US20120101018A1 - Bis-azo colorants for use as bluing agents - Google Patents

Bis-azo colorants for use as bluing agents Download PDF

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Publication number
US20120101018A1
US20120101018A1 US12/910,258 US91025810A US2012101018A1 US 20120101018 A1 US20120101018 A1 US 20120101018A1 US 91025810 A US91025810 A US 91025810A US 2012101018 A1 US2012101018 A1 US 2012101018A1
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United States
Prior art keywords
alkyl
bluing agent
laundry care
substituted
care composition
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Abandoned
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US12/910,258
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English (en)
Inventor
Gregory Scot Miracle
Robert L. Mahaffey
Xiaoyong Michael Hong
Eduardo Torres
Dominick J. Valenti
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Procter and Gamble Co
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Procter and Gamble Co
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Publication date
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Priority to US12/910,258 priority Critical patent/US20120101018A1/en
Assigned to THE PROCTER & GAMBLE COMPANY reassignment THE PROCTER & GAMBLE COMPANY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: TORRES, EDUARDO (NMN), VALENTI, DOMINICK J., HONG, XIAOYONG MICHAEL, MAHAFFEY, ROBERT L., MIRACLE, GREGORY SCOT
Priority to ARP110103893A priority patent/AR083503A1/es
Priority to CA2815479A priority patent/CA2815479C/en
Priority to EP11781907.8A priority patent/EP2630228A1/en
Priority to MX2013004460A priority patent/MX357342B/es
Priority to BR112013009794A priority patent/BR112013009794A2/pt
Priority to BR112013009798A priority patent/BR112013009798A2/pt
Priority to PL11785825T priority patent/PL2630229T3/pl
Priority to ES11785825T priority patent/ES2699751T3/es
Priority to EP11779294.5A priority patent/EP2630227B1/en
Priority to BR112013009793A priority patent/BR112013009793A2/pt
Priority to MX2013004462A priority patent/MX357338B/es
Priority to PCT/US2011/057262 priority patent/WO2012054820A1/en
Priority to BR112013009791-4A priority patent/BR112013009791B1/pt
Priority to PCT/US2011/057270 priority patent/WO2012054823A1/en
Priority to JP2013535118A priority patent/JP5833130B2/ja
Priority to BR112013009792A priority patent/BR112013009792A2/pt
Priority to CN201610101320.5A priority patent/CN105695160B/zh
Priority to MX2013004463A priority patent/MX357388B/es
Priority to MX2013004459A priority patent/MX357341B/es
Priority to PCT/US2011/057279 priority patent/WO2012054827A1/en
Priority to MX2013004461A priority patent/MX357340B/es
Priority to CN201180050981.5A priority patent/CN103180424B/zh
Priority to PCT/US2011/057264 priority patent/WO2012054821A1/en
Priority to EP11785825.8A priority patent/EP2630229B1/en
Priority to CN201180050982XA priority patent/CN103201370A/zh
Priority to CN201180051018.9A priority patent/CN103168097B/zh
Priority to EP11778758.0A priority patent/EP2630226A1/en
Priority to EP11778757.2A priority patent/EP2630225A1/en
Priority to CN201180050993.8A priority patent/CN103180425B/zh
Priority to PCT/US2011/057290 priority patent/WO2012054835A1/en
Priority to CN201180050989.1A priority patent/CN103339245B/zh
Priority to US13/313,283 priority patent/US9701930B2/en
Priority to US13/313,256 priority patent/US10876079B2/en
Priority to US13/313,395 priority patent/US9499775B2/en
Priority to US13/313,310 priority patent/US9708572B2/en
Priority to US13/313,340 priority patent/US9708573B2/en
Publication of US20120101018A1 publication Critical patent/US20120101018A1/en
Priority to ZA2013/02890A priority patent/ZA201302890B/en
Priority to JP2014249304A priority patent/JP6049679B2/ja
Priority to US14/747,099 priority patent/US20150291918A1/en
Abandoned legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/40—Dyes ; Pigments
    • C11D3/42—Brightening agents ; Blueing agents
    • 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
    • C09B31/00—Disazo and polyazo dyes of the type A->B->C, A->B->C->D, or the like, prepared by diazotising and coupling
    • C09B31/02—Disazo dyes
    • C09B31/06—Disazo dyes from a coupling component "C" containing a directive hydroxyl group
    • C09B31/068—Naphthols
    • C09B31/072—Naphthols containing acid groups, e.g. —CO2H, —SO3H, —PO3H2, —OSO3H, —OPO2H2; Salts thereof
    • 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
    • C09B31/00—Disazo and polyazo dyes of the type A->B->C, A->B->C->D, or the like, prepared by diazotising and coupling
    • C09B31/02—Disazo dyes
    • C09B31/08—Disazo dyes from a coupling component "C" containing directive hydroxyl and amino groups
    • 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
    • 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
    • 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
    • C09B69/106—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds containing an azo 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
    • C11D3/34—Organic compounds containing sulfur
    • C11D3/349—Organic compounds containing sulfur additionally containing nitrogen atoms, e.g. nitro, nitroso, amino, imino, nitrilo, nitrile groups containing compounds or their derivatives or thio urea
    • 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

Definitions

  • This invention relates to bis-azo colorants for use as bluing agents, laundry care compositions comprising bis-azo colorants that may serve as bluing agents, processes for making such bluing agents and laundry care compositions and methods of using the same.
  • the bluing agents are generally comprised of at least two components: at least one chromophore component and at least one polymeric component. These bluing agents are advantageous in providing a whitening effect to fabrics, while not building up over time and causing undesirable blue discoloration to the treated fabrics.
  • bluing agents As textile substrates age, their color tends to fade or yellow due to exposure to light, air, soil, and natural degradation of the fibers that comprise the substrates. Thus, the purpose of bluing agents is generally to visually brighten these textile substrates and counteract the fading and yellowing of the substrates. Typically, bluing agents may be found in laundry detergents, fabric softeners, or rinse aids and are therefore applied to textile substrates during the laundering process. However, it is important that bluing agents function to brighten treated textile substrates without causing undesirable staining of the textile substrates. Cellulosic substrates, in particular, tend to exhibit a yellow hue after exposure to light, air, and/or soiling. This yellowness is often difficult to reverse by normal laundering procedures.
  • the present invention offers advantages over previous efforts in this area, as this invention takes advantage of compounds having a non-sulfonic acid substituent in the terminal phenyl ring of the bis-azo structure.
  • Sulfonic acid groups are known to promote the deposition and staining of acid dyes on cellulosic fabrics. These groups are also essential for the solubility and compatibility of the dyes in laundry formulations. While it is necessary that bluing agents deposit from wash water, it is undesirable that they stain the fabric by inadvertent contact or by building up over time, i.e. overhueing.
  • the hueing compounds disclosed herein also absorb light at a wavelength appropriate to neutralize the yellowness of cellulosic substrates. These compounds function ideally as bluing agents for cellulosic substrates and may be incorporated into laundry care compositions for use by consumers.
  • This invention relates to laundry care compositions comprising bis-azo colorants that may serve as bluing agents, processes for making such laundry care compositions and methods of using the same.
  • the bluing agents are generally comprised of at least two components: at least one chromophore component and at least one polymeric component. These bluing agents are advantageous in providing a whitening effect to fabrics, while not building up over time and causing undesirable blue discoloration to the treated fabrics.
  • alkoxy is intended to include C 1 -C 6 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 1 -C 6 alkyl groups.
  • 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 there of. Such compositions may be, but need not be rinse added compositions.
  • cellulosic substrates are intended to include any substrate which comprises at least a majority by weight of cellulose.
  • Cellulose may be found in wood, cotton, linen, jute, and hemp.
  • Cellulosic substrates may be in the form of powders, fibers, pulp and articles formed from powders, fibers and pulp.
  • Cellulosic fibers include, without limitation, cotton, rayon (regenerated cellulose), acetate (cellulose acetate), triacetate (cellulose triacetate), and mixtures thereof.
  • Articles formed from cellulosic fibers include textile articles such as fabrics.
  • Articles formed from pulp include paper.
  • test methods disclosed in the Test Methods Section of the present application should be used to determine the respective values of the parameters of Applicants' inventions.
  • component or composition levels are in reference to the active portion of that component or composition, and are exclusive of impurities, for example, residual solvents or by-products, which may be present in commercially available sources of such components or compositions.
  • the bluing agents employed in the present laundry care compositions may be dyes, pigments, or polymeric colorants comprising a chromophore constituent and a polymeric constituent.
  • the chromophore constituent is characterized in that it absorbs light in the wavelength range of blue, red, violet, purple, or combinations thereof upon exposure to light.
  • the chromophore constituent exhibits an absorbance spectrum maximum from about 520 nanometers to about 640 nanometers in water and/or methanol, and in another aspect, from about 560 nanometers to about 610 nanometers in water and/or methanol.
  • suitable polymeric constituents include polyoxyalkylene chains having multiple repeating units.
  • the polymeric constituents include polyoxyalkylene chains having from 2 to about 30 repeating units, from 2 to about 20 repeating units, from 2 to about 10 repeating units or even from about 3 or 4 to about 6 repeating units.
  • Non-limiting examples of polyoxyalkylene chains include ethylene oxide, propylene oxide, glycidol oxide, butylene oxide and mixtures thereof.
  • the bluing agent employed in the present laundry care compositions may have the following general structure (I):
  • suitable bluing agents may have the following general Structure (II):
  • suitable bluing agents may have the following general Structure (III):
  • said bluing agent may comprise:
  • said bluing agent may comprise a polyoxyalkylene chain having from 2 to about 20 repeating units.
  • said bluing agent may comprise a polyoxyalkylene chain having from 2 to about 10 repeating units.
  • bluing agent may comprise a polyoxyalkylene chain having from about 4 to about 6 repeating units.
  • bluing agent may comprise an alkoxylated bis-azo polymeric colorant.
  • bluing agent's chromophore may exhibit an absorbance spectrum maximum in water of from about 520 nanometers to about 640 nanometers.
  • said bluing agent's chromophore may exhibit an absorbance spectrum maximum in water of from about 560 nanometers to about 610 nanometers.
  • said bluing agent may exhibit an absolute hue angle in the range of 265° to 310°.
  • bluing agent may exhibit an absolute hue angle in the range of 273° to 287°.
  • said bluing agent may have the following structure:
  • R 1 is alkoxy and R 2 is alkyl.
  • suitable bluing agents include, but are not limited to the following structures:
  • the base utilized in the first step of the reaction may be selected from sodium carbonate, sodium acetate, sodium hydroxide, or other cationic salts of these respective bases, and tertiary amines.
  • Acid hydrolysis may be carried out utilizing a strong acid such as hydrochloric acid or sulfuric acid.
  • the bis-azo colorants disclosed herein may be made according to various procedures known in the art and/or in accordance with the examples of the present invention.
  • coupling may be carried out using polyalkyleneoxy substituted aniline compounds derived by known procedures from starting materials such as 4-methyoxy-2-nitrophenol or 4-methyl-2-nitrophenol, both of which are available from VWR International, LLC (West Chester, Pa., USA).
  • any of the bluing agents described in the present specification may be incorporated into laundry care compositions including but not limited to laundry detergents and fabric care compositions.
  • the laundry care compositions including laundry detergents may be in solid or liquid form, including a gel form.
  • Such compositions may comprise one or more of said bluing agents and a laundry care ingredient.
  • the bluing agents may be added to substrates using a variety of application techniques. For instance, for application to cellulose-containing textile substrates, the bluing agent may be included as a component of a laundry detergent. Thus, application to a cellulose-containing textile substrate actually occurs when a consumer adds laundry detergent to a washing machine.
  • the bluing agent may be present in the laundry detergent composition in an amount from about 0.0001% to about 10% by weight of the composition, from about 0.0001% to about 5% by weight of the composition, and even from about 0.0001% to about 1% by weight of the composition.
  • the laundry detergent composition typically comprises a surfactant in an amount sufficient to provide desired cleaning properties.
  • the laundry detergent composition may comprise, based on total laundry detergent composition weight, from about 5% to about 90% of the surfactant, from about 5% to about 70% of the surfactant, or even from about 5% to about 40% of the surfactant.
  • the surfactant may comprise anionic, nonionic, cationic, zwitterionic and/or amphoteric surfactants.
  • the detergent composition comprises anionic surfactant, nonionic surfactant, or mixtures thereof.
  • Fabric care compositions are typically added in the rinse cycle, which is after the detergent solution has been used and replaced with the rinsing solution in typical laundering processes.
  • the fabric care compositions disclosed herein may be comprise a rinse added fabric softening active and a suitable bluing agent as disclosed in the present specification
  • the fabric care composition may comprise, based on total fabric care composition weight, from about 1% to about 90%, or from about 5% to about 50% fabric softening active.
  • the bluing agent may be present in the fabric care composition in an amount from about 0.5 ppb to about 50 ppm, or from about 0.5 ppm to about 30 ppm.
  • a laundry care composition comprising a laundry care ingredient and a bluing agent comprising:
  • said bluing agent comprises a polyoxyalkylene chain having from 2 to about 30 repeating units.
  • said bluing agent comprises a polyoxyalkylene chain having from 2 to about 20 repeating units.
  • said bluing agent comprises a polyoxyalkylene chain having from 2 to about 10 repeating units.
  • bluing agent comprises a polyoxyalkylene chain having from about 4 to about 6 repeating units.
  • bluing agent comprises an alkoxylated bis-azo polymeric colorant.
  • bluing agent's chromophore exhibits an absorbance spectrum maximum in water of from about 520 nanometers to about 640 nanometers.
  • said bluing agent's chromophore exhibits an absorbance spectrum maximum in water of from about 560 nanometers to about 610 nanometers.
  • said bluing agent exhibits an absolute hue angle in the range of 265° to 310°.
  • said bluing agent has the following structure:
  • R 1 is alkoxy and R 2 is alkyl.
  • 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 aspects 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 aspect. The total amount of such adjuncts may range, once the amount of dye is taken into consideration from about 90% to about 99.99999995% by weight of the laundry care composition.
  • Suitable laundry care ingredients include, but are not limited to, fabric softening actives, 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 pigments.
  • suitable examples of such other adjuncts and levels of use are found in U.S. Pat. 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 aspects of Applicants' compositions do not contain one or more of the following adjuncts materials: fabric softening actives, 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 pigments.
  • one or more adjuncts may be present as detailed below:
  • 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 C 10 -C 16 alkyl benzene sulfonic acids, or C 11 -C 14 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 11 -C 14 e.g., C 12
  • 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′—O—(C 2 H 4 O) n —SO 3 M wherein R′ is a C 8 -C 20 alkyl group, n is from about 1 to 20, and M is a salt-forming cation.
  • R′ is C 10 -C 18 alkyl, n is from about 1 to 15, and M is sodium, potassium, ammonium, alkylammonium, or alkanolammonium.
  • R′ is a C 12 -C 16 , n is from about 1 to 6 and M is sodium.
  • non-alkoxylated, e.g., non-ethoxylated, alkyl ether sulfate surfactants are those produced by the sulfation of higher C 8 -C 20 fatty alcohols.
  • Conventional primary alkyl sulfate surfactants have the general formula: ROSO 3 -M + wherein R is typically a linear C 8 -C 20 hydrocarbyl group, which may be straight chain or branched chain, and M is a water-solubilizing cation.
  • R is a C 10 -C 15 alkyl
  • M is alkali metal, more specifically R is C 12 -C 14 and M is sodium.
  • anionic surfactants useful herein include: a) C 11 -C 18 alkyl benzene sulfonates (LAS); b) C 10 -C 20 primary, branched-chain and random alkyl sulfates (AS); c) C 10 -C 18 secondary (2,3) alkyl sulfates having formulae (I) and (II): wherein M in formulae (I) and (II) is hydrogen or a cation which provides charge neutrality, and all M units, whether associated with a surfactant or adjunct ingredient, can either be a hydrogen atom or a cation depending upon the form isolated by the artisan or the relative pH of the system wherein the compound is used, with non-limiting examples of suitable cations including sodium, potassium, ammonium, and mixtures thereof, and x is an integer of at least about 7, or at least about 9, and y is an integer of at least 8, or at least about 9; d) C 10 -C 18 alkyl alkyl alkyl al
  • MLAS modified alkylbenzene sulfonate
  • MES methyl ester sulfonate
  • AOS alpha-olefin sulfonate
  • 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. In one aspect, 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 C 8 -C 16 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, or 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, or from about 3 to 10 ethylene oxide moieties per molecule.
  • 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 from about 6 to 15, or 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.
  • 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(EO) x (PO) y (BO) z N(O)(CH 2 R) 2 .qH 2 O.
  • R is a relatively long-chain hydrocarbyl moiety which can be saturated or unsaturated, linear or branched, and can contain from 8 to 20, 10 to 16 carbon atoms, or is a C 12 -C 16 primary alkyl.
  • R′ is a short-chain moiety, in one aspect R′ may be selected from hydrogen, methyl and —CH 2 OH.
  • EO is ethyleneoxy
  • PO propyleneneoxy
  • BO butyleneoxy.
  • Amine oxide surfactants are illustrated by C 12-14 alkyldimethyl amine oxide.
  • Non-limiting examples of nonionic surfactants include: a) C 12 -C 18 alkyl ethoxylates, such as, NEODOL® nonionic surfactants from Shell; b) C 6 -C 12 alkyl phenol alkoxylates wherein the alkoxylate units are a mixture of ethyleneoxy and propyleneoxy units; c) C 12 -C 18 alcohol and C 6 -C 12 alkyl phenol condensates with ethylene oxide/propylene oxide block polymers such as Pluronic® from BASF; d) C 14 -C 22 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.
  • 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, C 8 to C 18 (in one aspect C 12 to C 18 ) amine oxides and sulfo and hydroxy betaines, such as N-alkyl-N,N-dimethylammino-1-propane sulfonate where the alkyl group can be C 8 to C 18 , or C 10 to C 14 .
  • 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.
  • the laundry care compositions may be in the form of a solid, either in tablet or particulate form, including, but not limited to particles, flakes, sheets, or the like, or the compositions may be in the form of a liquid.
  • the liquid detergent compositions may 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 liquid detergent compositions may comprise, based on total liquid detergent composition weight, from about 5% to about 90%, from about 10% to about 70%, or from about 20% to about 70% of the aqueous, non-surface active liquid carrier.
  • aqueous, non-surface active liquid carrier is typically water. Accordingly, the aqueous, non-surface active liquid carrier component will generally be mostly, if not completely, comprised of water. While other types of water-miscible liquids, such alkanols, diols, other polyols, ethers, amines, and the like, have been conventionally been added to liquid detergent compositions as co-solvents or stabilizers, for purposes of the present invention, the utilization of such water-miscible liquids typically is minimized to hold down composition cost. Accordingly, the aqueous liquid carrier component of the liquid detergent products herein will generally comprise water present in concentrations ranging from about 5% to about 90%, or from about 5% to about 70%, by weight of the liquid detergent composition.
  • the cleaning compositions of the present invention may comprise one or more bleaching agents.
  • Suitable bleaching agents other than bleaching catalysts include photobleaches, bleach activators, hydrogen peroxide, sources of hydrogen peroxide, pre-formed 5 peracids and mixtures thereof.
  • the compositions of the present invention may comprise from about 0.1% to about 50% or even from about 0.1% to about 25% bleaching agent by weight of the subject cleaning composition.
  • suitable bleaching agents include:
  • photobleaches for example sulfonated zinc phthalocyanine
  • Suitable preformed peracids include, but are not limited to, compounds selected from the group consisting of percarboxylic acids and salts, percarbonic acids and salts, perimidic acids and salts, peroxymonosulfuric acids and salts, for example, Oxzone®, and mixtures thereof.
  • Suitable percarboxylic acids include hydrophobic and hydrophilic peracids having the formula R—(C ⁇ O)O—O-M wherein R is an alkyl group, optionally branched, having, when the peracid is hydrophobic, from 6 to 14 carbon atoms, or from 8 to 12 carbon atoms and, when the peracid is hydrophilic, less than 6 carbon atoms or even less than 4 carbon atoms; and M is a counterion, for example, sodium, potassium or hydrogen;
  • inorganic perhydrate salts including alkali metal salts such as sodium salts of perborate (usually mono- or tetra-hydrate), percarbonate, persulphate, perphosphate, persilicate salts and mixtures thereof.
  • the inorganic perhydrate salts are selected from the group consisting of sodium salts of perborate, percarbonate and mixtures thereof.
  • inorganic perhydrate salts are typically present in amounts of from 0.05 to 40 wt %, or 1 to 30 wt % of the overall composition and are typically incorporated into such compositions as a crystalline solid that may be coated. Suitable coatings include, inorganic salts such as alkali metal silicate, carbonate or borate salts or mixtures thereof, or organic materials such as water-soluble or dispersible polymers, waxes, oils or fatty soaps; and
  • bleach activators having R—(C ⁇ O)-L wherein R is an alkyl group, optionally branched, having, when the bleach activator is hydrophobic, from 6 to 14 carbon atoms, or from 8 to 12 carbon atoms and, when the bleach activator is hydrophilic, less than 6 carbon atoms or even less than 4 carbon atoms; and L is leaving group.
  • suitable leaving groups are benzoic acid and derivatives thereof—especially benzene sulphonate.
  • Suitable bleach activators include dodecanoyl oxybenzene sulphonate, decanoyl oxybenzene sulphonate, decanoyl oxybenzoic acid or salts thereof, 3,5,5-trimethyl hexanoyloxybenzene sulphonate, tetraacetyl ethylene diamine (TAED) and nonanoyloxybenzene sulphonate (NOBS).
  • TAED tetraacetyl ethylene diamine
  • NOBS nonanoyloxybenzene sulphonate
  • Suitable bleach activators are also disclosed in WO 98/17767. While any suitable bleach activator may be employed, in one aspect of the invention the subject cleaning composition may comprise NOBS, TAED or mixtures thereof.
  • the peracid and/or bleach activator is generally present in the composition in an amount of from about 0.1 to about 60 wt %, from about 0.5 to about 40 wt % or even from about 0.6 to about 10 wt % based on the composition.
  • One or more hydrophobic peracids or precursors thereof may be used in combination with one or more hydrophilic peracid or precursor thereof.
  • the amounts of hydrogen peroxide source and peracid or bleach activator may be selected such that the molar ratio of available oxygen (from the peroxide source) to peracid is from 1:1 to 35:1, or even 2:1 to 10:1.
  • Bleach Boosting Compounds The compositions herein 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.
  • an active oxygen transfer agent such as a dioxirane, an oxaziridine, or an oxaziridinium.
  • 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.
  • imine bleach boosting compounds of the present invention include those of the general structure:
  • R 1 -R 4 may be a hydrogen or an unsubstituted or substituted radical selected from the group consisting of phenyl, aryl, heterocyclic ring, alkyl and cycloalkyl radicals.
  • Suitable bleach boosting compounds include zwitterionic bleach boosters zwitterionic bleach boosters, which are described in U.S. Pat. Nos. 5,576,282 and 5,718,614.
  • Other bleach boosting compounds include cationic bleach boosters described in U.S. Pat. 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 typically employed in conjunction with a peroxygen source in the bleaching systems of the present invention.
  • 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 Oct. 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 gas:liquid ratio in the solution should be maintained from about 1:2.5 to about 1:6.
  • U.S. Pat. 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 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 aspect, 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.
  • DQA (1) suitable as a FSA in the present CFSC includes a compound comprising the formula:
  • each R substituent is either hydrogen, a short chain C 1 -C 6 , for example C 1 -C 3 alkyl or hydroxyalkyl group, e.g., methyl, ethyl, propyl, hydroxyethyl, and the like, poly (C 2-3 alkoxy), for example.
  • Suitable 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:
  • each R 1 is a C 6 -C 22 , or C 14 -C 20 , but no more than one being less than about C 12 and then the other is at least about 16, hydrocarbyl, or substituted hydrocarbyl substituent, for example, C 10 -C 20 alkyl or alkenyl (unsaturated alkyl, including polyunsaturated alkyl, also referred to sometimes as “alkylene”), in one aspect C 12 -C 18 alkyl or alkenyl, and branch or unbranched.
  • the Iodine Value (IV) of the FSA is from about 1 to 70; each R is H or a short chain C 1 -C 6 , or C 1 -C 3 alkyl or hydroxyalkyl group, e.g., methyl, ethyl, propyl, hydroxyethyl, and the like, benzyl, or (R 20 ) 2-4 H where each R 2 is a C 1-6 alkylene group; and A ⁇ is a softener compatible anion, suitable anions include chloride, bromide, methylsulfate, ethylsulfate, sulfate, phosphate, or nitrate; in one aspect the anions are chloride or methyl sulfate.
  • FSAs include dialkydimethylammonium salts and dialkylenedimethylammonium salts such as ditallowedimethylammonium and ditallowedimethylammonium methylsulfate.
  • dialkylenedimethylammonium salts examples include di-hydrogenated tallow dimethyl ammonium chloride and ditallowedimethyl 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.
  • 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
  • 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.
  • 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.
  • 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, ⁇ -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.
  • the liquid detergent compositions are in the form of an aqueous solution or uniform dispersion or suspension of surfactant, bluing agent, 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, or 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, or even 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 bluing agent is first combined with one or more liquid components to form a bluing agent premix, and this bluing agent 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 bluing agent premix and the enzyme component are added at a final stage of component additions.
  • the bluing agent is encapsulated prior to addition to the detergent composition, the encapsulated bluing agent 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, flakes or sheets. Various techniques for forming detergent compositions in such solid forms are well known in the art and may be used herein.
  • the bluing agent is provided in particulate form, optionally including additional but not all components of the laundry detergent composition.
  • the bluing agent particulate is combined with one or more additional particulates containing a balance of components of the laundry detergent composition.
  • the bluing agent optionally including additional but not all components of the laundry detergent composition, may be provided in an encapsulated form, and the bluing agent 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 fabrics.
  • an effective amount of such compositions is added to water, for example in a conventional fabric laundering automatic washing machine, to form such aqueous laundering solutions.
  • the aqueous washing solution so formed is then contacted, typically 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, or from about 1,000 to 3,000 ppm of the detergent compositions herein will be provided in aqueous washing solution.
  • Certain of the consumer products disclosed herein can be used to clean or treat a situs inter alia a surface or fabric.
  • a situs is contacted with an embodiment of Applicants' consumer product, in neat form or diluted in a liquor, for example, a wash liquor and then the situs may be optionally washed and/or rinsed.
  • a situs is optionally washed and/or rinsed, contacted with an aspect of the consumer product and then optionally washed and/or rinsed.
  • washing includes but is not limited to, scrubbing, and mechanical agitation.
  • the fabric may comprise most any fabric capable of being laundered or treated in normal consumer use conditions.
  • Liquors that may comprise the disclosed compositions may have a pH of from about 3 to about 11.5. Such compositions are typically employed at concentrations of from about 500 ppm to about 15,000 ppm in solution.
  • the wash solvent is water
  • the water temperature typically ranges from about 5° C. to about 90° C.
  • the situs comprises a fabric
  • the water to fabric ratio is typically from about 1:1 to about 30:1.
  • the following bis-azo colorants are prepared as described herein.
  • the UV-visible spectrum of each colorant is determined by dissolving it in a suitable solvent, typically water or methanol, at a concentration that gives an absorbance at the lambda max of less than 1.0 at a path length of 1.0 cm.
  • a Beckman Coulter DU 800 spectrophotometer was used to measure the UV-visible spectrum and determine the lambda max (“ ⁇ max ”) of each sample.
  • the resulting diazonium salt is added to a cooled solution of 6.85 grams of 2-methoxy-5-methylaniline in dilute aqueous hydrochloric acid resulting in a deep orange red product.
  • This product is further diazotized at 0-5° C. by adding 3.58 grams of sodium nitrite with additional hydrochloric acid as necessary to keep the pH at ⁇ 2.
  • the mixture is stirred for 2 hours.
  • the resulting diazonium salt is added to a cooled (0-5° C.) aqueous solution of H-acid in water containing sufficient sodium hydroxide to dissolve the H-acid.
  • the pH of the reaction mixture is kept at 10-12 during the addition of the diazonium salt by adding sodium hydroxide solution as necessary. This resulted in a solution of the deep violet colored product represented as Formula BA4 herein.
  • the product has a ⁇ max of 569 nm in water.
  • the product represented as Formula BA13 herein is prepared in a similar manner to Example 1 except 7.65 grams of 2,5-dimethoxyaniline are substituted for 2-methoxy-5-methylaniline.
  • the product has a ⁇ max of 583 nm in water.
  • the product represented as Formula BA31 herein is prepared in a similar manner to Example 1 except 9.75 grams of N-acetyl-H acid are substituted for H acid.
  • the product has a ⁇ max of 560 nm in water.
  • the product represented as Formula BA58 herein is prepared in a similar manner to Example 1 except 15.75 grams of N-phenyl J acid are substituted for H acid.
  • the product has a ⁇ max of 545 nm in water.
  • the product represented as Formula BA herein is prepared in a similar manner to Example 2 except 15.75 grams of N-phenyl J acid are substituted for H acid.
  • the product has a ⁇ max of 558 nm in water.
  • the product represented as Formula BA5 herein is prepared in a similar manner to Example 1 except 8.85 grams of 3-(2-(2-methoxyethoxy)ethoxy)propylamine are substituted for 3-(2-(2-hydroxyethoxy)ethoxy)propylamine.
  • the product has a ⁇ max of 577 nm in water.
  • the product represented as Formula BA14 herein is prepared in a similar manner to Example 6 except 7.65 grams of 2,5-dimethoxyaniline are substituted for 2-methoxy-5-methylaniline.
  • the product has a ⁇ max of 608 nm in methanol.
  • the product represented as Formula BA12 herein is prepared in a similar manner to Example 7 except 30.70 grams of Surfonamine® B60 are substituted for 3-(2-(2-methoxyethoxy)ethoxy)propylamine.
  • the product has a ⁇ max of 590 nm in water.
  • the product represented as Formula BA2 herein is prepared in a similar manner to Example 6 except 52.90 grams of Surfonamine® L100 are substituted for 3-(2-(2-methoxyethoxy)ethoxy)propylamine.
  • the product has a ⁇ max of 581 nm in water.
  • the product represented as Formula BAH herein is prepared in a similar manner to Example 8 except 52.90 grams of Surfonamine® L100 are substituted for 3-(2-(2-methoxyethoxy)ethoxy)propylamine.
  • the product has a ⁇ max of 578 nm in water.
  • the pH is kept at 10-12 by the addition of aqueous sodium hydroxide solution. This resulted in a violet colored product represented as Formula BA18 herein.
  • the product has a ⁇ max of 574 nm in methanol.
  • the product represented as Formula BA15 herein is prepared in a similar manner to Example 2 except 27.45 grams of p-polyalkyleneoxyphenylamine are substituted for 3-(2-(2-hydroxyethoxy)ethoxy)propylamine.
  • the product has a ⁇ max of 574 nm in methanol.
  • the product represented as Formula BA17 herein is prepared in a similar manner to Example 2 except 5.25 grams of diethanolamine are substituted for 3-(2-(2-hydroxyethoxy)ethoxy)propylamine.
  • the product has a ⁇ max of 581 nm in water.
  • the product represented as Formula BA1 herein is prepared in a similar manner to Example 1 except 35.75 grams of Jeffamine® M715 are substituted for 3-(2-(2-hydroxyethoxy)ethoxy)propylamine.
  • the product has a ⁇ max of 578 nm in water.
  • the product represented as Formula BA28 herein is prepared in a similar manner to Example 3 except 35.75 grams of Jeffamine® M715 are substituted for 3-(2-(2-hydroxyethoxy)ethoxy)propylamine.
  • the product has a ⁇ max of 563 nm in water.
  • the product represented as Formula BASS herein is prepared in a similar manner to Example 4 except 35.75 grams of Jeffamine® M715 are substituted for 3-(2-(2-hydroxyethoxy)ethoxy)propylamine.
  • the product has a ⁇ max of 545 nm in methanol.
  • the product represented as Formula BA34 herein is prepared in a similar manner to Example 3 except 3.65 grams of diethylamine are substituted for 3-(2-(2-hydroxyethoxy)ethoxy)propylamine.
  • the product has a ⁇ max of 560 nm in water.
  • the product represented as Formula BA61 herein is prepared in a similar manner to Example 17 except 15.75 grams of N-phenyl J acid are substituted for N-acetyl H acid.
  • the product has a ⁇ max of 551 nm in methanol.
  • the product represented as Formula BA7 herein is prepared in a similar manner to Example 17 except 15.90 grams of H acid are substituted for N-acetyl H acid.
  • the product has a ⁇ max of 599 nm in methanol.
  • the bis-azo colorants set forth in Table A conform generally to Structure (II) and are prepared according to the methods described herein.
  • the Molar Absorptivity is determined by dissolving a known amount of the compound in a suitable solvent and measuring the absorbance of the solution on an ultraviolet-visible spectrophotometer. The absorptivity is calculated by dividing the absorbance by the molar concentration in moles/liter and the path length which is typically one centimeter.
  • L*, a* and b* values are measured on each fabric (four internal replicates for each wash condition) using a Hunter LabScan XE reflectance spectrophotometer with D65 illumination, 10° observer and UV filter excluded, and difference values calculated against a nil-dye HDL reference.
  • wash solution absorbance vs. ⁇ b* From the plot of wash solution absorbance vs. ⁇ b*, the wash solution absorbance necessary to deliver a ⁇ b* of ⁇ 2.0 on fabric is determined by linear interpolation of the two data points that bracket the target ⁇ b*.
  • the relative hue angle ⁇ R is then calculated as 270+arctan(
  • the absolute hue angle ⁇ A is calculated as 270+arctan(
  • the surface color of an article may be quantified using a series of measurements—L*, a*, and b*—generated by measuring the samples using a spectrophotometer.
  • the equipment used for this test is a Gretag Macbeth Color Eye 7000A spectrophotometer.
  • the software program used is “Color imatch.” “L” is a measure of the amount of white or black in a sample; higher “L” values indicate a lighter colored sample. A measure of the amount of red or green in a sample is determined by “a*” values. A measure of the amount of blue or yellow in a sample is determined by “b*” values; lower (more negative) b* values indicate more blue on a sample.
  • DE* eff (( L* c ⁇ L* s ) 2 +( a* c ⁇ a* s ) 2 +( b* c ⁇ b* s ) 1/2
  • This procedure uses three fabric types to determine the propensity of a dye dissolved in a detergent matrix to stain fabric in a manner similar to a home laundry pre-treat scenario.
  • the three primary fibers examined are cotton, nylon, and spandex (a synthetic polymer having urethane blocks) that comprise the following fabrics:
  • 16 oz cotton interlock knit fabric (270 g/square meter, brightened with Uvitex BNB fluorescent whitening agent, obtained from Test Fabrics. P.O. Box 26, Weston, Pa., 18643), 6.3 oz 90% Cotton/10% Lycra®, Stock # CLF, obtained from Dharma Trading Co., 1604 Fourth St. San Rafael, Calif. 94901, 80% Nylon/20% Spandex, Item #983684GN, obtained from Hancock Fabrics, One Fashion Way, Baldwyn, Miss. 38824.
  • a one inch diameter circle for each of the dyed detergent samples was drawn using a template and labeled with the dye identification on the test fabrics with a non-staining, acrylic ink textile marker (TEXPEN textile marker made by Mark-tex Corp., Englewood, N.J. 07631).
  • TEXPEN textile marker made by Mark-tex Corp., Englewood, N.J. 07631.
  • test fabrics were placed on top of a piece of plastic backed paper counter sheet, or alternatively, a single layer of paper towel over aluminum foil, and stained at the 16 hrs, 1 hr, and 15 min time intervals. Staining was done by placing approximately 0.5 g of the dyed detergent on the fabric allowing it to soak through the fabric with the excess being absorbed by the counter sheet so that the circular test area was saturated with detergent without spreading to adjacent test circles. Due to possible light fading of the dyes, they were placed under a covered area to prevent direct exposure to light while allowing air to pass over the fabrics. The 16 hr stains were applied in the evening while the 1 hr and 15 min swatches were stained the following morning prior to washing.
  • the approximate total amount of detergent applied is calculated by multiplying the total number of stained areas by the amount of detergent delivered for each stain. If this amount exceeds the recommended dosage for the detergent then divide the total detergent by the recommended dosage to determine the number of wash loads to distribute the stained fabrics. If the stained fabrics do not provide the total recommended amount of detergent for a load, then the balance of the detergent is filled with Tide Free (nil-dye) detergent.
  • the pretreated fabrics are washed in a full scale Kenmore top loading washer with 5.5 lbs of terry washcloths used as ballast under median North American conditions of 17 gallons of 90° F./6 grains per gallon of hardness wash water with a rinse of 60° F./6 grains per gallon of hardness water. After the wash is complete the test fabrics are dried with the ballast in a forced heated air drier at the highest temperature setting for 60 minutes, or until completely dry.
  • the circled stain areas were analyzed using a Hunter Colorquest or Labscan XE with D65 lighting, UV filter not included and a 0.5′′ port opening.
  • a nil-dye pre-treat control stain was used as the instrument reference standard for calculating the DE* because the detergent contains brightener.
  • Visual assessment is done under fluorescent lights with a white paper (92 brightness) background under the swatch.
  • the DE*/Visual Scale allows communication of stain intensity in a non-technical manner.
  • Test 1 Determination of Component Parts of Bis-Azo Colorants
  • A, B and C moieties used to construct bluing agents A—N ⁇ N—B—N ⁇ N—C.
  • the molar absorptivity ( ⁇ ) of each example is provided in Table 2.
  • Table 3 provides the deposition and hue angle for Examples 1-19. The data is sorted by variation in Components A, B and C, as determined previously.
  • absolute hue angle describes the actual hue angle of the fabric on the a*, b* plane. This is the angle that a consumer actually sees when looking at the fabric.
  • Relative hue angle is determined against a tracer fabric washed in nil-dye HDL (i.e. same detergent, but without dye), and thus gives the movement within the a*, b* plane relative to the nil-dye control.
  • the bluing agent of the present invention may have an absolute hue angle in the range of 265° to 310°, 265° to 300°, 265° to 295°, 270° to 295°, 270° to 290°, or even in the range of 273° to 287°.
  • Tables 4A and 4B provide examples of liquid detergent formulations which include at least one bluing agent of the present invention.
  • the formulations are shown in Table 4A as Formulations 1a through if and in Table 4B as Formulations 1g through 1l.
  • Liquid Detergent Formulations Comprising the Inventive Bluing Agent 1a 1b 1c 1d 1e 1f 5 Ingredient wt % wt % wt % wt % wt % sodium alkyl ether sulfate 14.4% 14.4% 9.2% 5.4% linear alkylbenzene sulfonic 4.4% 4.4% 12.2% 5.7% 1.3% 22.0% acid alkyl ethoxylate 2.2% 2.2% 8.8% 8.1% 3.4% 18.0% amine oxide 0.7% 0.7% 1.5% citric acid 2.0% 2.0% 3.4% 1.9% 1.0% 1.6% fatty acid 3.0% 3.0% 8.3% 16.0% protease 1.0% 1.0% 0.7% 1.0% 2.5% amylase 0.2% 0.2% 0.2% 0.3% lipase 0.2% borax 1.5% 1.5% 2.4% 2.9% calcium and sodium formate 0.2% 0.2% formic acid 1.1% amine ethoxylate polymers 1.8% 1.8% 2.1% 3.2% sodium polyacrylate 0.2% sodium polyacrylate 0.6% copolymer
  • Table 5 provides examples of granular detergent formulations which include at least one bluing agent of the present invention.
  • the formulations are shown in Table 5 as Formulations 2a through 2e.
  • Formulations 3a-3d Liquid Fabric Care Compositions
  • Table 6 provides examples of liquid fabric care compositions which include at least one bluing agent of the present invention.
  • the compositions are shown in Table 6 as Formulations 3a through 3d.
  • the present invention provides a bluing agent for textile and/or paper substrates comprising at least one chromophore component that comprises a bis-azo colorant and at least one polymeric component.
  • a laundry detergent composition and a rinse added fabric softener containing such a bluing agent is also contemplated herein.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Detergent Compositions (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
US12/910,258 2010-10-22 2010-10-22 Bis-azo colorants for use as bluing agents Abandoned US20120101018A1 (en)

Priority Applications (40)

Application Number Priority Date Filing Date Title
US12/910,258 US20120101018A1 (en) 2010-10-22 2010-10-22 Bis-azo colorants for use as bluing agents
ARP110103893A AR083503A1 (es) 2010-10-22 2011-10-20 Colorantes bis-azo para usar como colorantes azules
MX2013004461A MX357340B (es) 2010-10-22 2011-10-21 Composición detergente que comprende un agente colorante azul y un abrillantador que se solubiliza, rápidamente, en agua.
ES11785825T ES2699751T3 (es) 2010-10-22 2011-10-21 Colorantes diazoicos para usar como agentes de azulado
PCT/US2011/057290 WO2012054835A1 (en) 2010-10-22 2011-10-21 Bis-azo colorants for use as bluing agents
MX2013004460A MX357342B (es) 2010-10-22 2011-10-21 Composición detergente con bajo contenido de aditivo que comprende un agente colorante azul.
BR112013009794A BR112013009794A2 (pt) 2010-10-22 2011-10-21 composição detergente que compreende agente de azulamento e agente de remoção/antirredeposição de sujeira argilosa
BR112013009798A BR112013009798A2 (pt) 2010-10-22 2011-10-21 composição detergente de baixo teor de builder que compreende agente de azulamento
PL11785825T PL2630229T3 (pl) 2010-10-22 2011-10-21 Barwniki diazowe do stosowania jako środki nadające niebieski odcień
PCT/US2011/057279 WO2012054827A1 (en) 2010-10-22 2011-10-21 Detergent composition comprising bluing agent and clay soil removal / anti-redeposition agent
EP11779294.5A EP2630227B1 (en) 2010-10-22 2011-10-21 Detergent composition comprising bluing agent and rapidly water-soluble brightener
BR112013009793A BR112013009793A2 (pt) 2010-10-22 2011-10-21 composição detergente que compreende agente de azulamento e agente de remoçao/antirreposição de sujeira argilosa
MX2013004462A MX357338B (es) 2010-10-22 2011-10-21 Composición detergente que comprende agente de azulado y agente de eliminación de suciedad arcillosa/antirredepósito.
PCT/US2011/057262 WO2012054820A1 (en) 2010-10-22 2011-10-21 Detergent composition comprising bluing agent and rapidly water-soluble brightener
BR112013009791-4A BR112013009791B1 (pt) 2010-10-22 2011-10-21 Composição para cuidado na lavagem de roupas compreendendo corantes bis-azo para uso como agentes de azulamento
PCT/US2011/057270 WO2012054823A1 (en) 2010-10-22 2011-10-21 Detergent composition comprising bluing agent and clay soil removal / anti-redeposition agent
JP2013535118A JP5833130B2 (ja) 2010-10-22 2011-10-21 青み付け剤としての使用を目的としたビズアゾ系染料
BR112013009792A BR112013009792A2 (pt) 2010-10-22 2011-10-21 composição detergente que compreende agente de azulamento e alvejante rapidamente soluvel em agua
CN201610101320.5A CN105695160B (zh) 2010-10-22 2011-10-21 用作上蓝剂的双偶氮着色剂
MX2013004463A MX357388B (es) 2010-10-22 2011-10-21 Composicion detergente que comprende agente azulado y agente de eliminacion se suciedad arcillosa/antirredeposito.
CN201180050981.5A CN103180424B (zh) 2010-10-22 2011-10-21 包含上蓝剂和粘土污垢移除/抗再沉积剂的洗涤剂组合物
CA2815479A CA2815479C (en) 2010-10-22 2011-10-21 Modified bis-azo colorants for use as bluing agents
CN201180050989.1A CN103339245B (zh) 2010-10-22 2011-10-21 包含上蓝剂和快速水溶性增白剂的洗涤剂组合物
MX2013004459A MX357341B (es) 2010-10-22 2011-10-21 Colorantes bis-azoicos para usarse como agentes de azulado.
PCT/US2011/057264 WO2012054821A1 (en) 2010-10-22 2011-10-21 Low built detergent composition comprising bluing agent
EP11785825.8A EP2630229B1 (en) 2010-10-22 2011-10-21 Bis-azo colorants for use as bluing agents
CN201180050982XA CN103201370A (zh) 2010-10-22 2011-10-21 用作上蓝剂的双偶氮着色剂
CN201180051018.9A CN103168097B (zh) 2010-10-22 2011-10-21 包含上蓝剂和粘土污垢移除/抗再沉积剂的洗涤剂组合物
EP11778758.0A EP2630226A1 (en) 2010-10-22 2011-10-21 Detergent composition comprising bluing agent and clay soil removal / anti-redeposition agent
EP11778757.2A EP2630225A1 (en) 2010-10-22 2011-10-21 Detergent composition comprising bluing agent and clay soil removal / anti-redeposition agent
CN201180050993.8A CN103180425B (zh) 2010-10-22 2011-10-21 包含上蓝剂的低复配洗涤剂组合物
EP11781907.8A EP2630228A1 (en) 2010-10-22 2011-10-21 Low built detergent composition comprising bluing agent
US13/313,340 US9708573B2 (en) 2010-10-22 2011-12-07 Detergent composition comprising bluing agent and clay soil removal / anti-redeposition agent
US13/313,283 US9701930B2 (en) 2010-10-22 2011-12-07 Low built detergent composition comprising bluing agent
US13/313,256 US10876079B2 (en) 2010-10-22 2011-12-07 Bis-azo colorants for use as bluing agents
US13/313,395 US9499775B2 (en) 2010-10-22 2011-12-07 Detergent composition comprising bluing agent and rapidly water-soluble brightener
US13/313,310 US9708572B2 (en) 2010-10-22 2011-12-07 Detergent composition comprising bluing agent and clay soil removal / anti-redeposition agent
ZA2013/02890A ZA201302890B (en) 2010-10-22 2013-04-22 Bis-azo colorants for use as bluing agents
JP2014249304A JP6049679B2 (ja) 2010-10-22 2014-12-09 青み付け剤としての使用を目的としたビズアゾ系染料
US14/747,099 US20150291918A1 (en) 2010-10-22 2015-06-23 Bis-azo colorants for use as bluing agents

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US12/910,258 US20120101018A1 (en) 2010-10-22 2010-10-22 Bis-azo colorants for use as bluing agents

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PCT/US2011/057264 Continuation WO2012054821A1 (en) 2010-10-22 2011-10-21 Low built detergent composition comprising bluing agent
PCT/US2011/057262 Continuation WO2012054820A1 (en) 2010-10-22 2011-10-21 Detergent composition comprising bluing agent and rapidly water-soluble brightener
PCT/US2011/057279 Continuation WO2012054827A1 (en) 2010-10-22 2011-10-21 Detergent composition comprising bluing agent and clay soil removal / anti-redeposition agent
PCT/US2011/057270 Continuation WO2012054823A1 (en) 2010-10-22 2011-10-21 Detergent composition comprising bluing agent and clay soil removal / anti-redeposition agent
PCT/US2011/057290 Continuation WO2012054835A1 (en) 2010-10-22 2011-10-21 Bis-azo colorants for use as bluing agents
USPCT/US2011/572290 Continuation 2011-10-21

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US12/910,258 Abandoned US20120101018A1 (en) 2010-10-22 2010-10-22 Bis-azo colorants for use as bluing agents
US13/313,310 Active US9708572B2 (en) 2010-10-22 2011-12-07 Detergent composition comprising bluing agent and clay soil removal / anti-redeposition agent
US13/313,395 Expired - Fee Related US9499775B2 (en) 2010-10-22 2011-12-07 Detergent composition comprising bluing agent and rapidly water-soluble brightener
US13/313,340 Active 2031-03-19 US9708573B2 (en) 2010-10-22 2011-12-07 Detergent composition comprising bluing agent and clay soil removal / anti-redeposition agent
US13/313,283 Active US9701930B2 (en) 2010-10-22 2011-12-07 Low built detergent composition comprising bluing agent
US13/313,256 Active 2031-05-11 US10876079B2 (en) 2010-10-22 2011-12-07 Bis-azo colorants for use as bluing agents
US14/747,099 Abandoned US20150291918A1 (en) 2010-10-22 2015-06-23 Bis-azo colorants for use as bluing agents

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US13/313,310 Active US9708572B2 (en) 2010-10-22 2011-12-07 Detergent composition comprising bluing agent and clay soil removal / anti-redeposition agent
US13/313,395 Expired - Fee Related US9499775B2 (en) 2010-10-22 2011-12-07 Detergent composition comprising bluing agent and rapidly water-soluble brightener
US13/313,340 Active 2031-03-19 US9708573B2 (en) 2010-10-22 2011-12-07 Detergent composition comprising bluing agent and clay soil removal / anti-redeposition agent
US13/313,283 Active US9701930B2 (en) 2010-10-22 2011-12-07 Low built detergent composition comprising bluing agent
US13/313,256 Active 2031-05-11 US10876079B2 (en) 2010-10-22 2011-12-07 Bis-azo colorants for use as bluing agents
US14/747,099 Abandoned US20150291918A1 (en) 2010-10-22 2015-06-23 Bis-azo colorants for use as bluing agents

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JP (2) JP5833130B2 (es)
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AR (1) AR083503A1 (es)
BR (5) BR112013009798A2 (es)
CA (1) CA2815479C (es)
ES (1) ES2699751T3 (es)
MX (5) MX357342B (es)
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