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WO2022197295A1 - Colorants polymères à tachage réduit - Google Patents

Colorants polymères à tachage réduit Download PDF

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Publication number
WO2022197295A1
WO2022197295A1 PCT/US2021/022808 US2021022808W WO2022197295A1 WO 2022197295 A1 WO2022197295 A1 WO 2022197295A1 US 2021022808 W US2021022808 W US 2021022808W WO 2022197295 A1 WO2022197295 A1 WO 2022197295A1
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WO
WIPO (PCT)
Prior art keywords
compositions
colorant
polymeric
alkyl
group
Prior art date
Application number
PCT/US2021/022808
Other languages
English (en)
Inventor
Wesley A. Freund
Sanjeev K. DEY
Original Assignee
Milliken & Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Milliken & Company filed Critical Milliken & Company
Priority to PCT/US2021/022808 priority Critical patent/WO2022197295A1/fr
Publication of WO2022197295A1 publication Critical patent/WO2022197295A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B69/00—Dyes not provided for by a single group of this subclass
    • C09B69/10—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds
    • C09B69/103—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds containing a diaryl- or triarylmethane dye
    • 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
    • C11D3/3707—Polyethers, e.g. polyalkyleneoxides
    • 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
    • C11D3/40—Dyes ; Pigments
    • 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
    • C11D3/40—Dyes ; Pigments
    • C11D3/42—Brightening agents ; Blueing agents
    • 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
    • D06P5/13—Fugitive dyeing or stripping dyes
    • D06P5/138—Fugitive dyeing or stripping dyes fugitive dyeing
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/12—Soft surfaces, e.g. textile
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces

Definitions

  • This invention relates to polymeric colorants that do not stain clothing, plastic or metal when used in consumer products, such as laundry detergents, fabric softeners and dish detergents.
  • the polymeric colorants contain at least one carboxymethyl capped alkyleneoxy chain to improve the fugitivity and staining properties.
  • fugitive, or non-permanent, colorants have been used to color code textiles during production and/or finishing operations to identify certain synthetic or natural fibers.
  • Such fugitive colorants may be water fugitive, solvent fugitive or both water and solvent fugitive.
  • Colorants containing one or more polyethyleneoxy groups wherein the polyethyleneoxy group contains at least 2 repeating ethyleneoxy units in the molecule are generally considered water fugitive colorants; whereas colorants containing one or more propyleneoxy groups having similar repeating propyleneoxy units in the molecule are considered solvent fugitive.
  • Fugitive colorants which include polyethylene oxide colorants are described in
  • Such colorants are a combination of a dyestuff radical and one or more polyethyleneoxy groups.
  • Dyestuff radicals disclosed in the patent include nitroso, nitro, azo, diphenylmethane, triphenylmethane, xanthene, acridine, methine, thiazole, indamine, azine, oxazine, or anthraquinone radicals.
  • such radicals are attached to the polymeric constituents of the colorant compositions by an amino nitrogen.
  • Another type of fugitive colorant includes the alkaline-stable fugitive colorant of the triphenylmethane type as described in U.S. Patent No. 3,927,044 to Foster et al. These colorants are alkaline stable due to the use of aromatic aldehydes containing an electron withdrawing substituent in the ortho position. They are considered alkaline stable if the colorant is capable of retaining its color in an alkaline solution, such as in a solution of sodium hydroxide at a pH of 11.
  • U.S. Patent No. 2598660 to Glickman discloses polyalkeneoxy-based triphenylmethane dyes with unusually high water solubility.
  • fugitive colorants are the ester capped alkyleneoxy fugitive colorants disclosed in U.S. Patent No. 4,167,510 to Brendle.
  • Such fugitive colorants comprise an organic dyestuff molecule having from 1 to 5 capped alkyleneoxy units wherein the total alkyleneoxy capped units in the molecule are from 2 to about 300.
  • the alkylene moiety of the alkyleneoxy units contains from about 2 to 4 carbon atoms and the colorants of the invention can be made water and/or organic solvent soluble depending upon the particular capping moiety employed, the presence or absence of at least one ionic group and the total number of alkyleneoxy units present in the colorant molecule.
  • the solubility, and thus the fugitivity of the colorants may be achieved irrespective of whether the relatively large dyestuff molecule is hydrophobic or hydrophilic.
  • Still another category of fugitive colorants includes those disclosed in U.S.
  • Patent No. 4,400,320 to Keller et al. These colorants are made from an aromatic compound containing between 6 and 20 carbon atoms and a linking moiety which are converted into a hydroxyalkylated compound.
  • a further step includes the addition of a diazo compound to the hydroxyalkylated compound to form the final product.
  • These colorants are red or purple in nature.
  • U.S. Patent No. 5, 520,943 to Brendle discusses the utilization of alkyleneoxy-substituted fugitive colorants for use as spray pattern indicators. These fugitive colorants are an improvement over permanent dyes in that they are washable from most surfaces including skin, textiles, and equipment. Additionally, these water soluble polyoxyalkylene substituted colorants are remarkably less toxic than dyes to aquatic organisms. However, on exposure to porous surfaces, such as concrete or brick, spray pattern indicators of this class can leave highly visible stains than may require days or weeks to fade. The presence of visual stains on these porous surfaces is unsightly and serves no purpose after the spray has been applied.
  • U.S. Patent No. 7632682 to Hong et al. discloses anthraquinone colorants with improved impurity levels and staining for use in consumer products.
  • U.S. Patent No. 8735533 to Hong et al. discloses polymeric violet anthraquinone colorants with non-staining properties for use in coloring consumer products.
  • the invention relates to a polymeric colorant of the formula: wherein:
  • A is a chromophore selected from nitro, nitroso, monazo, bisazo, diarylmethane, triarylmethane, acridine, ethine, thiazole, indamine, oxazine, pthalocyanine, or anthraquinone;
  • Ri is selected from nitrogen, oxygen, or sulfur
  • R2 is hydrogen
  • R3 is a methyl or ethyl group; a is an integer of from 0-40, or from 0-10, or even 0-5; b is an integer of from 0-40, or from 0-10, or even 0-5; c is one when Ri is oxygen or sulfur and two when Ri is nitrogen; and B is — CH2COOH and its salt forms.
  • the invention described herein is a polymeric colorant containing at least one carboxymethyl capped alkyleneoxy chain which provides improvement in fugitivity and non staining properties.
  • non-staining generally refers to a colorant composition that may be washed or removed from substrate surfaces (e.g. skin, fabric, wood, concrete) with relatively little effort and without staining the substrate to an appreciable extent.
  • substrate surfaces e.g. skin, fabric, wood, concrete
  • non-bleeding generally refers to a colorant composition that does not substantially color the material surrounding the colorant composition under conditions wherein the material is not intended to be colored.
  • the colorant composition may be present in a powdered laundry detergent as a colored speckle (i.e. a colored particle that is not chemically a part of the detergent particles during storage).
  • the colorant composition will be considered to be “non-bleeding” if it fails to substantially color the surrounding powdered detergent in its unused state (i.e. while it remains in the package).
  • the term “fugitive” means a temporary colorant that can be removed easily by the processes of light exposure, exposure to rain or watering, or time.
  • alkoxy is intended to include C Cs alkoxy and alkoxy derivatives of polyols having repeating units such as butylene oxide, glycidol oxide, ethylene oxide or propylene oxide.
  • alkyl and alkyl capped are intended to include C 2 to Cioo alkyl groups, C 2 to C50 alkyl groups, Cs-C 2 5 alkyl groups, or even Cio-C 2 o alkyl groups.
  • aryl is intended to include C 6 -Ci 2 aryl groups.
  • arylalkyl is intended to include C1-C18 alkyl groups and, in one aspect, C1-C6 alkyl groups.
  • alkanoyl refers to univalent groups of the formula — C(0)R a , where R a is an alkyl group, preferably a C3-C 2g alkyl group.
  • alkenyl refers to univalent groups derived from acyclic olefinic hydrocarbons by removal of a hydrogen atom from any carbon atom.
  • acyclic olefinic hydrocarbons refers to acyclic hydrocarbons containing one or more carbon-carbon double bonds.
  • alkenoyl refers to univalent groups of the formula — C(0)R b , where R b is an alkenyl group, preferably a C3-C 2g alkenyl group.
  • aroyl refers to univalent groups of the formula — C(0)R c , where R c is an aryl group, preferably a C6-C10 aryl group.
  • R c is an aryl group, preferably a C6-C10 aryl group.
  • polymeric colorant generally refers to a colorant having at least one chromophore portion attached to at least one oligomeric or polymeric chain, wherein the chain has at least three repeating units.
  • the oligomeric or polymeric constituent can be bound to the chromophore via any suitable means, such as a covalent bond, an ionic bond, or suitable electrostatic interaction.
  • the polymeric colorant may be characterized by having an absorbance in the range of between about 300 nanometers and about 900 nanometers, as measured by UV-vis spectroscopy.
  • the polymeric colorant has a molecular weight that is typically represented as a molecular weight distribution.
  • the molecular weight of the polymeric colorant is generally reported as an average molecular weight, as determined by its molecular weight distribution.
  • the chromophore group of the colorant may vary widely and may include compounds characterized in the art as dyestuffs or as pigments. The actual group used will depend to a large extent upon, for instance, the desired color and colorfastness characteristics.
  • the chromophore group may be attached to at least one polyalkyleneoxy- substituent through a suitable linking moiety of nitrogen, oxygen, sulfur, etc.
  • chromophore groups include nitroso, nitro, azo (including monoazo, disazo, trisazo, tetrakisazo, polyazo, formazan, azomethine and metal complexes thereof), stilbene, diarylmethane, triarylmethane, xanthene acridine, quinoline, methine (including polymethine), thiazole, indamine, indophenol, azine, thiazine, oxazine, aminoketone, hydroxyketone, anthraquinone (including anthrapyrazolines, anthrone, anthrapyridone, anthrapyrimidine, flavanthrone, pyranthrone, benzanthrone, perylene, perinone, naphthalimide and other structures formally related to anthraquinone), indigoid (including thioindigoid), and phthalocyanine chromophor
  • polymeric chains are polyalkyleneoxy chains.
  • polyalkyleneoxy generally refers to molecular structures containing the following repeating units: -CH 2 CH 2 0-, CH 2 CH 2 CH 2 0-, -CH 2 CH 2 CH 2 CH 2 0-, -CH 2 CH(CH 3 )0-, -CH 2 CH(CH 2 CH 3 )0- CH 2 CH 2 CH(CH 3 )0-, and any combinations thereof.
  • Typical of such groups which may be attached to the chromophore group are the polymeric epoxides, such as the polyalkylene oxides and copolymers thereof.
  • Typical polyalkylene oxides and copolymers of same which may be employed to provide the colorants include those made from alkylene oxide monomers containing from two to twenty carbon atoms, or more preferably, from two to six carbon atoms.
  • Examples include: polyethylene oxides; polypropylene oxides; polybutylene oxides; oxetanes; tetrahydrafurans; copolymers of polyethylene oxides, polypropylene oxides and polybutylene oxides; and other copolymers including block copolymers, in which a majority of the polymeric substituent is polyethylene oxide, polypropylene oxide and/or polybutylene oxide.
  • polyalkyleneoxy group may have an average molecular weight in the range of from about 132 to about 10,000, preferably from about 176 to about 5000.
  • the colorants may not ordinarily be chemically bound to the carrier particles, the precise chemical identity of the end group on the polyalkyleneoxy group may not be critical insofar as the proper functioning of the colorant is concerned in the composition.
  • certain most preferred colorants will be defined where certain end groups will be identified. Such recitation of end groups is not to be construed as limiting the invention in its broader embodiments in any way. According to such a most preferred embodiment the colorants may be characterized as follows: wherein:
  • A is a chromophore selected from nitro, nitroso, monazo, bisazo, diarylmethane, triarylmethane, acridine, methine, thiazole, indamine, oxazine, pthalocyanine, or anthraquinone;
  • Ri is selected from nitrogen, oxygen, or sulfur
  • R2 is hydrogen
  • R3 is a methyl or ethyl group; a is an integer of from 0-40; b is an integer of from 0-40; c is one when Ri is oxygen or sulfur and two when Ri is nitrogen; and B is — CH2COOH and its salt forms.
  • Salt forms of B could consist of a cation moiety of an alkali metal, an alkali earth metal, a transition metal or ammonium.
  • the process(es) for making the colorants often result in the synthesis of certain impurities of various amounts.
  • the processes and colorants made therefrom as described herein may contain one or more impurities.
  • Typical impurities that may be present could be terminal aldehydes that result from autoxidation of the terminal hydroxyl of the polyalkyleneoxy chain. Additionally, displacement of the terminal hydroxyl of the polyoxyalkylene chain by halogens such as chlorine and bromine may occur during reaction conditions.
  • the oligomeric constituent can be any suitable constituent including, but not limited to, oligomeric constituents selected from the group consisting of (i) oligomers comprising at least three monomers, or repeating units, selected from the group consisting of C2-C20 alkyleneoxy groups, glycidol groups, and glycidyl groups, (ii) aliphatic oligomeric esters conforming to structure (I) and (iii) combinations of (i) and (ii).
  • R2 and R3 are independently selected from the group consisting of hydrogen and C1-C10 alkyl groups, f is an integer between and including 1 and 10, and g is any positive integer or fraction between and including 1 and 20.
  • suitable values for g include both integers and fractions because the length of the oligomeric constituent on the individual polymeric colorant molecules may vary.
  • the value for g represents an average length of the ester chain for a given sample or collection of polymeric colorant molecules.
  • the polymeric colorant can comprise one or more oligomeric constituents consisting of three or more ethylene oxide monomer groups.
  • the polymeric colorant can comprise any suitable alkyleneoxy group.
  • Suitable alkyleneoxy groups include those of Formula (C) below:
  • each R 101 and R 102 group is independently selected from the group consisting of hydrogen, alkyl, aryl, alkoxyalkyl, and aryloxyalkyl.
  • R 105 is a terminal group for the oxyalkylene and can be selected from the group consisting of hydrogen, alkyl groups (e.g., C1-C4 alkyl groups), and aryl groups, with hydrogen being preferred.
  • each R 101 and R 102 group is independently selected from the group consisting of hydrogen and alkyl (e.g., C1-C4 alkyl).
  • the variable a is an integer equal to or greater than 1 (e.g., from 1 to about 100).
  • the R 101 and R 102 groups are independently selected from the recited group.
  • the alkyleneoxy group can be comprised of two or more monomer units covalently bonded to form the alkyleneoxy group, or even three or more monomer units.
  • the alkyleneoxy group comprises two or more monomer units (or even three or more monomer units), these monomer units can be arranged in either a block configuration or in a random configuration, but a block configuration generally is more preferred.
  • the alkyleneoxy group comprises monomer units independently selected from the group consisting of ethyleneoxy, propyleneoxy, and butyleneoxy.
  • a suitable example of such an alkyleneoxy group is Formula (Cl) below:
  • the variables x, y, and z are independently selected from the group consisting of zero and positive integers (e.g., positive integers from 1 to about 100).
  • the sum of x, y, and z is 2 or more or 3 or more (e.g., 2 to about 300, 3 to about 300, 2 to about 200, 3 to about 200, 2 to about 100, 3 to about 100, 2 to about 50, 3 to about 50, 2 to about 30, 3 to about 30, 2 to about 25, 3 to about 25, 2 to about 20, 3 to about 20, 2 to about 15, 3 to about 15, 2 to about 10, or 3 to about 10).
  • R 105 is a terminal group for the oxyalkylene and can be selected from the group consisting of hydrogen, alkyl groups (e.g., C1-C4 alkyl groups), and aryl groups, with hydrogen being preferred.
  • the alkyleneoxy group comprises ethyleneoxy and propyleneoxy monomer units arranged in a block configuration. Suitable examples of such alkyleneoxy groups include those of Formulae (CM) and (Cl II) below
  • the variables, t, u, v, q, r, and s are independently selected from the group consisting of zero and positive integers (e.g., positive integers from 1 to about 100).
  • the sum of t, u, and v and q, r, and s is 2 or more or 3 or more (e.g., 2 to about 300, 3 to about 300, 2 to about 200, 3 to about 200, 2 to about 100, 3 to about 100, 2 to about 50, 3 to about 50, 2 to about 30, 3 to about 30, 2 to about 25, 3 to about 25, 2 to about 20, 3 to about 20, 2 to about 15, 3 to about 15, 2 to about 10, or 3 to about 10).
  • R 105 is a terminal group for the oxyalkylene and can be selected from the group consisting of hydrogen, alkyl groups (e.g., C1-C4 alkyl groups), and aryl groups, with hydrogen being preferred.
  • a method for preparing the polymeric colorant of the present invention is comprised of the following steps: reacting an alkoxylated intermediate with a reagent, such as sodium chloroacetate or other means in the literature, to introduce a carboxymethyl group to the end of the polyalkyleneoxy chain. If an intermediate, the intermediate can then be reacted to obtain the polymeric dyes or interest.
  • a reagent such as sodium chloroacetate or other means in the literature
  • At least one polymeric colorant as described herein may be added to a laundry care composition.
  • the invention also encompasses a textile substrate containing at least one polymeric colorant that contains at least one carboxymethyl capped alkyleneoxy chain.
  • Suitable CrCs alkoxy or alkoxy derivative of polyol having repeating units include alkylene oxides.
  • Alkylene oxides may be selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, and mixtures thereof.
  • Alkylene oxide groups may be in the form of polymeric chains known as polyalkyleneoxy chains.
  • polyalkyleneoxy generally refers to molecular structures containing the following repeating units: -CH 2 CH 2 0-, CH 2 CH 2 CH 2 0-, -CH 2 CH 2 CH 2 CH 2 0-, - CH 2 CH(CH 3 )0-, -CH 2 CH(CH 2 CH 3 )0- CH 2 CH 2 CH(CH 3 )0-, and any combinations thereof.
  • Typical of such groups are the polymeric epoxides, such as the polyalkylene oxides and copolymers thereof.
  • Typical polyalkylene oxides and copolymers of same include those made from alkylene oxide monomers containing from two to twenty carbon atoms, or more preferably, from two to six carbon atoms.
  • Examples include: polyethylene oxides; polypropylene oxides; polybutylene oxides; oxetanes; tetrahydrafurans; copolymers of polyethylene oxides, polypropylene oxides and polybutylene oxides; and other copolymers including block copolymers, in which a majority of the polymeric substituent is polyethylene oxide, polypropylene oxide and/or polybutylene oxide.
  • polyalkyleneoxy group may have an average molecular weight in the range of from about 132 to about 10,000, preferably from about 176 to about 5000.
  • the alkoxy molecules form caps for the ends of the chains comprising the polymeric colorant.
  • the resulting alkoxylated polymeric colorant containing at least one carboxymethyl capped alkyleneoxy chain substituted compound may have an average degree of alkoxylation of from 0.5 to 50, or from 1 to 50, or from 1 to 30, or from 1 to 20, or from 1 to 10, or from 2 to 50, or from 2 to 30, or from 2 to 20, or from 2 to 10, or from 3 to 50 or from 3 to 30, or from 3 to 20, or from 3 to 10, or from 4 to 50, or from 4 to 30, or from 4 to 20, or from 4 to 10.
  • the polymeric colorant of the present invention may be incorporated into a hard surface cleaner.
  • Hard surface cleaners include, for example, compositions ideally suited for cleaning flooring (such as ceramic tile, vinyl tile, and the like), toilets, bathtubs, showers, faucets, countertops, glass (such as windows), and the like.
  • the hard surface cleaner may contain at least one polymeric colorant as described herein and at least one hard surface ingredient.
  • Hard surface ingredients may include, without limitation, surfactants; antibacterial/antimicrobial agents; aqueous, non-surface active liquid carriers; bleaching agents; non-tinting dyes; detersive builders; enzymes; enzyme stabilizers (such as propylene glycol, boric acid and/or borax); suds suppressors, soil suspending agents; soil release agents; other fabric care benefit agents; pH adjusting agents; chelating agents; smectite clays; solvents; hydrotropes and phase stabilizers; structuring agents; opacifying agents; optical brighteners; perfumes/fragrances; and coloring agents.
  • the polymeric colorant of the present invention may be incorporated into a laundry care composition including but not limited to laundry detergents and fabric treatment compositions.
  • laundry care composition includes, unless otherwise indicated, granular, powder, liquid, gel, paste, unit dose bar form and/or flake type washing agents and/or fabric treatment compositions.
  • fabric treatment composition includes, unless otherwise indicated, fabric softening compositions, fabric enhancing compositions, fabric freshening compositions, and combinations thereof. Such compositions may be, but need not be, rinse added compositions.
  • Laundry care compositions of the present invention comprise one or more of said polymeric colorants containing at least one carboxymethyl capped alkyleneoxy chain and a laundry care ingredient.
  • the polymeric colorant may be added to substrates using a variety of application techniques.
  • the polymeric colorant is preferably included as an additive in laundry detergent.
  • RAFS rinse added fabric softening
  • the laundry care compositions including laundry detergents may be in solid or liquid form, including a gel form.
  • the laundry care compositions including laundry detergents may also be in a unit dose pouch.
  • the laundry detergent composition comprises a surfactant in an amount sufficient to provide desired cleaning properties.
  • the polymeric colorant may be present in the laundry care composition (such as the laundry detergent composition) in an amount from about 0.0001% to about 10% by weight of the composition, more preferably from about 0.0001% to about 5% by weight of the composition, and even more preferably from about 0.0001% to about 1% by weight of the composition.
  • the laundry detergent composition comprises a surfactant in an amount sufficient to provide desired cleaning properties.
  • the laundry detergent composition comprises, by weight, from about 5% to about 90% of the surfactant, and more specifically from about 5% to about 70% of the surfactant, and even more specifically from about 5% to about 40%.
  • the surfactant may comprise anionic, nonionic, cationic, zwitterionic and/or amphoteric surfactants.
  • the detergent composition comprises anionic surfactant, nonionic surfactant, or mixtures thereof.
  • Suitable anionic surfactants useful herein can comprise any of the conventional anionic surfactant types typically used in liquid detergent products. These include the alkyl benzene sulfonic acids and their salts as well as alkoxylated or non- alkoxylated alkyl sulfate materials.
  • Exemplary anionic surfactants are the alkali metal salts of C10-16 alkyl benzene sulfonic acids, preferably C U.M alkyl benzene sulfonic acids.
  • the alkyl group is linear and such linear alkyl benzene sulfonates are known as "LAS".
  • Alkyl benzene sulfonates, and particularly LAS are well known in the art. Such surfactants and their preparation are described for example in U.S. Pat. Nos. 2,220,099 and 2,477,383.
  • sodium and potassium linear straight chain alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl group is from about 11 to 14.
  • Sodium C H -C M e.g., C12, LAS is a specific example of such surfactants.
  • anionic surfactant comprises ethoxylated alkyl sulfate surfactants.
  • Such materials also known as alkyl ether sulfates or alkyl polyethoxylate sulfates, are those which correspond to the formula: R'--0--(C2H40) n --SC>3M wherein R' is a C8-C20 alkyl group, n is from about 1 to 20, and M is a salt-forming cation.
  • R' is C10-C18 alkyl, n is from about 1 to 15, and M is sodium, potassium, ammonium, alkylammonium, or alkanolammonium.
  • R' is a C12-C16, n is from about 1 to 6 or even from about 1 to 3 or from about 1 to 1.5 and M is sodium.
  • non- alkoxylated, e.g., non-ethoxylated, alkyl ether sulfate surfactants are those produced by the sulfation of higher C8-C20 fatty alcohols.
  • Conventional primary alkyl sulfate surfactants have the general formula: ROSC>3-M + wherein R is typically a linear C8-C20 hydrocarbyl group, which may be straight chain or branched chain, and M is a water-solubilizing cation.
  • R is a C10-C15 alkyl
  • M is alkali metal, more specifically R is C12- Ci4 and M is sodium.
  • anionic surfactants useful herein include: a)
  • C11-C18 alkyl benzene sulfonates (LAS); b) C10-C20 primary, branched-chain and random alkyl sulfates (AS); c) C10-C18 secondary (2,3) alkyl sulfates; d) C10-C18 alkyl alkoxy sulfates (AE x S) wherein preferably x is from 1-30; e) C10-C18 alkyl alkoxy carboxylates preferably comprising 1-5 ethoxy units; f) mid-chain branched alkyl sulfates as discussed in U.S. Pat. No. 6,020,303 and U.S. Pat. No.
  • Suitable nonionic surfactants useful herein can comprise any of the conventional nonionic surfactant types typically used in liquid detergent products. These include alkoxylated fatty alcohols and amine oxide surfactants. Preferred for use in the liquid detergent products herein are those nonionic surfactants which are normally liquid.
  • Suitable nonionic surfactants for use herein include the alcohol alkoxylate nonionic surfactants.
  • Alcohol alkoxylates are materials which correspond to the general formula: R 1 (C m H 2m O) n OH wherein R 1 is a Cs-Ci 6 alkyl group, m is from 2 to 4, and n ranges from about 2 to 12.
  • R 1 is an alkyl group, which may be primary or secondary, that comprises from about 9 to 15 carbon atoms, more preferably from about 10 to 14 carbon atoms.
  • the alkoxylated fatty alcohols will also be ethoxylated materials that contain from about 2 to 12 ethylene oxide moieties per molecule, more preferably from about 3 to 10 or even from about 7 to 9 ethylene oxide moieties per molecule.
  • the alkoxylated fatty alcohol materials useful in the liquid detergent compositions herein will frequently have a hydrophilic-lipophilic balance (HLB) which ranges from about 3 to 17. More preferably, the HLB of this material will range from about 6 to 15, most preferably from about 8 to 15.
  • HLB hydrophilic-lipophilic balance
  • Alkoxylated fatty alcohol nonionic surfactants have been marketed under the tradenames Neodol and Dobanol by the Shell Chemical Company.
  • Another suitable type of nonionic surfactant useful herein comprises the amine oxide surfactants. Amine oxides are materials which are often referred to in the art as "semi-polar" nonionics. Amine oxides have the formula:
  • R is a relatively long-chain hydrocarbyl moiety which can be saturated or unsaturated, linear or branched, and can contain from 8 to 20, preferably from 10 to 16 carbon atoms, and is more preferably C12-C16 primary alkyl.
  • R' is a short-chain moiety, preferably selected from hydrogen, methyl and -- CH2OH.
  • EO is ethyleneoxy
  • PO is propyleneneoxy
  • BO is butyleneoxy.
  • Amine oxide surfactants are illustrated by Ci2-i4alkyldimethyl amine oxide.
  • Non-limiting examples of nonionic surfactants include: a) C12-C18 alkyl ethoxylates, such as, NEODOL® nonionic surfactants from Shell; b) C6-C12 alkyl phenol alkoxylates wherein the alkoxylate units are a mixture of ethyleneoxy and propyleneoxy units; c) C12-C18 alcohol and C6-C12 alkyl phenol condensates with ethylene oxide/propylene oxide block polymers such as Pluronic® from BASF; d) C14-C22 mid-chain branched alcohols, BA, as discussed in U.S. Pat. No.
  • the detersive surfactant component may comprise combinations of anionic and nonionic surfactant materials.
  • the weight ratio of anionic to nonionic will typically range from 10:90 to 90:10, more typically from 30:70 to 70:30.
  • Cationic surfactants are well known in the art and non-limiting examples of these include quaternary ammonium surfactants, which can have up to 26 carbon atoms. Additional examples include a) alkoxylate quaternary ammonium (AQA) surfactants as discussed in U.S. Pat. No. 6,136,769; b) dimethyl hydroxyethyl quaternary ammonium as discussed in U.S. Pat. No. 6,004,922; c) polyamine cationic surfactants as discussed in WO 98/35002, WO 98/35003, WO 98/35004, WO 98/35005, and WO 98/35006; d) cationic ester surfactants as discussed in U.S. Pat. Nos. 4,228,042, 4,239,6604,260,529 and U.S. Pat.
  • AQA alkoxylate quaternary ammonium
  • Non-limiting examples of zwitterionic surfactants include derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. See U.S. Pat. No. 3,929,678 to Laughlin et al., issued Dec.
  • betaine including alkyl dimethyl betaine and cocodimethyl amidopropyl betaine, Cs to Cis (preferably Ci2 to Cis) amine oxides and sulfo and hydroxy betaines, such as N-alkyl-N,N- dimethylammino-1-propane sulfonate where the alkyl group can be Cs to Cis, preferably Cio to CM.
  • Non-limiting examples of ampholytic surfactants include aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic radical can be straight- or branched-chain.
  • One of the aliphatic substituents comprises at least about 8 carbon atoms, typically from about 8 to about 18 carbon atoms, and at least one comprises an anionic water-solubilizing group, e.g. carboxy, sulfonate, sulfate. See U.S. Pat. No. 3,929,678 to Laughlin et al., issued Dec. 30, 1975 at column 19, lines 18-35, for examples of ampholytic surfactants.
  • compositions may be in the form of a solid, either in tablet or particulate form, including, but not limited to particles, flakes, or the like, or the compositions may be in the form of a liquid.
  • the liquid detergent compositions comprise an aqueous, non surface active liquid carrier.
  • the amount of the aqueous, non-surface active liquid carrier employed in the compositions herein will be effective to solubilize, suspend or disperse the composition components.
  • the compositions may comprise, by weight, from about 5% to about 90%, more specifically from about 10% to about 70%, and even more specifically from about 20% to about 70% of the aqueous, non-surface active liquid carrier.
  • aqueous, non-surface active liquid carrier is, of course, water itself. Accordingly, the aqueous, non-surface active liquid carrier component will generally be mostly, if not completely, comprised of water. However, other types of water-miscible liquids, such alkanols, diols, other polyols, ethers, amines, and the like, and mixtures thereof, may also be added to liquid detergent compositions as co solvents or stabilizers in addition to or in place of water. Accordingly, the aqueous non surface active liquid carrier component of the liquid detergent composition will generally be present in concentrations ranging from about 5% to about 90% by weight of the composition, more preferably from about 20% to about 70% by weight of the composition.
  • Detergent compositions may also contain bleaching agents.
  • Suitable bleaching agents include, for example, hydrogen peroxide sources, such as those described in detail in the herein incorporated Kirk Othmer's Encyclopedia of Chemical Technology, 4th Ed (1992, John Wiley & Sons), Vol. 4, pp. 271-300 "Bleaching Agents (Survey)." These hydrogen peroxide sources include the various forms of sodium perborate and sodium percarbonate, including various coated and modified forms of these compounds.
  • the preferred source of hydrogen peroxide used herein can be any convenient source, including hydrogen peroxide itself.
  • perborate e.g., sodium perborate (any hydrate but preferably the mono- or tetra-hydrate), sodium carbonate peroxyhydrate or equivalent percarbonate salts, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, or sodium peroxide
  • sources of available oxygen such as persulfate bleach (e.g., OXONE, manufactured by DuPont).
  • Sodium perborate monohydrate and sodium percarbonate are particularly preferred. Mixtures of any convenient hydrogen peroxide sources can also be used.
  • a suitable percarbonate bleach comprises dry particles having an average particle size in the range from about 500 micrometers to about 1,000 micrometers, not more than about 10% by weight of said particles being smaller than about 200 micrometers and not more than about 10% by weight of said particles being larger than about 1,250 micrometers.
  • the percarbonate can be coated with a silicate, borate or water- soluble surfactants.
  • Percarbonate is available from various commercial sources such as FMC, Solvay and Tokai Denka.
  • compositions of the present invention may also comprise as the bleaching agent a chlorine-type bleaching material.
  • a chlorine-type bleaching material such agents are well known in the art, and include for example sodium dichloroisocyanurate (“NaDCC").
  • NaDCC sodium dichloroisocyanurate
  • chlorine-type bleaches are less preferred for compositions which comprise enzymes.
  • the peroxygen bleach component in the composition is formulated with an activator (peracid precursor).
  • the activator is present at levels of from about 0.01%, preferably from about 0.5%, more preferably from about 1% to about 15%, preferably to about 10%, more preferably to about 8%, by weight of the composition.
  • a bleach activator as used herein is any compound which, when used in conjunction with a hydrogen peroxide, source leads to the in situ production of the peracid corresponding to the bleach activator.
  • activators are disclosed in U.S. Patent Nos. 5,576,282; 4,915,854 and 4,412,934. See also U.S. Patent No. 4,634,551 for other typical bleaches and activators useful herein.
  • Preferred activators are selected from the group consisting of tetraacetyl ethylene diamine (TAED), benzoylcaprolactam (BzCL), 4-nitrobenzoylcaprolactam, 3- chlorobenzoylcaprolactam, benzoyloxybenzenesulphonate (BOBS), nonanoyloxybenzene- sulphonate (NOBS), phenyl benzoate (PhBz), decanoyloxybenzenesulphonate (C-io-OBS), benzoylvalerolactam (BZVL), octanoyloxybenzenesulphonate (Cs-OBS), perhydrolyzable esters and mixtures thereof, most preferably benzoylcaprolactam and benzoylvalerolactam.
  • Particularly preferred bleach activators in the pH range from about 8 to about 11 are those selected having an OBS or VL leaving group.
  • Preferred hydrophobic bleach activators include, but are not limited to, nonanoyloxybenzenesulphonate (NOBS); 4-[N-(nonanoyl) amino hexanoyloxy]-benzene sulfonate sodium salt (NACA-OBS), an example of which is described in U.S. Patent No. 5,523,434; dodecanoyloxybenzenesulphonate (LOBS or C ⁇ -OBS); 10- undecenoyloxybenzenesulfonate (UDOBS or Cn-OBS with unsaturation in the 10 position); and decanoyloxybenzoic acid (DOBA).
  • NOBS nonanoyloxybenzenesulphonate
  • NACA-OBS 4-[N-(nonanoyl) amino hexanoyloxy]-benzene sulfonate sodium salt
  • DOBA decanoyloxybenzoic acid
  • Preferred bleach activators are those described in U.S. Patent No. 5,998,350 to Burns et al.; U.S. Patent No. 5,698,504 to Christie et al.; U.S. Patent No. 5,695,679 to Christie et al.; U.S. Patent No. 5,686,401 to Willey et al.; U.S. Patent No. 5,686,014 to Hartshorn et al.; U.S. Patent No. 5,405,412 to Wiley et al.; U.S. Patent No. 5,405,413 to Wiley et al.; U.S. Patent No. 5,130,045 to Mitchel et al.; and U.S. Patent No. 4,412,934 to Chung et al. , and copending Patent Application Serial No. 08/064,564, all of which are incorporated herein by reference.
  • the mole ratio of peroxygen source (as AvO) to bleach activator in the present invention generally ranges from at least 1:1, preferably from about 20:1, more preferably from about 10:1 to about 1:1, preferably to about 3:1.
  • Quaternary substituted bleach activators may also be included.
  • the present laundry compositions preferably comprise a quaternary substituted bleach activator (QSBA) or a quaternary substituted peracid (QSP, preferably a quaternary substituted percarboxylic acid or a quaternary substituted peroxyimidic acid); more preferably, the former.
  • QSBA structures are further described in U.S. Patent No. 5,686,015 to Willey et al.; U.S. Patent No. 5,654,421 to Taylor et al.; U.S. Patent No. 5,460,747 to Gosselink et al.; U.S. Patent No. 5,584,888 to Miracle et al.; U.S. Patent No. 5,578,136 to Taylor et al.; all of which are incorporated herein by reference.
  • bleach activators useful herein are amide-substituted as described in U.S. Patent Nos. 5,698,504; 5,695,679; and 5,686,014, each of which are cited herein above.
  • Preferred examples of such bleach activators include: (6-octanamidocaproyl) oxybenzenesulfonate, (6-nonanamidocaproyl)oxybenzenesulfonate, (6-decanamidocaproyl) oxybenzenesulfonate and mixtures thereof.
  • activators include benzoxazin-type activators, such as a
  • Nitriles such as acetonitriles and/or ammonium nitriles and other quaternary nitrogen containing nitriles, are another class of activators that are useful herein.
  • Non limiting examples of such nitrile bleach activators are described in U.S. Patent Nos. 6,133,216; 3,986,972; 6,063,750; 6,017,464; 5,958,289; 5,877,315; 5,741,437; 5,739,327;
  • bleaching results can be obtained from bleaching systems having an in-use pH of from about 6 to about 13, and preferably from about 9.0 to about 10.5.
  • activators with electron- withdrawing moieties are used for near-neutral or sub-neutral pH ranges.
  • Alkalis and buffering agents can be used to secure such pH.
  • compositions and methods of the present invention can also optionally include metal-containing bleach catalysts, preferably manganese and cobalt-containing bleach catalysts.
  • One type of metal-containing bleach catalyst is a catalyst system comprising a transition metal cation of defined bleach catalytic activity (such as copper, iron, titanium, ruthenium tungsten, molybdenum, or manganese cations), an auxiliary metal cation having little or no bleach catalytic activity (such as zinc or aluminum cations), and a sequestrate having defined stability constants for the catalytic and auxiliary metal cations, particularly ethylenediaminetetraacetic acid, ethylenediaminetetra (methylenephosphonic acid) and water-soluble salts thereof.
  • a transition metal cation of defined bleach catalytic activity such as copper, iron, titanium, ruthenium tungsten, molybdenum, or manganese cations
  • an auxiliary metal cation having little or no bleach catalytic activity such as zinc or aluminum cations
  • a sequestrate having defined stability constants for the catalytic and auxiliary metal cations, particularly ethylenediaminetetraacetic acid
  • the compositions herein can be catalyzed by means of a manganese compound.
  • a manganese compound Such compounds and levels of use are well known in the art and include, for example, the manganese-based catalysts disclosed in U.S. Patent Nos. 5,576,282; 5,246,621; 5,244,594; 5,194,416; and 5,114,606; and European Pat. App. Pub. Nos. 549,271 A1; 549,272 A1; 544,440 A2; and 544,490 A1.
  • Preferred examples of these catalysts include Mn ⁇ 2(u-0)3(1,4,7-trimethyl-1,4,7-triazacyclononane)2- (PFQ)2, Mn ⁇ 2( u -0)i(u-OAc)2(1,4,7-trimethyl-1,4,7-triazacyclononane)2(CI04)2, Mn'V ⁇ u- 0) Q (1,4,7-triazacyclononane)4(CIC>4)4, Mn ⁇ Mn ⁇ 4(u-0) '
  • metal-based bleach catalysts include those disclosed in U.S. Patent Nos. 4,430,243 and 5,114,611.
  • the use of manganese with various complex ligands to enhance bleaching is also reported in the following: U.S. Patent Nos. 4,728,455; 5,284,944; 5,246,612; 5,256,779; 5,280,117; 5,274,147; 5,153,161; and 5,227,084.
  • Cobalt Metal Complexes - Cobalt bleach catalysts useful herein are known, and are described, for example, in U.S. Patent Nos. 5,597,936; 5,595,967; and 5,703,030; and M. L. Tobe, "Base Hydrolysis of Transition-Metal Complexes", Adv. Inorg. Bioinorg. Mech., (1983), 2, pages 1-94.
  • cobalt catalyst useful herein are cobalt pentaamine acetate salts having the formula [Co(NH3)5 ⁇ 0Ac] Ty, wherein "OAc” represents an acetate moiety and “Ty” is an anion, and especially cobalt pentaamine acetate chloride, [CO(NH3) 5 OAC]CI 2 ; as well as [Co(NH 3 ) 5 OAc](OAc) 2 ; [Co(NH 3 ) 5 OAc](PF 6 ) 2 ;
  • Transition Metal Complexes of Macropolycyclic Rigid Ligands - Compositions herein may also suitably include as bleach catalyst a transition metal complex of a macropolycyclic rigid ligand.
  • the amount used is a catalytically effective amount, suitably about 1 ppb or more, for example up to about 99.9%, more typically about 0.001 ppm or more, preferably from about 0.05 ppm to about 500 ppm (wherein "ppb” denotes parts per billion by weight and "ppm” denotes parts per million by weight).
  • Transition-metal bleach catalysts of Macrocyclic Rigid Ligands which are suitable for use in the invention compositions can in general include known compounds where they conform with the definition herein, as well as, more preferably, any of a large number of novel compounds expressly designed for the present laundry or laundry uses, and are non-limitingly illustrated by any of the following:
  • compositions and methods herein can be adjusted to provide on the order of at least one part per hundred million of the active bleach catalyst species in the composition comprising a lipophilic fluid and a bleach system, and will preferably provide from about 0.01 ppm to about 25 ppm, more preferably from about 0.05 ppm to about 10 ppm, and most preferably from about 0.1 ppm to about 5 ppm, of the bleach catalyst species in the composition comprising a lipophilic fluid and a bleach system.
  • Bleach Boosting Compounds may comprise one or more bleach boosting compounds.
  • Bleach boosting compounds provide increased bleaching effectiveness in lower temperature applications.
  • the bleach boosters act in conjunction with conventional peroxygen bleaching sources to provide increased bleaching effectiveness. This is normally accomplished through in situ formation of an active oxygen transfer agent such as a dioxirane, an oxaziridine, or an oxaziridinium. Alternatively, preformed dioxiranes, oxaziridines and oxaziridiniums may be used.
  • Suitable bleach boosting compounds for use in accordance with the present invention are cationic imines, zwitterionic imines, anionic imines and/or polyionic imines having a net charge of from about +3 to about -3, and mixtures thereof.
  • These imine bleach boosting compounds of the present invention include those of the general structure: [A] where may be a hydrogen or an unsubstituted or substituted radical selected from the group consisting of phenyl, aryl, heterocyclic ring, alkyl and cycloalkyl radicals.
  • zwitterionic bleach boosters which are described in U.S. Patent Nos. 5,576,282 and 5,718,614.
  • bleach boosting compounds include cationic bleach boosters described in U.S. Patent Nos. 5,360,569; 5,442,066; 5,478,357; 5,370,826; 5,482,515; 5,550,256; and WO 95/13351, WO 95/13352, and WO 95/13353.
  • Peroxygen sources are well-known in the art and the peroxygen source employed in the present invention may comprise any of these well known sources, including peroxygen compounds as well as compounds, which under consumer use conditions, provide an effective amount of peroxygen in situ.
  • the peroxygen source may include a hydrogen peroxide source, the in situ formation of a peracid anion through the reaction of a hydrogen peroxide source and a bleach activator, preformed peracid compounds or mixtures of suitable peroxygen sources.
  • the bleach boosting compounds when present, are preferably employed in conjunction with a peroxygen source in the bleaching systems of the present invention.
  • Preformed Peracids are also suitable as bleaching agents.
  • the preformed peracid compound as used herein is any convenient compound which is stable and which under consumer use conditions provides an effective amount of peracid or peracid anion.
  • the preformed peracid compound may be selected from the group consisting of percarboxylic acids and salts, percarbonic acids and salts, perimidic acids and salts, peroxymonosulfuric acids and salts, and mixtures thereof. Examples of these compounds are described in U.S. Patent No. 5,576,282 to Miracle et al.
  • Organic peroxyacids suitable for use in the present invention can contain either one or two peroxy groups and can be either aliphatic or aromatic.
  • the organic peroxycarboxylic acid is aliphatic, the unsubstituted peracid has the general formula: wherein Y can be, for example, H, CH3, CH2CI, C(0)OH, or C(0)OOH; and n is an integer from 0 to 20.
  • the organic peroxycarboxylic acid is aromatic, the unsubstituted peracid has the general formula:
  • Y can be, for example, hydrogen, alkyl, alkylhalogen, halogen, C(0)0H or C(0)00H.
  • Typical monoperoxy acids useful herein include alkyl and aryl peroxyacids such as:
  • peroxybenzoic acid and ring-substituted peroxybenzoic acid e.g. peroxy-a- naphthoic acid, monoperoxyphthalic acid (magnesium salt hexahydrate), and o- carboxybenzamidoperoxyhexanoic acid (sodium salt);
  • aliphatic, substituted aliphatic and arylalkyl monoperoxy acids e.g. peroxylauric acid, peroxystearic acid, N-nonanoylaminoperoxycaproic acid (NAPCA), N,N-(3-octylsuccinoyl)aminoperoxycaproic acid (SAPA) and N,N- phthaloylaminoperoxycaproic acid (PAP);
  • amidoperoxyacids e.g. monononylamide of either peroxysuccinic acid (NAPSA) or of peroxyadipic acid (NAPAA).
  • NAPSA peroxysuccinic acid
  • NAPAA peroxyadipic acid
  • Typical diperoxyacids useful herein include alkyl diperoxyacids and aryldiperoxyacids, such as:
  • Sources also include 6-nonylamino-6- oxoperoxycaproic acid as described in U.S. Patent No. 4,634,551 to Burns et al.
  • Persulfate compounds such as for example OXONE, manufactured commercially by E.l. DuPont de Nemours of Wilmington, DE can also be employed as a suitable source of peroxymonosulfuric acid.
  • PAP is disclosed in, for example, U.S. Patent Nos. 5,487,818; 5,310,934; 5,246,620; 5,279,757 and 5,132,431.
  • Photobleaches - Suitable photobleaches for use in the treating compositions of the present invention include, but are not limited to, the photobleaches described in U.S. Patent Nos. 4,217,105 and 5,916,481.
  • Enzyme Bleaching - Enzymatic systems may be used as bleaching agents.
  • the hydrogen peroxide may also be present by adding an enzymatic system (i.e. an enzyme and a substrate therefore) which is capable of generating hydrogen peroxide at the beginning or during the washing and/or rinsing process.
  • an enzymatic system i.e. an enzyme and a substrate therefore
  • Such enzymatic systems are disclosed in EP Patent Application 91202655.6 filed October 9, 1991.
  • compositions and methods may utilize alternative bleach systems such as ozone, chlorine dioxide and the like.
  • Bleaching with ozone may be accomplished by introducing ozone-containing gas having ozone content from about 20 to about 300 g/m 3 into the solution that is to contact the fabrics.
  • the gasliquid ratio in the solution should be maintained from about 1:2.5 to about 1:6.
  • U.S. Patent No. 5,346, 588 describes a process for the utilization of ozone as an alternative to conventional bleach systems and is herein incorporated by reference.
  • the detergent compositions of the present invention may also include any number of additional optional ingredients.
  • additional optional ingredients include conventional laundry detergent composition components such as non-tinting dyes, detersive builders, enzymes, enzyme stabilizers (such as propylene glycol, boric acid and/or borax), suds suppressors, soil suspending agents, soil release agents, other fabric care benefit agents, pH adjusting agents, chelating agents, smectite clays, solvents, hydrotropes and phase stabilizers, structuring agents, dye transfer inhibiting agents, opacifying agents, optical brighteners, perfumes and coloring agents.
  • the various optional detergent composition ingredients, if present in the compositions herein, should be utilized at concentrations conventionally employed to bring about their desired contribution to the composition or the laundering operation. Frequently, the total amount of such optional detergent composition ingredients can range from about 0.01% to about 50%, more preferably from about 0.1% to about 30%, by weight of the composition.
  • the liquid detergent compositions are in the form of an aqueous solution or uniform dispersion or suspension of surfactant, polymeric colorant, and certain optional other ingredients, some of which may normally be in solid form, that have been combined with the normally liquid components of the composition, such as the liquid alcohol ethoxylate nonionic, the aqueous liquid carrier, and any other normally liquid optional ingredients.
  • a solution, dispersion or suspension will be acceptably phase stable and will typically have a viscosity which ranges from about 100 to 600 cps, more preferably from about 150 to 400 cps. For purposes of this invention, viscosity is measured with a Brookfield LVDV-II+ viscometer apparatus using a #21 spindle.
  • the liquid detergent compositions herein can be prepared by combining the components thereof in any convenient order and by mixing, e.g., agitating, the resulting component combination to form a phase stable liquid detergent composition.
  • a liquid matrix is formed containing at least a major proportion, and preferably substantially all, of the liquid components, e.g., nonionic surfactant, the non-surface active liquid carriers and other optional liquid components, with the liquid components being thoroughly admixed by imparting shear agitation to this liquid combination.
  • the liquid components e.g., nonionic surfactant, the non-surface active liquid carriers and other optional liquid components
  • shear agitation for example, rapid stirring with a mechanical stirrer may usefully be employed. While shear agitation is maintained, substantially all of any anionic surfactants and the solid form ingredients can be added.
  • Agitation of the mixture is continued, and if necessary, can be increased at this point to form a solution or a uniform dispersion of insoluble solid phase particulates within the liquid phase.
  • particles of any enzyme material to be included e.g., enzyme prills, are incorporated.
  • one or more of the solid components may be added to the agitated mixture as a solution or slurry of particles premixed with a minor portion of one or more of the liquid components.
  • agitation of the mixture is continued for a period of time sufficient to form compositions having the requisite viscosity and phase stability characteristics. Frequently this will involve agitation for a period of from about 30 to 60 minutes.
  • the polymeric colorant is first combined with one or more liquid components to form a polymeric colorant premix, and this premix is added to a composition formulation containing a substantial portion, for example more than 50% by weight, more specifically, more than 70% by weight, and yet more specifically, more than 90% by weight, of the balance of components of the laundry detergent composition.
  • a composition formulation containing a substantial portion, for example more than 50% by weight, more specifically, more than 70% by weight, and yet more specifically, more than 90% by weight, of the balance of components of the laundry detergent composition.
  • both the polymeric colorant premix and the enzyme component are added at a final stage of component additions.
  • the polymeric colorant is encapsulated prior to addition to the detergent composition, the encapsulated polymeric colorant is suspended in a structured liquid, and the suspension is added to a composition formulation containing a substantial portion of the balance of components of the laundry detergent composition.
  • the detergent compositions may be in a solid form. Suitable solid forms include tablets and particulate forms, for example, granular particles or flakes. Various techniques for forming detergent compositions in such solid forms are well known in the art and may be used herein. In one embodiment, for example when the composition is in the form of a granular particle, the polymeric colorant is provided in particulate form, optionally including additional but not all components of the laundry detergent composition.
  • the polymeric colorant particulate is combined with one or more additional particulates containing a balance of components of the laundry detergent composition. Further, the polymeric colorant, optionally including additional but not all components of the laundry detergent composition, may be provided in an encapsulated form, and the polymeric colorant encapsulate is combined with particulates containing a substantial balance of components of the laundry detergent composition.
  • compositions of this invention can be used to form aqueous washing solutions for use in the laundering of textile substrates such as fabrics.
  • an effective amount of such compositions is added to water, preferably in a conventional fabric laundering automatic washing machine, to form such aqueous laundering solutions.
  • the aqueous washing solution so formed is then contacted, preferably under agitation, with the fabrics to be laundered therewith.
  • An effective amount of the liquid detergent compositions herein added to water to form aqueous laundering solutions can comprise amounts sufficient to form from about 500 to 7,000 ppm of composition in aqueous washing solution. More preferably, from about 1,000 to 3,000 ppm of the detergent compositions herein will be provided in aqueous washing solution.
  • the polymeric colorant of the present invention may be included in a fabric treatment composition.
  • the fabric treatment composition may be comprised of at least one polymeric colorant and a rinse added fabric softening composition (“RAFS;” also known as rinse added fabric conditioning compositions). Examples of typical rinse added softening compositions can be found in U.S. Provisional Patent Application Serial No. 60/687582 filed on October 8, 2004.
  • the rinse added fabric softening compositions of the present invention may comprise (a) fabric softening active (“FSA”) and (b) a polymeric colorant containing at least one carboxymethyl capped alkyleneoxy chain.
  • the rinse added fabric softening composition may comprise from about 1% to about 90% by weight of the FSA, more preferably from about 5% to about 50% by weight of the FSA.
  • the polymeric colorant may be present in the rinse added fabric softening composition in an amount from about 0.5 ppb to about 50 ppm, more preferably from about 0.5 ppm to about 30 ppm.
  • the fabric softening active is a quaternary ammonium compound suitable for softening fabric in a rinse step.
  • the FSA is formed from a reaction product of a fatty acid and an aminoalcohol obtaining mixtures of mono-, di-, and, in one embodiment, triester compounds.
  • the FSA comprises one or more softener quaternary ammonium compounds such, but not limited to, as a monoalkyquaternary ammonium compound, a diamido quaternary compound and a diester quaternary ammonium compound, or a combination thereof.
  • the FSA comprises a diester quaternary ammonium (hereinafter “DQA”) compound composition.
  • DQA compounds compositions also encompasses a description of diamido FSAs and FSAs with mixed amido and ester linkages as well as the aforementioned diester linkages, all herein referred to as DQA.
  • a first type of DQA (“DQA (1)”) suitable as a FSA includes a compound comprising the formula:
  • each R substituent is either hydrogen, a short chain C-
  • each n is from 1 to about 4, preferably 2; each Y is -0-(0)C-, -C(0)-0-, -NR-C(O)-, or -C(0)-NR- and it is acceptable for each Y to be the same or different; the sum of carbons in each R " ', plus one when Y is -0-(0)C- or -NR-C(O) -, is C-
  • Preferred DQA compounds are typically made by reacting alkanolamines such as MDEA (methyldiethanolamine) and TEA (triethanolamine) with fatty acids.
  • alkanolamines such as MDEA (methyldiethanolamine) and TEA (triethanolamine)
  • Some materials that typically result from such reactions include N,N-di(acyl-oxyethyl)-N,N-dimethylammonium chloride or N,N-di(acyl-oxyethyl)-N,N-methylhydroxyethylammonium methylsulfate
  • the acyl group is derived from animal fats, unsaturated, and polyunsaturated, fatty acids, e.g., tallow, hardened tallow, oleic acid, and/or partially hydrogenated fatty acids, derived from vegetable oils and/or partially hydrogenated vegetable oils, such as, canola oil, safflower oil, peanut oil, sunflower oil, corn oil, soybean oil, tall oil, rice
  • the FSA comprises other actives in addition to DQA (1) or DQA.
  • the FSA comprises only DQA (1) or DQA and is free or essentially free of any other quaternary ammonium compounds or other actives.
  • the FSA comprises the precursor amine that is used to produce the DQA.
  • the FSA comprises a compound, identified as DTTMAC comprising the formula: wherein each m is 2 or 3, each R1 is a CQ-C22 > preferably C14-C2O’ but no more than one being less than about C12 and then the other is at least about 16, hydrocarbyl, or substituted hydrocarbyl substituent, preferably Ci0 3 ⁇ 40 alkyl or alkenyl (unsaturated alkyl, including polyunsaturated alkyl, also referred to sometimes as "alkylene”), most preferably C12-C18 alkyl or alkenyl, and branch or unbranched.
  • DTTMAC comprising the formula: wherein each m is 2 or 3, each R1 is a CQ-C22 > preferably C14-C2O’ but no more than one being less than about C12 and then the other is at least about 16, hydrocarbyl, or substituted hydrocarbyl substituent, preferably Ci0 3 ⁇ 40 alkyl or alkenyl (unsaturated alkyl, including poly
  • the Iodine Value (IV) of the FSA is from about 1 to 70; each R is H or a short chain C-
  • FSAs include dialkydimethylammonium salts and dialkylenedimethylammonium salts such as ditallowdimethylammonium and ditallowdimethylammonium methylsulfate.
  • dialkylenedimethylammonium salts such as ditallowdimethylammonium and ditallowdimethylammonium methylsulfate.
  • dialkylenedimethylammonium salts usable in the present invention are di-hydrogenated tallow dimethyl ammonium chloride and ditallowdimethyl ammonium chloride available from Degussa under the trade names Adogen® 442 and Adogen® 470 respectively.
  • the FSA comprises other actives in addition to DTTMAC.
  • the FSA comprises only compounds of the DTTMAC and is free or essentially free of any other quaternary ammonium compounds or other actives.
  • the FSA comprises an FSA described in U.S. Pat. Pub. No. 2004/0204337 A1, published Oct. 14, 2004 to Corona et al., from paragraphs 30 - 79.
  • the FSA is one described in U.S. Pat. Pub. No. 2004/0229769 A1, published Nov. 18, 2005, to Smith et al., on paragraphs 26 - 31; or U.S. Pat. No. 6,494,920, at column 1, line 51 et seq. detailing an “esterquat” or a quaternized fatty acid triethanolamine ester salt.
  • the FSA is chosen from at least one of the following: ditallowoyloxyethyl dimethyl ammonium chloride, dihydrogenated-tallowoyloxyethyl dimethyl ammonium chloride, ditallow dimethyl ammonium chloride, ditallowoyloxyethyl dimethyl ammonium methyl sulfate, dihydrogenated-tallowoyloxyethyl dimethyl ammonium chloride, dihydrogenated-tallowoyloxyethyl dimethyl ammonium chloride, or combinations thereof.
  • the FSA may also include amide containing compound compositions.
  • diamide comprising compounds may include but not limited to methyl-bis(tallowamidoethyl)-2-hydroxyethylammonium methyl sulfate (available from Degussa under the trade names Varisoft 110 and Varisoft 222).
  • An example of an amide- ester containing compound is N-[3-(stearoylamino)propyl]-N-[2-(stearoyloxy)ethoxy)ethyl)]- N-methylamine.
  • a rinse added fabric softening composition further comprising a cationic starch.
  • Cationic starches are disclosed in US 2004/0204337 A1.
  • the rinse added fabric softening composition comprises from about 0.1% to about 7% of cationic starch by weight of the fabric softening composition.
  • the cationic starch is HCP401 from National Starch.
  • laundry care ingredients While not essential for the purposes of the present invention, the non-limiting list of laundry care ingredients illustrated hereinafter are suitable for use in the laundry care compositions and may be desirably incorporated in certain embodiments of the invention, for example to assist or enhance performance, for treatment of the substrate to be cleaned, or to modify the aesthetics of the composition as is the case with perfumes, colorants, dyes or the like. It is understood that such ingredients are in addition to the components that were previously listed for any particular embodiment. The total amount of such adjuncts may range from about 0.1% to about 50%, or even from about 1% to about 30%, by weight of the laundry care composition.
  • laundry care ingredients include, but are not limited to, polymers, for example cationic polymers, surfactants, builders, chelating agents, dye transfer inhibiting agents, dispersants, enzymes, and enzyme stabilizers, catalytic materials, bleach activators, polymeric dispersing agents, clay soil removal/anti-redeposition agents, brighteners, suds suppressors, dyes, additional perfume and perfume delivery systems, structure elasticizing agents, fabric softeners, carriers, hydrotropes, processing aids and/or coloring agents.
  • suitable examples of such other adjuncts and levels of use are found in U.S. Patent Nos. 5,576,282, 6,306,812 B1 and 6,326,348 B1 that are incorporated by reference.
  • the laundry care ingredients are not essential to Applicants’ laundry care compositions.
  • certain embodiments of Applicants’ compositions do not contain one or more of the following adjuncts materials: bleach activators, surfactants, builders, chelating agents, dye transfer inhibiting agents, dispersants, enzymes, and enzyme stabilizers, catalytic metal complexes, polymeric dispersing agents, clay and soil removal/anti-redeposition agents, brighteners, suds suppressors, dyes, additional perfumes and perfume delivery systems, structure elasticizing agents, fabric softeners, carriers, hydrotropes, processing aids and/or coloring agents.
  • one or more adjuncts may be present as detailed below:
  • compositions according to the present invention can comprise a surfactant or surfactant system wherein the surfactant can be selected from nonionic and/or anionic and/or cationic surfactants and/or ampholytic and/or zwitterionic and/or semi-polar nonionic surfactants.
  • the surfactant is typically present at a level of from about 0.1%, from about 1%, or even from about 5% by weight of the cleaning compositions to about 99.9%, to about 80%, to about 35%, or even to about 30% by weight of the cleaning compositions.
  • compositions of the present invention can comprise one or more detergent builders or builder systems. When present, the compositions will typically comprise at least about 1% builder, or from about 5% or 10% to about 80%, 50%, or even 30% by weight, of said builder.
  • Builders include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates, alkali metal silicates, alkaline earth and alkali metal carbonates, aluminosilicate builders polycarboxylate compounds ether hydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulphonic acid, and carboxymethyl-oxysuccinic acid, the various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediamine tetraacetic acid and nitrilotriacetic acid, as well as polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5- tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.
  • compositions herein may also optionally contain one or more copper, iron and/or manganese chelating agents. If utilized, chelating agents will generally comprise from about 0.1% by weight of the compositions herein to about 15%, or even from about 3.0% to about 15% by weight of the compositions herein.
  • Dye Transfer Inhibiting Agents The compositions of the present invention may also include one or more dye transfer inhibiting agents.
  • Suitable polymeric dye transfer inhibiting agents include, but are not limited to, polyvinylpyrrolidone polymers, polyamine N- oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinyloxazolidones and polyvinylimidazoles or mixtures thereof.
  • the dye transfer inhibiting agents are present at levels from about 0.0001%, from about 0.01%, from about 0.05% by weight of the cleaning compositions to about 10%, about 2%, or even about 1% by weight of the cleaning compositions.
  • Dispersants - The compositions of the present invention can also contain dispersants.
  • Suitable water-soluble organic materials are the homo- or co-polymeric acids or their salts, in which the polycarboxylic acid may comprise at least two carboxyl radicals separated from each other by not more than two carbon atoms.
  • Enzymes - The compositions can comprise one or more detergent enzymes which provide cleaning performance and/or fabric care benefits.
  • suitable enzymes include, but are not limited to, hemicellulases, peroxidases, proteases, cellulases, xylanases, lipases, phospholipases, esterases, cutinases, pectinases, keratanases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, b-glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase, and amylases, or mixtures thereof.
  • a typical combination is a cocktail of conventional applicable enzymes like protease, lipase, cutinase and/or cellulase in conjunction with amylase.
  • Enzyme Stabilizers - Enzymes for use in compositions for example, detergents can be stabilized by various techniques.
  • the enzymes employed herein can be stabilized by the presence of water-soluble sources of calcium and/or magnesium ions in the finished compositions that provide such ions to the enzymes.
  • compositions may include catalytic metal complexes.
  • One type of metal-containing bleach catalyst is a catalyst system comprising a transition metal cation of defined bleach catalytic activity, such as copper, iron, titanium, ruthenium, tungsten, molybdenum, or manganese cations, an auxiliary metal cation having little or no bleach catalytic activity, such as zinc or aluminum cations, and a sequestrate having defined stability constants for the catalytic and auxiliary metal cations, particularly ethylenediaminetetraacetic acid, ethylenediaminetetra (methyl-enephosphonic acid) and water-soluble salts thereof.
  • a transition metal cation of defined bleach catalytic activity such as copper, iron, titanium, ruthenium, tungsten, molybdenum, or manganese cations
  • an auxiliary metal cation having little or no bleach catalytic activity, such as zinc or aluminum cations
  • a sequestrate having defined stability constants for the catalytic and
  • compositions herein can be catalyzed by means of a manganese compound.
  • a manganese compound Such compounds and levels of use are well known in the art and include, for example, the manganese-based catalysts disclosed in U.S. Patent No.
  • Cobalt bleach catalysts useful herein are known, and are described, for example, in U.S. Patent Nos. 5,597,936 and 5,595,967. Such cobalt catalysts are readily prepared by known procedures, such as taught for example in U.S. Patent Nos. 5,597,936, and 5,595,967.
  • compositions herein may also suitably include a transition metal complex of a macropolycyclic rigid ligand - abbreviated as “MRL”.
  • MRL macropolycyclic rigid ligand
  • the compositions and cleaning processes herein can be adjusted to provide on the order of at least one part per hundred million of the benefit agent MRL species in the aqueous washing medium, and may provide from about 0.005 ppm to about 25 ppm, from about 0.05 ppm to about 10 ppm, or even from about 0.1 ppm to about 5 ppm, of the MRL in the wash liquor.
  • Preferred transition-metals in the instant transition-metal bleach catalyst include manganese, iron and chromium.
  • Preferred MRL’s herein are a special type of ultra- rigid ligand that is cross-bridged such as 5,12-diethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexa- decane. Suitable transition metal MRLs are readily prepared by known procedures, such as taught for example in WO 00/32601, and U.S. Patent No. 6,225,464.
  • Table A provides examples of liquid detergent formulations which include at least one polymeric colorant containing at least one carboxymethyl capped alkyleneoxy chain of the present invention.
  • Table B provides examples of granular detergent formulations which include at least one polymeric colorant containing at least one carboxymethyl capped alkyleneoxy chain of the present invention.
  • Table C provides examples of liquid fabric treatment compositions which include at least one polymeric colorant containing at least one carboxymethyl capped alkyleneoxy chain of the present invention.
  • Table C - Liquid Fabric Treatment Compositions Comprising the Present Polymeric Colorant a N,N-di(tallowoyloxyethyl)-N,N-dimethylammonium chloride.
  • b Cationic starch based on common maize starch or potato starch, containing 25% to 95% amylose and a degree of substitution of from 0.02 to 0.09, and having a viscosity measured as Water Fluidity having a value from 50 to 84.
  • the polymeric colorant of the current invention may be ideal for use in thermoset materials (such as, for example, polyurethane foam).
  • thermoset materials such as, for example, polyurethane foam.
  • specific thermoset formulations which may be suitable for use with the polymeric colorant of the present invention, are disclosed in commonly assigned US Patent Nos. 4,284,729 to Cross et al. and 4,846,846 to Rekers et al.
  • polyurethane foam is produced through the catalyzed polymerization of the reaction products of polyols and isocyanates. Blowing agents present within the polymerization step typically provide the necessary foam-making capability. Such a reaction is well known throughout the polyurethane industry and has been practiced for many years.
  • thermoset material containing the polymeric colorant as described herein.
  • the thermoset material is a polyurethane foam material.
  • Polyurethanes are typically made by reacting isocyanate with active hydrogen-containing compounds. The polyurethane polymer is then expanded (or “blown”) to create a polyurethane foam material via the introduction of bubbles and a gas.
  • the present invention includes a polyurethane foam material that contains at least one polyurethane foam ingredient and the polymeric colorant described herein.
  • Polyurethane foam ingredients include, without limitation, one or more of the following: polyols, isocyanates, catalysts, silicones, antioxidants (such as phenols and hindered phenols), ultraviolent absorbing agents, blowing agents (such as carbon dioxide released from reaction of isocyanate with water), organic liquids, coloring agents (including dyes, pigments, polymeric colorants, and the like, and mixtures thereof), biocides, water, and the like.
  • Suitable polyols utilized within this invention include those comprising at least two alcohol moieties, preferably at least three.
  • the free hydroxyl groups react well with the isocyanates to form the urethane components which are then polymerized to form the desired polyurethanes.
  • Blowing agents present within the polymerization step provide the necessary foam-making capability.
  • Preferred polyols thus comprise between three and six alcohol moieties, comprising from between one and six carbon atoms per alcohol moiety.
  • a typical trifunctional polyol is utilized (such as 3022 polyol, available from Bayer).
  • Isocyanates such as diisocyanates
  • diisocyanates are well known components of such polyurethane foams and include any compounds which possess at least one free cyanate reactive group, and most preferably two, although more may be utilized. Such compounds are may also be aliphatic or aromatic in nature.
  • the most prominently utilized isocyanates are toluene diisocyanate and methylene diisocyanate. The polyol is generally reacted with a slight excess of isocyanate (ratio of from 1:1.04 to 1:1.12) to produce a soft foam product; the greater the ratio, the harder the foam thus produced).
  • the catalyst used for foam production encompasses any type that effectuates the polymerization of the isocyanate/polyol reactants noted above to form the desired polyurethane in foam form.
  • the term “tertiary amine-based hydroxy-containing catalyst” is intended to encompass any gelation/blowing catalyst utilized within polyurethane production which comprises at least one amine constituent. Amine-based catalysts, and more specifically, tertiary amine catalysts, are widely utilized within such specific foam-producing methods.
  • foam-making compositions may also be present within the foam-making composition.
  • Auxiliary blowing agents are required to provide the necessary foam blowing capability and reduce chances of combustion.
  • Such compounds include methylene chloride, acetone, carbon dioxide (which may be liberated during the reaction between water and isocyanate), and the like, and are present in amounts of between about 1.0 parts per hundred parts polyol (also referred to herein as “php”) and 10 php of the entire foam-making composition.
  • Water may thus also be added in relatively low amount (i.e., from about 3 to about 10 php; most preferably between about 3 and 7 php) to provide carbon dioxide for blowing purposes.
  • Silicones may be added to provide desired cell structure and foam stability and are present in an amount from about 0.1 to about 2 php of the entire foammaking composition; preferably from about 0.9 to about 1.6 php.
  • a polymeric colorant composition of the present invention may be comprised of at least one polymeric colorant containing at least one carboxymethyl capped alkyleneoxy chain as described herein and at least one solvent.
  • Solvents include, for example and without limitation, water, hydrocarbons (such as mineral oil), perchloroethylene, carbon tetrachloride, acetone, alcohol and the like.
  • solvents include C4-14 ethers and diethers, glycols, alkoxylated glycols, C 6 -Cie glycol ethers, alkoxylated aromatic alcohols, aromatic alcohols, aliphatic branched alcohols, alkoxylated aliphatic branched alcohols, alkoxylated linear C1-C5 alcohols, linear C1-C5 alcohols, amines, C S -C M alkyl and cycloalkyl hydrocarbons and halohydrocarbons, and mixtures thereof.
  • Additional solvents suitable for use in the present invention include those listed by the American Chemical Society, Division of Organic Chemistry, “Common Organic Solvents: Table of Properties,” which is located at https://www.organicdivision.org/orig/organic_solvents.html. Any combination of the aforementioned solvents may be utilized.
  • N-ethyl m-toluidine 5EO 50 g, 0.14 mol
  • the contents were heated to 70°C and finely ground KOH (11.1 g, 0.17 mol) was added, followed by the portion wise addition of sodium chloroacetate (19.7 g, 0.17 mol).
  • the reaction was heated at 70°C for 5 hours, whereby it was judged to be complete by TLC.
  • the pH was adjusted to 2.8 with concentrated HCI.
  • the N-ethyl m-toluidine 5EO carboxymethyl product was collected by phase separation.
  • the isolated leuco dye (4.6 g 0.0048 mol) was charged to a 100 mL 3-neck round bottom flask with temperature probe, condenser and overhead stirrer. Chloranil (2.4g, 0.01 mol) and 30 mL of methyl ethyl ketone were charged to the reactor. The contents were heated to 80°C for 1 hour, then cooled to room temperature. A mixture of concentrated HCI (2.5 g) and water (30 ml_) were added to the flask. The methyl ethyl ketone was evaporated, and the solids were filtered off. The aqueous filtrate containing the blue product was washed with dichloromethane to remove the residual oxidant and the aqueous layer was concentrated to dryness to obtain the product.

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Abstract

La présente invention concerne des colorants polymères qui ne tachent pas les vêtements, ni le plastique, ni le métal lorsqu'ils sont utilisés dans des produits de consommation, tels que des détergents à lessive, des assouplissants et des détergents à vaisselle. Les colorants polymères contiennent au moins une chaîne alkylèneoxy coiffée de carboxyméthyle pour améliorer les propriétés de déteinte et de tachage. On pense que l'incorporation d'une coiffe de carboxyméthyle sur l'extrémité de la chaîne alkylèneoxy de colorants polymères accroît l'hydrosolubilité, tout en ne diminuant pas le pouvoir colorant du colorant.
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Citations (128)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2220099A (en) 1934-01-10 1940-11-05 Gen Aniline & Flim Corp Sulphonic acids
US2477383A (en) 1946-12-26 1949-07-26 California Research Corp Sulfonated detergent and its method of preparation
US2598660A (en) 1948-12-16 1952-06-03 Gen Aniline & Film Corp Triphenylmethane dyes
US3157663A (en) 1962-11-20 1964-11-17 Ciba Geigy Corp 3-(amino-phenyl)-2-(pyridyl)-acrylonitriles
US3927044A (en) 1970-06-18 1975-12-16 Deering Milliken Res Corp Alkaline stable fugitive tints
US3929678A (en) 1974-08-01 1975-12-30 Procter & Gamble Detergent composition having enhanced particulate soil removal performance
US3986972A (en) 1975-10-24 1976-10-19 American Cyanamid Company Acyl nitrile compounds as peroxygen bleach activators
US4167510A (en) 1976-09-07 1979-09-11 Milliken Research Corporation Ester capped alkyleneoxy fugitive tints and method for producing same
US4217105A (en) 1977-03-28 1980-08-12 The Procter & Gamble Company Photoactivated bleach-compositions and processes
US4228042A (en) 1978-06-26 1980-10-14 The Procter & Gamble Company Biodegradable cationic surface-active agents containing ester or amide and polyalkoxy group
US4239660A (en) 1978-12-13 1980-12-16 The Procter & Gamble Company Detergent composition comprising a hydrolyzable cationic surfactant and specific alkalinity source
US4260529A (en) 1978-06-26 1981-04-07 The Procter & Gamble Company Detergent composition consisting essentially of biodegradable nonionic surfactant and cationic surfactant containing ester or amide
US4284729A (en) 1980-03-31 1981-08-18 Milliken Research Corporation Process for coloring thermosetting resins
US4400320A (en) 1981-07-13 1983-08-23 Milliken Research Corporation Alkyleneoxy fugitive tints containing a 2-amino, 6-methoxy benzathiazole group and process for preparing such fugitive tints
US4412934A (en) 1982-06-30 1983-11-01 The Procter & Gamble Company Bleaching compositions
US4430243A (en) 1981-08-08 1984-02-07 The Procter & Gamble Company Bleach catalyst compositions and use thereof in laundry bleaching and detergent compositions
US4483779A (en) 1982-04-26 1984-11-20 The Procter & Gamble Company Detergent compositions comprising polyglycoside and polyethoxylate surfactants and anionic fluorescer
US4483780A (en) 1982-04-26 1984-11-20 The Procter & Gamble Company Detergent compositions containing polyglycoside and polyethoxylate detergent surfactants
US4483781A (en) 1983-09-02 1984-11-20 The Procter & Gamble Company Magnesium salts of peroxycarboxylic acids
EP0133354A1 (fr) 1983-08-09 1985-02-20 Interox Chemicals Limited Composition de nettoyage pour prothèses dentaires
US4565647A (en) 1982-04-26 1986-01-21 The Procter & Gamble Company Foaming surfactant compositions
US4634551A (en) 1985-06-03 1987-01-06 Procter & Gamble Company Bleaching compounds and compositions comprising fatty peroxyacids salts thereof and precursors therefor having amide moieties in the fatty chain
US4728455A (en) 1986-03-07 1988-03-01 Lever Brothers Company Detergent bleach compositions, bleaching agents and bleach activators
US4810410A (en) 1986-12-13 1989-03-07 Interox Chemicals Limited Bleach activation
US4846846A (en) 1988-06-20 1989-07-11 Milliken Research Corporation Process for preparing polyurethane resins colored with anthraquinone colorants and products produced thereby
US4915854A (en) 1986-11-14 1990-04-10 The Procter & Gamble Company Ion-pair complex conditioning agent and compositions containing same
US4966723A (en) 1988-02-11 1990-10-30 Bp Chemicals Limited Bleach activators in detergent compositions
US5004558A (en) 1986-11-03 1991-04-02 Monsanto Company Sulfone peroxycarboxylic acids
WO1992006162A1 (fr) 1990-09-28 1992-04-16 The Procter & Gamble Company Detergent contenant des tensioactifs de sulfate d'alkyle et d'amide de l'acide gras de polyhydroxy
US5114606A (en) 1990-02-19 1992-05-19 Lever Brothers Company, Division Of Conopco, Inc. Bleaching composition comprising as a bleaching catalyst a complex of manganese with a non-carboxylate polyhydroxy ligand
US5114611A (en) 1989-04-13 1992-05-19 Lever Brothers Company, Divison Of Conopco, Inc. Bleach activation
US5130045A (en) 1987-10-30 1992-07-14 The Clorox Company Delayed onset active oxygen bleach composition
US5132431A (en) 1990-02-05 1992-07-21 Hoechst Aktiengesellschaft Process for the continuous preparation of imidoperoxycarboxylic acids
US5153161A (en) 1991-11-26 1992-10-06 Lever Brothers Company, Division Of Conopco, Inc. Synthesis of manganese oxidation catalyst
US5194416A (en) 1991-11-26 1993-03-16 Lever Brothers Company, Division Of Conopco, Inc. Manganese catalyst for activating hydrogen peroxide bleaching
EP0544440A2 (fr) 1991-11-20 1993-06-02 Unilever Plc Composition catalytique pour le blanchiment, fabrication et utilisation dans des compositions détergentes et/ou de blanchiment
EP0544490A1 (fr) 1991-11-26 1993-06-02 Unilever Plc Compositions détergentes de blanchiment
EP0549271A1 (fr) 1991-12-20 1993-06-30 Unilever Plc Activation de blanchiment
EP0549272A1 (fr) 1991-12-20 1993-06-30 Unilever Plc Activation de blanchiment
US5227084A (en) 1991-04-17 1993-07-13 Lever Brothers Company, Division Of Conopco, Inc. Concentrated detergent powder compositions
US5244594A (en) 1990-05-21 1993-09-14 Lever Brothers Company, Division Of Conopco, Inc. Bleach activation multinuclear manganese-based coordination complexes
US5246612A (en) 1991-08-23 1993-09-21 Lever Brothers Company, Division Of Conopco, Inc. Machine dishwashing composition containing peroxygen bleach, manganese complex and enzymes
US5246620A (en) 1990-04-21 1993-09-21 Hoechst Aktiengesellschaft Stable peroxycarboxylic acid granules
WO1993019038A1 (fr) 1992-03-26 1993-09-30 The Procter & Gamble Company Procede d'abaissement des niveaux de contaminants acides gras dans les tensioactifs a base d'amides d'acides gras polyhydroxy
WO1993019146A1 (fr) 1992-03-16 1993-09-30 The Procter & Gamble Company Compositions fluides renfermant des amides d'acides gras polyhydroxy
US5256779A (en) 1992-06-18 1993-10-26 Lever Brothers Company, Division Of Conopco, Inc. Synthesis of manganese oxidation catalyst
US5274147A (en) 1991-07-11 1993-12-28 Lever Brothers Company, Division Of Conopco, Inc. Process for preparing manganese complexes
US5280117A (en) 1992-09-09 1994-01-18 Lever Brothers Company, A Division Of Conopco, Inc. Process for the preparation of manganese bleach catalyst
US5279757A (en) 1990-04-06 1994-01-18 Hoechst Aktiengesellschaft Stable peroxycarboxylic acid granule comprising an imidoperoxycarboxylic acid or salt thereof
US5284944A (en) 1992-06-30 1994-02-08 Lever Brothers Company, Division Of Conopco, Inc. Improved synthesis of 1,4,7-triazacyclononane
WO1994009099A1 (fr) 1992-10-13 1994-04-28 The Procter & Gamble Company Compositions fluides contenant des amides d'acides gras polyhydroxy
US5310934A (en) 1992-02-21 1994-05-10 Ausimont S.P.A. Process for purifying phthalimidoperoxycaproic acid (PAP) in order to remove chlorinated solvent impurities from it
US5332528A (en) 1990-09-28 1994-07-26 The Procter & Gamble Company Polyhydroxy fatty acid amides in soil release agent-containing detergent compositions
US5346588A (en) 1989-10-30 1994-09-13 Lenzing Aktiengesellschaft Process for the chlorine-free bleaching of cellulosic materials with ozone
US5360569A (en) 1993-11-12 1994-11-01 Lever Brothers Company, Division Of Conopco, Inc. Activation of bleach precursors with catalytic imine quaternary salts
US5370826A (en) 1993-11-12 1994-12-06 Lever Brothers Company, Division Of Conopco, Inc. Quaternay oxaziridinium salts as bleaching compounds
WO1994028102A1 (fr) 1993-05-20 1994-12-08 The Procter & Gamble Company Composes de blanchiment comprenant du n-acyl caprolactame, utiles dans le lavage a la main ou dans d'autres systemes de nettoyage de textiles a faible teneur en eau
US5405412A (en) 1994-04-13 1995-04-11 The Procter & Gamble Company Bleaching compounds comprising N-acyl caprolactam and alkanoyloxybenzene sulfonate bleach activators
US5405413A (en) 1993-06-24 1995-04-11 The Procter & Gamble Co. Bleaching compounds comprising acyl valerolactam bleach activators
WO1995013353A1 (fr) 1993-11-12 1995-05-18 Unilever N.V. Activation de precurseurs d'agents de blanchiment a l'aide de sels quaternaires d'imine
WO1995013352A1 (fr) 1993-11-12 1995-05-18 Unilever N.V. Sels quaternaires d'imine utilises comme catalyseurs de blanchiment
US5460747A (en) 1994-08-31 1995-10-24 The Procter & Gamble Co. Multiple-substituted bleach activators
US5482515A (en) 1993-11-12 1996-01-09 Lever Brothers Company, Division Of Conopco, Inc. Imine quaternary salts as bleach catalysts
US5487818A (en) 1992-03-10 1996-01-30 Ausimont S.P.A. Process for separating phthalimido-peroxycaproic acid from solutions in organic solvents
US5520943A (en) 1993-10-27 1996-05-28 Nippon Tansan Co., Ltd. Method for modifying the quality of liquid foodstuff
US5523434A (en) 1995-03-15 1996-06-04 The Procter & Gamble Company Synthesis of bleach activators
US5574179A (en) 1993-03-01 1996-11-12 The Procter & Gamble Company Concentrated biodegradable quaternary ammonium fabric softener compositions and compouds containing intermediate iodine value unsaturated fatty acid chains
US5576282A (en) 1995-09-11 1996-11-19 The Procter & Gamble Company Color-safe bleach boosters, compositions and laundry methods employing same
US5578136A (en) 1994-08-31 1996-11-26 The Procter & Gamble Company Automatic dishwashing compositions comprising quaternary substituted bleach activators
US5584888A (en) 1994-08-31 1996-12-17 Miracle; Gregory S. Perhydrolysis-selective bleach activators
WO1996040197A1 (fr) * 1995-06-07 1996-12-19 La Jolla Pharmaceutical Company PEPTIDES A IMMUNOREACTION aPL, LEURS CONJUGUES, ET METHODES DE TRAITEMENT DES PATHOLOGIES INDUITES PAR LES ANTICORPS aPL
WO1996040661A1 (fr) 1995-06-07 1996-12-19 The Clorox Company Activateur de blanchiment a l'acetonitrile d'ammonium n-alkyle
US5595967A (en) 1995-02-03 1997-01-21 The Procter & Gamble Company Detergent compositions comprising multiperacid-forming bleach activators
US5597936A (en) 1995-06-16 1997-01-28 The Procter & Gamble Company Method for manufacturing cobalt catalysts
EP0790244A1 (fr) 1996-02-15 1997-08-20 Hoechst Aktiengesellschaft Activateurs de blanchiment à de nitriles d'ammonium
US5686014A (en) 1994-04-07 1997-11-11 The Procter & Gamble Company Bleach compositions comprising manganese-containing bleach catalysts
US5686015A (en) 1994-08-31 1997-11-11 The Procter & Gamble Company Quaternary substituted bleach activators
US5695679A (en) 1994-07-07 1997-12-09 The Procter & Gamble Company Detergent compositions containing an organic silver coating agent to minimize silver training in ADW washing methods
US5698504A (en) 1993-07-01 1997-12-16 The Procter & Gamble Company Machine dishwashing composition containing oxygen bleach and paraffin oil and benzotriazole compound silver tarnishing inhibitors
US5703030A (en) 1995-06-16 1997-12-30 The Procter & Gamble Company Bleach compositions comprising cobalt catalysts
US5718614A (en) 1995-08-28 1998-02-17 Electro-Matic Products Company Control apparatus for grinder
US5759990A (en) 1996-10-21 1998-06-02 The Procter & Gamble Company Concentrated fabric softening composition with good freeze/thaw recovery and highly unsaturated fabric softener compound therefor
WO1998035002A1 (fr) 1997-02-11 1998-08-13 The Procter & Gamble Company Compositions nettoyantes
WO1998035006A1 (fr) 1997-02-11 1998-08-13 The Procter & Gamble Company Composition nettoyante liquide
WO1998035003A1 (fr) 1997-02-11 1998-08-13 The Procter & Gamble Company Compose detergent
WO1998035005A1 (fr) 1997-02-11 1998-08-13 The Procter & Gamble Company Composition nettoyante
WO1998035004A1 (fr) 1997-02-11 1998-08-13 The Procter & Gamble Company Compositions detergentes solides
WO1999005241A1 (fr) 1997-07-21 1999-02-04 The Procter & Gamble Company Produits de nettoyage comportant des tensioactifs alkylarylsulfonate ameliores prepares a l'aide d'olefines de vinylidene et procedes de preparation desdits produits
WO1999005244A1 (fr) 1997-07-21 1999-02-04 The Procter & Gamble Company Tensio-actifs ameliores d'alkylarylsulfonate
WO1999005242A1 (fr) 1997-07-21 1999-02-04 The Procter & Gamble Company Tensio-actifs ameliores d'alkylbenzenesulfonate
WO1999005243A1 (fr) 1997-07-21 1999-02-04 The Procter & Gamble Company Compositions detergentes contenant des melanges de tensio-actifs a cristallinite disloquee
WO1999005082A1 (fr) 1997-07-21 1999-02-04 The Procter & Gamble Company Procedes ameliores de preparation de tensioactifs alkylbenzenesulfonate et produits contenant lesdits tensioactifs
WO1999005084A1 (fr) 1997-07-21 1999-02-04 The Procter & Gamble Company Procede de preparation de tensioactifs alkylbenzenesulfonate a partir d'alcools et produits contenant lesdits tensioactifs
WO1999007656A2 (fr) 1997-08-08 1999-02-18 The Procter & Gamble Company Procedes ameliores de fabrication de tensio-actifs selon une technique de separation par adsorption et produits ainsi obtenus
WO1999014296A1 (fr) 1997-09-16 1999-03-25 Clariant Gmbh Activateurs de blanchiment a base de nitrile d'ammonium sous forme de granules enrobes
WO1999014302A1 (fr) 1997-09-16 1999-03-25 Clariant Gmbh Activateurs de blanchiment sous forme de granules
US5916481A (en) 1995-07-25 1999-06-29 The Procter & Gamble Company Low hue photobleaches
US5998350A (en) 1993-05-20 1999-12-07 The Procter & Gamble Company Bleaching compounds comprising N-acyl caprolactam and/or peroxy acid activators
US6004922A (en) 1996-05-03 1999-12-21 The Procter & Gamble Company Laundry detergent compositions comprising cationic surfactants and modified polyamine soil dispersents
US6008181A (en) 1996-04-16 1999-12-28 The Procter & Gamble Company Mid-Chain branched Alkoxylated Sulfate Surfactants
US6020303A (en) 1996-04-16 2000-02-01 The Procter & Gamble Company Mid-chain branched surfactants
US6022844A (en) 1996-03-05 2000-02-08 The Procter & Gamble Company Cationic detergent compounds
WO2000023548A1 (fr) 1998-10-20 2000-04-27 The Procter & Gamble Company Detergents a lessive comprenant des alcoylbenzenesulfonates modifies
WO2000023549A1 (fr) 1998-10-20 2000-04-27 The Procter & Gamble Company Detergents a lessive comprenant des alcoylbenzenesulfonates modifies
US6060443A (en) 1996-04-16 2000-05-09 The Procter & Gamble Company Mid-chain branched alkyl sulfate surfactants
WO2000032601A2 (fr) 1998-11-30 2000-06-08 The Procter & Gamble Company Procede de preparation de tetraaza macrocycles pontes transversalement
US6093856A (en) 1996-11-26 2000-07-25 The Procter & Gamble Company Polyoxyalkylene surfactants
WO2000047708A1 (fr) 1999-02-10 2000-08-17 The Procter & Gamble Company Solides particulaires faible densite utilises dans les detergents pour lessive
US6136769A (en) 1996-05-17 2000-10-24 The Procter & Gamble Company Alkoxylated cationic detergency ingredients
US6140294A (en) 1998-11-10 2000-10-31 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Bleach and oxidation catalyst
US6150322A (en) 1998-08-12 2000-11-21 Shell Oil Company Highly branched primary alcohol compositions and biodegradable detergents made therefrom
US6221825B1 (en) 1996-12-31 2001-04-24 The Procter & Gamble Company Thickened, highly aqueous liquid detergent compositions
US6225464B1 (en) 1997-03-07 2001-05-01 The Procter & Gamble Company Methods of making cross-bridged macropolycycles
WO2001042408A2 (fr) 1999-12-08 2001-06-14 The Procter & Gamble Company Tensioactifs a base d'alcools poly(oxyalkyles) coiffes par un ether
US6287580B1 (en) 1999-08-13 2001-09-11 Unilever Home & Personal Care Usa, A Division Of Conopco, Inc. Cosmetic compositions with self-warming component
US6302921B1 (en) 1999-09-01 2001-10-16 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Method of bleaching stained fabrics
US6306812B1 (en) 1997-03-07 2001-10-23 Procter & Gamble Company, The Bleach compositions containing metal bleach catalyst, and bleach activators and/or organic percarboxylic acids
US6326348B1 (en) 1996-04-16 2001-12-04 The Procter & Gamble Co. Detergent compositions containing selected mid-chain branched surfactants
US6456498B1 (en) 2001-08-07 2002-09-24 Hewlett-Packard Co. CompactPCI-based computer system with mid-plane connector for equivalent front and back loading
US6482994B2 (en) 1997-08-02 2002-11-19 The Procter & Gamble Company Ether-capped poly(oxyalkylated) alcohol surfactants
US6494920B1 (en) 1999-02-04 2002-12-17 Cognis Deutschland Gmbh & Co. Kg Detergent mixtures
US20040204337A1 (en) 2003-03-25 2004-10-14 The Procter & Gamble Company Fabric care compositions comprising cationic starch
US20040229769A1 (en) 2000-12-27 2004-11-18 Colgate-Palmolive Company Thickened fabric conditioners
US20060177943A1 (en) * 2002-07-30 2006-08-10 Reverse Proteomics Research Institute Co., Ltd. Method of inhibiting nonspecific interaction between molecules on solid phase support
EP1950254A2 (fr) * 2007-01-12 2008-07-30 FUJIFILM Corporation Procédé de production de dispersion de particule fine de pigment organique, et particules fines de pigment organique, et dispersion de fine particule de pigment organique obtenue par ce procédé
US7632682B2 (en) 2004-12-08 2009-12-15 Milliken & Company Anthraquinone colorant compositions and methods for producing the same
US8735533B2 (en) 2009-11-24 2014-05-27 Milliken & Company Polymeric violet anthraquinone colorant compositions and methods for producing the same
CN104277818A (zh) * 2013-07-09 2015-01-14 中国石油化工股份有限公司 压裂液降阻剂及其应用

Patent Citations (148)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2220099A (en) 1934-01-10 1940-11-05 Gen Aniline & Flim Corp Sulphonic acids
US2477383A (en) 1946-12-26 1949-07-26 California Research Corp Sulfonated detergent and its method of preparation
US2598660A (en) 1948-12-16 1952-06-03 Gen Aniline & Film Corp Triphenylmethane dyes
US3157663A (en) 1962-11-20 1964-11-17 Ciba Geigy Corp 3-(amino-phenyl)-2-(pyridyl)-acrylonitriles
US3927044A (en) 1970-06-18 1975-12-16 Deering Milliken Res Corp Alkaline stable fugitive tints
US3929678A (en) 1974-08-01 1975-12-30 Procter & Gamble Detergent composition having enhanced particulate soil removal performance
US3986972A (en) 1975-10-24 1976-10-19 American Cyanamid Company Acyl nitrile compounds as peroxygen bleach activators
US4167510A (en) 1976-09-07 1979-09-11 Milliken Research Corporation Ester capped alkyleneoxy fugitive tints and method for producing same
US4217105A (en) 1977-03-28 1980-08-12 The Procter & Gamble Company Photoactivated bleach-compositions and processes
US4260529A (en) 1978-06-26 1981-04-07 The Procter & Gamble Company Detergent composition consisting essentially of biodegradable nonionic surfactant and cationic surfactant containing ester or amide
US4228042A (en) 1978-06-26 1980-10-14 The Procter & Gamble Company Biodegradable cationic surface-active agents containing ester or amide and polyalkoxy group
US4239660A (en) 1978-12-13 1980-12-16 The Procter & Gamble Company Detergent composition comprising a hydrolyzable cationic surfactant and specific alkalinity source
US4284729A (en) 1980-03-31 1981-08-18 Milliken Research Corporation Process for coloring thermosetting resins
US4400320A (en) 1981-07-13 1983-08-23 Milliken Research Corporation Alkyleneoxy fugitive tints containing a 2-amino, 6-methoxy benzathiazole group and process for preparing such fugitive tints
US4430243A (en) 1981-08-08 1984-02-07 The Procter & Gamble Company Bleach catalyst compositions and use thereof in laundry bleaching and detergent compositions
US4483779A (en) 1982-04-26 1984-11-20 The Procter & Gamble Company Detergent compositions comprising polyglycoside and polyethoxylate surfactants and anionic fluorescer
US4483780A (en) 1982-04-26 1984-11-20 The Procter & Gamble Company Detergent compositions containing polyglycoside and polyethoxylate detergent surfactants
US4565647A (en) 1982-04-26 1986-01-21 The Procter & Gamble Company Foaming surfactant compositions
US4565647B1 (en) 1982-04-26 1994-04-05 Procter & Gamble Foaming surfactant compositions
US4412934A (en) 1982-06-30 1983-11-01 The Procter & Gamble Company Bleaching compositions
EP0133354A1 (fr) 1983-08-09 1985-02-20 Interox Chemicals Limited Composition de nettoyage pour prothèses dentaires
US4483781A (en) 1983-09-02 1984-11-20 The Procter & Gamble Company Magnesium salts of peroxycarboxylic acids
US4634551A (en) 1985-06-03 1987-01-06 Procter & Gamble Company Bleaching compounds and compositions comprising fatty peroxyacids salts thereof and precursors therefor having amide moieties in the fatty chain
US4728455A (en) 1986-03-07 1988-03-01 Lever Brothers Company Detergent bleach compositions, bleaching agents and bleach activators
US5004558A (en) 1986-11-03 1991-04-02 Monsanto Company Sulfone peroxycarboxylic acids
US4915854A (en) 1986-11-14 1990-04-10 The Procter & Gamble Company Ion-pair complex conditioning agent and compositions containing same
US4810410A (en) 1986-12-13 1989-03-07 Interox Chemicals Limited Bleach activation
US5130045A (en) 1987-10-30 1992-07-14 The Clorox Company Delayed onset active oxygen bleach composition
US4966723A (en) 1988-02-11 1990-10-30 Bp Chemicals Limited Bleach activators in detergent compositions
US4846846A (en) 1988-06-20 1989-07-11 Milliken Research Corporation Process for preparing polyurethane resins colored with anthraquinone colorants and products produced thereby
US5114611A (en) 1989-04-13 1992-05-19 Lever Brothers Company, Divison Of Conopco, Inc. Bleach activation
US5346588A (en) 1989-10-30 1994-09-13 Lenzing Aktiengesellschaft Process for the chlorine-free bleaching of cellulosic materials with ozone
US5132431A (en) 1990-02-05 1992-07-21 Hoechst Aktiengesellschaft Process for the continuous preparation of imidoperoxycarboxylic acids
US5114606A (en) 1990-02-19 1992-05-19 Lever Brothers Company, Division Of Conopco, Inc. Bleaching composition comprising as a bleaching catalyst a complex of manganese with a non-carboxylate polyhydroxy ligand
US5279757A (en) 1990-04-06 1994-01-18 Hoechst Aktiengesellschaft Stable peroxycarboxylic acid granule comprising an imidoperoxycarboxylic acid or salt thereof
US5246620A (en) 1990-04-21 1993-09-21 Hoechst Aktiengesellschaft Stable peroxycarboxylic acid granules
US5246621A (en) 1990-05-21 1993-09-21 Lever Brothers Company, Division Of Conopco, Inc. Bleach activation by manganese-based coordination complexes
US5244594A (en) 1990-05-21 1993-09-14 Lever Brothers Company, Division Of Conopco, Inc. Bleach activation multinuclear manganese-based coordination complexes
US5332528A (en) 1990-09-28 1994-07-26 The Procter & Gamble Company Polyhydroxy fatty acid amides in soil release agent-containing detergent compositions
WO1992006162A1 (fr) 1990-09-28 1992-04-16 The Procter & Gamble Company Detergent contenant des tensioactifs de sulfate d'alkyle et d'amide de l'acide gras de polyhydroxy
US5227084A (en) 1991-04-17 1993-07-13 Lever Brothers Company, Division Of Conopco, Inc. Concentrated detergent powder compositions
US5274147A (en) 1991-07-11 1993-12-28 Lever Brothers Company, Division Of Conopco, Inc. Process for preparing manganese complexes
US5246612A (en) 1991-08-23 1993-09-21 Lever Brothers Company, Division Of Conopco, Inc. Machine dishwashing composition containing peroxygen bleach, manganese complex and enzymes
EP0544440A2 (fr) 1991-11-20 1993-06-02 Unilever Plc Composition catalytique pour le blanchiment, fabrication et utilisation dans des compositions détergentes et/ou de blanchiment
EP0544490A1 (fr) 1991-11-26 1993-06-02 Unilever Plc Compositions détergentes de blanchiment
US5194416A (en) 1991-11-26 1993-03-16 Lever Brothers Company, Division Of Conopco, Inc. Manganese catalyst for activating hydrogen peroxide bleaching
US5153161A (en) 1991-11-26 1992-10-06 Lever Brothers Company, Division Of Conopco, Inc. Synthesis of manganese oxidation catalyst
EP0549271A1 (fr) 1991-12-20 1993-06-30 Unilever Plc Activation de blanchiment
EP0549272A1 (fr) 1991-12-20 1993-06-30 Unilever Plc Activation de blanchiment
US5310934A (en) 1992-02-21 1994-05-10 Ausimont S.P.A. Process for purifying phthalimidoperoxycaproic acid (PAP) in order to remove chlorinated solvent impurities from it
US5487818A (en) 1992-03-10 1996-01-30 Ausimont S.P.A. Process for separating phthalimido-peroxycaproic acid from solutions in organic solvents
WO1993019146A1 (fr) 1992-03-16 1993-09-30 The Procter & Gamble Company Compositions fluides renfermant des amides d'acides gras polyhydroxy
WO1993019038A1 (fr) 1992-03-26 1993-09-30 The Procter & Gamble Company Procede d'abaissement des niveaux de contaminants acides gras dans les tensioactifs a base d'amides d'acides gras polyhydroxy
US5256779A (en) 1992-06-18 1993-10-26 Lever Brothers Company, Division Of Conopco, Inc. Synthesis of manganese oxidation catalyst
US5284944A (en) 1992-06-30 1994-02-08 Lever Brothers Company, Division Of Conopco, Inc. Improved synthesis of 1,4,7-triazacyclononane
US5280117A (en) 1992-09-09 1994-01-18 Lever Brothers Company, A Division Of Conopco, Inc. Process for the preparation of manganese bleach catalyst
WO1994009099A1 (fr) 1992-10-13 1994-04-28 The Procter & Gamble Company Compositions fluides contenant des amides d'acides gras polyhydroxy
US5574179A (en) 1993-03-01 1996-11-12 The Procter & Gamble Company Concentrated biodegradable quaternary ammonium fabric softener compositions and compouds containing intermediate iodine value unsaturated fatty acid chains
US5998350A (en) 1993-05-20 1999-12-07 The Procter & Gamble Company Bleaching compounds comprising N-acyl caprolactam and/or peroxy acid activators
US5686401A (en) 1993-05-20 1997-11-11 The Procter & Gamble Company Bleaching compounds comprising N-acyl caprolactam for use in hand-wash or other low-water cleaning systems
WO1994028102A1 (fr) 1993-05-20 1994-12-08 The Procter & Gamble Company Composes de blanchiment comprenant du n-acyl caprolactame, utiles dans le lavage a la main ou dans d'autres systemes de nettoyage de textiles a faible teneur en eau
US5503639A (en) 1993-06-24 1996-04-02 The Procter & Gamble Company Bleaching compounds comprising acyl valerolactam bleach activators
US5405413A (en) 1993-06-24 1995-04-11 The Procter & Gamble Co. Bleaching compounds comprising acyl valerolactam bleach activators
US5698504A (en) 1993-07-01 1997-12-16 The Procter & Gamble Company Machine dishwashing composition containing oxygen bleach and paraffin oil and benzotriazole compound silver tarnishing inhibitors
US5520943A (en) 1993-10-27 1996-05-28 Nippon Tansan Co., Ltd. Method for modifying the quality of liquid foodstuff
US5482515A (en) 1993-11-12 1996-01-09 Lever Brothers Company, Division Of Conopco, Inc. Imine quaternary salts as bleach catalysts
US5478357A (en) 1993-11-12 1995-12-26 Lever Brothers Company, Division Of Conopco, Inc. Activation of bleach precursors with imine quaternary salts
US5442066A (en) 1993-11-12 1995-08-15 Lever Brothers Company, Division Of Conopco, Inc. Quaternary oxaziridinium salts as bleaching compounds
WO1995013352A1 (fr) 1993-11-12 1995-05-18 Unilever N.V. Sels quaternaires d'imine utilises comme catalyseurs de blanchiment
WO1995013351A1 (fr) 1993-11-12 1995-05-18 Unilever N.V. Sels d'oxaziridinium quarternaire utilises comme composes de blanchiment
WO1995013353A1 (fr) 1993-11-12 1995-05-18 Unilever N.V. Activation de precurseurs d'agents de blanchiment a l'aide de sels quaternaires d'imine
US5550256A (en) 1993-11-12 1996-08-27 Lever Brothers Company, Division Of Conopco, Inc. Imine quaternary salts as bleach catalysts
US5370826A (en) 1993-11-12 1994-12-06 Lever Brothers Company, Division Of Conopco, Inc. Quaternay oxaziridinium salts as bleaching compounds
US5360569A (en) 1993-11-12 1994-11-01 Lever Brothers Company, Division Of Conopco, Inc. Activation of bleach precursors with catalytic imine quaternary salts
US5686014A (en) 1994-04-07 1997-11-11 The Procter & Gamble Company Bleach compositions comprising manganese-containing bleach catalysts
US5405412A (en) 1994-04-13 1995-04-11 The Procter & Gamble Company Bleaching compounds comprising N-acyl caprolactam and alkanoyloxybenzene sulfonate bleach activators
US5695679A (en) 1994-07-07 1997-12-09 The Procter & Gamble Company Detergent compositions containing an organic silver coating agent to minimize silver training in ADW washing methods
US5578136A (en) 1994-08-31 1996-11-26 The Procter & Gamble Company Automatic dishwashing compositions comprising quaternary substituted bleach activators
US5686015A (en) 1994-08-31 1997-11-11 The Procter & Gamble Company Quaternary substituted bleach activators
US5460747A (en) 1994-08-31 1995-10-24 The Procter & Gamble Co. Multiple-substituted bleach activators
US5654421A (en) 1994-08-31 1997-08-05 The Procter & Gamble Company Automatic dishwashing compositions comprising quaternary substituted bleach activators
US5584888A (en) 1994-08-31 1996-12-17 Miracle; Gregory S. Perhydrolysis-selective bleach activators
US5595967A (en) 1995-02-03 1997-01-21 The Procter & Gamble Company Detergent compositions comprising multiperacid-forming bleach activators
US5523434A (en) 1995-03-15 1996-06-04 The Procter & Gamble Company Synthesis of bleach activators
US5741437A (en) 1995-06-07 1998-04-21 The Clorox Company N-alkyl ammonium acetonitrile bleach activators
US6017464A (en) 1995-06-07 2000-01-25 The Clorox Company Dimeric N-alkyl ammonium acetonitrile bleach activators
US5958289A (en) 1995-06-07 1999-09-28 The Clorox Company N-alkyl ammonium acetonitrile bleach activators
US5877315A (en) 1995-06-07 1999-03-02 The Clorox Company Dimeric N-Alkyl ammonium acetonitrile bleach activators
EP0775127A1 (fr) 1995-06-07 1997-05-28 The Clorox Company Activateur de blanchiment a l'acetonitrile d'ammonium n-alkyle
WO1996040197A1 (fr) * 1995-06-07 1996-12-19 La Jolla Pharmaceutical Company PEPTIDES A IMMUNOREACTION aPL, LEURS CONJUGUES, ET METHODES DE TRAITEMENT DES PATHOLOGIES INDUITES PAR LES ANTICORPS aPL
WO1996040661A1 (fr) 1995-06-07 1996-12-19 The Clorox Company Activateur de blanchiment a l'acetonitrile d'ammonium n-alkyle
US5739327A (en) 1995-06-07 1998-04-14 The Clorox Company N-alkyl ammonium acetonitrile bleach activators
US5597936A (en) 1995-06-16 1997-01-28 The Procter & Gamble Company Method for manufacturing cobalt catalysts
US5703030A (en) 1995-06-16 1997-12-30 The Procter & Gamble Company Bleach compositions comprising cobalt catalysts
US5916481A (en) 1995-07-25 1999-06-29 The Procter & Gamble Company Low hue photobleaches
US5718614A (en) 1995-08-28 1998-02-17 Electro-Matic Products Company Control apparatus for grinder
US5576282A (en) 1995-09-11 1996-11-19 The Procter & Gamble Company Color-safe bleach boosters, compositions and laundry methods employing same
EP0790244A1 (fr) 1996-02-15 1997-08-20 Hoechst Aktiengesellschaft Activateurs de blanchiment à de nitriles d'ammonium
US6022844A (en) 1996-03-05 2000-02-08 The Procter & Gamble Company Cationic detergent compounds
US6008181A (en) 1996-04-16 1999-12-28 The Procter & Gamble Company Mid-Chain branched Alkoxylated Sulfate Surfactants
US6060443A (en) 1996-04-16 2000-05-09 The Procter & Gamble Company Mid-chain branched alkyl sulfate surfactants
US6020303A (en) 1996-04-16 2000-02-01 The Procter & Gamble Company Mid-chain branched surfactants
US6326348B1 (en) 1996-04-16 2001-12-04 The Procter & Gamble Co. Detergent compositions containing selected mid-chain branched surfactants
US6004922A (en) 1996-05-03 1999-12-21 The Procter & Gamble Company Laundry detergent compositions comprising cationic surfactants and modified polyamine soil dispersents
US6136769A (en) 1996-05-17 2000-10-24 The Procter & Gamble Company Alkoxylated cationic detergency ingredients
US5759990A (en) 1996-10-21 1998-06-02 The Procter & Gamble Company Concentrated fabric softening composition with good freeze/thaw recovery and highly unsaturated fabric softener compound therefor
US6093856A (en) 1996-11-26 2000-07-25 The Procter & Gamble Company Polyoxyalkylene surfactants
US6153577A (en) 1996-11-26 2000-11-28 The Procter & Gamble Company Polyoxyalkylene surfactants
US6221825B1 (en) 1996-12-31 2001-04-24 The Procter & Gamble Company Thickened, highly aqueous liquid detergent compositions
WO1998035006A1 (fr) 1997-02-11 1998-08-13 The Procter & Gamble Company Composition nettoyante liquide
WO1998035004A1 (fr) 1997-02-11 1998-08-13 The Procter & Gamble Company Compositions detergentes solides
WO1998035002A1 (fr) 1997-02-11 1998-08-13 The Procter & Gamble Company Compositions nettoyantes
WO1998035003A1 (fr) 1997-02-11 1998-08-13 The Procter & Gamble Company Compose detergent
WO1998035005A1 (fr) 1997-02-11 1998-08-13 The Procter & Gamble Company Composition nettoyante
US6306812B1 (en) 1997-03-07 2001-10-23 Procter & Gamble Company, The Bleach compositions containing metal bleach catalyst, and bleach activators and/or organic percarboxylic acids
US6225464B1 (en) 1997-03-07 2001-05-01 The Procter & Gamble Company Methods of making cross-bridged macropolycycles
WO1999005244A1 (fr) 1997-07-21 1999-02-04 The Procter & Gamble Company Tensio-actifs ameliores d'alkylarylsulfonate
WO1999005082A1 (fr) 1997-07-21 1999-02-04 The Procter & Gamble Company Procedes ameliores de preparation de tensioactifs alkylbenzenesulfonate et produits contenant lesdits tensioactifs
WO1999005084A1 (fr) 1997-07-21 1999-02-04 The Procter & Gamble Company Procede de preparation de tensioactifs alkylbenzenesulfonate a partir d'alcools et produits contenant lesdits tensioactifs
WO1999005243A1 (fr) 1997-07-21 1999-02-04 The Procter & Gamble Company Compositions detergentes contenant des melanges de tensio-actifs a cristallinite disloquee
WO1999005242A1 (fr) 1997-07-21 1999-02-04 The Procter & Gamble Company Tensio-actifs ameliores d'alkylbenzenesulfonate
WO1999005241A1 (fr) 1997-07-21 1999-02-04 The Procter & Gamble Company Produits de nettoyage comportant des tensioactifs alkylarylsulfonate ameliores prepares a l'aide d'olefines de vinylidene et procedes de preparation desdits produits
US6482994B2 (en) 1997-08-02 2002-11-19 The Procter & Gamble Company Ether-capped poly(oxyalkylated) alcohol surfactants
WO1999007656A2 (fr) 1997-08-08 1999-02-18 The Procter & Gamble Company Procedes ameliores de fabrication de tensio-actifs selon une technique de separation par adsorption et produits ainsi obtenus
EP1017773A1 (fr) 1997-09-16 2000-07-12 Clariant GmbH Activateurs de blanchiment a base de nitrile d'ammonium sous forme de granules enrobes
WO1999014296A1 (fr) 1997-09-16 1999-03-25 Clariant Gmbh Activateurs de blanchiment a base de nitrile d'ammonium sous forme de granules enrobes
EP1017776A1 (fr) 1997-09-16 2000-07-12 Clariant GmbH Activateurs de blanchiment sous forme de granules
US6133216A (en) 1997-09-16 2000-10-17 Clariant Gmbh Coated ammonium nitrile bleach activator granules
US6063750A (en) 1997-09-16 2000-05-16 Clariant Gmbh Bleach activator granules
WO1999014302A1 (fr) 1997-09-16 1999-03-25 Clariant Gmbh Activateurs de blanchiment sous forme de granules
US6150322A (en) 1998-08-12 2000-11-21 Shell Oil Company Highly branched primary alcohol compositions and biodegradable detergents made therefrom
WO2000023548A1 (fr) 1998-10-20 2000-04-27 The Procter & Gamble Company Detergents a lessive comprenant des alcoylbenzenesulfonates modifies
WO2000023549A1 (fr) 1998-10-20 2000-04-27 The Procter & Gamble Company Detergents a lessive comprenant des alcoylbenzenesulfonates modifies
US6140294A (en) 1998-11-10 2000-10-31 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Bleach and oxidation catalyst
WO2000032601A2 (fr) 1998-11-30 2000-06-08 The Procter & Gamble Company Procede de preparation de tetraaza macrocycles pontes transversalement
US6494920B1 (en) 1999-02-04 2002-12-17 Cognis Deutschland Gmbh & Co. Kg Detergent mixtures
WO2000047708A1 (fr) 1999-02-10 2000-08-17 The Procter & Gamble Company Solides particulaires faible densite utilises dans les detergents pour lessive
US6287580B1 (en) 1999-08-13 2001-09-11 Unilever Home & Personal Care Usa, A Division Of Conopco, Inc. Cosmetic compositions with self-warming component
US6302921B1 (en) 1999-09-01 2001-10-16 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Method of bleaching stained fabrics
WO2001042408A2 (fr) 1999-12-08 2001-06-14 The Procter & Gamble Company Tensioactifs a base d'alcools poly(oxyalkyles) coiffes par un ether
US20040229769A1 (en) 2000-12-27 2004-11-18 Colgate-Palmolive Company Thickened fabric conditioners
US6456498B1 (en) 2001-08-07 2002-09-24 Hewlett-Packard Co. CompactPCI-based computer system with mid-plane connector for equivalent front and back loading
US20060177943A1 (en) * 2002-07-30 2006-08-10 Reverse Proteomics Research Institute Co., Ltd. Method of inhibiting nonspecific interaction between molecules on solid phase support
US20040204337A1 (en) 2003-03-25 2004-10-14 The Procter & Gamble Company Fabric care compositions comprising cationic starch
US7632682B2 (en) 2004-12-08 2009-12-15 Milliken & Company Anthraquinone colorant compositions and methods for producing the same
EP1950254A2 (fr) * 2007-01-12 2008-07-30 FUJIFILM Corporation Procédé de production de dispersion de particule fine de pigment organique, et particules fines de pigment organique, et dispersion de fine particule de pigment organique obtenue par ce procédé
US8735533B2 (en) 2009-11-24 2014-05-27 Milliken & Company Polymeric violet anthraquinone colorant compositions and methods for producing the same
CN104277818A (zh) * 2013-07-09 2015-01-14 中国石油化工股份有限公司 压裂液降阻剂及其应用

Non-Patent Citations (13)

* Cited by examiner, † Cited by third party
Title
"Division of Organic Chemistry", AMERICAN CHEMICAL SOCIETY, article "Common Organic Solvents: Table of Properties"
BENJAMIN T. HOUSEMAN ET AL: "Efficient Solid-Phase Synthesis of Peptide-Substituted Alkanethiols for the Preparation of Substrates That Support the Adhesion of Cells", THE JOURNAL OF ORGANIC CHEMISTRY, vol. 63, no. 21, 1 October 1998 (1998-10-01), pages 7552 - 7555, XP055154242, ISSN: 0022-3263, DOI: 10.1021/jo981113s *
BLOND PASCALE ET AL: "Ready-to-Use Germanium Surfaces for the Development of FTIR-Based Biosensors for Proteins", LANGMUIR, vol. 36, no. 40, 13 October 2020 (2020-10-13), US, pages 12068 - 12076, XP055866389, ISSN: 0743-7463, Retrieved from the Internet <URL:https://pubs.acs.org/doi/pdf/10.1021/acs.langmuir.0c02681> DOI: 10.1021/acs.langmuir.0c02681 *
INORA. CHEM., vol. 18, 1979, pages 2023 - 2025
INORA. CHEM., vol. 21, 1982, pages 2881 - 2885
INORG. SYNTHESIS, 1960, pages 173 - 176
J. CHEM. ED., vol. 66, no. 12, 1989, pages 1043 - 45
JOURNAL OF PHYSICAL CHEMISTRY, vol. 56, 1952, pages 22 - 25
KAUFMANN GUNNAR F. ET AL: "Enzymatic Incorporation of an Antibody-Activated Blue Fluorophore into DNA", ANGEWANDTE CHEMIE INTERNATIONAL EDITION, vol. 44, no. 14, 29 March 2005 (2005-03-29), pages 2144 - 2148, XP055866114, ISSN: 1433-7851, DOI: 10.1002/anie.200461143 *
KIRK OTHMER'S: "Encyclopedia of Chemical Technology", vol. 17, 1982, JOHN WILEY AND SONS, article "Bleaching Agents (Survey", pages: 271 - 300
M. L. TOBE: "Base Hydrolysis of Transition-Metal Complexes", ADV. INORG. BIOINORG. MECH., vol. 2, 1983, pages 1 - 94, XP000616123
NALLURI SIVA KRISHNA MOHAN ET AL: "Light-Responsive Capture and Release of DNA in a Ternary Supramolecular Complex", ANGEWANDTE CHEMIE INTERNATIONAL EDITION, vol. 50, no. 41, 5 September 2011 (2011-09-05), pages 9747 - 9751, XP055866095, ISSN: 1433-7851, DOI: 10.1002/anie.201103707 *
W.L. JOLLY: "The Synthesis and Characterization of Inorganic Compounds", 1970, PRENTICE-HALL, pages: 461 - 3

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