which comprise an amide moiety
  • Examples of polymers wherem an amide unit is introduced into the polymer via a pendant group includes polyvmylpyrrohdone having the formula: [CH-CH 2 ] n -
  • each R' is independently hydrogen, C,-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:
  • each R' is independently hydrogen, C,-C 6 alkyl, or both R' units can be taken together to form a ring comp ⁇ smg 4-6 carbon atoms; poly(N-acrylylglycmam ⁇ de) having the formula: [CH-CH 2 ] n
  • each R' is independently hydrogen, C,-C 6 alkyl, or both R' units can be taken together to form a ring comp ⁇ s g 4-6 carbon atoms; poly(N-methacrylylglyc ⁇ nam ⁇ de) having the formula:
  • each R' is independently hydrogen, C,-C 6 alkyl, or both R' units can be taken together to form a ring comprising 4-6 carbon atoms.
  • D unit wherem the nitrogen of the dye transfer inhibiting moiety is incorporated into the polymer backbone is a poly(2-ethyl-2-oxazolme) having the formula:
  • 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 m effect shielded to a varying degree by the surrounding non-polar groups. This provides the polymers with an amphiphihc character.
  • Non-limiting examples include polyvmyl-pyrrohdones, polyvinyloxazo dones, N,N-d ⁇ subst ⁇ tuted polyacrylamides, and N,N-d ⁇ subst ⁇ tuted 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 crosslmked forms.
  • a preferred polymeric compound for the present invention is polyvmylpyrrohdone (PVP). This polymer has an amphiphilic character with a highly polar amide group conferring hydrophihc and polar-attracting properties, and also has non-polar methylene and methme groups, m 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 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 K-12, K-15, and K-30 are also available ex Polysciences, Inc. Wamngton, Pennsylvania,
  • PVP K-15, K-25, and K-30 and poly(2-ethyl-2-oxazohne) are available ex Ald ⁇ ch 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 Ald ⁇ ch is also suitable for use herein
  • Yet further PVP-type of material suitable for use m the present invention are polyvmylpyrro done-co-dimethylammoethylmethacrylate, commercially available commercially ex ISP in a quaternised form under the tradename Gafquat® or commercially available ex Ald ⁇ ch Chemical Co.
  • Another D unit which provides dye transfer inhibition enhancement to the fabric abrasion reducing polymers described herein, are N-oxide units having the formula:
  • 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., polyalkyleneamme backbone, or the N-oxide may be part of a pendant group attached to the polymer backbone.
  • a polymer which comp ⁇ ses an the N-oxide unit as a part of the polymer backbone is polyethyleneimme N-oxide.
  • Non-hmitmg examples of groups which can comprise an N-oxide moiety include the N-oxides of certain heterocycles inter alia py ⁇ dme, pyrrole, imidazole, pyrazole, pyrazme, py ⁇ midme, py ⁇ dazme, pipe ⁇ dme, pyrro dme, pyrrolidone, azohdine, morpholme.
  • a preferred polymer is poly(4- vmylpy ⁇ ding 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 am e 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 For example, 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 ammo units, or the formulator may control the oxidation level of the polymer during preparation.
  • the amme oxide unit of the polyamine N-oxides of the present invention have a Pk d 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 about 500 daltons, preferably from about 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.
  • Polymers Comprising Amide Units and N-oxide Units 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 desc ⁇ bed herein above.
  • Non-hmitmg examples include co-polymers of two monomers wherein the first monomer comprises an amide unit and the second monomer comprises an N- oxide unit.
  • ohgomers 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 Molecular weight
  • the above described fabric abrasion reducing 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 fab ⁇ c 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.
  • 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 withm this definition are components which can in some embodiments serve as fabric softener actives.
  • dye fixing agents are catiomc, and are based on quatermzed nitrogen compound oi on nitrogen compounds having a strong catiomc charge which is formed in situ under the conditions of usage.
  • Catiomc 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.
  • SANDOFIX TPS ex Sandoz
  • SANDOFIX SWE a catiomc resinous compound
  • a preferred dye fixing agent for use in the compositions of the present invention is CARTAFLX CB® ex Cla ⁇ ant.
  • Dye fixing agents suitable for use in the present invention are ammonium compounds such as fatty acid-diamine condensates mter 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.
  • CRT Cellulose Reactivity Test
  • 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. Chlorine Scavengers
  • 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:
  • each R is independently hydrogen, C,-C 4 alkyl, C r C 4 substituted alkyl, and mixtures thereof, preferably R is hydrogen or methyl, more preferably hydrogen.
  • R 1 is hydrogen C C 9 alkyl, C,-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 included 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.
  • CGIT Crystal Growth Inhibition Test
  • 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 HC1 and subsequently heating the solution until all of the hydroxyapatite is dissolved (heating for several
  • 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.
  • a solution of 50% aqueous KOH is added to the solution.
  • 1.5 L of distilled water is added, the solution stirred, then after settling again for 2 days the supernatant is removed.
  • This ⁇ nsing procedure is repeated six more time after which the pH of the solution is adjusted to neutrality using 2N HC1
  • the resulting slurry can be stored at 37°C for eleven months.
  • Crystal growth inhibitors which are suitable for use m 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 from chelatmg 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.
  • 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-d ⁇ carboxy-4-oxa-l,6-hexaned ⁇ oates and related compounds further disclosed m U.S. 4,566,984 incorporated herein by reference, C5-C20 alkyl, C5-C20 alkenyl succmic acid and salts thereof, of which dodecenyl succmate, lauryl succmate, myristyl succmate, palmityl succmate, 2-dodecenylsuccmate, 2-pentadecenyl succmate, are non- hmitmg examples.
  • Other suitable polycarboxylates are disclosed m 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- diphosphomc acid or salt which does not comprise a nitrogen atom”.
  • Preferred organic diphosphonic acids include C r 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, vmyhdene- 1,1 -diphosphonic acid , l,2-d ⁇ hydroxyethane-l,l- 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
  • 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:
  • each R is independently C j -Cg alkyl, C j -Cg hydroxyalkyl, benzyl, and mixtures thereof;
  • R* is preferably C ⁇ -C22 linear alkyl, C ⁇ 1-C22 branched alkyl, C ⁇ 1-C22 linear alkenyl, Cj j-C-22 branched alkenyl, and mixtures thereof;
  • Q is a carbonyl moiety independently selected from the units having the formula:
  • R ⁇ is hydrogen, Ci -C4 alkyl, preferably hydrogen; R ⁇ is C ⁇ -C4 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, sulfate, nitrate and mixtures thereof, more preferably chloride and methyl sulfate.
  • 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:
  • R 1 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. Yet more preferred are the Diester Quaternary Ammonium Compounds (DEQA's) wherein the index m is equal to 2.
  • 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! 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 1-C22 alkenyl, including polyalkenyl (polyunsaturated) units inter alia oleic, linoleic, linolenic.
  • the term "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".
  • the R 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
  • cis and trans isomers can be used, preferably with a cisltrans 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. Indeed, for compounds having the formula: +
  • a further preferred embodiment of the present invention comprises DEQA's wherein the average Iodine Value for R is approximately 45.
  • the R! 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 of a C ⁇ ⁇ 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(tallowyl-oxy-ethyl)-N,N-dimethyl ammonium chloride N,N-di(canolyl-oxy-ethyl)-N,N-dimethyl ammonium chloride;
  • 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 pnncipal solvent.
  • the level of principal solvent present m 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 noniomc surfactant.
  • the pnncipal solvents of the present invention are p ⁇ ma ⁇ ly used to obtain liquid compositions having sufficient clarity and viscosity. Pnncipal solvents must also be selected to mmmize solvent odor impact m the composition.
  • 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 comp ⁇ smg 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 pnncipal 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, m 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).
  • 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 expenmental 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);
  • 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 from 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 from about 10% to about 80%, preferably to about 50%, more preferably to about 25% by weight, of a hydrophobic polyamine dispersant having the formula:
  • R 1 units are preferably alkyleneoxy units having the formula:
  • 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
  • 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.
  • ionizable salts can be used.
  • suitable salts are the halides of the Group IA and IIA 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.
  • alkylene polyammonium salts include L-lysine, monohydrochloride and 1,5-diammonium 2-methyl pentane dihydrochloride.
  • Cationic Charge Boosters include L-lysine, monohydrochloride and 1,5-diammonium 2-methyl pentane dihydrochloride.
  • 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:
  • Rl, R ⁇ , R3, and R ⁇ are each independently C1 -C22 alkyl, C3-C22 alkenyl, R ⁇ -Q- (CH2) m -, wherein R ⁇ is C1-C22 alkyl, and mixtures thereof, m is from 1 to about 6; X is an anion.
  • R ⁇ is Cg-C22 alkyl, C -C22 alkenyl, and mixtures thereof, more preferably Ci ⁇ -C ⁇ g alkyl, Cj j-Cjg alkenyl, and mixtures thereof;
  • R ⁇ , R3. and R ⁇ are each preferably Ci - C4 alkyl, more preferably each R ⁇ , R3. and R ⁇ are methyl.
  • the formulator may similarly choose R to be a R ⁇ -Q-(CH2) m - moiety wherein R* 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 friglyceride 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* 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 friglyceride selected from the group consisting of tallow, partially
  • RNQ- 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
  • 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 -MTj unit hydrogens can be substituted by an alkyleneoxy unit having the formula:
  • RlO (RlO) x R2 wherein Rl is C2-C4 alkylene, R ⁇ is hydrogen, C1-C4 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:
  • 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:
  • R is substituted or unsubstituted C2-C12 alkylene, substituted or unsubstituted C2-C12 hydroxy alkylene; each Rl is independently Ci -C4 alkyl, each R ⁇ is independently C1-C22 alkyl, C3-C22 alkenyl, R ⁇ -Q-(CH2) m -, wherein R ⁇ is C1-C22 alkyl, C3-C22 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* IS methyl or ethyl, more preferably methyl; at least one R ⁇ IS preferably C -C4 alkyl, more preferably methyl. Preferably at least one R ⁇ IS C J 1-C22 alkyl, C 1 ⁇ -C22 alkenyl, and mixtures thereof.
  • the formulator may similarly choose R ⁇ to be a R ⁇ -Q-(CH2) m - moiety wherem R ⁇ 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 denved preferably de ⁇ ved from a source of t ⁇ glyce ⁇ de 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.
  • a source of t ⁇ glyce ⁇ de 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,
  • n Rl is methyl, one RNQ- 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 prefen-ed, 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 catiomc surfactants; (2) nonionic surfactants; (3) amine oxides; (4) fatty acids; and (5) mixtures thereof These aids are described m P&G Copendmg Application Serial No.
  • 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. Soil Release Agents
  • 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.
  • Any polymeric soil release agent known to those skilled in the art can optionally be employed in the compositions and processes of this invention.
  • 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%.
  • soil release polymers suitable for us in the present invention.
  • compositions of the present invention 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.
  • Linear Polyamines The bleach protection polyamines of the present invention have the formula:
  • R' is hydrogen or an alkyleneoxy unit having the formula:
  • 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,-C 4 alkyl, and mixtures thereof; preferably hydrogen.
  • R' may comprise any mixture of alkyleneoxy units.
  • R 2 is hydrogen, R', -RN(R') 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.
  • 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)-l,3- propylenediamine (TPTA).
  • Cyclic Amines The bleach protection cyclic polyamines of the present invention comprise polyamine backbones having the formula:
  • 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') 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.
  • R 1 is hydrogen or an alkyleneoxy unit having the formula:
  • 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,-C 4 alkyl, and mixtures thereof; preferably hydrogen.
  • R 1 may comprise any mixture of alkyleneoxy units. Examples of preferred optional polyamines of the present invention have the formula:
  • the present invention also relates to a method for enhancing the fabric integrity inter alia dye fidelity while reducing the damage to fabric due to the interaction of laundry adjunct ingredients and damage due to mechanical wear.
  • the method includes the step of contacting fabric with an aqueous solution containing a least 50 ppm, preferably at least about 100 ppm, more preferably at least about 200 ppm, said composition comprising: a) from about 0.01% by weight, of a fabric enhancement system, said fabric enhancement system comp ⁇ smg one or more modified polyamine compounds, said modified polyamine compounds are selected from: i) (PA) W (T) X, n) (PA) W (L) Z ; in) [(PA) tt (T) y [L] z ; and
  • PA is a grafted or non-grafted, modified or unmodified polyamine backbone unit
  • T is an amide forming polycarboxylic acid crosslinking unit
  • L is a non-amide forming crosslinking unit
  • the indices w and x have values such that the ratio of w to x is from 0.8 : 1 to 1.5 : 1; for compounds of type (n) the indices w and z have values such that said modified polyamine compound comprises from about 0.05, preferably from about 0.3 to 2 parts by weight of said L unit; for compounds of type (m) the indices y and z have values such that said modified polyamine compound comprises from about 0.05, preferably from about 0.3 to 2 parts by weight of said L unit; and b) the balance carriers and adjunct ingredients.
  • contacting is defined as "intimate contact of a fabric with an aqueous solution of the heremabove described composition which comprises a fabric abrasion reducing polymer.”
  • Contacting typically occurs by soaking, washing, rmsmg, spraying the composition onto fabric, but can also include contact of a substrate mter aha 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.
  • compositions of the present invention which comprise the polyamidoamme compounds which provide fabnc integrity benefits.
  • compositions which compnses a cationic fabnc softener active in combination with the fabric enhancement system of the present invention are non-hmitmg examples of liquid rmse-added compositions of the present invention which comprise the polyamidoamme compounds which provide fabnc integrity benefits.
  • the following is an example of a composition which compnses a cationic fabnc softener active in combination with the fabric enhancement system of the present invention.
  • Dye fixing agent ex Clariant under the tradename Cartafix CB ® .
  • composition which comprises the fabric enhancement system of the present invention.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Materials For Medical Uses (AREA)

Abstract

L'invention concerne des compositions d'amélioration de l'aspect des textiles, permettant d'obtenir un endommagement réduit des textiles, consécutif à une certaine abrasion. Ces compositions comprennent: a) environ 0,01 % en poids d'un système d'amélioration de l'aspect des textiles, lequel comporte au moins un composé polyamine modifié, ce composé étant choisi dans le groupe constitué par: i) (PA)w(T)x; ii) (PA)w(L)z; iii) [(PA)w(T)x]y[L]z, ou iv) des mélange de ceux-ci, PA représentant une unité à squelette polyamine, modifiée ou non, greffée ou non, T représentant une unité de réticulation d'acide polycarboxylique formant un amide, et L représentant une unité de réticulation ne formant pas un amide, à condition que, d'une part, pour les composés des types (i) et (iii) les indices w et x possèdent des valeurs telles que le rapport w/x soit compris entre 0,8/1 et 1,5/1, et d'autre part, pour les composé du type (ii), les indices w et z possèdent des valeurs telles que le composé polyamine modifié comprenne entre environ 0,05 et environ 2 parties en poids de l'unité L; b) environ 1 à environ 80 % en poids d'un agent adoucissant de textiles et c) le solde étant constitué par des excipients et des ingrédients d'adjonction.
PCT/US2000/003933 1999-02-19 2000-02-16 Compositions d'amelioration de l'aspect des textiles WO2000049122A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
BR0008373-9A BR0008373A (pt) 1999-02-19 2000-02-16 Composições de intensificação de tecido
US09/890,676 US6551986B1 (en) 2000-02-16 2000-02-16 Fabric enhancement compositions
JP2000599850A JP2002537491A (ja) 1999-02-19 2000-02-16 布地改良組成物
EP00908660A EP1153117A1 (fr) 1999-02-19 2000-02-16 Compositions d'amelioration de l'aspect des textiles
CA002359438A CA2359438A1 (fr) 1999-02-19 2000-02-16 Compositions d'amelioration de l'aspect des textiles
AU29962/00A AU2996200A (en) 1999-02-19 2000-02-16 Fabric enhancement compositions

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US12099699P 1999-02-19 1999-02-19
US60/120,996 1999-02-19

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001000767A1 (fr) * 1999-06-29 2001-01-04 The Procter & Gamble Company Compositions pouvant rehausser l'aspect des textiles et preserver leurs couleurs
WO2001023518A1 (fr) * 1999-09-27 2001-04-05 The Procter & Gamble Company Composition de detergent comportant un systeme d enlevement des salissures
WO2002048303A1 (fr) * 2000-12-11 2002-06-20 Unilever Plc Composition pour le soin du linge
US6653274B1 (en) 1999-09-27 2003-11-25 The Proctor & Gamble Company Detergent composition comprising a soil entrainment system
US6916775B1 (en) 1999-06-29 2005-07-12 The Procter & Gamble Company Fabric enhancement compositions having improved color fidelity

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US3320215A (en) * 1963-10-24 1967-05-16 Scott Paper Co Water-soluble nylon-type resins
DE1771814B1 (de) * 1968-07-16 1972-08-31 Bayer Ag Hilfsmittel-Verwendung für die Papierfabrikation
US4144123A (en) * 1974-07-19 1979-03-13 Basf Aktiengesellschaft Incorporating a crosslinked polyamidoamine condensation product into paper-making pulp
EP0158260A2 (fr) * 1984-04-09 1985-10-16 Henkel Kommanditgesellschaft auf Aktien Détergent pour textiles colorés
DE19643133A1 (de) * 1996-10-18 1998-04-23 Basf Ag Verwendung von wasserlöslichen oder in Wasser dispergierbaren vernetzten stickstoffhaltigen Verbindungen in Wasch- und Reinigungsmitteln
WO1998029530A2 (fr) * 1996-12-31 1998-07-09 The Procter & Gamble Company Compositions de detergent de lessive contenant des polyamide-polyamines pour conferer des qualites esthetiques a des tissus laves avec lesdites compositions
EP0978556A1 (fr) * 1998-08-03 2000-02-09 The Procter & Gamble Company Composition pour rendre infroissable

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3320215A (en) * 1963-10-24 1967-05-16 Scott Paper Co Water-soluble nylon-type resins
DE1771814B1 (de) * 1968-07-16 1972-08-31 Bayer Ag Hilfsmittel-Verwendung für die Papierfabrikation
US4144123A (en) * 1974-07-19 1979-03-13 Basf Aktiengesellschaft Incorporating a crosslinked polyamidoamine condensation product into paper-making pulp
EP0158260A2 (fr) * 1984-04-09 1985-10-16 Henkel Kommanditgesellschaft auf Aktien Détergent pour textiles colorés
DE19643133A1 (de) * 1996-10-18 1998-04-23 Basf Ag Verwendung von wasserlöslichen oder in Wasser dispergierbaren vernetzten stickstoffhaltigen Verbindungen in Wasch- und Reinigungsmitteln
WO1998029530A2 (fr) * 1996-12-31 1998-07-09 The Procter & Gamble Company Compositions de detergent de lessive contenant des polyamide-polyamines pour conferer des qualites esthetiques a des tissus laves avec lesdites compositions
EP0978556A1 (fr) * 1998-08-03 2000-02-09 The Procter & Gamble Company Composition pour rendre infroissable

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001000767A1 (fr) * 1999-06-29 2001-01-04 The Procter & Gamble Company Compositions pouvant rehausser l'aspect des textiles et preserver leurs couleurs
US6916775B1 (en) 1999-06-29 2005-07-12 The Procter & Gamble Company Fabric enhancement compositions having improved color fidelity
WO2001023518A1 (fr) * 1999-09-27 2001-04-05 The Procter & Gamble Company Composition de detergent comportant un systeme d enlevement des salissures
US6653274B1 (en) 1999-09-27 2003-11-25 The Proctor & Gamble Company Detergent composition comprising a soil entrainment system
WO2002048303A1 (fr) * 2000-12-11 2002-06-20 Unilever Plc Composition pour le soin du linge
US7091172B2 (en) 2000-12-11 2006-08-15 Unilever Home & Personal Care Usa Division Of Conopco, Inc. Textile laundering composition comprising a self-crosslinking cationic polymer

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MXPA01008390A (es) 2002-03-01
MX225387B (en) 2005-01-05
AU2996200A (en) 2000-09-04
BR0008373A (pt) 2001-11-06
JP2002537491A (ja) 2002-11-05
CA2359438A1 (fr) 2000-08-24

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