WO1998020099A1 - Compositions d'entretien des couleurs - Google Patents

Compositions d'entretien des couleurs Download PDF

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Publication number
WO1998020099A1
WO1998020099A1 PCT/US1997/019790 US9719790W WO9820099A1 WO 1998020099 A1 WO1998020099 A1 WO 1998020099A1 US 9719790 W US9719790 W US 9719790W WO 9820099 A1 WO9820099 A1 WO 9820099A1
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Prior art keywords
units
composition
formula
group
mixtures
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PCT/US1997/019790
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English (en)
Inventor
Ryan Matthew Heiden
Axel Masschelein
Joseph Fredrich Sherman
Christiaan Arthur Thoen
Richard Martin Ward
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The Procter & Gamble Company
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Priority to JP52158598A priority Critical patent/JP2001503822A/ja
Priority to EP97946411A priority patent/EP0937128A1/fr
Priority to BR9712858-9A priority patent/BR9712858A/pt
Priority to CA002270389A priority patent/CA2270389A1/fr
Publication of WO1998020099A1 publication Critical patent/WO1998020099A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • C11D17/047—Arrangements specially adapted for dry cleaning or laundry dryer related applications
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/62—Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/001—Softening compositions
    • C11D3/0015—Softening compositions liquid
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/046—Salts
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3723—Polyamines or polyalkyleneimines
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3749—Polyolefins; Halogenated polyolefins; Natural or synthetic rubber; Polyarylolefins or halogenated polyarylolefins
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3792—Amine oxide containing polymers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38645—Preparations containing enzymes, e.g. protease or amylase containing cellulase
    • 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
    • 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
    • D06P1/673—Inorganic compounds
    • D06P1/67333—Salts or hydroxides
    • 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 a color care composition with reduced malodour on treated fabrics
  • modified amino-functional polymer it is meant that the polyamine backbones are modified in such a manner that at least one nitrogen of the polyamine chain is substituted, quaternized, oxidized, or combinations thereof.
  • a problem now encountered with compositions comprising modified amino-functional polymer is the resulting malodours on the treated fabrics.
  • the formulator of a color care composition is faced with the dual problem of formulating a composition which provides care to the fabrics without being detrimental to the scent of the treated fabrics.
  • Chlorine oxidant include for example sodium hypochlorite, chlorine, as well as chlorine dioxide. Chlorine is a common component in domestic treatments. Indeed, chlorine is used in many parts of the world to sanitize water. To ensure that the water is safe, a small residual amount, typically about 1 to 2 parts per million (ppm), of chlorine is left in the water. At least about 10% of U.S. households has about 2 ppm or more of chlorine in its tap water at some time. Chlorine may also be carried over from the wash where hypochlorite bleaches are used in washing compositions or as additives.
  • the present invention is a composition comprising a modified amino- functional polymer and a chlorine scavenger, and wherein said chlorine scavenger is selected from the group consisting of ammonium salts.
  • the present invention also encompasses the use of a chlorine scavenger, in a composition comprising a modified amino-functional polymer, for reducing malodours on treated fabrics.
  • a chlorine scavenger in a composition comprising a modified amino-functional polymer, for reducing malodours on treated fabrics.
  • One of the essential component of the invention is a modified amino- functional polymer comprising a polyamine backbone.
  • the amino-functional polymers of the present invention are water-soluble or dispersible, polyamines.
  • the amino-functional polymers for use herein have a molecular weight between 200 and 1 0 ⁇ , preferably between 600 and 20,000, most preferably between 1 000 and 1 0,000.
  • These polyamines comprise backbones that can be either linear or cyclic.
  • the polyamine backbones can also comprise polyamine branching chains to a greater or lesser degree.
  • the polyamine backbones described herein are modified in such a manner that at least one, preferably each nitrogen of the polyamine chain is thereafter described in terms of a unit that is substituted, quaternized, oxidized, or combinations thereof.
  • the term "modification" as it relates to the chemical structure of the polyamines is defined as replacing a backbone -NH hydrogen atom by an R' unit (substitution), quaternizing a backbone nitrogen (quaternized) or oxidizing a backbone nitrogen to the N- oxide (oxidized).
  • substitution and “substitution” are used interchangably when referring to the process of replacing a hydrogen atom attached to a backbone nitrogen with an R' unit. Quaternization or oxidation may take place in some circumstances without substitution, but substitution is preferably accompanied by oxidation or quaternization of at least one backbone nitrogen.
  • linear or non-cyclic polyamine backbones that comprise the amino- functional polymer have the general formula:
  • cyclic polyamine backbones that comprise the amino-functional polymer have the general formula: i R
  • the above backbones prior to optional but preferred subsequent modification comprise primary, secondary and tertiary amine nitrogens connected by R "linking" units
  • primary amine nitrogens comprising the backbone or branching chain once modified are defined as V or Z "terminal" units.
  • V or Z "terminal" units when a primary amine moiety, located at the end of the main polyamine backbone or branching chain having the structure
  • H2N-R]- is modified according to the present invention, it is thereafter defined as a V "terminal" unit, or simply a V unit.
  • V terminal unit
  • some or all of the primary amine moieties can remain unmodified subject to the restrictions further described herein below. These unmodified primary amine moieties by virtue of their position in the backbone chain remain “terminal” units.
  • a primary amine moiety located at the end of the main polyamine backbone having the structure
  • -NH 2 is modified according to the present invention, it is thereafter defined as a Z "terminal" unit, or simply a Z unit. This unit can remain unmodified subject to the restrictions further described herein below.
  • secondary amine nitrogens comprising the backbone or branching chain once modified are defined as W "backbone" units.
  • W backbone
  • H — [N-R]- is modified according to the present invention, it is thereafter defined as a W "backbone” unit, or simply a W unit.
  • W backbone
  • some or all of the secondary amine moieties can remain unmodified. These unmodified secondary amine moieties by virtue of their position in the backbone chain remain "backbone” units.
  • tertiary amine nitrogens comprising the backbone or branching chain once modified are further referred to as Y "branching" units.
  • Y branch point of either the polyamine backbone or other branching chains or rings, having the structure
  • I — [N-R]- is modified according to the present invention, it is thereafter defined as a Y "branching" unit, or simply a Y unit.
  • some or all or the tertiary amine moieties can remain unmodified. These unmodified tertiary amine moieties by virtue of their position in the backbone chain remain “branching" units.
  • the R units associated with the V, W and Y unit nitrogens which serve to connect the polyamine nitrogens, are described herein below.
  • V(n-k + 1 )W m YnY'kZ for cyclic amino-functional polymer.
  • [N-R]— serves as a branch point for a backbone or branch ring.
  • Y' unit there is a Y unit having the formula
  • the polyamine backbone has the formula
  • the polyamine backbones of the present invention comprise no rings.
  • the ratio of the index n to the index m relates to the relative degree of branching.
  • a fully non-branched linear modified polyamine according to the present invention has the formula vw m z that is, n is equal to 0. The greater the value of n (the lower the ratio of m to n), the greater the degree of branching in the molecule.
  • the value for m ranges from a minimum value of 2 to 700, preferably 4 to 400, however larger values of m, especially when the value of the index n is very low or nearly 0, are also preferred.
  • Each polyamine nitrogen whether primary, secondary or tertiary, once modified according to the present invention, is further defined as being a member of one of three general classes; simple substituted, quaternized or oxidized. Those polyamine nitrogen units not modified are classed into V, W, Y, Y' or Z units depending on whether they are primary, secondary or tertiary nitrogens. That is unmodified primary amine nitrogens are V or Z units, unmodified secondary amine nitrogens are W units or Y' units and unmodified tertiary amine nitrogens are Y units for the purposes of the present invention.
  • Modified primary amine moieties are defined as V "terminal" units having one of three forms: a) simple substituted units having the structure:
  • Modified secondary amine moieties are defined as W "backbone" units having one of three forms: a) simple substituted units having the structure:
  • modified secondary amine moieties are defined as Y' units having one of three forms: a) simple substituted units having the structure:
  • Modified tertiary amine moieties are defined as Y "branching" units having one of three forms: a) unmodified units having the structure: — N-R—
  • Certain modified primary amine moieties are defined as Z "terminal" units having one of three forms: a) simple substituted units having the structure:
  • a primary amine unit comprising one R' unit in the form of a hydroxyethyl moiety is a V terminal unit having the formula (HOCH2CH2>HN-.
  • the Z "terminal” unit derives from a terminal primary amino moiety of the structure -NH2.
  • Non-cyclic polyamine backbones according to the present invention comprise only one Z unit whereas cyclic polyamines can comprise no Z units.
  • the Z "terminal” unit can be substituted with any of the R' units described further herein below, except when the Z unit is modified to form an N-oxide. In the case where the Z unit nitrogen is oxidized to an N-oxide, the nitrogen must be modified and therefore R' cannot be a hydrogen.
  • the polyamines of the present invention comprise backbone R "linking" units that serve to connect the nitrogen atoms of the backbone.
  • R units comprise units that for the purposes of the present invention are referred to as “hydrocarbyl R” units and “oxy R” units.
  • the "hydrocarbyl" R units are C2-C1 2 alkylene, C4-C1 2 alkenylene, C3-C-1 2 hydroxyalkylene wherein the hydroxyl moiety may take any position on the R unit chain except the carbon atoms directly connected to the polyamine backbone nitrogens; C4- C-
  • a dialkylarylene unit has the formula
  • the unit need not be 1 ,4-substituted, but can also be 1 ,2 or 1 ,3 substitutedC2-C-
  • the "oxy" R units comprise - (R 1 O) x R 5 (OR 1 ) x -, -CH2CH(OR 2 )CH 2 O) z (R 1 O) y Rl (OCH 2 CH(OR 2 )CH2) w -, - CH2CH(OR 2 )CH2-, -(R 1 O) x R 1 -, and mixtures thereof.
  • R units are selected from the group consisting of C2-C1 2 alkylene, C3-C1 2 hydroxyalkylene, C4-C1 2 dihydroxyalkylene, Cs-C-
  • the most preferred backbones of the present invention comprise at least 50% R units that are ethylene.
  • R 1 units are C2-C6 alkylene, and mixtures thereof, preferably ethylene.
  • R 2 is hydrogen, and -(R 1 O) x B, preferably hydrogen.
  • R 3 is C1 - 1 8 a'kyl, 7-C1 2 arylalkylene, C7-C1 2 alkyl substituted aryl, CQ-C - ⁇ 2 arv '' anc * mixtures thereof , preferably C1 -C1 2 alkyl, C7-C1 2 arylalkylene, more preferably C-
  • R3 units serve as part of R' units described herein below.
  • R 4 is C-] -C-
  • R 5 is C-
  • R ⁇ is C2-C-J 2 alkylene or C ⁇ -C-] 2 arylene.
  • the preferred "oxy" R units are further defined in terms of the R-! , R 2 , and R5 units.
  • Preferred "oxy" R units comprise the preferred R1 , R 2 , and R ⁇ units.
  • the preferred cotton soil release agents of the present invention comprise at least 50% R 1 units that are ethylene.
  • Preferred R 1 , R 2 , and R ⁇ units are combined with the "oxy” R units to yield the preferred "oxy” R units in the following manner. i) Substituting more preferred R ⁇ into
  • R' units are selected from the group consisting of hydrogen, C1 -C22 alkyl, C3-C22 alkenyl, C7-C22 arylalkyl, C2-C22 hydroxyalkyl, -(CH2> p CO2M, - (CH 2 ) q SO 3 M, -CH(CH 2 CO 2 M)CO 2 M, -(CH 2 ) p PO 3 M, -(Rl ⁇ ) m B, -C(O)R 3 , preferably hydrogen, C2-C22 hydroxyalkylene, benzyl, C1 -C22 alkylene, - (R 1 O) m B, -C(0)R3, -(CH 2 ) p CO 2 M, -(CH 2 )qSO 3 M, -CH(CH 2 CO 2 M)CO 2 M, more preferably C-
  • R' units do not comprise hydrogen atom when the V, W or Z units are oxidized, that is the nitrogens are N-oxides.
  • the backbone chain or branching chains do not comprise units of the following structure:
  • R' units do not comprise carbonyl moieties directly bonded to a nitrogen atom when the V, W or Z units are oxidized, that is, the nitrogens are N-oxides.
  • the R' unit -C(O)R 3 moiety is not bonded to an N-oxide modified nitrogen, that is, there are no
  • B is hydrogen, Ci -Cg alkyl, -(CH2> q SO3M, -(CH2> p CO2M, - ⁇ CH2) q - (CHSO 3 M)CH 2 SO 3 M, -(CH2)q(CHSO2M)CH 2 SO 3 M, -(CH2) p PO 3 M, - PO 3 M, preferably hydrogen, -(CH 2 ) q SO 3 M, -(CH2) q (CHSO 3 M)CH2SO 3 M, - (CH2)q-(CHSO2M)CH2SO3M, more preferably hydrogen or -(CH2> q SO3M.
  • M is hydrogen or a water soluble cation in sufficient amount to satisfy charge balance.
  • a sodium cation equally satisfies (CH2> p CO2M, and -(CH2) q SO3M, thereby resulting in -
  • CH2> p CO2Na, and -(CH2)qSO3Na moieties More than one monovalent cation, (sodium, potassium, etc.) can be combined to satisfy the required chemical charge balance. However, more than one anionic group may be charge balanced by a divalent cation, or more than one mono-valent cation may be necessary to satisfy the charge requirements of a poly-anionic radical.
  • a -(CH2) p PO3M moiety substituted with sodium atoms has the formula -(CH2> p PO3Na3.
  • Divalent cations such as calcium (Ca 2 + ) or magnesium (Mg 2 + ) may be substituted for or combined with other suitable mono-valent water soluble cations.
  • Preferred cations are sodium and potassium, more preferred is sodium.
  • X is a water soluble anion such as chlorine (Cl " ), bromine (Br) and iodine
  • (I " ) or X can be any negatively charged radical such as sulfate (SO4 2" ) and methosulfate (CH3SO3 " ).
  • indices have the following values: p has the value from 1 to 6, q has the value from 0 to 6; r has the value 0 or 1 ; w has the value 0 or 1 , x has the value from 1 to 100; y has the value from 0 to 1 00; z has the value 0 or 1 ; m has the value from 2 to 700, preferably from 4 to 400, n has the value from 0 to 350, preferably from 0 to 200; m + n has the value of at least 5.
  • x has a value lying in the range of from 1 to 20, preferably from 1 to 10.
  • the preferred amino-functional polymers of the present invention comprise polyamine backbones wherein less than 50% of the R groups comprise "oxy" R units, preferably less than 20% , more preferably less than 5%, most preferably the R units comprise no "oxy" R units.
  • the most preferred amino-functional polymers which comprise no "oxy" R units comprise polyamine backbones wherein less than 50% of the R groups comprise more than 3 carbon atoms.
  • ethylene, 1 ,2- propylene, and 1 ,3-propylene comprise 3 or less carbon atoms and are the preferred "hydrocarbyl" R units. That is when backbone R units are C2-C12 alkylene, preferred is C2-C3 alkylene, most preferred is ethylene.
  • the amino-functional polymers of the present invention comprise modified homogeneous and non-homogeneous polyamine backbones, wherein 100% or less of the -NH units are modified.
  • the term "homogeneous polyamine backbone” is defined as a polyamine backbone having R units that are the same (i.e., all ethylene). However, this sameness definition does not exclude polyamines that comprise other extraneous units comprising the polymer backbone which are P resent due to an artifact of the chosen method of chemical synthesis.
  • ethanolamine may be used as an "initiator" in the synthesis of polyethyleneimines, therefore a sample of polyethyleneimine that comprises one hydroxyethyl moiety resulting from the polymerization "initiator” would be considered to comprise a homogeneous polyamine backbone for the purposes of the present invention.
  • a polyamine backbone comprising all ethylene R units wherein no branching Y units are present is a homogeneous backbone.
  • a polyamine backbone comprising all ethylene R units is a homogeneous backbone regardless of the degree of branching or the number of cyclic branches present.
  • non-homogeneous polymer backbone refers to polyamine backbones that are a composite of various R unit lengths and R unit types.
  • a non-homogeneous backbone comprises R units that are a mixture of ethylene and 1 ,2- propylene units.
  • a mixture of "hydrocarbyl” and “oxy” R units is not necessary to provide a non- homogeneous backbone.
  • Preferred amino-functional polymers of the present invention comprise homogeneous polyamine backbones that are totally or partially substituted by polyethyleneoxy moieties, totally or partially quaternized amines, nitrogens totally or partially oxidized to N-oxides, and mixtures thereof.
  • polyethyleneoxy moieties totally or partially quaternized amines
  • nitrogens totally or partially oxidized to N-oxides, and mixtures thereof.
  • backbone amine nitrogens must be modified in the same manner, the choice of modification being left to the specific needs of the formulator.
  • the degree of ethoxylation is also determined by the specific requirements of the formulator.
  • the preferred amino-functional polymers that comprise the backbone of the compounds of the present invention are generally polyalkyleneimines (PAI's), preferably polyethyleneimines (PEI's), or PEI's connected by moieties having longer R units than the parent PAI's or PEI's.
  • Preferred amine polymer backbones comprise R units that are C2 alkylene (ethylene) units, also known as polyethylenimines (PEI's).
  • Preferred PEI's have at least moderate branching, that is the ratio of m to n is less than 4: 1 , however PEI's having a ratio of m to n of 2: 1 are most preferred.
  • Preferred backbones, prior to modification have the general formula:
  • PEI's will have a molecular weight greater than 200 daltons.
  • the relative proportions of primary, secondary and tertiary amine units in the polyamine backbone will vary, depending on the manner of preparation.
  • Each hydrogen atom attached to each nitrogen atom of the polyamine backbone chain represents a potential site for subsequent substitution, quaternization or oxidation.
  • polyamines can be prepared, for example, by polymerizing ethyleneimine in the presence of a catalyst such as carbon dioxide, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid, etc.
  • a catalyst such as carbon dioxide, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid, etc.
  • Specific methods for preparing these polyamine backbones are disclosed in U.S. Patent 2, 182,306, Ulrich et al., issued December 5, 1 939; U.S. Patent 3,033,746, Mayle et al., issued May 8, 1962; U.S. Patent 2,208,095, Esselmann et al., issued July 16, 1940; U.S. Patent 2,806,839, Crowther, issued September 17, 1957; and U.S. Patent 2,553,696, Wilson, issued May 21 , 1951 ; all herein incorporated by reference.
  • Formula I depicts an amino-functional polymer comprising a PEI backbone wherein all substitutable nitrogens are modified by replacement of hydrogen with a polyoxyalkyleneoxy unit, -(CH2CH2 ⁇ )H, having the formula
  • Formula II depicts an amino-functional polymer comprising a PEI backbone wherein all substitutable primary amine nitrogens are modified by replacement of hydrogen with a polyoxyalkyleneoxy unit, -(CH2CH2 ⁇ )2H, the molecule is then modified by subsequent oxidation of all oxidizable primary and secondary nitrogens to N-oxides, said polymer having the formula
  • Formula III depicts an amino-functional polymer comprising a PEI backbone wherein all backbone hydrogen atoms are substituted and some backbone amine units are quaternized.
  • the substituents are polyoxyalkyleneoxy units, -(CH2CH2 ⁇ )7H, or methyl groups.
  • the modified PEI has the formula
  • Formula IV depicts an amino-functional polymer comprising a PEI backbone wherein the backbone nitrogens are modified by substitution (i.e. by - (CH2CH2O>3H or methyl), quaternized, oxidized to N-oxides or combinations thereof.
  • the resulting polymer has the formula
  • not all nitrogens of a unit class comprise the same modification.
  • the present invention allows the formulator to have a portion of the secondary amine nitrogens ethoxylated while having other secondary amine nitrogens oxidized to N-oxides.
  • This also applies to the primary amine nitrogens, in that the formulator may choose to modify all or a portion of the primary amine nitrogens with one or more substituents prior to oxidation or quaternization. Any possible combination of R' groups can be substituted on the primary and secondary amine nitrogens, except for the restrictions described herein above.
  • Commercially available amino-functional polymer suitable for use herein are hydroxyethylated poly(ethyleneimine) from Polysciences, with a MW2000, and 80% hydroxyethylated poly(ethyleneimine) from Aldrich.
  • a typical amount of amino-functional polymer to be employed in the composition of the invention is preferably up to 90% by weight, preferably from 0.01 % to 50% active by weight, more preferably from 0.1 % to 20% by weight and most preferably from 0.5% to 5% by weight of the composition.
  • a chlorine scavenger is the other essential component of the invention. Not to be bound by theory, it is believed that the benefit provided by the invention composition is due to the higher reaction rate of the chlorine scavengers with chlorine when compared to the reaction rate of the modified amino-functional polymers with chlorine.
  • Suitable levels of chlorine scavengers in the compositions of the present invention range from about 0.01 % to about 1 5%, preferably from about 0.02% to about 10%, most preferably from about 0.25% to about 5%, by weight of total composition. If both the cation and the anion of the scavenger react with chlorine, which is desirable, the level may be adjusted to react with an equivalent amount of available chlorine.
  • chlorine scavengers are selected from the group consisting of ammonium salts, e.g., ammonium chloride, ammonium sulfate; and mixtures thereof.
  • Ammonium chloride is a preferred inexpensive chlorine scavenger for use herein.
  • the composition may also contain optional components which may be suitable for further improving the aesthetic appearance of the fabrics treated therewith.
  • optional components are selected from the group consisting of a dye fixing agent, a polyolefin dispersion, a fabric softener component, detersive ingredients, additional components and mixtures thereof.
  • An optional component of the invention is a dye fixing agent.
  • Dye fixing agents or “fixatives”, 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 are fabric softeners or those described hereinafter as amino-functional polymers.
  • Cationic fixatives are available under various trade names from several suppliers. Representative examples include: CROSCOLOR PMF (July 1 981 , Code No. 7894) and CROSCOLOR NOFF (January 1 988, Code No. 8544) from Crosfield; INDOSOL E-50 (February 27, 1 984, Ref. No.
  • Dye fixing agents suitable for use in the present invention are ammonium compounds such as fatty acid - diamine condensates e.g.
  • a typical amount of the dye fixing agent to be employed in the composition of the invention is preferably up 90% by weight, preferably up to 50% by weight, more preferably from 0.001 % to 1 0% by weight, most preferably from 0.5% to 5% active by weight of the composition.
  • a polyolefin dispersion may optionally be used in the composition of the invention in order to provide anti-wrinkles and improved water absorbency benefits to the fabrics.
  • 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 emulsifing agent.
  • the polyolefin suspension or emulsion preferably has from 1 to 50%, more preferably from 10 to 35% by weight, and most preferably from 1 5 to 30% by weight of polyolefin in the emulsion.
  • the polyolefin preferably has a molecular weight of from 1 ,000 to 1 5,000 and more preferably from 4,000 to 1 0,000.
  • 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 : 1 0 to 3: 1 .
  • the emulsion includes from 0.1 to 50%, more preferably from 1 to 20% and most preferably from 2.5 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 from HOECHST 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 will contain from 0.01 % to 8% by weight of the dispersible polyolefin, more preferably from 0.1 % to 5% by weight and most preferably from 0.1 % to 3% by weight of the polyolefin.
  • the polyolefin is added to the compositions of the present invention as an emulsion or suspension, the emulsion or suspension is added at sufficient enough quantities to provide the above noted levels of dispersible polyolefin in the compositions.
  • a fabric softener component may also be suitably used in the composition of the invention so as to provide softeness and antistastic properties to the treated fabrics.
  • the fabric softener component will typically be present at a level sufficient to provide softening and antistatic properties. Typical levels are those conventionally used in fabric softening compositions, i.e from 1 % to 99% by weight of the composition.
  • the composition will preferably comprise a level of fabric softening components for liquid compositions of from 1 % to 5% by weight for the diluted compositions or from 5% to 80%, more preferably 10% to 50%, most preferably 15% to 35% by weight for concentrated compositions.
  • the level of nonionic softener component in the composition will typically be from 0.1 % to 10%, preferably from 1 % to 5% by weight.
  • the preferred level of fabric softener component will preferably be from 20% to 99%, more preferably from 30% to 90% by weight, and even more preferably from 35% to 85% by weight.
  • Said fabric softening component may be selected from cationic, nonionic, amphoteric or anionic fabric softening component.
  • the preferred, typical cationic fabric softening components include the water-insoluble quaternary-ammonium fabric softening actives, the most commonly used having been di-long alkyl chain ammonium chloride or methyl sulfate.
  • Preferred cationic softeners among these include the following:
  • DTDMAC ditallowyl dimethylammonium chloride
  • the quaternary ammonium compounds and amine precursors herein have the formula (I) or (II), below :
  • Q is selected from -O-C(O)-, -C(O)-O-, -O-C(O)-O-, -NR 4 -C(O)-,
  • R1 is (CH 2 ) n -Q-T 2 or T3;
  • R 2 is (CH 2 ) m -Q-T 4 or T ⁇ or R 3 ;
  • R3 is C1 - 4 alkyl or C1 - 4 hydroxyalkyl or H;
  • R 4 is H or C ⁇ - 4 alkyl or C-1 -C4 hydroxyalkyl
  • T ⁇ , T 2 , T3, T 4 , T ⁇ are independently C ⁇ -C22 a'kyl or alkenyl; n and m are integers from 1 to 4; and
  • X is a softener-compatible anion.
  • Non-limiting examples of softener-compatible anions include chloride or methyl sulfate.
  • the alkyl, or alkenyl, chain T 1 , T 2 , T 3 , T 4 , T 5 must contain at least 6 carbon atoms, preferably at least 1 1 carbon atoms, more preferably at least 1 6 carbon atoms.
  • the chain may be straight or branched.
  • Tallow is a convenient and inexpensive source of long chain alkyl and alkenyl material.
  • the compounds wherein T ⁇ , T 2 , ⁇ 3, T 4 , T ⁇ represents the mixture of long chain materials typical for tallow are particularly preferred.
  • quaternary ammonium compounds suitable for use in the aqueous fabric softening compositions herein include :
  • DSOEDMAC di(stearoyloxyethyl) dimethylammonium chloride
  • N,N-di(tallowoyl-oxy-ethyl)-N,N-dimethyl ammonium chloride where the tallow chains are at least partially unsaturated.
  • the level of unsaturation of the fatty chain can be measured by the Iodine Value (IV) of the corresponding fatty acid, which in the present case should preferably be in the range of from 5 to 200, preferably 5 to 1 50, and more preferably 5 to 100 with two categories of compounds being distinguished, having a IV below or above 25.
  • IV Iodine Value
  • the anion is merely present as a counterion of the positively charged quaternary ammonium compounds.
  • the nature of the counterion is not critical at all to the practice of the present invention.
  • the scope of this invention is not considered limited to any particular anion.
  • amine precursors thereof is meant the secondary or tertiary amines corresponding to the above quaternary ammonium compounds, said amines being substantially protonated in the present compositions due to the pH values.
  • Additional fabric softening materials may be used in addition or alternatively to the cationic fabric softener. These may be selected from nonionic, amphoteric or anionic fabric softening material. Disclosure of such materials may be found in US 4,327, 1 33; US 4,421 ,792; US 4,426,299; US 4,460,485; US 3,644,203; US 4,661 ,269; U.S 4,439,335; U.S 3,861 ,870; US 4,308, 1 51 ; US 3,886,075; US 4,233, 1 64; US 4,401 ,578; US 3,974,076; US 4,237,01 6 and EP 472, 1 78.
  • nonionic fabric softener materials typically have a HLB of from 2 to 9, more typically from 3 to 7.
  • Such nonionic fabric softener materials tend to be readily dispersed either by themselves, or when combined with other materials such as single-long-chain alkyl cationic surfactant described in detail hereinafter. Dispersibility can be improved by using more single-long- chain alkyl cationic surfactant, mixture with other materials as set forth hereinafter, use of hotter water, and/or more agitation.
  • the materials selected should be relatively crystalline, higher melting, (e.g. > 40°C) and relatively water-insoluble.
  • Preferred nonionic softeners are fatty acid partial esters of polyhydric alcohols, or anhydrides thereof, wherein the alcohol, or anhydride, contains from 2 to 1 8, preferably from 2 to 8, carbon atoms, and each fatty acid moiety contains from 1 2 to 30, preferably from 1 6 to 20, carbon atoms.
  • such softeners contain from one to 3, preferably 2 fatty acid groups per molecule.
  • the polyhydric alcohol portion of the ester can be ethylene glycol, glycerol, poly (e.g., di-, tri-, tetra, penta-, and/or hexa-) glycerol, xylitol, sucrose, erythritol, pentaerythritol, sorbitol or sorbitan. Sorbitan esters and polyglycerol monostearate are particularly preferred.
  • the fatty acid portion of the ester is normally derived from fatty acids having from 1 2 to 30, preferably from 1 6 to 20, carbon atoms, typical examples of said fatty acids being lauric acid, myristic acid, palmitic acid, stearic acid and behenic acid.
  • Highly preferred optional nonionic softening agents for use in the present invention are the sorbitan esters, which are esterified dehydration products of sorbitol, and the glycerol esters.
  • sorbitan monostearate is a suitable material. Mixtures of sorbitan stearate and sorbitan palmitate having stearate/palmitate weight ratios varying between 1 0: 1 and 1 : 10, and 1 ,5-sorbitan esters are also useful.
  • Glycerol and polyglycerol esters especially glycerol, diglycerol, triglycerol, and polyglycerol mono- and/or di-esters, preferably mono-, are preferred herein (e.g. polyglycerol monostearate with a trade name of Radiasurf 7248).
  • Useful glycerol and polyglycerol esters include mono-esters with stearic, oleic, palmitic, lauric, isostearic, myristic, and/or behenic acids and the diesters of stearic, oleic, palmitic, lauric, isostearic, behenic, and/or myristic acids. It is understood that the typical mono-ester contains some di- and tri- ester, etc.
  • the "glycerol esters” also include the polyglycerol, e.g., diglycerol through octaglycerol esters.
  • the polyglycerol polyols are formed by condensing glycerin or epichlorohydrin together to link the glycerol moieties via ether linkages.
  • the mono- and/or diesters of the polyglycerol polyols are preferred, the fatty acyl groups typically being those described hereinbefore for the sorbitan and glycerol esters.
  • the pH of the liquid compositions herein is an essential parameter of the present invention. Indeed, it influences the stability of the quaternary ammonium or amine precursors compounds, especially in prolonged storage conditions.
  • the pH as defined in the present context, is measured in the neat compositions at 20°C.
  • the neat pH measured in the above-mentioned conditions, must be in the range of from 2.0 to 4.5.
  • the pH of the neat composition is in the range of 2.0 to 3.5, while if it is in a diluted form, the pH of the neat composition is in the range of 2.0 to 3.0.
  • the pH of these compositions herein can be regulated by the addition of a Bronsted acid.
  • Suitable acids include the inorganic mineral acids, carboxylic acids, in particular the low molecular weight (C1 -C5) carboxylic acids, and alkylsulfonic acids.
  • Suitable inorganic acids include HCI, H2SO4, HNO3 and H3PO4.
  • Suitable organic acids include formic, acetic, citric, methylsulfonic and ethylsulfonic acid.
  • Preferred acids are citric, hydrochloric, phosphoric, formic, methylsulfonic acid, and benzoic acids.
  • Fully formulated fabric softening compositions preferably contain, in addition to the hereinbefore described components, one or more of the following ingredients.
  • composition herein can optionally employ one or more enzymes such as lipases, proteases, cellulase, amylases and peroxidases.
  • a preferred enzyme for use herein is a cellulase enzyme. Indeed, this type of enzyme will further provide a color care benefit to the treated fabric.
  • Cellulases usable herein include both bacterial and fungal types, preferably having a pH optimum between 5 and 9.5. U.S.
  • compositions herein will typically comprise from 0.001 % to 5%, preferably 0.01 %-1 % by weight of a commercial enzyme preparation.
  • activity units are preferred (e.g. CEVU or cellulase Equivalent Viscosity Units).
  • the compositions of the present invention can contain cellulase enzymes at a level equivalent to an activity from about 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.
  • Concentrated compositions of the present invention may require organic and/or inorganic concentration aids to go to even higher concentrations and/or to meet higher stability standards depending on the other ingredients.
  • Surfactant concentration aids are typically selected from the group consisting of single long chain alkyl cationic surfactants; nonionic surfactants; amine oxides; fatty acids; or mixtures thereof, typically used at a level of from 0 to 1 5% of the composition.
  • Inorganic viscosity control agents which can also act like or augment the effect of the surfactant concentration aids, include water-soluble, ionizable salts which can also optionally be incorporated into the compositions of the present invention.
  • ionizable salts can be used. Examples of suitable salts are the halides of the Group IA and IIA metals of the Periodic Table of the Elements, e.g., calcium chloride, magnesium 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 20 to 20,000 parts per million (ppm), preferably from 20 to 1 1 ,000 ppm, by weight 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.
  • 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 may improve softness performance. These agents may stabilize the viscosity over a broader range of temperature, especially at low temperatures, compared to the inorganic electrolytes.
  • alkylene polyammonium salts include l-lysine monohydrochloride and 1 ,5-diammonium 2-methyl pentane dihydrochloride.
  • the liquid carrier employed in the instant compositions is preferably at least primarily water due to its low cost, relative availability, safety, and environmental compatibility.
  • the level of water in the liquid carrier is preferably at least 50%, most preferably at least 60%, by weight of the carrier.
  • Mixtures of water and low molecular weight, e.g., ⁇ 200, organic solvent, e.g., lower alcohols such as ethanol, propanol, isopropanol or butanol are useful as the carrier liquid.
  • Low molecular weight alcohols include monohydric, dihydric (glycol, etc.) trihydric (glycerol, etc.), and higher polyhydric (polyols) alcohols.
  • Soil Release Polymers bacteriocides, colorants, perfumes, preservatives, optical brighteners, anti ionisation agents, antifoam agents, and the like.
  • adjunct ingredients may also be used to provide fully- formulated detergent compositions.
  • the following ingredients are described for the convenience of the formulator, but are not intended to be limiting thereof.
  • Detersive ingredients may also be used in the composition of the invention. Suitable detersive ingredients are those conventional to the detergent formulators of laundry and cleaning products. Typical of such conventional detersive ingredients include detersive surfactants, builders, bleaching compounds, and mixtures thereof. Detersive Surfactants - Nonlimiting examples of surfactants useful herein typically at levels from 1 % to 55%, by weight, include the conventional C-
  • the conventional nonionic and amphoteric surfactants such as the C1 2-C1 8 a'M ethoxylates ("AE") including the so- called narrow peaked alkyl ethoxylates and C6-C1 2 alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), C-] 2" i 8 betaines and sulfobetaines ("sultaines”), Ci O" -
  • the C1 0-C1 8 N- alkyl polyhydroxy fatty acid amides can also be used.
  • Typical examples include the C-
  • Other sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as C 10-C1 8 N-(3-methoxypropyl) glucamide. The N-propyl through N-hexyl C-
  • 0" C20 conventional soaps may also be used. If high sudsing is desired, the branched-chain C-
  • Builders - Detergent builders can optionally be included in the compositions herein to assist in controlling mineral hardness. Inorganic as well as organic builders can be used. Builders are typically used in fabric laundering compositions to assist in the removal of particulate soils.
  • the level of builder can vary widely depending upon the end use of the composition and its desired physical form.
  • the compositions will typically comprise at least 1 % builder, preferably from 1 % to 80%.
  • Liquid formulations typically comprise from 5% to 50%, more typically 5% to 30%, by weight, of detergent builder.
  • Granular formulations typically comprise from 1 % to 80%, more typically from 5% to 50% by weight, of the detergent builder.
  • Lower or higher levels of builder are not meant to be excluded.
  • Inorganic or P-containing detergent builders include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates (exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric meta-phosphates), phosphonates, phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulphates, and aluminosilicates.
  • non-phosphate builders are required in some locales.
  • compositions herein function surprisingly well even in the presence of the so-called “weak” builders (as compared with phosphates) such as citrate, or in the so-called “underbuilt” situation that may occur with zeolite or layered silicate builders.
  • silicate builders are the alkali metal silicates, particularly those having a SiO2:Na2O ratio in the range 1 .0: 1 to 3.2: 1 and layered silicates, such as the layered sodium silicates described in U.S. 4,664,839.
  • NaSKS-6 is the trademark for a crystalline layered silicate marketed by Hoechst (commonly abbreviated herein as "SKS-6").
  • the Na SKS-6 silicate builder does not contain aluminum.
  • NaSKS-6 has the delta- Na2Si ⁇ 5 morphology form of layered silicate. It can be prepared by methods such as those described in German DE-A-3, 41 7,649 and DE-A- 3,742,043.
  • SKS-6 is a highly preferred layered silicate for use herein, but other such layered silicates, such as those having the general formula NaMSi x ⁇ 2 ⁇ + 1 yH2 ⁇ wherein M is sodium or hydrogen, x is a number from 1 .9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0 can be used herein.
  • Various other layered silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-1 1 , as the alpha, beta and gamma forms.
  • the delta-Na2SiO5 (NaSKS-6 form) is most preferred for use herein.
  • silicates may also be useful such as for example magnesium silicate, which can serve as a crispening agent in granular formulations, as a stabilizing agent for oxygen bleaches, and as a component of suds control systems.
  • carbonate builders are the alkaline earth and alkali metal carbonates as disclosed in German Patent Application No. 2,321 ,001 published on November 1 5, 1 973.
  • Aluminosilicate builders are useful in the present invention. Aluminosilicate builders are of great importance in most currently marketed heavy duty granular detergent compositions, and can also be a significant builder ingredient in liquid detergent formulations. Aluminosilicate builders include those having the empirical formula:
  • z and y are integers usually of at least 6, the molar ratio of z to y is in the range from 1 .0 to 0, and x is an integer from 0 to 264
  • M is a Group IA or HA element, e.g., Na, K, Mg, Ca with valence n.
  • aluminosilicate ion exchange materials are commercially available. These aluminosilicates can be crystalline or amorphous in structure and can be naturally-occurring aluminosilicates or synthetically derived. A method for producing aluminosilicate ion exchange materials is disclosed in U.S. Patent 3,985,669, Krummel, et al, issued October 12, 1976. Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X. In an especially preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula:
  • the aluminosilicate has a particle size of 0.1 -10 microns in diameter.
  • Organic detergent builders suitable for the purposes of the present invention include, but are not restricted to, a wide variety of polycarboxylate compounds.
  • polycarboxylate refers to compounds having a plurality of carboxylate groups, preferably at least 3 carboxylates.
  • Polycarboxylate builder can generally be added to the composition in acid form, but can also be added in the form of a neutralized salt. When utilized in salt form, alkali metals, such as sodium, potassium, and lithium, or alkanolammonium salts are preferred. Included among the polycarboxylate builders are a variety of categories of useful materials.
  • polycarboxylate builders encompasses the ether polycarboxylates, including oxydisuccinate, as disclosed in Berg, U.S. Patent 3, 1 28,287, issued April 7, 1 964, and Lamberti et al, U.S. Patent 3,635,830, issued January 1 8, 1 972. See also "TMS/TDS" builders of U.S. Patent 4,663,071 , issued to Bush et al, on May 5, 1 987.
  • Suitable ether polycarboxylates also include cyclic compounds, particularly alicyclic compounds, such as those described in U.S. Patents 3,923,679; 3,835, 1 63; 4, 1 58,635; 4, 1 20,874 and 4, 102,903.
  • ether hydroxypolycarboxylates copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1 , 3, 5- trihydroxy benzene-2, 4, 6-trisulphonic acid, and carboxymethyloxysuccinic acid
  • various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediamine tetraacetic acid and nitrilotriacetic acid
  • polycarboxylates such as mellitic acid, pyromellitic, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1 ,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.
  • Citrate builders e.g., citric acid and soluble salts thereof (particularly sodium salt), are polycarboxylate builders of particular importance for heavy duty liquid detergent formulations due to their availability from renewable resources and their biodegradability. Citrates can also be used in granular compositions, especially in combination with zeolite and/or layered silicate builders. Oxydisuccinates are also especially useful in such compositions and combinations.
  • succinic acid builders include the C5-C20 alkyl and alkenyl succinic acids and salts thereof.
  • a particularly preferred compound of this type is dodecenylsuccinic acid.
  • succinate builders include: laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like. Laurylsuccinates are the preferred builders of this group, and are described in EP 0,200,263.
  • Fatty acids e.g., C -
  • 2"Cl 8 monocarboxylic acids such as oleic acid and/or its salts
  • oleic acid and/or its salts can also be incorporated into the compositions alone, or in combination with the aforesaid builders, especially citrate and/or the succinate builders, to provide additional builder activity.
  • Such use of fatty acids will generally result in a diminution of sudsing, which should be taken into account by the formulator.
  • the various alkali metal phosphates such as the well-known sodium tripolyphosphates, sodium pyrophosphate and sodium orthophosphate can be used.
  • Phosphonate builders such as ethane-1 -hydroxy-1 , 1 -diphosphonate and other known phosphonates (see, for example, U.S. Patents 3, 1 59,581 ; 3,21 3,030; 3,422,021 ; 3,400, 148 and 3,422, 1 37) can also be used.
  • Bleaching Compounds - Bleaching Agents and Bleach Activators - The detergent compositions herein may optionally contain bleaching agents or bleaching compositions containing a bleaching agent and one or more bleach activators.
  • bleaching agents will typically be at levels of from 1 % to 30%, more typically from 5% to 20%, of the detergent composition, especially for fabric laundering.
  • the amount of bleach activators will typically be from 0.1 % to 60%, more typically from 0.5% to 40% of the bleaching composition comprising the bleaching agent- plus-bleach activator.
  • the bleaching agents used herein can be any of the bleaching agents useful for detergent compositions in textile cleaning or other cleaning purposes that are now known or become known. These include oxygen bleaches as well as other bleaching agents.
  • Perborate bleaches e.g., sodium perborate (e.g., mono- or tetra-hydrate) can be used herein.
  • Another category of bleaching agent that can be used without restriction encompasses percarboxylic acid bleaching agents and salts thereof. Suitable examples of this class of agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of metachloro perbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecanedioic acid.
  • Such bleaching agents are disclosed in U.S 4,483,781 , U.S 740,446, EP 0, 1 33,354, and U.S 4,41 2,934.
  • Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid as described in U.S 4,634,551 .
  • Peroxygen bleaching agents can also be used. Suitable peroxygen bleaching compounds include sodium carbonate peroxyhydrate and equivalent "percarbonate” bleaches, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide. Persulfate bleach (e.g., OXONE, manufactured commercially by DuPont) can also be used.
  • a preferred percarbonate bleach comprises dry particles having an average particle size in the range from 500 micrometers to 1 ,000 micrometers, not more than 10% by weight of said particles being smaller than 200 micrometers and not more than 10% by weight of said particles being larger than 1 ,250 micrometers.
  • the percarbonate can be coated with silicate, borate or water-soluble surfactants.
  • Percarbonate is available from various commercial sources such as FMC, Solvay and Tokai Denka.
  • Mixtures of bleaching agents can also be used.
  • Peroxygen bleaching agents, the perborates, the percarbonates, etc. are preferably combined with bleach activators, which lead to the in situ production in aqueous solution (i.e., during the washing process) of the peroxy acid corresponding to the bleach activator.
  • bleach activators Various nonlimiting examples of activators are disclosed in U.S 4,91 5,854, and U.S 4,41 2,934.
  • NOBS nonanoyloxybenzene sulfonate
  • ISONOBS 3,5,5-tri-methyl hexanoyl oxybenzene sulfonate
  • TAED tetraacetyl ethylene diamine
  • amido-derived bleach activators are those of the formulae: R l N(R 5 )C(O)R 2 C(O)L or Rl C(O)N(R 5 )R 2 C(O)L wherein R ⁇ is an alkyl group containing from 6 to 1 2 carbon atoms, R 2 is an alkylene containing from 1 to 6 carbon atoms, R ⁇ is H or alkyl, aryl, or alkaryl containing from 1 to 10 carbon atoms, and L is any suitable leaving group.
  • a leaving group is any group that is displaced from the bleach activator as a consequence of the nucleophilic attack on the bleach activator by the perhydrolysis anion.
  • a preferred leaving group is phenyl sulfonate.
  • bleach activators of the above formulae include (6- octanamido-caproyDoxybenzenesulfonate, (6-nonanamidocaproyl)- oxybenzenesulfonate, (6-decanamido-caproyl)oxybenzenesulfonate, and mixtures thereof as described in U.S. Patent 4,634,551 , incorporated herein by reference.
  • Another class of bleach activators comprises the benzoxazin-type activators disclosed by Hodge et al in U.S. Patent 4,966,723.
  • a highly preferred activator of the benzoxazin-type is:
  • Still another class of preferred bleach activators includes the acyl lactam activators, especially acyl caprolactams and acyl valerolactams of the formulae:
  • lactam activators include benzoyl caprolactam, octanoyl caprolactam, 3,5,5-trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam, undecenoyl caprolactam, benzoyl valerolactam, octanoyl valerolactam, decanoyl valerolactam, undecenoyl valerolactam, nonanoyl valerolactam, 3,5,5- trimethylhexanoyl valerolactam and mixtures thereof. See also U.S. Patent 4,545,784, issued to Sanderson, October 8, 1 985, incorporated herein by reference, which discloses acyl caprolactams, including benzoyl caprolactam, adsorbed into
  • Bleaching agents other than oxygen bleaching agents are also known in the art and can be utilized herein.
  • One type of non-oxygen bleaching agent of particular interest includes photoactivated bleaching agents such as the sulfonated zinc and/or aluminum phthalocyanines. See U.S. Patent 4,033,71 8, issued July 5, 1 977 to Holcombe et al. If used, detergent compositions will typically contain from 0.025% to 1 .25%, by weight, of such bleaches, especially sulfonate zinc phthalocyanine.
  • the bleaching compounds can be catalyzed by means of a manganese compound.
  • a manganese compound Such compounds are well known in the art and include, for example, the manganese-based catalysts disclosed in U.S. 5,246,621 , U.S. 5,244,594; U.S. 5, 1 94,416; U.S.
  • catalysts include Mn' V 2(u-O)3(1 ,4,7-trimethyl-1 ,4,7- triazacyclononane)2(PF6)2' Mn'"2(u-O) -
  • metal-based bleach catalysts include those disclosed in U.S. Pat. 4,430,243 and U.S. 5, 1 14,61 1 .
  • the use of manganese with various complex ligands to enhance bleaching is also reported in the following US Patents: 4,728,455; 5,284,944; 5,246,61 2; 5,256,779; 5,280, 1 1 7; 5,274, 147; 5, 1 53, 1 61 ; and 5,227,084.
  • compositions and processes herein can be adjusted to provide on the order of at least one part per ten million of the active bleach catalyst species in the aqueous washing liquor, and will preferably provide from 0.1 ppm to 700 ppm, more preferably from 1 ppm to 500 ppm, of the catalyst species in the laundry liquor.
  • Other preferred optional ingredients include enzyme stabilisers, polymeric soil release agents, materials effective for inhibiting the transfer of dyes from one fabric to another during the cleaning process (i.e., dye transfer inhibiting agents), polymeric dispersing agents, suds suppressors, optical brighteners or other brightening or whitening agents, chelating agents, fabric softening clay, anti-static agents, other active ingredients, carriers, hydrotropes, processing aids, dyes or pigments, solvents for liquid formulations and solid fillers for bar compositions.
  • enzyme stabilisers materials effective for inhibiting the transfer of dyes from one fabric to another during the cleaning process (i.e., dye transfer inhibiting agents), polymeric dispersing agents, suds suppressors, optical brighteners or other brightening or whitening agents, chelating agents, fabric softening clay, anti-static agents, other active ingredients, carriers, hydrotropes, processing aids, dyes or pigments, solvents for liquid formulations and solid fillers for bar compositions.
  • Liquid detergent compositions can contain water and other solvents as carriers.
  • Low molecular weight primary or secondary alcohols exemplified by methanol, ethanol, propanol, and isopropanol are suitable.
  • Monohydric alcohols are preferred for solubilizing surfactant, but polyols such as those containing from 2 to 6 carbon atoms and from 2 to 6 hydroxy groups (e.g., 1 ,3-propanediol, ethylene glycol, glycerine, and 1 ,2-propanediol) can also be used.
  • the compositions may contain from 5% to 90%, typically 1 0% to 50% of such carriers.
  • Granular detergents can be prepared, for example, by spray-drying (final product density 520 g/l) or agglomerating (final product density above 600 g/l) the Base Granule.
  • the remaining dry ingredients can then be admixed in granular or powder form with the Base Granule, for example in a rotary mixing drum, and the liquid ingredients (e.g., nonionic surfactant and perfume) can be sprayed on.
  • the detergent compositions herein will preferably be formulated such that, during use in aqueous cleaning operations, the wash water will have a pH of between 6.5 and 1 1 , preferably between 7.5 and 10.5. Laundry products are typically at pH 9-1 1 . Techniques for controlling pH at recommended usage levels include the use of buffers, alkalis, acids, etc., and are well known to those skilled in the art.
  • the present invention encompasses the use of a chlorine scavenger, in a composition comprising a modified polyamine polymer, for reducing malodours on treated fabrics.
  • a method for providing color care to fabrics upon domestic treatment which comprises the step of contacting the fabrics with an aqueous medium comprising a composition as defined hereinbefore.
  • said aqueous medium is at a temperature between 2 to 40°C, more preferably between 5 to 25°C.
  • the composition of the invention may be applied on a substrate, such as a dryer-sheet.
  • a method for providing color care on treated fabrics upon domestic treatment which comprises the step of contacting the fabrics with a composition as defined hereinbefore, wherein said composition is applied on a substrate, preferably a dryer-sheet.
  • the compositions are used in tumble-drying processes.
  • color care it is meant that fabrics which have been in contact with a composition of the invention, as defined hereinbefore, and which after, and/or prior and/or simultaneously washed with a detergent composition exhibit a better fabric color appearance compared to fabrics which have not been contacted with said composition.
  • compositions of the invention are suitable for use in any steps of the domestic treatment, that is as a pre-treatment composition, as a wash additive as a composition suitable for use in the rinse-cycle of the laundry cycle or applied on a dryer-sheet.
  • a pre-treatment composition of the invention may also be in a spray, foam, or aerosol form which for example can be suitable for use while ironing, or applied on the surfaces of the tumble dryer.
  • the color care benefit may either be assessed visually or by determination of the so-called delta-E values.
  • PSU panel score unit
  • Delta E is the computed color difference as defined in ASTM D2244, i.e 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 1 976 CIELAB opponent-color space, the Hunter opponent-color space, the Friele- Mac Adam-Chickering color space or any equivalent color space.
  • DEQA Di-(tallowyl-oxy-ethyl) dimethyl ammonium chloride DOEQA Di-(oleyloxyethyl) dimethyl ammonium methylsulfate
  • DTDMAC Ditallow dimethylammonium chloride
  • DHEQA Di-(soft-tallowyl-oxy-ethyl) hydroxyethyl methyl ammonium methylsulfate
  • Fatty acid tallow fatty acid IV 1 8 Electrolyte Calcium chloride DTDMAMS Ditallow dimethyl ammonium methylsulfate SDASA 1 :2 Ratio of stearyldimethyl amine:triple-pressed stearic acid Glycosperse S-20 Polyethoxylated sorbitan monostearate available from
  • PEI 1 800 E1 Ethoxylated polyethylene imine (MW 1 800, at 50% active) as synthesised in Synthesis example 1
  • PEI 1 800 E3 Ethoxylated polyethylene imine (MW 1 800, at 50% active) as synthesised as per Synthesis example 1
  • PEI 1 200 E1 Ethoxylated polyethylene imine (MW 1 200, at 50% active in water) as synthesised in Synthesis example
  • PEI 1 200 E7 Ethoxylated polyethylene imine (MW 1 200, at 50% active in water) as synthesised per Synthesis example
  • Dye Fix 1 Cationic dye fixing agent (50% active) available under the tradename Tinofix Eco from Ciba-Geigy
  • Dye Fix 2 Emulsified cationic dye fixative (30% active) available under the tradename Rewin SRF-O from CHT-Beitlich
  • Ci 2-1 5 branched primary alcohol condensed with an average of 3 moles of ethylene oxide
  • Citric acid Anhydrous citric acid Carbonate Anhydrous sodium carbonate with a particle size between 200 ⁇ m and 900 ⁇ m
  • Silicate Amorphous Sodium Silicate Si ⁇ 2:Na2 ⁇ ; 2.0 ratio
  • Lipolase Lipolytic enzyme of activity 1 0OkLU/g all sold by NOVO Industries A/S and of activity mentioned above unless otherwise specified PB4 Sodium perborate tetrahydrate of nominal formula
  • Siloxane-oxyalkylene copolymer as dispersing agent with a ratio of said foam controller to said dispersing agent of 10: 1 to 100: 1 .
  • Step A)-The ethoxylation is conducted in a 2 gallon stirred stainless steel autoclave equipped for temperature measurement and control, pressure measurement, vacuum and inert gas purging, sampling, and for introduction of ethylene oxide as a liquid.
  • a ⁇ 20 lb. net cylinder of ethylene oxide (ARC) is set up to deliver ethylene oxide as a liquid by a pump to the autoclave with the cylinder placed on a scale so that the weight change of the cylinder could be monitored.
  • PEI polyethyleneimine
  • the autoclave is then sealed and purged of air (by applying vacuum to minus 28" Hg followed by pressurization with nitrogen to 250 psia, then venting to atmospheric pressure).
  • the autoclave contents are heated to 1 30 °C while applying vacuum.
  • the autoclave is charged with nitrogen to about 250 psia while cooling the autoclave to about 1 05 °C.
  • Ethylene oxide is then added to the autoclave incrementally over time while closely monitoring the autoclave pressure, temperature, and ethylene oxide flow rate.
  • the ethylene oxide pump is turned off and cooling is applied to limit any temperature increase resulting from any reaction exotherm.
  • the temperature is maintained between 1 00 and 1 1 0 °C while the total pressure is allowed to gradually increase during the course of the reaction.
  • Step B)- The reaction mixture is then deodorized by passing about 1 00 cu. ft. of inert gas (argon or nitrogen) through a gas dispersion frit and through the reaction mixture while agitating and heating the mixture to 1 30 °C.
  • inert gas argon or nitrogen
  • the final reaction product is cooled slightly and collected in glass containers purged with nitrogen.
  • Step A If a PEI 1 800 E7 is desired, the following step of catalyst addition will be included between Step A and B.
  • Vacuum is continuously applied while the autoclave is cooled to about 50 ° C while introducing 376 g of a 25% sodium methoxide in methanol solution ( 1 .74 moles, to achieve a 10% catalyst loading based upon PEI nitrogen functions).
  • the methoxide solution is sucked into the autoclave under vacuum and then the autoclave temperature controller setpoint is increased to 1 30 °C.
  • a device is used to monitor the power consumed by the agitator.
  • the agitator power is monitored along with the temperature and pressure. Agitator power and temperature values gradually increase as methanol is removed from the autoclave and the viscosity of the mixture increases and stabilizes in about 1 hour indicating that most of the methanol has been removed.
  • the mixture is further heated and agitated under vacuum for an additional 30 minutes. Vacuum is removed and the autoclave is cooled to 105 °C while it is being charged with nitrogen to 250 psia and then vented to ambient pressure. The autoclave is charged to 200 psia with nitrogen. Ethylene oxide is again added to the autoclave incrementally as before while closely monitoring the autoclave pressure, temperature, and ethylene oxide flow rate while maintaining the temperature between 1 00 and 1 10 °C and limiting any temperature increases due to reaction exotherm. After the addition of 4500 g of ethylene oxide (resulting in a total of 7 moles of ethylene oxide per mole of PEI nitrogen function) is achieved over several hours, the temperature is increased to 1 1 0 °C and the mixture stirred for an additional hour.
  • reaction mixture is then collected in nitrogen purged containers and eventually transferred into a 22 L three neck round bottomed flask equipped with heating and agitation.
  • the strong alkali catalyst is neutralized by adding 1 67 g methanesulfonic acid ( 1 .74 moles).
  • PEI 1 800 E2, PEI 1 800 E3, PEI 1 800 E1 5 and PEI 1 800 E20 can be prepared by the above method by adjusting the reaction time and the relative amount of ethylene oxide used in the reaction.
  • Dimethyl sulfate (Aldrich, 3.8g, 0.030 mol) is added all at once to the rapidly stirring solution, which is then stoppered and stirred at room temperature overnight.
  • the flask is stoppered, and after an initial exotherm the solution is stirred at room temperature overnight.
  • a 1 H-NMR (D2O) spectrum shows the total shifting of the methylene peaks at 2.5-3.0ppm to ⁇ 3.5ppm.
  • To the solution is added ⁇ 5g of 0.5% Pd on alumina pellets, and the solution is allowed to stand at room temperature for ⁇ 3 days.
  • Peroxide indicator paper shows that no peroxide is left in the system. The material is stored as a 46.5% solution in water.
  • PEI-1 800, E7 polyethyleneimine having a molecular weight of 1 800 and ethoxylated to a degree of about 7 ethoxy groups per nitrogen
  • hydrogen peroxide 120 g of a 30 wt % solution in water, 1 .06 mol
  • the resonances ascribed to methylene protons adjacent to unoxidized nitrogens have shifted from the original position at - 2.5 ppm to ⁇ 3.5 ppm.
  • To the reaction solution is added approximately 5 g of 0.5% Pd on alumina pellets, and the solution is allowed to stand at room temperature for approximately 3 days. The solution is tested and found to be negative for peroxide by indicator paper.
  • the material as obtained is suitably stored as a 51 .1 % active solution in water.
  • Step A)-The ethoxylation is conducted in a 2 gallon stirred stainless steel autoclave equipped for temperature measurement and control, pressure measurement, vacuum and inert gas purging, sampling, and for introduction of ethylene oxide as a liquid.
  • a ⁇ 20 lb. net cylinder of ethylene oxide (ARC) is set up to deliver ethylene oxide as a liquid by a pump to the autoclave with the cylinder placed on a scale so that the weight change of the cylinder could be monitored.
  • PEI polyethyleneimine
  • Ethylene oxide is then added to the autoclave incrementally over time while closely monitoring the autoclave pressure, temperature, and ethylene oxide flow rate.
  • the ethylene oxide pump is turned off and cooling is applied to limit any temperature increase resulting from any reaction exotherm.
  • the temperature is maintained between 1 00 and 1 1 0 °C while the total pressure is allowed to gradually increase during the course of the reaction.
  • Step B)- The reaction mixture is then deodorized by passing about 1 00 cu. ft. of inert gas (argon or nitrogen) through a gas dispersion frit and through the reaction mixture while agitating and heating the mixture to 1 30 °C.
  • inert gas argon or nitrogen
  • the final reaction product is cooled slightly and collected in glass containers purged withi nitrogen.
  • Vacuum is continuously applied while the autoclave is cooled to about 50 ° C while introducing 376 g of a 25% sodium methoxide in methanol solution ( 1 .74 moles, to achieve a 1 0% catalyst loading based upon PEI nitrogen functions).
  • the methoxide solution is sucked into the autoclave under vacuum and then the autoclave temperature controller setpoint is increased to 1 30 °C.
  • a device is used to monitor the power consumed by the agitator.
  • the agitator power is monitored along with the temperature and pressure. Agitator power and temperature values gradually increase as methanol is removed from the autoclave and the viscosity of the mixture increases and stabilizes in about 1 hour indicating that most of the methanol has been removed.
  • the mixture is further heated and agitated under vacuum for an additional 30 minutes.
  • Vacuum is removed and the autoclave is cooled to 105 °C while it is being charged with nitrogen to 250 psia and then vented to ambient pressure.
  • the autoclave is charged to 200 psia with nitrogen.
  • Ethylene oxide is again added to the autoclave incrementally as before while closely monitoring the autoclave pressure, temperature, and ethylene oxide flow rate while maintaining the temperature between 100 and 1 1 0 °C and limiting any temperature increases due to reaction exotherm.
  • 4500 g of ethylene oxide resulting in a total of 7 moles of ethylene oxide per mole of PEI nitrogen function
  • the temperature is increased to 1 10 °C and the mixture stirred for an additional hour.
  • reaction mixture is then collected in nitrogen purged containers and eventually transferred into a 22 L three neck round bottomed flask equipped with heating and agitation.
  • the strong alkali catalyst is neutralized by adding 1 67 g methanesulfonic acid ( 1 .74 moles).
  • PEI 1 200 E2, PEI 1 200 E3, PEI 1 200 E1 5 and PEI 1 200 E20 can be prepared by the above method by adjusting the reaction time and the relative amount of ethylene oxide used in the reaction.
  • the corresponding amine oxide of the above ethoxylated PEI can also be prepared following synthesis Example 4.
  • Dimethyl sulfate (Aldrich, 8.48g, 0.067 mol) is added all at once to the rapidly stirring solution, which is then stoppered and stirred at room temperature overnight.
  • acetonitrile is evaporated on the rotary evaporator at ⁇ 60°C, followed by a Kugelrohr apparatus (Aldrich) at - 80° C to afford ⁇ 220g of the desired material as a dark brown viscous liquid.
  • a 1 c-NMR (D2O) spectrum shows the absence of a peak at ⁇ 58ppm corresponding to dimethyl sulfate.
  • a ⁇ H-NMR (D2O) spectrum shows the partial shifting of the peak at 2.5ppm (methylenes attached to unquaternized nitrogens) to ⁇ 3.0ppm.
  • poly(ethyleneimine) poly(ethyleneimine), MW 1 200 which has been ethoxylated to a degree of 7, and - 9.5% quaternized with dimethyl sulfate ( 1 44g, - 0.37 mol oxidizeable nitrogen, prepared as in Example 6), hydrogen peroxide (Aldrich, 35.4g of a 50 wt% solution in water, 0.52 mol), and water ( 1 00g).
  • the flask is stoppered, and after an initial exotherm the solution is stirred at room temperature overnight.
  • a ⁇ H-NMR (D2O) spectrum shows the total shifting of the methylene peaks at 2.5-3.0ppm to ⁇ 3.5ppm.
  • Example 1 The following compositions are in accordance with the present invention.
  • compositions for use as dryer-added sheets are in accordance with the invention.
  • liquid detergent formulation according to the present invention was prepared:

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Abstract

Cette invention se rapporte à une composition d'entretien des couleurs qui comporte une polyamine modifiée et un capteur de chlore, ce dernier servant à réduire les mauvaises odeurs associées aux compositions qui ne contiennent pas de tel capteur de chlore.
PCT/US1997/019790 1996-11-01 1997-10-30 Compositions d'entretien des couleurs WO1998020099A1 (fr)

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JP52158598A JP2001503822A (ja) 1996-11-01 1997-10-30 カラーケア組成物
EP97946411A EP0937128A1 (fr) 1996-11-01 1997-10-30 Compositions d'entretien des couleurs
BR9712858-9A BR9712858A (pt) 1996-11-01 1997-10-30 Composições para o cuidado como cores
CA002270389A CA2270389A1 (fr) 1996-11-01 1997-10-30 Compositions d'entretien des couleurs

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US6075000A (en) * 1997-07-02 2000-06-13 The Procter & Gamble Company Bleach compatible alkoxylated polyalkyleneimines
US6127331A (en) * 1998-06-23 2000-10-03 The Procter & Gamble Company Laundry compositions comprising alkoxylated polyalkyleneimine dispersants
WO2011131412A1 (fr) 2010-04-22 2011-10-27 Unilever Plc Améliorations apportées à des agents de traitement pour textiles
EP1876227B2 (fr) † 2006-07-07 2020-08-12 The Procter and Gamble Company Compositions de lavage
US11732218B2 (en) 2018-10-18 2023-08-22 Milliken & Company Polyethyleneimine compounds containing N-halamine and derivatives thereof

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CA2304870C (fr) * 1997-09-25 2006-09-19 The Procter & Gamble Company Composition assouplissante ajoutee dans le seche-linge, comprenant un piegeur de chlore et destinee a respecter les couleurs des textiles et a les doter d'autres qualites
WO1999015611A1 (fr) * 1997-09-25 1999-04-01 The Procter & Gamble Company Utilisation d'une composition assouplissante ajoutee dans le seche-linge et destinee a respecter les couleurs des textiles et a leur donner un bel aspect
CN1332787A (zh) * 1998-10-23 2002-01-23 宝洁公司 织物护理组合物和方法
US7041630B1 (en) 1998-10-23 2006-05-09 The Procter & Gamble Company Fabric color care method for rejuvenating and/or restoring color to a faded fabric
CN1216138C (zh) * 1998-11-25 2005-08-24 宝洁公司 形成附聚颗粒的方法
US6514929B1 (en) 1998-11-25 2003-02-04 The Procter & Gamble Company Process for forming an agglomerated particle
JP2003513178A (ja) * 1999-10-22 2003-04-08 ザ、プロクター、エンド、ギャンブル、カンパニー 非反応性布地強化処理剤
WO2002012424A1 (fr) * 2000-08-04 2002-02-14 Cuno, Incorporated Milieu d'absorption de colorant à charge modifiée
DE60121033D1 (de) 2000-11-16 2006-08-03 Procter & Gamble Verfahren zur farbauffrischung von textilien
EP1337916A4 (fr) 2000-11-20 2007-09-05 Procter & Gamble Procede predictif pour polymeres
ES2305496T5 (es) 2002-09-12 2012-03-05 The Procter & Gamble Company Sistemas de pol�?meros y composiciones limpiadoras que los comprenden.
DE102006004697A1 (de) * 2006-01-31 2007-08-02 Henkel Kgaa Wasch- oder Reinigungsmittel mit Farbübertragungsinhibitor
EP3039109B1 (fr) 2013-08-26 2017-09-13 The Procter and Gamble Company Compositions comprenant des polyamines alcoxylées à bas points de fusion
EP2862921A1 (fr) * 2013-10-17 2015-04-22 The Procter and Gamble Company Composition liquide pour lessive comprenant un polymère alcoxylé et un colorant de nuançage
US11299591B2 (en) 2018-10-18 2022-04-12 Milliken & Company Polyethyleneimine compounds containing N-halamine and derivatives thereof
US11518963B2 (en) 2018-10-18 2022-12-06 Milliken & Company Polyethyleneimine compounds containing N-halamine and derivatives thereof
US11466122B2 (en) 2018-10-18 2022-10-11 Milliken & Company Polyethyleneimine compounds containing N-halamine and derivatives thereof

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EP0111984A2 (fr) * 1982-12-23 1984-06-27 THE PROCTER & GAMBLE COMPANY Polymères d'amines éthoxylées ayant des propriétés pour enlever des taches et la contre-redéposition utilisables dans des compositions détergentes
EP0135217A1 (fr) * 1983-07-22 1985-03-27 THE PROCTER & GAMBLE COMPANY Oxydes d'amines éthoxylés ayant des propriétés pour enlever des taches et d'antiredéposition, utilisables dans les compositions détergentes
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Publication number Priority date Publication date Assignee Title
US6075000A (en) * 1997-07-02 2000-06-13 The Procter & Gamble Company Bleach compatible alkoxylated polyalkyleneimines
US6127331A (en) * 1998-06-23 2000-10-03 The Procter & Gamble Company Laundry compositions comprising alkoxylated polyalkyleneimine dispersants
EP1876227B2 (fr) † 2006-07-07 2020-08-12 The Procter and Gamble Company Compositions de lavage
WO2011131412A1 (fr) 2010-04-22 2011-10-27 Unilever Plc Améliorations apportées à des agents de traitement pour textiles
US11732218B2 (en) 2018-10-18 2023-08-22 Milliken & Company Polyethyleneimine compounds containing N-halamine and derivatives thereof

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AR010540A1 (es) 2000-06-28
WO1998020098A1 (fr) 1998-05-14
JP2001503822A (ja) 2001-03-21
EP0937128A1 (fr) 1999-08-25
AU7527096A (en) 1998-05-29

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