WO2001031116A1 - Traitement permettant d'ameliorer l'aspect d'un textile non-reactif - Google Patents

Traitement permettant d'ameliorer l'aspect d'un textile non-reactif Download PDF

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Publication number
WO2001031116A1
WO2001031116A1 PCT/US2000/028823 US0028823W WO0131116A1 WO 2001031116 A1 WO2001031116 A1 WO 2001031116A1 US 0028823 W US0028823 W US 0028823W WO 0131116 A1 WO0131116 A1 WO 0131116A1
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weight
optionally
units
polyamines
fabric
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PCT/US2000/028823
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English (en)
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Neil James Gordon
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The Procter & Gamble Company
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Priority to EP00970990A priority Critical patent/EP1238138A1/fr
Priority to AU80292/00A priority patent/AU8029200A/en
Priority to JP2001533246A priority patent/JP2003513178A/ja
Priority to BR0014962-4A priority patent/BR0014962A/pt
Priority to MXPA02004045A priority patent/MXPA02004045A/es
Publication of WO2001031116A1 publication Critical patent/WO2001031116A1/fr

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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
    • D06P1/5264—Macromolecular compounds obtained otherwise than by reactions involving only unsaturated carbon-to-carbon bonds
    • D06P1/5278—Polyamides; Polyimides; Polylactames; 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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0021—Dye-stain or dye-transfer inhibiting compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3723—Polyamines or polyalkyleneimines
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/61—Polyamines polyimines
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/60—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing polyethers
    • D06P1/607—Nitrogen-containing polyethers or their quaternary derivatives
    • D06P1/6076—Nitrogen-containing polyethers or their quaternary derivatives addition products of amines and alkylene oxides or oxiranes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/64—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds without sulfate or sulfonate groups
    • D06P1/642—Compounds containing nitrogen
    • D06P1/6428—Compounds containing aminoxide groups
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/655—Compounds containing ammonium groups
    • D06P1/66—Compounds containing ammonium groups containing quaternary ammonium groups
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/02—After-treatment
    • D06P5/04—After-treatment with organic compounds
    • D06P5/06—After-treatment with organic compounds containing nitrogen
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/02—After-treatment
    • D06P5/04—After-treatment with organic compounds
    • D06P5/08—After-treatment with organic compounds macromolecular

Definitions

  • the present invention relates to non-reactive textile and fabric treatment systems which can be suitably applied by the processor or manufacturer of textiles.
  • the treatment systems of the present invention provide a wide range of enduring fabric benefits, inter alia, anti-encrustation, anti-static, anti-abrasion, dye integrity, without the necessity to react with the fabric material itself.
  • the present invention meets the aforementioned needs in that it has been surprisingly discovered that textile finishes which provide enhanced fabric benefits can be applied by the fabric manufacturers or the garment fabricators to fabric, preferably cellulosic fiber containing fabric.
  • the finishes can be applied to the treated material at any point in the processing of the fabric, preferably after the fabric has been desized.
  • the compositions of the present invention do not comprise materials which are fabric reactive, for example, resins which are capable of chemically reacting with the textile material, inter alia, the cellulosic material of cotton.
  • the first aspect of the present invention relates to the treatment of textiles or fabric during any point in the manufacture process including after fabrication into an article of manufacture, inter aha, articles of apparel.
  • the present invention relates to textile enhancement compositions comprising: a) from about 0.05% by weight, of a polyamine fabric enhancement system, said system comprising one or more polyamines selected from the group consisting of: i) polyamines comprising two or more backbone nitrogens; ii) polyamines comprising one or more cationic backbone nitrogens; iii) polyamines comprising one or more alkoxylated backbone nitrogens; iv) polyamines comprising one or more cationic backbone nitrogens and one or more alkoxylated backbone nitrogens; and v) mixtures thereof; b) from about 0.001 % to about 90% by weight, of one or more dye fixing agents; c) optionally less than about 15% by weight, of a principal solvent, preferably said principal solvent has a ClogP of from about 0.15 to
  • the present invention further relates to a method for providing textile and fabric enhancement benefits, said method comprising the step of contacting textiles or fabric with the compositions of the present invention at a point during manufacture or after fashioning into an article of apparel.
  • Cotton rayon and other cellulose based fabrics, including polyester blends, are well suited for apparel.
  • Cellulosic fabric is relatively robust to the rigors of mechanical abrasion whether due to wearing of the fabric or whether due to the laundering process.
  • Cotton is hydrophilic, efficiently absorbing perspiration and providing a "breathable" feel to the wearer. Cotton is easily fabricated and dyed.
  • Non-durable finishes are meant to provide the fabric with an aesthetic value that is typically lost during subsequent washings whereas durable finishes, inter alia, permanent press, anti-wrinkle treatments, are applied for the life of the fabric.
  • durable presses are usually applied to fabric by treating the fabric with an aqueous solution of the reaction product of a urea and a condensation product prepared by reacting an aldehyde, an amine and an inorganic acid, and thereafter drying and curing the treated fabric.
  • the finishes are, therefore, permanent, but are fabric modifying.
  • the textile enhancement compositions of the present invention are applied to fabric or textiles and, because they are fabric substantive, remain on the fabric preventing one or more pejorative effects which occur during fabric life.
  • the compounds of the present invention are capable of providing fabric dye integrity while preventing the loss and/or redeposition of fugitive dyes onto the fabric surface.
  • the compositions of the present invention further act to ameliorate the buildup of hard water crystals on the fabric surface, said crystals which act to attenuate fabric softness and smooth feel.
  • compositions of the present invention comprise from about 0.05%, preferably from about 0.1%, more preferably from about 0.5% to about 10%, more preferably to about 7.5%, most preferably to about 5% by weight, of a polyamine fabric enhancement system, said system comprising one or more polyamines selected from the group consisting of: i) polyamines comprising two or more backbone nitrogens; ii) polyamines comprising one or more cationic backbone nitrogens; iii) polyamines comprising one or more alkoxylated backbone nitrogens; iv) polyamines comprising one or more cationic backbone nitrogens and one or more alkoxylated backbone nitrogens; and v) mixtures thereof.
  • the polymers of the present invention are comprised of a polyamine backbone wherein the backbone units which connect the amino units can be modified by the formulator to achieve varying levels of product enhancement.
  • the fonnulator may preferably substitute one or more of the backbone amino unit hydrogens by other units, inter alia, alkyleneoxy units having a terminal anionic moiety.
  • the nitrogens of the backbone may be oxidized to the N-oxide.
  • cationic units are defined as “units which are capable of having a positive charge”.
  • the cationic units are the quaternary ammonium nitrogens of the polyamine backbones or quaternary ammonium units which comprise the units which substitute the polyamine backbone.
  • anionic units are defined as "units which are capable of having a negative charge”.
  • the anionic units are "units which alone, or as a part of another unit, substitute for hydrogens along the polyamine backbone" a non-limiting example of which is a -(CH 2 CH 2 0) 2 oS0 3 Na which is capable of replacing a backbone hydrogen on a nitrogen or oxygen atom.
  • Linear Polyamines are "units which alone, or as a part of another unit, substitute for hydrogens along the polyamine backbone" a non-limiting example of which is a -(CH 2 CH 2 0) 2 oS0 3 Na which is capable of replacing a backbone hydrogen on a nitrogen or oxygen atom.
  • the enhanced fabric appearance compositions of the present invention may comprise one or more propyleneimines, propyleneamines, polypropyleneimines (branched), or polypropyleneamines (linear) which contain modified or unmodified backbone nitrogen units.
  • polyamines having propylene spacing are used alone, together, or interchangeably throughout the present specification to refer to the hereinbelow described modified or unmodified amines and each term is meant to stand equally well for the others unless a distinction is specifically pointed out.
  • polypropyleneimine is used throughout the present specification to refer to any polyamine, linear or branched, which comprises at least one propylene unit.
  • polyamines of the present invention have the formula:
  • R 2 (R') 2 N-R— [N - R]— N(R ! ) 2 wherein R is 1,2-propylene, 1,3 -propylene, and mixtures thereof; preferably 1,3-propylene.
  • R 1 is hydrogen, methyl, ethyl, 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 is hydrogen, Cj-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.
  • linear polyamine has a backbone wherein R is 1,3-propylene, R 2 is hydrogen, or alkoxy, and n is equal to 2, N,N'-bis(3-aminopropyl)-l,3-propylenediamine (TPTA).
  • TPTA N,N'-bis(3-aminopropyl)-l,3-propylenediamine
  • This preferred backbone can then be substituted or left unsubstituted in a manner which affords the formulator the maximal fabric benefit and compatibility of the low molecular weight amine with the particular embodiment.
  • R 1 and R 2 are each equal to hydrogen, dye fixative properties, in certain liquid fabric conditioning embodiments comprising bleach, are maximal.
  • Examples of preferred polyamines of the present invention having propylene unit backbones have the following backbone formulae prior to modification:
  • the backbones of the linear polyamines of the present invention comprise at least one 1,3-propylene unit, preferably at least two 1,3-propylene units.
  • polyamines which comprise alkylated polyamines are preferred, for example, tetramethyl dipropylenetriamine having the formula:
  • a backbone nitrogen when referred to as "unmodified” the nitrogen contains only hydrogen atoms.
  • “Modified” polyamines have one or more alkyleneoxy units as described herein above. Preferably when the backbone units are modified all of the nitrogens are modified. Preferred substituents are ethyleneoxy, l,2-propyleneoxyl,2- butylencoxy and mixtures thereof, more preferably 1,2-propyleneoxy. Cyclic Amines
  • the enhanced fabric appearance compositions of the present invention may comprise one or more cyclic polyalkyleneamines which contain modified or unmodified backbone nitrogen units.
  • polyamines having propylene spacing are used alone, together, or interchangeably throughout the present specification to refer to the hcreinbelow described modified or unmodified amines which comprise at least one 3-carbon propylene spacer between adjacent backbone nitrogen atoms.
  • N,N'-bis(aminoalkylene)cyclic amines is also used throughout the present specification to refer to any of the low molecular weight polyamines which provide fabric appearance benefits.
  • the low molecular weight 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 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.
  • R 1 is hydrogen, C ⁇ -C 2 alkyl, 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.
  • Preferred polyamines of the present invention 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.
  • the backbone of the cyclic amines of the present invention comprise a N,N '-bis- substituted 1,4-piperazine ring having the formula:
  • Examples of carbonyl containing rings which comprise L units are 1,4-diketopiperizines.
  • the backbones of the polyamines of the present invention, prior to modification, have the fonnula:
  • each R unit is -(CH 2 )3NH 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 of the present invention preferably comprise at least one 1,3-propylene unit, more preferably at least two 1,3-propylene units.
  • a backbone nitrogen when referred to as "unmodified” the nitrogen contains only hydrogen atoms.
  • “Modified” polyamines have one or more substituent units as described herein above. Preferably when the backbone units are modified all of the nitrogens are modified.
  • Preferred alkyleneoxy substituents arc ethyleneoxy, 1 ,2-propyleneoxy, and mixtures thereof, more preferably 1,2-propyleneoxy. Effects of Backbone Modifications
  • the polyamines of the present invention provide a multiplicity of fabric care and fabric enhancement benefits. Chlorine scavenging benefits are achieved with all of the polyamines independent of the degree of branching (i.e. the number of primary, secondary, and tertiary nitrogens).
  • the negative chelation effects are overcome and optimal dye integrity is achieved when the polyamine backbone comprises C 2 -C 3 , preferably C 3 (1,3-propylene) units, and the backbone nitrogens are per-substituted, preferably by sterically hindered substituents.
  • the choice of nitrogen substituents is left to the formulator, the choice being affected by the other properties which are desired and to the compatibility of the polyamine within the final formulation.
  • polyalkyleneimines having the formula:
  • [J— R] pulp-J wherein the [J-R] units represent the amino units which comprise the main backbone and any branching chains.
  • the polyamines prior to modification, inter aha, quatcmization, substitution of a backbone unit hydrogen with an alkyleneoxy unit have backbones which comprise from 3 to about 100 amino units.
  • the index n which describes the number of backbone units present is further described herein below.
  • J units are the backbone amino units, said units are selected from the group consisting of: i) primary amino units having the formula:
  • [J-R] — represent a continuation of the polyamine backbone by branching.
  • the number of B units present, as well as, any further amino units which comprise the branches are reflected in the total value of the index n.
  • substituted is defined herein as "compatible moieties which replace a hydrogen atom".
  • substituents are hydroxy; nitrilo; oximino; halogen; nitro; carboxyl, inter alia, -CHO, C0 2 H, -C0 2 R ⁇ -CONH 2 , - CONHR'; -CONR' 2 , wherein R' is C ⁇ -C ]2 linear or branched alkyl; amino; C ⁇ -C !2 mono- and di- alkylamino; -OS0 3 M; -S0 3 M; -OP0 3 M; -OR" wherein R" is C 1 -C 12 linear or branched alkyl; and mixtures thereof.
  • the backbone amino units of the polymers are connected by one or more R units, said R units are selected from the group consisting of: i) C 2 -C ⁇ 2 linear alkylene, C3-C ⁇ 2 branched alkylene, C ⁇ -Ci 6 substituted or unsubstituted arylene, C7-C 0 substituted or unsubstituted alkylenearylene having the formula:
  • R is linear alkylene
  • R is preferably C 2 -C ⁇ alkylene.
  • preferred embodiments of the present invention combine R units which are linear alkylene with one or more of the other R units listed herein below.
  • R is branched alkylene
  • R is preferably 1,2- propylene, 1,2-butylene, 1,2-hexylene, and mixtures thereof.
  • R is substituted or unsubstituted phenylene
  • R is preferably 1,4-phenylene.
  • the alkylene backbone unit which separates said units are C units or greater.
  • R units comprise only linear or branched alkylene units
  • a preferred embodiment of the present invention relates to mixed linear and branched units, for example, units having backbones with the repeating formula:
  • backbone branching is not provided by a secondary amino unit, secondary quaternary amino unit, or secondary N-oxide J unit as described herein above but instead is branched in the R backbone unit itself, ii) alkyleneoxyalkylene units having the formula:
  • R 2 is selected from the group consisting of ethylene, 1,2-propylene, 1,3-propylene, 1,2- butylene, 1,4-butylene, and mixtures thereof;
  • R 3 is C 2 -Cs linear alkylene, C 3 -C 8 branched alkylene, phenylene, substituted phenylene, and mixtures thereof; the index w is from 0 to about 25.
  • R 2 and R 3 units may also comprise other backbone units.
  • R 2 and R 3 units are preferably mixtures of ethylene, propylene and butylene and the index w is from 1, preferably from about 2 to about 10, preferably to about 6.
  • An example of a backbone comprising a mixture of R 2 units has the formula:
  • R 4 is hydrogen, C]-C 4 alkyl, -(R 2 0) t Y, and mixtures thereof.
  • R units comprise hydroxyalkylene units
  • R 4 is preferably hydrogen or -(R 2 0) t Y wherein the index t is greater than 0, preferably from 10 to 30, and Y is hydrogen or an anionic unit, preferably -SO 3 M.
  • the indices x, y, and z are each independently from 0 to 20, preferably the indices are each at least equal to 1 and
  • R 4 is hydrogen (2-hydroxypropylene unit) or (R 2 0) t Y, or for polyhydroxy units y is preferably 2 or
  • a preferred hydroxyalkylene unit is the 2-hydroxypropylene unit which can, for example, be suitably formed from glycidyl ether forming reagents, inter alia, epihalohydrin.
  • glycidyl ether forming reagents inter alia, epihalohydrin.
  • R unit which comprises the index y greater than 1 has the formula:
  • R 2 , R 4 , and the indices w, x, y, and z are the same as defined herein above.
  • X is oxygen or the amino unit -NR 4 -, the index r is 0 or 1.
  • the indices j and k are each independently from 1 to 20. When alkyleneoxy units are absent the index w is 0.
  • Non-limiting examples of preferred hydroxyalkylene/oxyalkylene units have the formula:
  • the formulator may suitably combine any of the above described R units to make a polyamine having a greater or lesser degree of hydrophilic character.
  • R 1 units are the units which are attached to the backbone nitrogens.
  • R 1 units are selected from the group consisting of: i) hydrogen; which is the unit typically present prior to any backbone modification, ii) C ⁇ -C 22 alkyl, preferably C ⁇ -C 4 alkyl, more preferably methyl or ethyl, most preferably methyl.
  • R 1 units are attached to quaternary units (iv) or (v)
  • R 1 is the same unit as quatemizing unit Q.
  • a J unit having the formula:
  • R 5 is Ci- ⁇ linear or branched alkyl, n' is 0 or 1.
  • R 6 is hydrogen, C 1 -C 1 5 alkyl, and mixtures thereof; a preferred R 1 unit which is an alkylenearyl unit is benzyl; m' is from 1 to 16.
  • the value of the index s is from 0 to 5.
  • the index t is expressed as an average value, said average value from about 0.5 to about 100.
  • the formulator may lightly alkyleneoxylate the backbone nitrogens in a manner wherein not every nitrogen atom comprises an R 1 unit which is an alkyleneoxy unit thereby rendering the value of the index t less than 1.
  • the average value of the index t is from about 0.5 to 30, wherein for others the average value of the index t is from about 10 to about 30, for another embodiment from about 5 to about 15.
  • the value of the index t allows the formulator to adjust the amount of alkyleneoxy units which are present and, therefore, may change due to the simple addition of a specific adjunct ingredient to the formulation, vi) Anionic units as described herein below.
  • the formulator may suitably combine one or more of the above described R 1 units when substituting the backbone of the polymers of the present invention.
  • Q is a quatemizing unit selected from the group consisting of C ⁇ -C linear alkyl, benzyl, and mixtures thereof, preferably methyl. As described herein above, preferably Q is the same as R 1 when R 1 comprises an alkyl unit.
  • R 1 for each backbone N unit (quaternary nitrogen) there will be an anion to provide charge neutrality.
  • the anionic groups of the present invention include both units which are covalently attached to the polymer, as well as, external anions which are present to achieve charge neutrality.
  • Non-limiting examples of anions suitable for use include halogen, inter aha, chloride; methyl sulfate; hydrogen sulfate, and sulfate.
  • the formulator will recognize by the herein described examples that the anion will typically be a unit which is part of the quatemizing reagent, inter alia, methyl chloride, dimethyl sulfate, benzyl bromide.
  • X is oxygen, -NR 4 -, and mixtures thereof, preferably oxygen.
  • Y is hydrogen, or an anionic unit.
  • Anionic units are defined herein as "units or moieties which are capable of having a negative charge". For example, a carboxyhc acid unit, -C0 2 H, is neutral, however upon de-protonation the unit becomes an anionic unit, -C0 , the unit is therefore,
  • Non-limiting examples of anionic Y units include - (CH 2 ) f C0 2 M, -C(0)(CH 2 ) f C0 2 M, -(CH 2 ) f P0 3 M, -(CH 2 )j P0 3 M, -(CH 2 )iS0 3 M, -CH 2 (CHS0 3 M)- (CH 2 ) f S0 3 M, -CH 2 (CHS0 2 M)(CH 2 ) f S0 3 M, -C(0)CH 2 CH(S0 3 M)C0 2 M, - C(0)CH 2 CH(C0 2 M)NHCH(C0 2 M)CH 2 C0 2 M, -C(0)CH 2 CH(C0 2 M)NHCH 2 C0 2 M, - CH 2 CH(OZ)CH 2 0(R'0) t Z, -(CH 2 ),CH-[0(R 2 0) t Z]CH f O(R 2 ),CH-[0(R 2
  • M is a cation which provides charge neutrality.
  • Y units may also be oligomeric or polymeric, for example, the anionic Y unit having the formula:
  • CH 2 CHCH 2 0— CH 2 CHCH 2 S0 3 Na may be oligomerized or polymerized to form units having the general formula:
  • index n represents a number greater than 1.
  • Y units which can be suitably oligomerized or polymerized include:
  • Certain embodiments of the present invention may require polyamines which comprise one or more anionic units which are substituted on the polyamine backbone.
  • the number of Y units which comprise an anionic unit will vary from embodiment to embodiment.
  • M is hydrogen, a water - soluble cation, and mixtures thereof; the index f is from 0 to 6.
  • the index n represents the number of backbone units wherein the number of amino units in the backbone is equal to n + 1.
  • the index n is from 2 to about 1000.
  • Branching units B are included in the total number of backbone units.
  • n 4
  • the following is a non-limiting example of a polyamine backbone which is fully quatemized.
  • polyamine comprising a PEI backbone wherein all substitutable nitrogens are modified by replacement of hydrogen with a polyalkyleneoxy unit, -(CH2CH2 ⁇ )7H, having the formula
  • the formulator may desire a polyamine which will not be adulterated by the presence of bleach
  • One means available to mitigate against the effects of bleaching agents is to form N-oxides of the backbone nitrogens
  • the example below illustrates a polymer comprising a PEI backbone wherein all substitutable primary amine nitrogens are modified by replacement of hydrogen with a polyalkyleneoxy unit, -(C ⁇ C ⁇ O ⁇ H, the molecule is then modified by subsequent oxidation of all oxidizable primary and secondary nitrogens to N-oxides having the formula
  • compositions Illustrated below is a polymer which comprises a PEI backbone wherem all backbone hydrogen atoms are substituted and some backbone amine umts are quatemized
  • the substituents are polyalkyleneoxy units, -(C ⁇ C ⁇ O ⁇ H, or methyl groups
  • the modified, catiomcly charged backbone polymer has the formula
  • a preferred polyamine polymer according to the present invention is a bleach stable polyamine which comprises no N-oxide units, having the formula:
  • each R unit is an ethylene or propylene unit;
  • R 1 units are -[CH 2 CH(OR 4 )CH 2 0] s -(R 2 0) t Y units; wherein R 2 is ethylene, 1,2-propylene, and mixtures thereof;
  • Y is hydrogen, and the value of the index s is 0.
  • the values of the indices w', x', and y' are such that the polyamine has a backbone molecular weight prior to modification of from 600 daltons to about 3000 daltons.
  • Preferred backbone molecular weights are 600 daltons, 1200 daltons, 1800 daltons, and 3000 daltons.
  • An example of a preferred polyalkylene amine according to the present invention is a polyamine wherein each R is ethylene and the backbone has a molecular weight of about 3000 daltons and each hydrogen of the backbone amino units are substituted by a polyalkylene R 1 unit wherein either one or three 1,2-propyleneoxy units are directly attached to the polyamine chain followed by sufficient ethyleneoxy units to provide an R 1 units which has an average of 30 alkyleneoxy units present.
  • One class of preferred polymers of the present invention has the formula:
  • R units have the formula -(R 2 0) w R 3 - wherein R 2 and R 3 are each independently selected from the group consisting of C 2 -Cg linear alkylene, C 3 -C8 branched alkylene, phenylene, substituted phenylene, and mixtures thereof.
  • R 2 units of the formula above which comprise -(R 2 0) t Y units, are each ethylene; Y is hydrogen, -S0 3 M, and mixtures thereof, the index t is from 15 to 25; the index m is from 0 to 20, preferably from 0 to 10, more preferably from 0 to 4, yet more preferably from 0 to 3, most preferably from 0 to 2; the index w is from 1, preferably from about 2 to about 10, preferably to about 6.
  • R unit having the formula -(R 2 0) w R 3 - is the backbone:
  • One class of preferred polymers of the present invention preferably comprise polyamine backbones which are derivatives of two types of backbone units: i) normal oligomers which comprise R units of type (i), which are preferably polyamines having the formula:
  • each backbone comprises a mixture of R units.
  • the formulator may form polymers which have an excess of charge or an equivalent amount of charge type.
  • An example of a preferred polyamine according to the present invention which has an excess of anionic charged units has the formula: wherein R is a l,3-propyleneoxy-l,4-butyleneoxy-l,3-propylene unit, w is 2; R 1 is -(R 2 0) t Y, wherein R 2 is ethylene, each Y is -S0 3 " , Q is methyl, m is 0, n is 0, t is 20.
  • the final polyamine mixture comprises at least about 90% Y units which are -S0 3 ' units.
  • polyamines which may be present as a formulated admixture or a product by process composition, or a mixture of both.
  • These prefered compounds can be represented by the formulae: i) (PA) W (T) X, ii) (PA) W (L) Z ; iii) [(PA) w (T) x ] 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.
  • 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.
  • crosslinked polyamines having the formula (PA) W (T) X 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 .
  • Polyamine Backbone (PA units) The modified polyamine compounds of the present invention comprise a Polyamine Backbone, PA unit, which can be optionally, but preferably grafted.
  • PA units are non- limiting examples of suitable PA units according to the present invention.
  • a preferred PA unit according to the present invention are polyalkyleneimines and polyalkyleneamines having the general formula:
  • R is C 2 -Ci 2 linear alkylene, C 3 -C ]2 branched alkylene, and mixtures thereof; preferably R is ethylene, 1,3-propylene, and 1,6-hexylene, more preferred is ethylene.
  • the index w typically has the value of y + 1.
  • the simplest of the low molecular weight polyamines of this type is ethylene diamine which may be present up to about 10% by weight of the PA unit mixture.
  • Non-limiting examples of low molecular weight polyalkyleneimine PA units include diethylene triamine, triethylene tetramine, tetraethylene pentamine, dipropylene triamine, tripropylene tetramine, and dihexamethylene triamine.
  • 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 diamines as described herein above, wherein the amount of diamines, inter a a, ethylene diamine, hexamethylene diamine may be present up to about 10% by weight, of the PA unit mixture.
  • Medium Range Molecular Weight Polyalkyleneimines For medium range molecular weight polyalkyleneimines having the formula:
  • R is C 2 -C 4 linear alkylene, C3- branched alkylene, and mixtures thereof; preferably R is ethylene,
  • PEFs polyethylencimines
  • the indices w, x, and y are such that the molecular weight of said polyamines 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.
  • 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.
  • PA unit 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:
  • 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.
  • Another optional but preferred 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 ⁇ 0 -C ⁇ 8 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] z .
  • 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:
  • 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.
  • the presence of R 2 units can result, for example, from the use of diisocyanates as crosslinking agents.
  • Non- limiting examples of dibasic acids which are used as a source for T units in the above formula include succinic acid, maleic acid, adipic acid, glutaric acid, suberic acid, sebacic acid, and terephthalic acid.
  • the formulator is not limited to crosslinking T units deriving from dibasic acids, for example, tribasic crosslinking T units, inter alia, citrate, may be used to link the PA units of the present invention.
  • Examples of (PA) W (T) X compounds according to the present invention are obtained by condensation of dicarboxylic acids inter alia succinic acid, maleic acid, adipic acid, terephthalic acid, with polyalkylene polyamines inter alia diethylenetriamine, triethylenetetramine, dipropylenetriamine, tripropylenetetramine wherein the ratio of the dicarboxylic acid to polyalkyleneamine 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 crosslinked material has a viscosity in a 50% by weight, aqueous solution of more than 100 centipoise at 25 °C.
  • dicarboxylic acids inter alia succinic acid, maleic acid, adipic acid, terephthalic acid
  • polyalkylene polyamines inter alia diethylenetriamine, triethylenetetramine, dipropylenetriamine, tripropylenete
  • polyamines of the present invention are (PA) W (T) X units which are further crosslinked by L units to form polyamido amines having the formula [(PA) w (T) x ] y [L] z or are reacted with PA units to form non-amide polyamines having the formula (PA) W (L) Z .
  • the L units of the present invention are any unit which suitably crosslinks PA units or (PA) W (T) X units.
  • Preferred L linking units comprise units which are derived from the use of epihalohydrins, preferably epichlorohydrin, as a crosslinking agent.
  • the epihalohydrins can be used directly with the PA units or suitably combined with other crosslinking adjuncts non-limiting examples of which include alkyleneglycols, and polyalkylene polyglycols inter alia ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol-l,6-glycerol, oligoglycerol, pentaerythrites, polyols which are obtained by the reduction of carbohydrates (sorbitol, mannitol), monosaccharides, disaccharides, oligosaccharides, polysaccharides, polyvinyl alcohols, and mixtures thereof.
  • alkyleneglycols and polyalkylene polyglycols inter alia ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol,
  • a suitable L unit is a dodecylene unit having the formula: (CH 2 ) 12 wherein an equivalent of 1,12-dichlorododecane is reacted, for example, with a suitable amount of a PA unit to produce a polyamine which is crosslinked via dodecylene units.
  • L crosslinking units which comprise only carbon and hydrogen are considered to be "hydrocarbyl" L units.
  • Preferred hydrocarbyl units are polyalkylene units have the formula: (CH 2 ) n wherein n is from 1 to about 50.
  • 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.
  • 1,12-dihydroxydodecane is reacted with epichlorohydrin to form the bis-epoxide non-amide forming L unit precursor having the formula: r CH 2 0— (CH 2 ) 12 — OCH 2 ⁇ 1 o o which when reacted with one or more PA units or (PA) W (T) X units results in an L crosslinking unit having the formula:
  • the 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.
  • crosslinking L units which utilize one or more epihalohydrin connecting units include polyalkyleneoxy L units having the formula:
  • 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) W (T) X , [(PA) w (T) x ] y [L] z , [(PA)] W [L] Z , and mixtures thereof, wherein 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. In the cases wherein no crosslinking takes place the indices w and y will be equal to 1 and x and z will be equal to 0.
  • 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 O.
  • 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 dicarboxylic acid with a polyalkylene polyamine (i.e., diethylenetriamine) to the extent wherein at least about 10% of the -NH backbone hydrogens are unmodified by reaction with said dicarboxylic acid, then optionally reacting the obtained polyamine condensation product with up to 12 ethyleneimine 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 0.3 to about 2 parts by weight, of an L units, inter alia the reaction product of a polyalkylene oxide having from 8 to 100 alkylene oxide units with epichlorohydrin at a temperature of form about 20 °C to about 100 °C.
  • 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 ethyleneimines, and mixtures thereof; with b) at least bifunctional halogen-free cross-linking agents, said agents selected from the group consisting of: i) ethylene carbonate, propylene carbonate, urea, and mixtures thereof; ii) mono-carboxylic acids comprising one olefin moiety inter alia acrylic acid, methacrylic acid, crotonic acid; and the esters, amides, and anhydrides thereof; polycarboxylic acids inter alia oxalic acid, succinic acid, tartaric acid, itaconic acid, maleic acid; and the esters, amides, and anhydrides thereof; iii) reaction products of polyetherdiamines, alkylenediamines, polyalkylene- diamines, and mixtures thereof, with mono-carboxylic
  • the (PA) W (T) X polyamine compound may be partially amidated ("capped" as described herein above) by treatment with a mono carboxyhc acid or the esters of mono carboxyhc 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 (also referred to herein as "resins") arc preferably formed from the reaction of one or more grafted, cross-linked polyethyleneimines 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.
  • a further example of preferred polyamines according to the present invention are polyamines derived from amino acid residues.
  • the term "residue” is defined as "one unit which comprises the polymeric material of the present invention".
  • a non-limiting example of a residue which comprises the polymeric material is a lysine residue having the formula:
  • said lysine residue forms the backbone of said polymeric material by forming a bond to the ⁇ -amino unit, however, the lysine residue may be suitably incorporated into the backbone via the -amino unit; or an omithine residue having the formula:
  • said omithine residue forms the backbone of said polymeric material by forming a bond to the ⁇ -amino unit, however, the omithine residue may be optionally incorporated into the backbone via the ⁇ -amino unit; and said lysine residue or omithine residue may have any optical isomer form, i.e., dextrorotatory, levorotatory.
  • the amino acid-based polymers of the present invention comprise at least about 5% by weight of lysine, omithine, or mixtures thereof, preferably at least about 10%, more preferably at least about 20%, most preferably at least about 40% by weight of lysine, omithine, or mixtures thereof.
  • N-term and C-term are defined as an “amino terminating unit” and a “carboxyl terminating unit” respectively and are used throughout the present specification to indicate the capping units of the main polymeric chain as well as any branching chains.
  • the polymeric material of the present invention has the formula:
  • the lysine and omithine residues are preferably incorporated into the polymeric chain via the ⁇ -amino residue and the carboxylate residue.
  • this "normal" incorporation does not preclude incorporation of a lysine or omithine residue into the backbone or branch chain via two amino units whereby the carboxyl unit remains un-incorporatcd into any chain.
  • AA units are amino acid or other chain propagating residues having the formula:
  • index n is from 0 to 10, preferably 1, 2 and 4; the preferred R units are independently selected from the group consisting of: i) hydrogen;
  • R 2 is -OH, for example wherein said amino acid, AA residue is glutamic acid, aspartic acid, etc.;
  • R 2 is an amino lactam C-terminal capping group, preferably a unit having the formula:
  • R 2 is an N-terminal residue of a cross-linking chain comprising one or more residues which provides cross-linking between two polymeric material chains, for example, R 2 may comprise one end of a diamine inter alia hexamethylene diamine, an N-terminal residue which links the main polymeric chain to a branched chain, for example, a branched chain having the general formula:
  • R 2 when R 2 is an amide-forming unit, R 2 is derived from the reaction of the lysine/omithine polymeric material with caprolactam, amino caproic acid, and mixtures thereof; the index m is from 0 to 3, preferably the index m is 1 or 2, more preferably 1; iii) benzyl; iv) 4-hydroxybenzyl; v) 3-(guanidinyl)propyl; vi) (lH-indol-3-yl)methyl; vii) (lH-imidazol-5-yl)methyl; viii) is mixtures thereof.
  • R 1 units are independently selected form the group consisting of: i) hydrogen; preferred unit; ii) the C terminal end of a cross-linking chain comprising one or more residues which provides either cross-linking between two polymeric material chains or a branching of the polymer chain, preferably when R 1 is a C terminal unit, said unit is derived from the reaction of the lysine/omithine polymeric material with caprolactam, amino caproic acid, and mixtures thereof; iii) C1-C 1 8 linear or branched alkyl, preferably methyl; iv) C 2 -Ci 8 linear or branched alkenyl; v) C 2 -Cis linear or branched hydroxyalkyl; vi) C 3 -C 8 cycloalkyl; vii) aryl; viii) C ⁇ -Cis substituted or unsubstituted alkylenearyl, preferably benzyl; ix) one end of a di-carboxylic acid linking
  • Non-limiting examples of preferred AA amino acid residues are arginine, tryptophan, tyrosine, histidine, aspartic acid, glutamic acid, asparagine, glutamine, serine, threonine, and mixtures thereof. More preferred AA amino acid residues are selected form the group consisting of arginine, tryptophan, and mixtures thereof.
  • N-term amino terminal capping groups terminate, truncate or end the amine terminus of the main polymeric chain or branch chains.
  • Preferred amino terminal capping groups are selected from the group consisting of: i) hydrogen (most preferred); ii) C 1 -C 1 8 linear or branched alkyl, preferably methyl; iii) C 2 -Ci8 linear or branched alkenyl; iv) C 3 -Cs cycloalkyl; v) aryl; vi) C 6 -Ci8 substituted or unsubstituted alkylenearyl, preferably benzyl; vii) C1-C 1 8 linear or branched acyl, preferably the N-terminal units of the polymer are capped (partially amidated) with an acyl unit inter alia lauric acid, myristic acid, behenic acid; viii) C 2 -C 22 diacyl units, for example units derived from dicarboxylic acids or esters thereof
  • C-term carboxy terminal capping groups terminate, tmncate, or end the carboxy terminus of the main polymeric chain or branch chains.
  • Preferred carboxy terminal capping groups are selected from the group consisting of: i) -OM wherein M is hydrogen or a salt forming cation, most preferred capping unit is -OH; ii) -N(R 3 ) 2 wherein each R 3 is independently C ⁇ -C ⁇ 8 linear or branched alkyl; C 2 -C 1 8 linear or branched hydroxyalkyl, C 3 -C 8 cycloalkyl, and mixtures thereof, preferably methyl; iii) preferably an amino lactam unit having the formula:
  • v) units having an amine function including: a) mono amines having the formula:
  • R*R 2 NH wherein R 1 and R 2 are each independently hydrogen or a hydrocarbyl unit comprising from 1 to 22 carbon atoms; b) polyamines having the formula:
  • the polyamines which serve as carbonyl end units may serve to cap one or more carboxy terminal units of the same chain or two or more different chains.
  • the preferred polymer chains of the present invention have the amino terminus (N-term unit) of the main chain and branch chains capped with hydrogen and the carboxy terminus (C-term unit) of the main chain and branch chains capped with -OH.
  • the formulator may, preferably partially amidate the compounds of the present invention by treatment with a mono carboxyhc acid or the esters of mono carboxyhc 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.
  • an amino acid having two amine moieties inter aha lysine, omithine is co-condensed with caprolactam or aminocaproic acid to form a co-condensation product.
  • Other preferred co-condensates include reaction of lysine or omithine with lauric acid to form the amidated polymer.
  • amino units of any lysine, omithine, or AA unit may be optionally quatemized, preferably quatemized by one or more units selected from the group consisting of C ⁇ -C 4 linear or branched alkyl, benzyl, and mixtures thereof.
  • N-terminal or C-terminal capping units which have more than one functionality inter a a two carboxy units of a diacid (succinic acid), may crosslink two or more poly lysine or poly omithine comprising chains. Therefore, in addition to capping, and therefore truncating the N- terminal ends of two separate polyamine backbones, a unit such as succinic acid may crosslink two polyamine chains.
  • the molecular weight of the amino acid-based polymeric materials of the present invention are preferably from about 400 daltons, more preferably from about 1000 daltons, most preferably from about 2000 daltons to preferably about 500,000 daltons, more preferably to about 25,000 daltons, most preferably to about 10,000 daltons.
  • Tethered Polymeric Amines are preferably from about 400 daltons, more preferably from about 1000 daltons, most preferably from about 2000 daltons to preferably about 500,000 daltons, more preferably to about 25,000 daltons, most preferably to about 10,000 daltons.
  • polyamines of the present invention are the polyamines wherein the amine nitrogen is tethered to an alkylene backbone.
  • the following are non-limiting examples of tethered polymeric amines according to the present invention.
  • the tethered polymeric amines of the present invention have the general formula:
  • R' and R" are each independently hydrogen, Ci-C ⁇ alkyl, phenyl, substituted phenyl, C - C 22 alkylenearyl, and mixtures thereof
  • R 3 is an amine comprising unit, non-limiting examples of which include: -N(R) 2; -N + (R) 3 , -C(0)N(R) 2 , -C(0)N + (R) 3 , and mixtures thereof; wherein R is hydrogen, -C 12 linear or branched alkyl, benzyl, or alkyleneoxy having the formula (R' ⁇ ) z Y, wherein R 1 is Ci-C ⁇ linear or branched alkylene, Y is hydrogen or an anionic unit.
  • Each cationic nitrogen will have an anionic unit X which provides charge neutrality to the polymer.
  • the index x is from about 5 to about 1,000,000 (one million) depending upon the properties which the formulator may wish to provide via the tethered polyamine.
  • One class of tethered polymeric amines are the quatemized and non-quaternized polyvinylamines having the formula:
  • R is hydrogen, C 1 - 2 linear or branched alkyl, benzyl, or alkyleneoxy having the formula (R'O ⁇ Y, wherein R 1 is C C 6 linear or branched alkylene, Y is hydrogen or an anionic unit, non- limiting examples of which include, -(CH 2 ) f C0 2 M, -C(0)(CH 2 ) f C0 2 M, -(CH 2 ) f P0 3 M, - (CH 2 ) f 0P0 3 M, -(CH 2 ) f S0 3 M, -CH 2 (CHS0 3 M)-(CH 2 ) f S0 3 M, -CH 2 (CHS0 3 M)-(CH 2 ) f S0 3 M, -CH 2 (CHS0 2 M)(CH 2 ) f S0 3 M, - C(0)CH 2 CH(S0 3 M)C0 2 M, -C(0)CH 2 CH(C0 2 M)NHCH(C
  • the index x has the value from about 50 to about 1,500; preferably the index x has a value such that the resulting polymeric suds stabilizer has an average molecular weight of from about 2,500, preferably from about 10,000, more preferably from about 20,000 to about 150,000, preferably to about 90,000, more preferably to about 80,000 daltons.
  • compositions of the present invention 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-0 and 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 aha the hydrochloride, acetate, metosulphate and benzyl hydrochloride salts of diamine esters.
  • Non-limiting examples include oleyldiethyl aminoethylamide, oleylmethyl diethylenediamine methosulphate, monostcarylethylene diaminotrimethylammonium methosulphate.
  • N-oxides of tertiary amines are suitable for use as dye fixatives in the compositions of the present invention.
  • the fabric conditioning and fabric appearance compositions of the present invention may optionally comprise the following optional ingredients.
  • Transition Metal-Comprising Dye Protection System
  • transition metal-comprising dye protection One textile enhancing benefit which can be delivered to textiles in the mill, before fabrication into an article of manufacture, or after manufacture of said article, preferably an article of apparel, is transition metal-comprising dye protection. Color integrity is an important aspect of fabric enhancement, and it is especially critical to deliver dye protection at the manufacture stage.
  • transition metal-comprising dye protecting polyamines arc deposited onto fabric they enhance color fidelity via various mechanisms, inter alia, by intercepting peroxygen bleaching agents at the fabric surface.
  • the transition metal-comprising dye protecting polyamines attenuate the chelation, and hence the extraction of, these heavy metals, a process which is minous to the fidelity of fabric color
  • the transition metal-comprising dye protection system of the present invention prevents the loss of color from fabric due to the chelation of heavy metal ions which comprise fabric dyes by laundry composition ingredients.
  • the textile treatment compositions of the present invention comprise, when transition metal-comprising dye protecting amine are present, from about 0.05%, preferably from about 0.1%, more preferably from about 0.5% to about 10%, more preferably to about 7.5%, most preferably to about 5% by weight, of a transition metal-comprising dye protection system.
  • the transition metal-comprising dye protection agents are preferably oligomers which are formed from the reaction of one or more substituted of unsubstituted polymerizable imidazoles with an epihalohydrin crosslinking agent, preferably epichlorohydrin.
  • the oligomers are preferably formed from the reaction of: i) 1 part by weight of an epihalohydrin; and ii) from 0.5, preferably from 0.75, more preferably from 1 to 2, preferably to about
  • substituted imidazole is defined as "an imidazole which has the hydrogen atom at the number 2-carbon atom substituted by a Ci-Cig alkyl unit".
  • the imidazoles suitable for use in forming the oligomers of the present invention have the formula:
  • R is hydrogen, Ci-Cis alkyl, and mixtures thereof; preferably hydrogen or Ci-Cs alkyl; more preferably hydrogen or C ⁇ -C 4 alkyl, most preferably hydrogen.
  • the imidazoles may be as the free compounds or the salts thereof.
  • the oligomers have the formula:
  • R is defined herein above and X is a water soluble cation, preferably X is derived from the leaving group of the epihalohydrin, inter alia, chlorine.
  • a further example of materials suitable for use in the transition metal-comprising dye protection system of the present invention are gallic acid comprising resins, for example, gallate ester resins derived from reducing or non-reducing sugars, inter alia, tannic acid.
  • resins for example, gallate ester resins derived from reducing or non-reducing sugars, inter alia, tannic acid.
  • tannins derived from flavanol resins are also as suitable for use as transition metal-comprising dye protection agents.
  • 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%o, 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 Vi 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, hydroxyethylcne 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 alkyl, C ⁇ -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 micro- crystals.
  • the procedure of Nancollas et al., described in "Calcium Phosphate Nucleation and Growth in Solution", Prog. Crystal Growth Charact., Vol 3, 77-102, (1980), incorporated herein by reference, is a method which is suitable for evaluating compounds for their crystal growth inhibition.
  • the graph below serves as an example of a plot indicating the time delay (t-lag) in crystal formation afforded by a hypothetical crystal growth inhibitor.
  • the 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 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 HC1. 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 carboxyhc compounds, organic diphosphonic acids, and mixtures thereof. The following are non-limiting examples of preferred crystal growth inhibitors.
  • Non-limiting examples of carboxyhc compounds which serve as crystal growth inhibitors include glycolic acid, phytic acid, polycarboxylic acids, polymers and co-polymers of carboxyhc 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 carboxyhc 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 m 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, each of which is mcluded herem by reference
  • 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-t ⁇ hydroxybenzene, 2, 4, 6-tnsulphonic acid, and carboxymethyloxysuccinic acid are also useful Alkali metal salts of polyacetic acids, for example, ethylenediamrne tetraacetic acid and nit ⁇ lot ⁇ acetic acid, and the alkali metal salts of polycarboxylates, for example, melhtic acid, succimc acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5-t ⁇ carboxyhc acid, carboxymethyloxysuccinic acid, are suitable for use in the present invention as crystal growth inhibitors
  • the polymers and copolymers which are useful as crystal growth inhibitors have a molecular weight which is preferably greater than about 500 daltons to about 100,000 daltons, more preferably to about 50,000 daltons
  • Examples of commercially available materials for use as crystal growth inhibitors include, polyacrylate polymers Good-Rite® ex BF Goodrich, Acrysol® ex Rohm & Haas, Sokalan® ex BASF, and Norasol® ex Norso Haas Preferred are the Norasol® polyacrylate polymers, more preferred are Norasol® 410N (MW 10,000) and Norasol® 440N (MW 4000) which is an ammo phosphomc acid modified polyacrylate polymer, and also more preferred is the acid form of this modified polymer sold as Norasol® QR 784 (MW 4000) ex Norso-Haas
  • Polycarboxylate crystal growth inhibitors mclude citrates, e g , citnc 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 succinic acid and salts thereof, of which dodecenyl succmate, lauryl succmate, my ⁇ styl succmate, palmityl succmate, 2-dodecenylsuccmate, 2-pentadecenyl succmate, are non-hmiting 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 diphosphomc acid are also suitable for use as crystal growth inhibitors
  • Preferred organic diphosphonic acids include C ⁇ -C 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 , l,2-dihydroxyethane-l,l- diphosphonic acid, hydroxy-ethane 1,1 diphosphonic acid, the salts thereof, and mixtures thereof.
  • hydroxyethane- 1,1 -diphosphonic acid HEDP
  • phosphonic acid is 2-phosphonobutane-l,2,4-tricarboxylic acid available as BAYHIBIT AM ® ex Bayer. 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 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:
  • 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: [CR 2 -CR 2 ] or [(CR 2 ) X -L] — wherein each R unit is independently hydrogen, C ⁇ -C ⁇ 2 alkyl, C ⁇ -C ⁇ 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: R 1 O o O O
  • R 1 is hydrogen, C 1 -C 12 alkyl, C 6 -C ⁇ 2 aryl, and mixtures thereof.
  • R 2 is C 1 -C 12 alkyl, C 1 -C 12 alkoxy, C 6 -C ]2 aryloxy, and mixtures thereof; preferably methyl and methoxy.
  • R 3 is hydrogen -C ⁇ alkyl, C 6 -C ⁇ 2 aryl, and mixtures thereof; preferably hydrogen or C ⁇ -C 4 alkyl, more preferably hydrogen.
  • R 4 is C 1 -C 12 alkyl, C ⁇ -Cn 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: or the D unit may be incorporated into the backbone as a pendant group to a backbone unit having, for example, the formula: [CR-CR 2 ] or [(CR) X -L]—
  • 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 are 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-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:
  • N(R) 2 wherein 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: CH 3
  • 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; poly(N-acrylylglycinamide) having the formula: [CH-CH 2 ] n
  • each R' is independently hydrogen, Ci-C ⁇ alkyl, or both R' units can be taken together to form a ring comprising 4-6 carbon atoms.
  • D unit wherein the nitrogen of the dye transfer inhibiting moiety is incorporated into the polymer backbone is a poly(2-cthyl-2-oxazoline) having the formula: [CH 2 -CH 2 -N] n —
  • 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, polyvinyloxazolidoncs, 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 polyvinylpyrrolidonc (PVP).
  • PVP polyvinylpyrrolidonc
  • 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 K-12, K-15, and K-30 are also available ex Polysciences, Inc. Warrington, Pennsylvania, 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 1.3 MM, 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 quatemised 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.
  • 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., polyalkyleneamine backbone, or the N-oxide may be part of a pendant group attached to the polymer backbone.
  • a polymer which comprises an the N-oxide unit as a part of the polymer backbone is polyemyleneimine 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 ratio 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 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 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. In addition, oligomers or block polymers comprising these units can be taken together to form the mixed amide/N-oxide polymers. However, the resulting polymers must retain the water solubility requirements described herein above. Molecular weight
  • the above polymer of the invention it 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.
  • the high molecular weight enables the abrasion occurring subsequent to treatment with the polymer to be reduced, especially in a later washing procedure.
  • this benefit is partly due to the high molecular weight, thereby enabling the deposition of the polymer on the fabric surface and providing sufficient substantivity that the polymer is able to remain adhered to the fabric during the subsequent use and washing of the fabric.
  • increasing the molecular weight will increase the substantivity of the polymer to the fabric surface.
  • the balance of charge density and molecular weight will provide both a sufficient rate of deposition onto the fabric surface and a sufficient adherence to the fabric during a subsequent wash cycle.
  • Increasing molecular weight is considered preferable to increasing charge density as it allows a greater choice in the range of materials which are able to provide the benefit and avoids the negative impact that increasing charge density can have such as the attraction of soil and residue onto treated fabrics. It should be noted however that a similar benefit may be predicted from the approach of increasing charge density while retaining a lower molecular weight material.
  • compositions of the present invention may optionally comprise from about 10%, preferably from about 12%, more preferably from about 14% to about 40%, preferably to about 35%, more preferably to about 25%, most preferably to about 20% by weight of one or more solvents (liquid carriers).
  • solvents liquid carriers
  • the use of solvents is especially critical when fonnulating clear, isotropic liquid fabric conditioning compositions comprising cationic fabric softening actives.
  • the solvent is selected to minimize solvent odor impact in the composition and to provide a low viscosity to the final composition. For example, isopropyl alcohol is not very effective and has a strong odor, n- Propyl alcohol is more effective, but also has a distinct odor.
  • butyl alcohols also have odors but can be used for effective clarity/stability, especially when used as part of a ease of formulation solvent system to minimize their odor.
  • the alcohols are also selected for optimum low temperature stability, that is they are able to form compositions that are liquid with acceptable low viscosities and translucent, preferably clear, down to about 40°F (about 4.4°C) and are able to recover after storage down to about 20°F (about 6.7°C).
  • any solvent for the formulation of embodiments which are clear isotropic liquids is surprisingly selective.
  • Suitable solvents can be selected based upon their octanol/water partition coefficient (P) as defined in WO 97/03169.
  • the solvents suitable for use herein are selected from those having a ClogP of from about 0.15 to about 0.64, preferably from about 0.25 to about 0.62, and more preferably from about 0.40 to about 0.60, said ease of formulation solvent preferably being at least somewhat asymmetric, and preferably having a melting, or solidification, point that allows it to be liquid at, or near room temperature.
  • Solvents that have a low molecular weight and are biodegradable are also desirable for some purposes.
  • Non-limiting examples of solvents include mono-ols, C6 diols, C7 diols, octanediol isomers, butanediol derivatives, trimethylpentanediol isomers, ethylmethylpentanediol isomers, propyl pentanediol isomers, dimethylhexanediol isomers, ethylhexanediol isomers, methylheptanediol isomers, octanediol isomers, nonanediol isomers, alkyl glyceryl ethers, di(hydroxy alkyl) ethers, and aryl glyceryl ethers, aromatic glyceryl ethers, alicyclic diols and derivatives, C 3 -C 7 diol alkoxylated derivatives, aromatic diols, and unsaturated
  • compositions and processes herein can optionally employ one or more enzymes inter alia lipases, proteases, cellulase, amylases 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 of the present invention optionally comprise from about 0.01%, preferably from about 0.1% to about 8%, preferably to about 5%, more preferably to about 3% by weight, of a poly olefin emulsion or suspension in order to provide anti-wrinkle and improved water absorbency benefits to the fabrics treated by the fabric care compositions of the present invention.
  • the polyolefin is a polyethylene, polypropylene or mixtures thereof.
  • the polyolefin may be at least partially modified to contain various functional groups, such as carboxyl, carbonyl, ester, ether, alkylamide, sulfonic acid or amide groups. More preferably, the polyolefin employed in the present invention is at least partially carboxyl modified or, in other words, oxidized. In particular, oxidized or carboxyl modified polyethylene is preferred in the compositions of the present invention.
  • the polyolefin is preferably introduced as a suspension or an emulsion of polyolefin dispersed by use of an emulsifying agent.
  • the polyolefin suspension or emulsion preferably has from 1, preferably from 10%, more preferably from 15% to 50%, more preferably to 35% more preferably to 30% by weight, of polyolefin in the emulsion.
  • the polyolefin preferably has a molecular weight of from 1,000, preferably from 4,000 to 15,000, preferably to 10,000.
  • the emulsifier may be any suitable emulsification or suspending agent.
  • the emulsifier is a cationic, nonionic, zwitterionic or anionic surfactant or mixtures thereof.
  • any suitable cationic, nonionic or anionic surfactant may be employed as the emulsifier.
  • Preferred emulsifiers are cationic surfactants such as the fatty amine surfactants and in particular the ethoxylated fatty amine surfactants.
  • the cationic surfactants are preferred as emulsifiers in the present invention.
  • the polyolefin is dispersed with the emulsifier or suspending agent in a ratio of emulsifier to polyolefin of from 1 : 10 to 3 : 1.
  • the emulsion includes from 0.1, preferably from 1 %, more preferably from 2.5% to 50%, preferably to 20%, more preferably to 10% by weight, of emulsifier in the polyolefin emulsion.
  • Polyethylene emulsions and suspensions suitable for use in the present invention are available under the tradename VELUSTROL exHOECHST Aktiengesellschaft of Frankfurt am Main, Germany.
  • the polyethylene emulsions sold under the tradename VELUSTROL PKS, VELUSTROL KPA, or VELUSTROL P-40 may be employed in the compositions of the present invention.
  • compositions of the present invention can optionally comprise from about 0.01%, preferably from about 0.035% to about 0.2%, more preferably to about 0.1% for antioxidants, preferably to about 0.2% for reductive agents, of a stabilizer.
  • stabilizer includes antioxidants and reductive agents. These agents assure good odor stability under long term storage conditions for the compositions and compounds stored in molten form. The use of antioxidants and reductive agent stabilizers is especially critical for low scent products (low perfume).
  • Non-limiting examples of antioxidants that can be added to the compositions of this invention include a mixture of ascorbic acid, ascorbic palmitate, propyl gallate, ex Eastman Chemical Products, Inc., under the trade names Tenox® PG and Tenox S-l; a mixture of BHT (butylated hydroxytoluene), BHA (butylated hydroxyanisole), propyl gallate, and citric acid, ex Eastman Chemical Products, Inc., under the trade name Tenox-6; butylated hydroxytoluene, available from UOP Process Division under the trade name Sustane® BHT; tertiary butylhydroquinone, Eastman Chemical Products, Inc., as Tenox TBHQ; natural tocopherols, Eastman Chemical Products, Inc., as Tenox GT-l/GT-2; and butylated hydroxyanisole, Eastman Chemical Products, Inc., as BHA; long chain esters (C8-C22) of gallic acid, e.g., dodec
  • the fabric care compositions of the present invention may 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.
  • Fabric softening actives are typically an essential element of fabric softening compositioins.
  • the preferred fabric softening actives according to the present invention are amines having the formula:
  • each R is independently Ci -Cg alkyl, Ci -Cg hydroxyalkyl, benzyl, and mixtures thereof;
  • R! is preferably Ci 1-C22 linear alkyl, Ci 1-C22 branched alkyl, Ci 1 -C22 linear alkenyl, C j ] -C22 branched alkenyl, and mixtures thereof;
  • Q is a carbonyl moiety independently selected from the group consisting of esters, secondary amides, tertiary amides, carbonate, mono carbonyl substituted alkylene, poly carbonyl substituted alkylene, and mixtures thereof, preferably ester or secondary amide;
  • X is a softener compatible anion;
  • 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.
  • N,N-di(tallowyl-oxy-ethyl)-N,N-dimethyl ammonium chloride N,N-di(canolyl-oxy-ethyl)-N,N-dimethyl ammonium chloride;
  • 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./ Chem. Inf. Comput. Sci., 27a,21 (1987); Viswanadhan's fragmentation method as disclosed in ./ 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:
  • R 1 units are preferably alkyleneoxy units having the formula:
  • any suitable clay/soil dispersent or anti-redepostion agent can b ⁇ , 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 for control of phase stability, viscosity, and/or clarity.
  • the presence of certain electrolytes inter a a 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 mter 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 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. 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. Cationic Charge Boosters
  • 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 mter alia hexyleneglycol to aid in formulation of the final composition. This is especially true in clear, translucent, isotropic compositions.
  • 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: R2 Rl— N- R? X
  • R1, R R- ⁇ and R ⁇ are each independently Ci -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, Cg-C22 alkenyl, and mixtures thereof, more preferably 11 " 18 alkyl, C 1 1 -C 1 g alkenyl, and mixtures thereof;
  • R ⁇ , R-> , and R ⁇ are each preferably C 1 - C4 alkyl, more preferably each R Rf, 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 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, com oil, soybean oil, tall oil, rice bran oil, etc. and mixtures thereof.
  • R ⁇ -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
  • 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 -NH2 unit hydrogens can be substituted by an alkyleneoxy unit having the formula:
  • Rl is C2-C4 alkylene
  • R ⁇ is hydrogen, Ci -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 hydroxyalkylene; each R is independently Ci -C4 alkyl, each R ⁇ is independently Ci -C22 alkyl, C3-C22 alkenyl, R ⁇ -Q-(CH2) m -, wherein R ⁇ is Ci -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 Ci -C4 alkyl, more preferably methyl. Preferably at least one R ⁇ is Ci 1 -C22 alkyl, l 1"C22 alkenyl, and mixtures thereof.
  • the formulator may similarly choose R ⁇ to be a R ⁇ -Q-(CH2) m - moiety wherein 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 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, com oil, soybean oil, tall oil, rice bran oil, etc. and mixtures thereof.
  • 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 derived preferably derived from a source of triglyceride selected from the group consisting of tallow, partially hydrogenated tallow, lard, partially hydrogenated
  • R is methyl, one R ⁇ units is methyl and the other R ⁇ unit is R ⁇ -Q-(CH2) m -wherein R-*- 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.
  • the fabric enhancement compositions of the present invention 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 compound having the formula:
  • R is C ⁇ 0 -C ⁇ 8 alkyl, each R 1 is independently C ⁇ -C 4 alkyl, X is a water soluble anion; preferably R is C ⁇ -C H , preferably R 1 is methyl.
  • Preferred X is halogen, more preferably chlorine. Examples of cationic nitrogen compounds suitable for use in the fabric care compositions of the present invention are
  • Non-limiting examples of preferred cationic nitrogen compounds are N,N,N-trimethyl-N- dodecyl ammonium chloride, 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 textile enhancement compositions of the present invention may be in any form inter aha liquid, granular, paste. Depending upon the specific form of the textile enhancement composition the formulator may use different polyamine/active combinations.
  • the formulations comprise: a) from about 0.05% by weight, of a polyamine fabric enhancement system, said system comprising one or more polyamines selected from the group consisting of: i) polyamines comprising two or more backbone nitrogens; ii) polyamines comprising one or more cationic backbone nitrogens; iii) polyamines comprising one or more alkoxylated backbone nitrogens; iv) polyamines comprising one or more cationic backbone nitrogens and one or more alkoxylated backbone nitrogens; and v) mixtures thereof; b) from about 0.001% to about 90% by weight, of one or more dye fixing agents; c) optionally less than about 15% by weight, of a principal solvent, preferably said principal solvent has a ClogP of from about 0.15 to
  • compositions of the present invention can be applied by the manufacturer at any point, inter a a, while weaving the fabric, after manufacture into an article of apparel.
  • the formulations may be applied by any means, inter aha, by dipping of the fabric, squeezing via roller, padding or sprayed.
  • the present invention further relates to a method for providing textile and fabric enhancement benefits, preferably to clothing, said method comprising the step of contacting textiles or fabric with the compositions of the present invention at a point during manufacture or after fashioning into an article of apparel, said composition comprising: a) from about 0.05% by weight, of a polyamine fabric enhancement system, said system comprising one or more polyamines selected from the group consisting of: i) polyamines comprising two or more backbone nitrogens; ii) polyamines comprising one or more cationic backbone nitrogens; iii) polyamines comprising one or more alkoxylated backbone nitrogens; iv) polyamines comprising one or more cationic backbone nitrogens and one or more alkoxylated backbone nitrogens; and v) mixtures thereof; b) from about 0.001% to about 90% by weight, of one or more dye fixing agents; c) optionally less than about 15% by weight, of a principal solvent, preferably said principal solvent has a ClogP
  • compositions according to the present invention are non-limiting examples of compositions according to the present invention.
  • Oligomeric polyamine formed from the condensation of 1 part epichlorohydrin and 1.4 parts imidazole and comprising about 94% oligomer and about 6% imidazole, said oligomer having an average molecular weight of about 2000 daltons.
  • Lupasol ® SK ex BASF 2.
  • Polyvinylpyrrolidone K85 available ex BASF as Luviskol ® K85.
  • Balance to 100% can, for example, include minors like perfume, additional water, and means for adjusting pH.
  • Polyvinylpyrrolidone K85 available ex BASF as Luviskol ® K85.
  • Balance to 100% can, for example, include minors like perfume, additional water, and means for adjusting pH.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)

Abstract

L'invention concerne une composition permettant d'améliorer l'aspect d'un textile. Cette composition comprend: a) au moins environ 0,05 % en poids d'un système permettant d'améliorer l'aspect d'un textile polyamine comprenant une ou plusieurs polyamines choisies dans le groupe comprenant: i) des polyamines contenant deux ou plusieurs azotes squelettes; ii) des polyamines contenant deux ou plusieurs azotes squelettes cationiques; iii) des polyamines contenant un ou plusieurs azotes squelettes alcoxylés; iv) des polyamines contenant un ou plusieurs azotes squelettes et un ou plusieurs azotes squelettes alcoxylés; et v) des mélanges de ces éléments; b) au moins environ de 0,001 % à environ 90 % en poids, d'un ou de plusieurs agents pour le traitement subséquent des teintures; c) le solde constitué d'excipients et d'ingrédients d'adjonction. Ces compositions peuvent être utilisées à n'importe quelle étape de fabrication, y compris après l'utilisation du textile pour la conception d'un article manufacturé, de préférence un vêtement.
PCT/US2000/028823 1999-10-22 2000-10-18 Traitement permettant d'ameliorer l'aspect d'un textile non-reactif WO2001031116A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
EP00970990A EP1238138A1 (fr) 1999-10-22 2000-10-18 Traitement permettant d'ameliorer l'aspect d'un textile non-reactif
AU80292/00A AU8029200A (en) 1999-10-22 2000-10-18 Non-reactive fabric enhancement treatment
JP2001533246A JP2003513178A (ja) 1999-10-22 2000-10-18 非反応性布地強化処理剤
BR0014962-4A BR0014962A (pt) 1999-10-22 2000-10-18 Tratamento para realçar tecido não reativo
MXPA02004045A MXPA02004045A (es) 1999-10-22 2000-10-18 Tratamiento para mejoramiento de telas no reactivas.

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US60/161,153 1999-10-22

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011131412A1 (fr) 2010-04-22 2011-10-27 Unilever Plc Améliorations apportées à des agents de traitement pour textiles
CN108084343A (zh) * 2017-11-20 2018-05-29 杭州美高华颐化工有限公司 一种无甲醛固色剂的制备方法

Citations (7)

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Publication number Priority date Publication date Assignee Title
EP0422683A1 (fr) * 1989-10-13 1991-04-17 Nihon Surfactant Kogyo K.K. Composition de lavage pour articles en fibre de cellulose teints
EP0790348A1 (fr) * 1996-02-15 1997-08-20 DyStar Textilfarben GmbH & Co. Deutschland KG Procédé de lavage d'impressions textils de tissues à base de cellulose régéneré ou de coton aminé et de fibres de soie
WO1998012295A1 (fr) * 1996-09-19 1998-03-26 The Procter & Gamble Company Compositions respectant les couleurs
WO1998020098A1 (fr) * 1996-11-01 1998-05-14 The Procter & Gamble Company Compositions respectant les couleurs
WO1998038378A1 (fr) * 1997-02-26 1998-09-03 Textilcolor Ag Compose polymere a faible poids moleculaire, modifie avec du carbamate, et son utilisation pour le traitement ulterieur de materiau textile a base de cellulose, teint ou imprime
EP0918089A1 (fr) * 1997-11-24 1999-05-26 The Procter & Gamble Company Compositions d'entretien du tissu
EP0924293A1 (fr) * 1997-11-24 1999-06-23 The Procter & Gamble Company Utilisation d'un inhibiteur de la croissance de cristaux afin de réduire l'abrasion des tissus

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0422683A1 (fr) * 1989-10-13 1991-04-17 Nihon Surfactant Kogyo K.K. Composition de lavage pour articles en fibre de cellulose teints
EP0790348A1 (fr) * 1996-02-15 1997-08-20 DyStar Textilfarben GmbH & Co. Deutschland KG Procédé de lavage d'impressions textils de tissues à base de cellulose régéneré ou de coton aminé et de fibres de soie
WO1998012295A1 (fr) * 1996-09-19 1998-03-26 The Procter & Gamble Company Compositions respectant les couleurs
WO1998020098A1 (fr) * 1996-11-01 1998-05-14 The Procter & Gamble Company Compositions respectant les couleurs
WO1998038378A1 (fr) * 1997-02-26 1998-09-03 Textilcolor Ag Compose polymere a faible poids moleculaire, modifie avec du carbamate, et son utilisation pour le traitement ulterieur de materiau textile a base de cellulose, teint ou imprime
EP0918089A1 (fr) * 1997-11-24 1999-05-26 The Procter & Gamble Company Compositions d'entretien du tissu
EP0924293A1 (fr) * 1997-11-24 1999-06-23 The Procter & Gamble Company Utilisation d'un inhibiteur de la croissance de cristaux afin de réduire l'abrasion des tissus

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011131412A1 (fr) 2010-04-22 2011-10-27 Unilever Plc Améliorations apportées à des agents de traitement pour textiles
CN108084343A (zh) * 2017-11-20 2018-05-29 杭州美高华颐化工有限公司 一种无甲醛固色剂的制备方法

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EP1238138A1 (fr) 2002-09-11
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MXPA02004045A (es) 2002-10-11
CN1382238A (zh) 2002-11-27
AU8029200A (en) 2001-05-08

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