EP2104729A1 - Composition de lessive munis d'un agent de blanchiment pour substrats cellulosiques - Google Patents

Composition de lessive munis d'un agent de blanchiment pour substrats cellulosiques

Info

Publication number
EP2104729A1
EP2104729A1 EP07700644A EP07700644A EP2104729A1 EP 2104729 A1 EP2104729 A1 EP 2104729A1 EP 07700644 A EP07700644 A EP 07700644A EP 07700644 A EP07700644 A EP 07700644A EP 2104729 A1 EP2104729 A1 EP 2104729A1
Authority
EP
European Patent Office
Prior art keywords
whitening agent
laundry care
care composition
mixtures
group
Prior art date
Legal status (The legal status 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 status listed.)
Granted
Application number
EP07700644A
Other languages
German (de)
English (en)
Other versions
EP2104729B1 (fr
Inventor
Eugene Steven Sadlowski
Mark Robert Sivik
Michael David Cummings
Donna D'angelo Morrall
Kevin Lee Kott
Keith Homer Baker
Brian Joseph Loughnane
Michael A Valenti
Laurent D Kieken
Xiaoyong Michael Hong
Eduardo Torres
Dominick J Valenti
Patrick D Moore
Leonard J Starks
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Procter and Gamble Co
Original Assignee
Procter and Gamble Co
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 Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to PL10155140T priority Critical patent/PL2192169T3/pl
Priority to AT10155140T priority patent/ATE557080T1/de
Priority to EP10155140A priority patent/EP2192169B1/fr
Priority to PL07700644T priority patent/PL2104729T3/pl
Publication of EP2104729A1 publication Critical patent/EP2104729A1/fr
Application granted granted Critical
Publication of EP2104729B1 publication Critical patent/EP2104729B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • 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

Definitions

  • the whitening agents are comprised of at least two components: at least one chromophore component and at least one polymeric component. Suitable chromophore components generally fluoresce blue, red, violet, or purple color when exposed to ultraviolet light, or they may absorb light to reflect these same shades.
  • the whitening agents are further characterized by having a dispersion component value of the Hansen Solubility Parameter of less than or equal to about 17 MPa 0 .
  • These whitening agents may be ideal for use in laundry care compositions including but not limited to liquid and/or powder laundry detergent formulations and rinse added fabric softening (RAFS) compositions.
  • RAFS rinse added fabric softening
  • whitening agents either optical brighteners or blueing agents
  • textile applications are well known in the prior art.
  • whitening agents may be found in laundry detergents, fabric softeners, or rinse aids and are therefore applied to textile substrates during the laundering process.
  • whitening agents function to brighten treated textile substrates without causing undesirable staining of the textile substrates.
  • Cellulosic substrates 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.
  • improved whitening agents which are capable of eliminating the yellowness exhibited by ageing cellulosic substrates. By utilizing such improved whitening agents, the life of the textile substrates, such as clothing articles, table linens, etc., may be extended.
  • the present invention offers advantages over US Patents No. 4,137,243, 5,039,782 and US Patent Application Publication No. 2005/0288206 as this invention takes advantage of compounds having a Hansen Solubility Parameter of less than or equal to about 17 MPa 05 and which emit light with wavelengths in the range of blue, red, violet, purple, or combinations thereof upon exposure to ultraviolet light (or, they absorb light to produce the same shades) in order to neutralize the yellowness of cellulosic substrates. These compounds function ideally as whitening agents for cellulosic substrates and may be incorporated into laundry detergent formulations for use by consumers during the laundering process.
  • the whitening agents are comprised of at least two components: at least one chromophore component and at least one polymeric component. Suitable chromophore components generally fluoresce blue, red, violet, or purple color when exposed to ultraviolet light, or they may absorb light to reflect these same shades.
  • the whitening agents are further characterized by having a dispersion component value of the Hansen Solubility Parameter of less than or equal to about 17 MPa 0 .
  • This invention also relates to laundry care compositions including but not limited to liquid and/or powder laundry detergent formulations and rinse added fabric softening (RAFS) compositions that comprise such whitening agents.
  • RAFS fabric softening
  • Figure 1 is a graphical representation of dispersion component values of the Hansen Solubility Parameter versus CIELab b* values for various whitening agents after 1 rinse cycle.
  • 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
  • Articles formed from cellulosic fibers include textile articles such as fabrics.
  • Articles formed from pulp include paper.
  • the term "laundry care composition” includes, unless otherwise indicated, granular, powder, liquid, gel, paste, 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.
  • 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.
  • all 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 whitening agents of the present invention may be dyes, pigments, or polymeric colorants comprising a chromophore constituent and a polymeric constituent.
  • the chromophore constituent is characterized in that it emits or absorbs wavelength in the range of blue, red, violet, purple, or combinations thereof upon exposure to light.
  • the chromophore constituent exhibits an absorbance spectrum value from about 520 nanometers to about 640 nanometers in water, and more preferably from about 570 nanometers to about 610 nanometers in water.
  • the chromophore constituent exhibits an emission spectrum value from about 400 nanometers to about 480 nanometers in water.
  • suitable polymeric constituents include polyoxyalkylene chains having multiple repeating units.
  • the polymeric constituents include polyoxyalkylene chains having from 2 to about 20 repeating units, and more preferably from 2 to about 10 or even from about 4 to about 6 repeating units.
  • Non-limiting examples of polyoxyalkylene chains include ethylene oxide, propylene oxide, glycidol oxide, butylene oxide and mixtures thereof.
  • Another characteristic of the whitening agent of the present invention is its affinity for cellulosic material. Affinity may be determined quantitatively from using the dispersion force component of the Hansen Solubility Parameter.
  • the Hansen Solubility Parameter is a three component measuring system that includes a dispersion force component ( ⁇ d ), a hydrogen bonding component ( ⁇ h ), and a polar component ( ⁇ p ).
  • the Hansen Solubility Parameter " ⁇ " is derived from the fact that the total cohesive energy, which is the energy required to break all the cohesive bonds, is the combination of the dispersion forces (d), the molecular dipole forces (p), and the hydrogen bonding forces (h) according to the following equation:
  • Dispersion forces are weak attractive forces between non-polar molecules. The magnitude of these forces depends on the polarizability of the molecule, and the dispersion Hansen Solubility Parameter, ⁇ d , typically increases with increasing volume (and size) of the molecule, all other properties being roughly equal.
  • ⁇ p increases with increasing polarity of the molecule.
  • Hansen Solubility Parameters are calculated at 25 0 C with ChemSW's Molecular Modeling Pro v.6.1.9 software package which uses an unpublished proprietary algorithm that is based on values published in the Handbook of Solubility Parameters and Other Parameters by Allan F.M. Barton (CRC Press, 1983) for solvents obtained experimentally by Hansen. All values of the Hansen Solubility Parameter reported herein are in units of MPa 0 (square root of megaPascals). Hansen originally determined the solubility parameter of solvents for polymer solutions. While Hansen Solubility Parameter calculation has been applied successfully to a wide range of applications such as solubility of biological materials, characterization of pigments, fillers and fibers, etc., it has not heretofore been adapted to polymeric colorants.
  • the dispersion force component of the Hansen Solubility Parameter, ⁇ d is less than or equal to about 17, and more preferably less than or equal to about 15. It may also be desirable that the dispersion force component of the Hansen Solubility Parameter is from about 12 to about 17, and more preferably from about 12 to about 15. While the affinity of the whitening agent to the cellulosic material appears to correlate very well with the Hansen Solubility Dispersion Component parameter, the invention is not limited to the use of ⁇ d .
  • molecular descriptors which are directly or indirectly related to ⁇ d such as, for example, polarizability, radius of gyration, molecular volume, and Jurs descriptors based on partial atomic charges mapped on solvent-accessible surface area, were also considered. However, the goodness of fit of the univariate correlations of the affinity with these descriptors was not as good as with ⁇ d.
  • the affinity of the whitening agents for the cellulose substrates may be ascribed to Van der Waals forces, the attractive forces that exist between electrically neutral molecules in close proximity to one another. It is also postulated that if the cellulose substrate is comprised of porous regions, the whitening agent, or portions thereof, may be physically trapped in the pores of the cellulose, depending on the size of the molecule as compared to the diameter of the pores. This physical entrapment may provide some level of durability to protect the whitening agent from being easily removed form the cellulose substrate upon exposure to washing or rinsing.
  • the whitening agent's described in the present specification may be incorporated into a laundry care composition including but not limited to laundry detergents and fabric care compositions. Such compositions comprise one or more of said whitening agents and a laundry care ingredient.
  • the whitening agent may be added to cellulose substrates using a variety of application techniques. For application to cellulose-containing textile substrates, the whitening agent is preferably included as an additive in laundry detergent. Thus, application to the cellulose- containing textile substrate actually occurs when a consumer adds laundry detergent to a washing machine. Similarly, RAFS 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. For application to cellulosic paper substrates, the whitening agent may be added to the paper pulp mixture prior to formation of the final paper product.
  • the laundry care compositions including laundry detergents may be in solid or liquid form, including a gel form.
  • the laundry detergent composition comprises a surfactant in an amount sufficient to provide desired cleaning properties.
  • the whitening agent may be present in 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 C.sub.10-16 alkyl benzene sulfonic acids, preferably C.sub.11-14 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 Cn-Ci 4 e.g., Cn, 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 Ci 0 -Ci 8 alkyl, n is from about 1 to 15, and M is sodium, potassium, ammonium, alkylammonium, or alkanolammonium.
  • R' is a Ci 2 -Ci6, 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 "1" 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 Ci 2 -Ci 4 and M is sodium.
  • anionic surfactants useful herein include: a) Cn-Ci 8 alkyl benzene sulfonates (LAS); b) C 1 0-C 2 0 primary, branched-chain and random alkyl sulfates (AS); c) Ci O -Ci 8 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 preferred cations including sodium, potassium, ammonium, and mixtures thereof, and x is an integer of at least about 7, preferably at least about 9, and y is an integer of at least 8, preferably at least about 9; d) Ci O -
  • 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 Cg-Ci ⁇ 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 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.
  • 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, preferably from 10 to 16 carbon atoms, and is more preferably Ci 2 -Ci 6 primary alkyl.
  • R' is a short-chain moiety, preferably selected from hydrogen, methyl and -CH 2 OH. When x+y+z is different from 0, EO is ethyleneoxy, PO is propyleneneoxy and BO is butyleneoxy. Amine oxide surfactants are illustrated by Ci 2-I4 alkyldimethyl amine oxide.
  • Non-limiting examples of nonionic surfactants include: a) Ci 2 -Ci S alkyl ethoxylates, such as, NEODOL® nonionic surfactants from Shell; b) C O -C I2 alkyl phenol alkoxylates wherein the alkoxylate units are a mixture of ethyleneoxy and propyleneoxy units; c) Ci 2 -Ci 8 alcohol and C 6 - Ci 2 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.
  • 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$ to Ci 8 (preferably Ci 2 to Ci 8 ) amine oxides and sulfo and hydroxy betaines, such as N-alkyl-N,N-dimethylammino-l -propane sulfonate where the alkyl group can be Cg to Ci 8 , preferably Ci 0 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.
  • 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 The most cost effective type of 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. 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 should be minimized to hold down composition cost.
  • 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%, 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
  • 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 benzoylcaprolactam
  • 4-nitrobenzoylcaprolactam 3-chlorobenzoylcaprolactam
  • benzoyloxybenzenesulphonate BOBS
  • NOBS nonanoyloxybenzenesulphonate
  • PhBz decanoyloxybenzenesulphonate
  • BZVL benzoylvalerolactam
  • octanoyloxybenzenesulphonate Cg-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, nonanoyloxybenzene- sulphonate (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 ⁇ 2"0BS); 10-undecenoyloxybenzenesulfonate
  • 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
  • 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 quaternary substituted bleach activator
  • QSP quaternary substituted peracid
  • Preferred QSBA structures are further described in U.S. Patent No. 5,686,015 to Willey et al.; U.S. Patent No.
  • 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.
  • 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; 5,004,558; and in EP Nos. 790 244, 775 127, 1 017 773, 1 017 776; and in WO 99/14302, WO 99/14296, WO96/40661, all of which are incorporated herein by reference.
  • 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.
  • Acyl lactam activators as described in U.S. Patent Nos. 5,698,504; 5,695,679 and 5,686,014, each of which is cited herein above, are very useful herein, especially the acyl caprolactams (see for example WO 94-28102 A) and acyl valerolactams (see U.S. Patent No. 5,503,639 to Willey et al. incorporated herein by reference).
  • 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 Al; 549,272 Al; 544,440 A2; and 544,490 Al. Preferred examples of these catalysts include
  • Other 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 pentaamine acetate salts having the formula [Co(NH3)5 ⁇ Ac] Ty, wherein "OAc” represents an acetate moiety and “Ty” is an anion, and especially cobalt pentaamine acetate chloride, [Co(NH3)5 ⁇ Ac]Cl2; as well as [Co(NH 3 ) 5 OAc](OAc) 2 ; [Co(NH 3 ) 5 OAc](PF 6 ) 2 ; [Co(NH 3 ) 5 OAc](SO 4 ); [Co-
  • cobalt catalysts are readily prepared by known procedures, such as taught for example in U.S. Patent Nos. 6,302,921; 6,287,580; 6,140,294; 5,597,936; 5,595,967; and 5,703,030; in the Tobe article and the references cited therein; and in U.S. Patent No. 4,810,410; J. Chem. Ed. (1989), 66 (12), 1043-45; The Synthesis and Characterization of Inorganic Compounds, W.L. Jolly (Prentice-Hall; 1970), pp. 461-3; Inorg. Chem., 18, 1497-1502 (1979); Inorg. Chem., 21, 2881-2885 (1982); Inorg. Chem.. 18, 2023-2025 (1979); Inorg. Synthesis, 173-176 (1960); and Journal of Physical Chemistry. 56, 22-25 (1952).
  • 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.
  • imine bleach boosting compounds of the present invention include those of the general structure:
  • RI - R ⁇ may be a hydrogen or an unsubstituted or substituted radical selected from the group consisting of phenyl, aryl, heterocyclic ring, alkyl and cycloalkyl radicals.
  • bleach boosting compounds are zwitterionic bleach boosters, which are described in U.S. Patent Nos. 5,576,282 and 5,718,614.
  • Other 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.
  • 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. When the organic peroxycarboxylic acid is aliphatic, the unsubstituted peracid has the general formula:
  • Y can be, for example, H, CH3, CH2CI, C(O)OH, or C(O)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(O)OH or
  • 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
  • diperoxy acids useful herein include alkyl diperoxy acids and aryldiperoxy acids, such as: (i) 1,12-diperoxydodecanedioic acid;
  • diperoxybrassylic acid diperoxysebacic acid and diperoxyisophthalic acid
  • iv 2-decyldiperoxybutane-l,4-dioic acid
  • v 4,4'-sulfonylbisperoxybenzoic acid.
  • Such bleaching agents are disclosed in U.S. Patent Nos. 4,483,781 to Hartman and 4,634,551 to Burns et al.; European Patent Application 0,133,354 to Banks et al.; and U.S. Patent No. 4,412,934 to Chung et al.
  • 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.I. 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.
  • 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 gas:liquid 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.
  • 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, whitening 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, 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 whitening agent is first combined with one or more liquid components to form a whitening agent premix, and this whitening 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 whitening agent premix and the enzyme component are added at a final stage of component additions.
  • the whitening agent is encapsulated prior to addition to the detergent composition, the encapsulated whitening 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 or flakes. Various techniques for forming detergent compositions in such solid forms are well known in the art and may be used herein.
  • the whitening agent is provided in particulate form, optionally including additional but not all components of the laundry detergent composition.
  • the whitening agent particulate is combined with one or more additional particulates containing a balance of components of the laundry detergent composition.
  • the whitening agent optionally including additional but not all components of the laundry detergent composition, may be provided in an encapsulated form, and the whitening 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, 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 whitening agents of the present invention may be included in a fabric care composition.
  • the fabric care composition may be comprised of at least one whitening agent 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 and (b) a thiazolium dye.
  • 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 whitening agent 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 (hereinafter "FSA") 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 monoalky quaternary 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 (I) DQA (I)
  • FSA FSA in the present CFSC
  • each R substituent is either hydrogen, a short chain C ⁇ -Cg, preferably C1-C3 alkyl or hydroxyalkyl group, e.g., methyl (most preferred), ethyl, propyl, hydroxyethyl, and the like, poly (C2-3 alkoxy), preferably polyethoxy, group, benzyl, or mixtures thereof; each m is 2 or 3; each n is from 1 to about 4, preferably 2; each Y is -0-(O)C-, -C(O)-O-, -NR-C(O)-, or -C(O)- NR- and it is acceptable for each Y to be the same or different; the sum of carbons in each R.1, plus one when Y is -0-(O)C- or -NR-C(O) -, is C12-C22,
  • 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, hardended 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
  • 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 RI is a Cg-C22 > preferably C ⁇ 4-C20 > but no more than one being less than about C ⁇ 2 an d then the other is at least about 16, hydrocarbyl, or substituted hydrocarbyl substituent, preferably C ⁇ Q-C20 alkyl or alkenyl (unsaturated alkyl, including polyunsaturated alkyl, also referred to sometimes as "alkylene"), most preferably C ⁇ 2-Cig 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 ⁇ -Cg, preferably C1-C3 alkyl or hydroxyalkyl group, e.g., methyl (most preferred), ethyl, propyl, hydroxyethyl, and the like, benzyl, or (R z O)2-4.H where each R ⁇ is a C ⁇ .g alkylene group; and A " is a softener compatible anion, preferably, chloride, bromide, methylsulfate, ethylsulfate, sulfate, phosphate, or nitrate; more preferably chloride or methyl sulfate.
  • 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 Al, 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 Al, 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, di tallow 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 Al.
  • 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.
  • Suitable 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 pigments.
  • suitable examples of such other adjuncts and levels of use are found in U.S. Patent Nos. 5,576,282, 6,306,812 Bl and 6,326,348 Bl that are incorporated by reference.
  • 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 pigments.
  • 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.
  • 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, poly amine 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.
  • Catalytic Metal Complexes - Applicants' 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.
  • Such catalysts are disclosed in U.S. patent 4,430,243.
  • 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 5,576,282.
  • Cobalt bleach catalysts useful herein are known, and are described, for example, in U.S. patents 5,597,936 and 5,595,967. Such cobalt catalysts are readily prepared by known procedures, such as taught for example in U.S. patents 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-l,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 6,225,464.
  • A. Sample Preparation Each sample is prepared by adding 0.5 grams of whitening agent (0.1% based on weight of the cellulosic substrate) to a solution containing 3 grams of powdered laundry detergent (AATCC powder laundry detergent) and 50OmL of room temperature water. Each colorant loading is corrected for absorbance to assure equal amount of color units. The formulation is then combined with 50 grams of cellulose powder (available from Aldrich) and the mixture is agitated for 10 minutes. The mixture is then filtered to separate the cellulose particles from the liquid, and the cellulose particles are allowed to air dry. Both the cellulose particles and the liquid are measured for color using a Gretag Macbeth Color Eye 7000A spectrophotometer, as described previously.
  • the cellulose particles are then placed in a container containing 500 rriL of tap water and agitated for 10 minutes. The mixture is filtered to separate the cellulose particles from the liquid, and the cellulose particles are again allowed to air dry. Both the cellulose particles and the liquid are again measured for color using the Gretag Macbeth Color Eye 7000A spectrophotometer. A Control Sample is also prepared that contained untreated cellulose particles (no whitening agent added).
  • the whitening agents shown in Tables IA and IB are prepared as described herein and tested for various parameters. All violet colorants are synthesized according to the procedure disclosed in US Patent No. 4,912,203 to Kluger et al. Note also that ethylene oxide, propylene oxide and butylenes oxide are shown below by their typical designation of "EO,” "PO” and “BO,” respectively.
  • the average length and composition of the polymeric components of the whitening agents in Tables IA and IB is obtained from the formula: (Block 1 + Block 2 + Block 3)/(number of chains).
  • the average structure for Violet thiophene_5EO consists of a thiophene chromophore with 2 chains on the nitrogen, one equal to 3EO and one equal to 2EO. Chain caps are present on all polymeric components.
  • WI (D*Y) + (P*x) + (Q*y) + C, where Y, x and y are colorimetric values and D, P, Q and C are formula parameters.
  • 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 CMC is a measure of the overall color difference for all uniform color spaces, where DE CMC represents the magnitude of difference between a color and a reference (in this case, a pure white standard). The higher the DE CMC value, the more pronounced the difference in color. In other words, smaller DE CMC values represent colors that are closer to white.
  • the Gretag Macbeth Color Eye 7000A Spectrophotometer calculates DE CMC values based on wavelength and reflectance data for each sample.
  • Descriptors can be categorized in the following categories: 1. Structural, 2. Functional, 3. Energetic, 4. Topological, 5. Spatial, and 6. Thermodynamic.
  • Test 1 Whiteness Test As Determined by CIELab b* Values and the Ganz Whiteness Index
  • Examples 1 through 17 are tested for whiteness to determine CIELab b* values and Ganz Whiteness Index ("Ganz WI") values. Test results are provided in Table 3. Lower (more negative) CIELab b* values and higher positive Ganz WI values indicate that more blueing, or whitening effect, is exhibited by the treated cellulose particles.
  • Example 2 which contained 5 ethylene oxide repeating units, and Example 12, which contained a glycidol unit, performed the best under these test conditions.
  • the data reveals a relatively linear correlation between CIELab b* color values and the Ganz WI values.
  • Test 2 Measurement of CIELab b* Values and the Dispersion Component Values of Hansen Solubility Parameter
  • Examples 1 through 17 are tested to determine CIELab b* values and the dispersion component values of the Hansen Solubility Parameter. Note that Examples 1 through 14 contain a violet thiophene chromophore, while Examples 15 through 17 contain triphenylmethane colorants. Examples 18 through 25 are tested to determine the dispersion component value of the Hansen Solubility Parameter only.
  • Test results are provided in Table 4. Larger negative CIELab b* values indicate that more blueing, or whitening effect, is exhibited by the treated cellulose particles. "N/ A” indicates that data are not available.
  • the test results reveal a relatively linear correlation between the blueing parameter, CIELab b*, and the dispersion component value of the Hansen Solubility Parameter.
  • the color value b* decreases (i.e. blueing performance increases) linearly as ⁇ d decreases.
  • Test 3 Prediction of CIELab b* Values Based on the Dispersion Component Values of Hansen Solubility Parameter
  • Examples 1 - 10 and 15 - 17 are first used to train a model based on the dispersion component value of the Hansen Solubility Parameter.
  • the CIELab b* value is calculated for these Examples using Equation 3, as shown below, which utilizes the dispersion component value obtained after 1 rinse cycle:
  • Equation 3 This equation is very similar to Equation 2, which is derived using all of the Examples.
  • the model represented by Equation 3 is validated with test compounds in Examples 11 - 14.
  • Equation 3 is used to generate predictions for the CIELab b* value of molecules in Examples 11 - 14 (test molecules) before these molecules are synthesized and tested for whitening efficiency.
  • the predicted CIELab b* values obtained from Equation 3 are compared to the measured values previously obtained from the Gretag Macbeth Color Eye 7000A spectrophotometer. The percent difference between measured b* color values and predicted b* color values is also determined.
  • Comparative Example 1 is a blue polymeric anthraquinone dye disclosed in Example III of USPN 4,127,243 to Farmer.
  • Comparative Example 2 is Basic Violet 3, as disclosed in Table 2 of US Patent Application Publication No. 2005/0288206 to Sadlowski et al.
  • Example 11 (Violet thiophene_5EO_COCH3) and Example 12 (Violet thiophene_glycidol) are synthesized and tested to verify that the model can explain the effects of the functionality of the polymeric chain end caps.
  • Example 12 has four hydroxyl groups, while whitening agents with EO or PO end groups have only 2 hydroxyl groups.
  • Example 11 has roughly the same size as Example 12, but the acetate caps are less polar than the OH groups.
  • Figure 1 provides a graphical representation of the data.
  • the phrase "violet thiophene” is shown as “violet” and “triphenylmethane” is shown as “TPM” on Figure 1.
  • the data points represent the measured CIELab b* color values.
  • the solid line represents Equation 3, which is the predicted data.
  • the linear correlation between color value b* and ⁇ d suggests that the smaller the molecule the stronger the deposition on the cellulose powder.
  • the size of the whitening agent compound may influence its ability to access and diffuse into the pores of the cellulose powder.
  • the calculations also show that triphenylmethane-containing whitening agents are preferred whitening agents.
  • Tables 6A and 6B provide examples of liquid detergent formulations which include at least one whitening agent of the present invention.
  • the formulations are shown in Table 6A as Formulations Ia through If and in Table 6B as Formulations Ig through 11.
  • Table 7 provides examples of granular detergent formulations which include at least one whitening agent of the present invention.
  • the formulations are shown in Table 7 as Formulations 2a through 2e.
  • Exemplary Fabric Care Compositions Formulations 3a - 3d Liquid Fabric Care Compositions
  • Table 8 provides examples of liquid fabric care compositions which include at least one whitening agent of the present invention.
  • the compositions are shown in Table 8 as Formulations 3a through 3d.
  • 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.
  • c Copolymer of ethylene oxide and terephthalate having the formula described in US 5,574,179 at col.15, lines 1-5, wherein each X is methyl, each n is 40, u is 4, each R 1 is essentially 1,4- phenylene moieties, each R 2 is essentially ethylene, 1 ,2-propylene moieties, or mixtures thereof.
  • e KATHON ® CG available from Rohm and Haas Co.
  • f Silicone antifoam agent available from Dow Corning Corp. under the trade name DC2310.
  • the present invention provides a whitening agent for cellulosic substrates comprising at least one chromophore component that comprises a thiophene or triphenylmethane colorant and at least one polymeric component; wherein the whitening agent possesses a dispersion component value of the Hansen Solubility Parameter of less than or equal to about 17 MPa 05 .
  • a laundry detergent containing such a whitening agent is also contemplated herein.
  • a laundry detergent containing such a whitening agent is also contemplated herein.
  • Test results provided herein tend to indicate that deposition of the whitening agent on the cellulose powder may be controlled, at least in part, by the size of the whitening agent compound and by its chain cap functionality. Test results also suggest that larger molecules may be too bulky to diffuse into the pores of the cellulose powder which may decrease the whitening effect after multiple washing and/or rinsing cycles.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Cosmetics (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
EP07700644A 2007-01-19 2007-01-19 Composition de lessive munis d'un agent de blanchiment pour substrats cellulosiques Active EP2104729B1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
PL10155140T PL2192169T3 (pl) 2007-01-19 2007-01-19 Kompozycja środka piorącego zawierająca środki wybielające dla substratów celulozowych
AT10155140T ATE557080T1 (de) 2007-01-19 2007-01-19 Wäschepflegezusammensetzung mit bleichmittel für cellulosesubstrate
EP10155140A EP2192169B1 (fr) 2007-01-19 2007-01-19 Composition pour le soin du linge comprenant un agent de blanchiment pour substrats cellulosiques
PL07700644T PL2104729T3 (pl) 2007-01-19 2007-01-19 Kompozycja do prania zawierająca środek wybielający do substratów celulozowych

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/IB2007/050192 WO2008087497A1 (fr) 2007-01-19 2007-01-19 Composition de lessive munis d'un agent de blanchiment pour substrats cellulosiques

Related Child Applications (1)

Application Number Title Priority Date Filing Date
EP10155140.6 Division-Into 2010-03-02

Publications (2)

Publication Number Publication Date
EP2104729A1 true EP2104729A1 (fr) 2009-09-30
EP2104729B1 EP2104729B1 (fr) 2010-11-03

Family

ID=38475950

Family Applications (2)

Application Number Title Priority Date Filing Date
EP10155140A Not-in-force EP2192169B1 (fr) 2007-01-19 2007-01-19 Composition pour le soin du linge comprenant un agent de blanchiment pour substrats cellulosiques
EP07700644A Active EP2104729B1 (fr) 2007-01-19 2007-01-19 Composition de lessive munis d'un agent de blanchiment pour substrats cellulosiques

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP10155140A Not-in-force EP2192169B1 (fr) 2007-01-19 2007-01-19 Composition pour le soin du linge comprenant un agent de blanchiment pour substrats cellulosiques

Country Status (11)

Country Link
EP (2) EP2192169B1 (fr)
JP (1) JP5122583B2 (fr)
CN (1) CN101583704B (fr)
AT (2) ATE557080T1 (fr)
BR (1) BRPI0720944B1 (fr)
CA (1) CA2673239C (fr)
DE (1) DE602007010350D1 (fr)
ES (2) ES2355763T3 (fr)
MX (1) MX2009007746A (fr)
PL (2) PL2104729T3 (fr)
WO (1) WO2008087497A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2118256B2 (fr) † 2007-01-26 2020-02-12 Unilever PLC Composition de nuançage

Families Citing this family (345)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2680619B1 (fr) * 1991-08-21 1993-12-24 Sgs Thomson Microelectronics Sa Predicteur d'image.
EP2163608A1 (fr) * 2008-09-12 2010-03-17 The Procter & Gamble Company Particule pour composition de lavage comprenant un colorant azurant et du savon
EP2166078B1 (fr) * 2008-09-12 2018-11-21 The Procter & Gamble Company Particule pour composition de lavage comprenant un colorant azurant
EP2228429A1 (fr) 2009-03-13 2010-09-15 Unilever PLC Combinaison de colorant d'ombrage et de catalyseur
EP2354214B2 (fr) 2010-01-06 2022-06-08 Unilever IP Holdings B.V. Taux d'agent tensioactif dans des formulations de colorants
EP2563893B1 (fr) 2010-04-29 2014-05-14 Unilever PLC Colorants azoïques bis-hétérocycliques
WO2011163457A1 (fr) 2010-06-23 2011-12-29 The Procter & Gamble Company Produit pour le prétraitement et le blanchissage de tissu taché
BR112013000044B1 (pt) 2010-07-02 2022-01-04 The Procter & Gamble Company Método para a distribuição de agentes ativos a artigos de tecido ou superfícies duras
CN105332075B (zh) 2010-07-02 2017-11-24 宝洁公司 包含活性剂的长丝、非织造纤维网和制备它们的方法
ES2560218T3 (es) 2010-07-02 2016-02-17 The Procter & Gamble Company Proceso para fabricar películas a partir de bandas de material no tejido
RU2541275C2 (ru) 2010-07-02 2015-02-10 Дзе Проктер Энд Гэмбл Компани Филаменты, содержащие неароматизированный активный агент, нетканые полотна и способы их получения
RU2553295C2 (ru) 2010-07-02 2015-06-10 Дзе Проктер Энд Гэмбл Компани Моющий продукт и способы его изготовления
CN103154220B (zh) 2010-10-22 2015-11-25 荷兰联合利华有限公司 与洗衣产品有关的改进
WO2011011799A2 (fr) * 2010-11-12 2011-01-27 The Procter & Gamble Company Colorants azoïques thiophéniques et compositions de lessive les contenant
US8715368B2 (en) 2010-11-12 2014-05-06 The Procter & Gamble Company Thiophene azo dyes and laundry care compositions containing the same
CA3111256C (fr) 2011-05-05 2023-05-09 Danisco Us Inc. Procedes et compositions comprenant des variants de la serine protease
CN106065381B (zh) 2011-05-05 2019-07-26 宝洁公司 包含丝氨酸蛋白酶变体的组合物和方法
US8946139B2 (en) 2011-05-26 2015-02-03 Conopco Inc. Liquid laundry composition
BR112013030993B1 (pt) * 2011-06-01 2021-04-20 Unilever Ip Holdings B.V composição detergente líquida de lavagem de roupas e método doméstico de tratar um artigo têxtil
US20140371435A9 (en) * 2011-06-03 2014-12-18 Eduardo Torres Laundry Care Compositions Containing Thiophene Azo Dyes
MX2013014021A (es) * 2011-06-03 2014-01-23 Procter & Gamble Composiciones que comtienen colorantes par el cuidado en el lavado de ropa.
US9163146B2 (en) * 2011-06-03 2015-10-20 Milliken & Company Thiophene azo carboxylate dyes and laundry care compositions containing the same
US8888865B2 (en) 2011-06-03 2014-11-18 The Procter & Gamble Company Thiophene azo carboxylate dyes and laundry care compositions containing the same
US20120324655A1 (en) 2011-06-23 2012-12-27 Nalini Chawla Product for pre-treatment and laundering of stained fabric
US8828920B2 (en) 2011-06-23 2014-09-09 The Procter & Gamble Company Product for pre-treatment and laundering of stained fabric
WO2013002786A1 (fr) 2011-06-29 2013-01-03 Solae Compositions alimentaires destinées à être cuites au four et contenant des protéines de lait de soja isolées à partir de flux de traitement
EP2540824A1 (fr) 2011-06-30 2013-01-02 The Procter & Gamble Company Compositions de nettoyage comprenant une référence de variantes dýamylase à une liste de séquences
WO2013011071A1 (fr) 2011-07-21 2013-01-24 Unilever Plc Composition de lessive liquide
EP2551335A1 (fr) 2011-07-25 2013-01-30 The Procter & Gamble Company Composition détergente liquide enzymatique stabilisee
US8921299B2 (en) 2011-07-25 2014-12-30 The Procter & Gamble Company Detergents having acceptable color
MX342855B (es) 2011-08-15 2016-10-13 Procter & Gamble Composiciones detergentes que contienen compuestos de piridinol-n-oxido.
CA2849149A1 (fr) 2011-09-20 2013-03-28 The Procter & Gamble Company Compositions detergentes comprenant des systemes de tensioactifs durables comprenant des tensioactifs derives d'isoprenoides
AR088757A1 (es) 2011-09-20 2014-07-02 Procter & Gamble Composiciones detergentes con alta espuma que comprenden surfactantes con base de isoprenoide
WO2013043803A2 (fr) 2011-09-20 2013-03-28 The Procter & Gamble Company Compositions détergentes comprenant des rapports de mélange spécifiques d'agents tensio-actifs à base d'isoprénoïde
MX2014003278A (es) 2011-09-20 2014-05-21 Procter & Gamble Composiciones detergentes que comprenden sistemas surfactantes primarios que comprenden surfactantes con base de isoprenoide altamente ramificados y otros surfactantes.
WO2013043852A2 (fr) 2011-09-20 2013-03-28 The Procter & Gamble Company Compositions détergentes faciles à rincer comprenant des agents tensio-actifs à base d'isoprénoïde
WO2013070559A1 (fr) 2011-11-11 2013-05-16 The Procter & Gamble Company Compositions de traitement de surface comprenant des sels protecteurs
CA2860659C (fr) 2012-01-04 2017-08-29 The Procter & Gamble Company Structures fibreuses comprenant des particules et leurs procedes de fabrication
CN104040060B (zh) 2012-01-04 2017-05-17 宝洁公司 具有多个区域的含活性物质纤维结构
CN106906573B (zh) 2012-01-04 2019-08-27 宝洁公司 具有不同密度的多个区域的含活性物质纤维结构
IN2014DN06191A (fr) 2012-02-03 2015-10-23 Procter & Gamble
EP2828340A1 (fr) 2012-03-19 2015-01-28 The Procter & Gamble Company Compositions d'entretien du linge contenant des colorants
WO2013149858A1 (fr) 2012-04-02 2013-10-10 Novozymes A/S Variantes de lipase et polynucléotides codant pour celles-ci
WO2013171241A1 (fr) 2012-05-16 2013-11-21 Novozymes A/S Composition comprenant une lipase et procédés d'utilisation associés
US9249379B2 (en) 2012-06-21 2016-02-02 Conopco, Inc. Liquid laundry detergent
WO2014009473A1 (fr) 2012-07-12 2014-01-16 Novozymes A/S Polypeptides ayant une activité lipase et polynucléotides codant pour ceux-ci
CN104471049B (zh) 2012-07-17 2017-07-21 荷兰联合利华有限公司 明亮的洗涤剂组合物
EP2877562B1 (fr) 2012-07-26 2018-04-25 The Procter and Gamble Company Compositions de nettoyage liquides à faible ph et à enzymes
EP2712915A1 (fr) 2012-10-01 2014-04-02 The Procter and Gamble Company Procédés de traitement d'une surface et compositions pour utilisation dudit procédé
CA2888342A1 (fr) 2012-10-24 2014-05-01 The Procter & Gamble Company Compositions anti-mousse contenant des polyorganosiliciums partiellement porteurs de groupes phenyle
CA2888341A1 (fr) 2012-10-24 2014-05-01 The Procter & Gamble Company Compositions anti-mousse contenant des polyorganosiliciums porteurs de groupes aryle
EP2740785A1 (fr) 2012-12-06 2014-06-11 The Procter and Gamble Company Utilisation de composition pour réduire le suintement et la migration à travers un film soluble dans l'eau
EP2929005A1 (fr) 2012-12-06 2015-10-14 The Procter & Gamble Company Sac soluble comprenant un colorant teintant
EP2767581B1 (fr) 2013-02-19 2020-10-21 The Procter & Gamble Company Procédé de lavage d'un textile
EP2767579B1 (fr) 2013-02-19 2018-07-18 The Procter and Gamble Company Procédé de lavage d'un textile
EP2767582A1 (fr) 2013-02-19 2014-08-20 The Procter and Gamble Company Procédé de lavage d'un textile
WO2014147127A1 (fr) 2013-03-21 2014-09-25 Novozymes A/S Polypeptides ayant une activité lipase et polynucléotides les codant
US10577564B2 (en) 2013-03-28 2020-03-03 The Procter & Gamble Company Cleaning compositions containing a polyetheramine
WO2014168776A1 (fr) 2013-04-12 2014-10-16 The Procter & Gamble Company Structures à fibres de polymères hydroxylés comprenant des sels de sulfonate d'alkyle d'ammonium et procédés de fabrication correspondants
WO2014168775A1 (fr) 2013-04-12 2014-10-16 The Procter & Gamble Company Structures fibreuses présentant des valeurs d'indice de blancheur améliorées
CA2909458C (fr) 2013-04-12 2018-07-31 The Procter & Gamble Company Structures fibreuses comprenant des filaments polysaccharidiques
CN105164211B (zh) * 2013-05-03 2017-05-24 荷兰联合利华有限公司 烷氧基化双偶氮染料
RU2020101263A (ru) 2013-05-14 2020-02-17 Новозимс А/С Моющие композиции
CA2911332A1 (fr) 2013-05-28 2014-12-04 The Procter & Gamble Company Compositions de traitement de surface comprenant des colorants photochromes
WO2015004102A1 (fr) 2013-07-09 2015-01-15 Novozymes A/S Polypeptides à activité lipase et polynucléotides codant pour ceux-ci
US9834682B2 (en) 2013-09-18 2017-12-05 Milliken & Company Laundry care composition comprising carboxylate dye
JP6185182B2 (ja) * 2013-09-18 2017-08-23 ザ プロクター アンド ギャンブル カンパニー チオフェンアゾカルボキシレート染料を含有する洗濯ケア組成物
EP3047009B1 (fr) 2013-09-18 2018-05-16 The Procter and Gamble Company Composition d'entretien du linge comprenant un colorant carboxylate
CN105555936A (zh) 2013-09-18 2016-05-04 宝洁公司 包含羧化物染料的衣物洗涤护理组合物
MX2016003536A (es) * 2013-09-18 2016-06-28 Procter & Gamble Composicion para el cuidado de la ropa que comprende colorante de carboxilato.
EP4253649A3 (fr) 2013-12-09 2023-12-06 The Procter & Gamble Company Structures fibreuses comprenant un agent actif et dotées d'un graphique imprimé dessus
EP3097173B1 (fr) 2014-01-22 2020-12-23 The Procter and Gamble Company Composition de traitement de tissu
EP3097172A1 (fr) 2014-01-22 2016-11-30 The Procter & Gamble Company Procédé de traitement de surfaces textiles
EP2899260A1 (fr) 2014-01-22 2015-07-29 Unilever PLC Procédé de préparation d'une formulation de détergent liquide
EP3097174A1 (fr) 2014-01-22 2016-11-30 The Procter & Gamble Company Procédé de traitement de surfaces textiles
US10208297B2 (en) 2014-01-22 2019-02-19 Novozymes A/S Polypeptides with lipase activity and polynucleotides encoding same for cleaning
EP3097175B1 (fr) 2014-01-22 2018-10-17 The Procter and Gamble Company Composition de traitement de textile
US20150210964A1 (en) 2014-01-24 2015-07-30 The Procter & Gamble Company Consumer Product Compositions
US9556406B2 (en) 2014-02-19 2017-01-31 Milliken & Company Compositions comprising benefit agent and aprotic solvent
WO2015127004A1 (fr) 2014-02-19 2015-08-27 The Procter & Gamble Company Composition contenant un agent bénéfique et un solvant aprotique
WO2015130669A1 (fr) 2014-02-25 2015-09-03 The Procter & Gamble Company Procédé de production d'intermédiaires pour agents tensio-actifs renouvelables et agents tensioactifs produits à partir de graisses et d'huiles, et produits correspondants
WO2015130653A1 (fr) 2014-02-25 2015-09-03 The Procter & Gamble Company Procédé de production d'intermédiaires d'agents tensio-actifs renouvelables et tensioactifs obtenus à partir de graisses et d'huiles et produits associés
US10155935B2 (en) 2014-03-12 2018-12-18 Novozymes A/S Polypeptides with lipase activity and polynucleotides encoding same
CN106062163B (zh) * 2014-03-17 2019-10-08 荷兰联合利华有限公司 长烷基链偶氮染料和洗衣洗涤剂组合物
WO2015148360A1 (fr) 2014-03-27 2015-10-01 The Procter & Gamble Company Compositions de nettoyage contenant une polyétheramine
WO2015148361A1 (fr) 2014-03-27 2015-10-01 The Procter & Gamble Company Compositions de nettoyage contenant une polyétheramine
CN106715465B (zh) 2014-04-15 2021-10-08 诺维信公司 具有脂肪酶活性的多肽和编码它们的多核苷酸
WO2015171592A1 (fr) 2014-05-06 2015-11-12 Milliken & Company Compositions pour l'entretien du linge
WO2015181118A1 (fr) 2014-05-27 2015-12-03 Novozymes A/S Procédés de production de lipases
WO2015181119A2 (fr) 2014-05-27 2015-12-03 Novozymes A/S Variants lipasiques et polynucléotides codant pour ceux-ci
EP3152288A1 (fr) 2014-06-06 2017-04-12 The Procter & Gamble Company Composition détergente comprenant des polymères à base de polyalkylèneimine
EP2987849A1 (fr) 2014-08-19 2016-02-24 The Procter and Gamble Company Procédé de lavage d'un textile
EP2987848A1 (fr) 2014-08-19 2016-02-24 The Procter & Gamble Company Procédé de lavage d'un textile
US9809782B2 (en) 2014-08-27 2017-11-07 The Procter & Gamble Company Detergent composition comprising a cationic polymer and anionic/nonionic surfactant mixture
WO2016032991A1 (fr) 2014-08-27 2016-03-03 The Procter & Gamble Company Composition détergente comprenant un polymère cationique
EP3186345A1 (fr) 2014-08-27 2017-07-05 The Procter and Gamble Company Composition détergente comprenant un polymère cationique
EP3186348B1 (fr) 2014-08-27 2022-08-03 The Procter & Gamble Company Procédé de traitement d'un tissu
US9617502B2 (en) 2014-09-15 2017-04-11 The Procter & Gamble Company Detergent compositions containing salts of polyetheramines and polymeric acid
US20160090552A1 (en) 2014-09-25 2016-03-31 The Procter & Gamble Company Detergent compositions containing a polyetheramine and an anionic soil release polymer
JP6396583B2 (ja) 2014-09-25 2018-09-26 ザ プロクター アンド ギャンブル カンパニー ポリエーテルアミンを含有する洗浄組成物
JP6430632B2 (ja) 2014-09-25 2018-11-28 ザ プロクター アンド ギャンブル カンパニー ポリエーテルアミンを含有する布地ケア組成物
US9388368B2 (en) 2014-09-26 2016-07-12 The Procter & Gamble Company Cleaning compositions containing a polyetheramine
US20160137956A1 (en) 2014-11-17 2016-05-19 The Procter & Gamble Company Benefit agent delivery compositions
EP3227442B1 (fr) 2014-12-05 2022-02-16 Novozymes A/S Variantes de la lipase et polynucléotides les codant
WO2016160868A1 (fr) 2015-03-30 2016-10-06 The Procter & Gamble Company Composition de détergent pour le lavage du linge à solide particulaire à écoulement libre
CN107438658B (zh) 2015-03-30 2020-04-21 宝洁公司 自由流动的固体颗粒状衣物洗涤剂组合物
US20160289616A1 (en) 2015-03-30 2016-10-06 The Procter & Gamble Company Solid free-flowing particulate laundry detergent composition
RU2668718C1 (ru) 2015-03-30 2018-10-02 Дзе Проктер Энд Гэмбл Компани Твердая композиция моющего средства для стирки из легкосыпучих частиц
US20160289609A1 (en) 2015-03-30 2016-10-06 The Procter & Gamble Company Solid free-flowing particulate laundry detergent composition
EP3075824B1 (fr) 2015-03-30 2018-02-21 The Procter and Gamble Company Composition particulaire solide à écoulement libre de détergent à lessive
MX2017012564A (es) 2015-03-30 2018-01-25 Procter & Gamble Composicion detergente solida particulada para lavanderia de flujo libre.
EP3075823A1 (fr) 2015-03-30 2016-10-05 The Procter and Gamble Company Particule de base de détergent à lessive séchée par un spray
EP3075826B1 (fr) 2015-03-30 2018-01-31 The Procter and Gamble Company Composition particulaire solide à écoulement libre de détergent à lessive
US20160289610A1 (en) 2015-04-02 2016-10-06 The Procter & Gamble Company Solid free-flowing particulate laundry detergent composition
WO2016161218A1 (fr) 2015-04-02 2016-10-06 The Procter & Gamble Company Composition détergente pour le lavage du linge constituée de matières particulaires solides à écoulement libre
WO2016161219A1 (fr) 2015-04-02 2016-10-06 The Procter & Gamble Company Composition détergente particulaire solide à écoulement libre pour lavage du linge
EP3088502B1 (fr) 2015-04-29 2018-05-23 The Procter and Gamble Company Procédé de traitement d'un textile
CN107548415A (zh) 2015-04-29 2018-01-05 宝洁公司 洗涤织物的方法
CN107532116B (zh) 2015-04-29 2021-05-07 宝洁公司 处理织物的方法
EP3088505B1 (fr) 2015-04-29 2020-06-03 The Procter and Gamble Company Procédé de traitement d'un textile
WO2016176241A1 (fr) 2015-04-29 2016-11-03 The Procter & Gamble Company Composition détergente
JP6866302B2 (ja) 2015-05-04 2021-04-28 ミリケン・アンド・カンパニーＭｉｌｌｉｋｅｎ ＆ Ｃｏｍｐａｎｙ ランドリーケア組成物中の青味剤としてのロイコトリフェニルメタン色素
US10336971B2 (en) 2015-05-19 2019-07-02 Novozymes A/S Odor reduction
BR112017024403B1 (pt) 2015-05-27 2022-03-08 Unilever Ip Holdings B.V. Composição de detergente para lavagem de roupas e método doméstico de tratamento de um tecido
WO2016192905A1 (fr) 2015-06-02 2016-12-08 Unilever Plc Composition détergente pour lessive
JP6878314B2 (ja) 2015-06-11 2021-05-26 ザ プロクター アンド ギャンブル カンパニーＴｈｅ Ｐｒｏｃｔｅｒ ＆ Ｇａｍｂｌｅ Ｃｏｍｐａｎｙ 表面に組成物を塗布するための装置及び方法
US10858637B2 (en) 2015-06-16 2020-12-08 Novozymes A/S Polypeptides with lipase activity and polynucleotides encoding same
WO2017001673A1 (fr) 2015-07-01 2017-01-05 Novozymes A/S Procédés de réduction d'odeur
CN114292829A (zh) 2015-07-06 2022-04-08 诺维信公司 脂肪酶变体以及编码它们的多核苷酸
BR112018006212B1 (pt) 2015-10-01 2022-04-12 Unilever Ip Holdings B.V. Composição de detergente em pó formada por carbonato sem fosfato e método de tratamento doméstico de um tecido
EP3153426B1 (fr) 2015-10-06 2018-07-18 The Procter & Gamble Company Sac de boîte flexible comprenant une poche de détergent en dose unitaire soluble
EP3153425B1 (fr) 2015-10-06 2018-07-04 The Procter and Gamble Company Sac de boîte flexible comprenant une poudre détergente et une pelle
US9902923B2 (en) 2015-10-13 2018-02-27 The Procter & Gamble Company Polyglycerol dye whitening agents for cellulosic substrates
US9745544B2 (en) * 2015-10-13 2017-08-29 The Procter & Gamble Company Whitening agents for cellulosic substrates
US10155868B2 (en) * 2015-10-13 2018-12-18 Milliken & Company Whitening agents for cellulosic substrates
US10597614B2 (en) 2015-10-13 2020-03-24 The Procter & Gamble Company Whitening agents for cellulosic substrates
MX2018006475A (es) 2015-11-26 2018-09-28 Procter & Gamble Composiciones detergentes liquidas que comprenden proteasa y lipasa encapsulada.
US10870838B2 (en) 2015-12-01 2020-12-22 Novozymes A/S Methods for producing lipases
BR112018016674B1 (pt) 2016-02-17 2022-06-07 Unilever Ip Holdings B.V. Composição de detergente para lavagem de roupas e método doméstico de tratamento de um tecido
BR112018016129B1 (pt) 2016-02-17 2022-06-07 Unilever Ip Holdings B.V. Composição de detergente para lavagem de roupas e método doméstico de tratamento de um tecido
EP3433346B1 (fr) 2016-03-21 2020-12-30 Unilever PLC Composition de détergent pour lessive
WO2017174251A1 (fr) 2016-04-08 2017-10-12 Unilever Plc Composition de détergent à lessive
US10689603B2 (en) 2016-05-09 2020-06-23 The Procter & Gamble Company Detergent composition
EP3556834B1 (fr) 2016-05-09 2020-10-14 The Procter & Gamble Company Composition de détergent comprenant une decarboxylase d'acide gras
EP3511403B1 (fr) 2016-05-09 2020-12-02 The Procter & Gamble Company Composition de détergent
AU2017267127B2 (en) 2016-05-17 2020-04-02 Unilever Global Ip Limited Liquid laundry detergent compositions
CN109196083A (zh) 2016-05-17 2019-01-11 荷兰联合利华有限公司 液体洗衣洗涤剂组合物
US11326152B2 (en) 2016-07-18 2022-05-10 Novozymes A/S Lipase variants, polynucleotides encoding same and the use thereof
WO2018060139A1 (fr) 2016-09-27 2018-04-05 Unilever Plc Procédé de blanchissage domestique
ES2758226T3 (es) 2016-10-03 2020-05-04 Procter & Gamble Proceso de preparación de una partícula de detergente para lavado de ropa secada por pulverización
EP3301157B1 (fr) 2016-10-03 2019-11-20 The Procter & Gamble Company Composition de détergent pour lessive
RU2709518C1 (ru) 2016-10-03 2019-12-18 Дзе Проктер Энд Гэмбл Компани Композиция моющего средства для стирки с низким показателем ph
CN109844082A (zh) 2016-10-03 2019-06-04 宝洁公司 衣物洗涤剂组合物
WO2018067488A1 (fr) 2016-10-03 2018-04-12 The Procter & Gamble Company Composition de détergent à lessive à faible ph
CN109790487A (zh) 2016-10-03 2019-05-21 宝洁公司 衣物洗涤剂组合物
EP3301154B1 (fr) 2016-10-03 2023-01-25 The Procter & Gamble Company Composition de détergent pour lessive
MX2019003845A (es) 2016-10-03 2019-06-24 Procter & Gamble Composición detergente para lavandería con un ph bajo.
EP3301168B1 (fr) 2016-10-03 2019-09-11 The Procter and Gamble Company Composition de détergent pour lessive
EP3529342B1 (fr) 2016-10-18 2020-03-18 Unilever PLC Composition d'agent azurant
JP6790257B2 (ja) 2016-11-01 2020-11-25 ザ プロクター アンド ギャンブル カンパニーＴｈｅ Ｐｒｏｃｔｅｒ ＆ Ｇａｍｂｌｅ Ｃｏｍｐａｎｙ 洗濯ケア組成物における青味剤としてのロイコ着色剤、その包装、キット及び方法
CA3038855A1 (fr) 2016-11-01 2018-05-11 The Procter & Gamble Company Leuco-colorants utilises en tant qu'agents d'azurage dans des compositions d'entretien du linge
BR112019006576A2 (pt) 2016-11-01 2019-07-02 Milliken & Co corantes leuco como agentes de azulamento em composições de cuidados de lavanderia
US20180119056A1 (en) 2016-11-03 2018-05-03 Milliken & Company Leuco Triphenylmethane Colorants As Bluing Agents in Laundry Care Compositions
WO2018102478A1 (fr) 2016-12-02 2018-06-07 The Procter & Gamble Company Compositions de nettoyage comprenant des enzymes
US10550443B2 (en) 2016-12-02 2020-02-04 The Procter & Gamble Company Cleaning compositions including enzymes
MX2019006422A (es) 2016-12-02 2019-08-01 Procter & Gamble Composiciones de limpieza que incluyen enzimas.
EP3555255B1 (fr) 2016-12-15 2020-06-24 Unilever PLC Composition de détergent pour lessive
EP3339419A1 (fr) 2016-12-22 2018-06-27 The Procter & Gamble Company Composition de détergent pour lessive
EP3339417A1 (fr) 2016-12-22 2018-06-27 The Procter & Gamble Company Composition de détergent pour lessive
EP3339413A1 (fr) 2016-12-22 2018-06-27 The Procter & Gamble Company Composition de détergent pour lessive
EP3339407A1 (fr) 2016-12-22 2018-06-27 The Procter & Gamble Company Composition de détergent pour lessive
EP3339418A1 (fr) 2016-12-22 2018-06-27 The Procter & Gamble Company Composition de détergent pour lessive
EP3339416A1 (fr) 2016-12-22 2018-06-27 The Procter & Gamble Company Composition de détergent pour lessive
EP3339422B1 (fr) 2016-12-22 2020-10-21 The Procter & Gamble Company Composition de détergent pour lessive
EP3339415A1 (fr) 2016-12-22 2018-06-27 The Procter & Gamble Company Composition de détergent pour lessive
EP3339421A1 (fr) 2016-12-22 2018-06-27 The Procter & Gamble Company Composition de détergent pour lessive
EP3339414A1 (fr) 2016-12-22 2018-06-27 The Procter & Gamble Company Composition de détergent pour lessive
US11697906B2 (en) 2017-01-27 2023-07-11 The Procter & Gamble Company Active agent-containing articles and product-shipping assemblies for containing the same
US11697904B2 (en) 2017-01-27 2023-07-11 The Procter & Gamble Company Active agent-containing articles that exhibit consumer acceptable article in-use properties
US11697905B2 (en) 2017-01-27 2023-07-11 The Procter & Gamble Company Active agent-containing articles that exhibit consumer acceptable article in-use properties
CN115742472A (zh) 2017-01-27 2023-03-07 宝洁公司 表现出消费者可接受的制品应用特性的含活性剂的制品
WO2018202846A1 (fr) 2017-05-05 2018-11-08 Novozymes A/S Compositions comprenant une lipase et un sulfite
WO2019008035A1 (fr) 2017-07-07 2019-01-10 Unilever Plc Composition de lessive pour le linge
WO2019008036A1 (fr) 2017-07-07 2019-01-10 Unilever Plc Composition de blanchiment
CN111356762A (zh) 2017-09-27 2020-06-30 诺维信公司 脂肪酶变体和包含此类脂肪酶变体的微囊组合物
CA3074938A1 (fr) 2017-10-12 2019-04-18 The Procter & Gamble Company Leuco-colorants en tant qu'agents d'azurage dans des compositions d'entretien du linge
JP6945947B2 (ja) 2017-10-12 2021-10-06 ザ プロクター アンド ギャンブル カンパニーＴｈｅ Ｐｒｏｃｔｅｒ ＆ Ｇａｍｂｌｅ Ｃｏｍｐａｎｙ 洗濯ケア組成物中の青味剤として第２のホワイトニング剤と組み合わせたロイコ着色剤
TWI715878B (zh) 2017-10-12 2021-01-11 美商美力肯及公司 隱色著色劑及組成物
WO2019075148A1 (fr) 2017-10-12 2019-04-18 The Procter & Gamble Company Leuco-colorants en tant qu'agents d'azurage dans des compositions d'entretien du linge
EP3697957A4 (fr) 2017-10-20 2021-08-04 Everyone's Earth Inc. Compositions de blanchiment pour tissu contenant de la cellulose
EP3704193A1 (fr) 2017-11-01 2020-09-09 Milliken & Company Leucodérivés, composés colorants, et compositions les contenant
EP3717616B1 (fr) 2017-11-30 2021-10-13 Unilever IP Holdings B.V. Composition détergente comprenant de la protéase
EP3720954A1 (fr) 2017-12-04 2020-10-14 Novozymes A/S Variants de lipases et polynucléotides codant pour ces derniers
CA3084211A1 (fr) 2017-12-08 2019-06-13 Novozymes A/S Variants d'alpha-amylase et polynucleotides codant pour ces derniers
EP3749760A1 (fr) 2018-02-08 2020-12-16 Novozymes A/S Variants de lipase et compositions en comprenant
CN111868239A (zh) 2018-02-08 2020-10-30 诺维信公司 脂肪酶、脂肪酶变体及其组合物
EP3755782B1 (fr) 2018-02-23 2021-10-13 Unilever Global IP Limited Produit détergent en dose unitaire comportant une partie solide brillante
EP3546557B1 (fr) 2018-03-28 2020-10-07 The Procter & Gamble Company Inhibition de la catalase, lors d'un processus de lavage
EP3546555A1 (fr) 2018-03-28 2019-10-02 The Procter & Gamble Company Procédé de préparation d'une particule de détergent à lessive séchée par pulvérisation
JP2021516273A (ja) 2018-03-28 2021-07-01 ザ プロクター アンド ギャンブル カンパニーＴｈｅ Ｐｒｏｃｔｅｒ ＆ Ｇａｍｂｌｅ Ｃｏｍｐａｎｙ 噴霧乾燥洗濯洗剤粒子を調製するための方法
WO2019191171A1 (fr) 2018-03-28 2019-10-03 The Procter & Gamble Company Composition de détergent pour lessive
EP3546554A1 (fr) 2018-03-28 2019-10-02 The Procter & Gamble Company Procédé de séchage par atomisation
EP3546558A1 (fr) 2018-03-28 2019-10-02 The Procter & Gamble Company Composition de detergent
EP3546559A1 (fr) 2018-03-28 2019-10-02 The Procter & Gamble Company Composition de détergent pour lessive
CN111971372B (zh) 2018-04-03 2022-03-11 联合利华知识产权控股有限公司 染料颗粒
WO2019219531A1 (fr) 2018-05-17 2019-11-21 Unilever Plc Composition de nettoyage
EP3775122A1 (fr) 2018-05-17 2021-02-17 Unilever PLC Composition de nettoyage comprenant des tensioactifs à base de rhamnolipide et d'alkyl éther carboxylate
US11708542B2 (en) 2018-06-20 2023-07-25 The Procter & Gamble Company Product comprising polysaccharide derivatives
EP3594319B1 (fr) 2018-07-12 2021-05-05 The Procter & Gamble Company Composition de détergent de blanchisserie particulaire solide à écoulement libre
BR112021000774A2 (pt) 2018-07-17 2021-04-13 Unilever Ip Holdings B.V. Uso de ramnolipídio em um sistema de tensoativo para detergentes para lavagem manual
CN112703246A (zh) 2018-09-17 2021-04-23 联合利华知识产权控股有限公司 洗涤剂组合物
BR112021009828A2 (pt) 2018-11-20 2021-08-17 Unilever Ip Holdings B.V. composição detergente líquida, método de tratamento de um substrato de tecido e uso de uma enzima esterol esterase
WO2020104155A1 (fr) 2018-11-20 2020-05-28 Unilever Plc Composition détergente
WO2020104159A1 (fr) 2018-11-20 2020-05-28 Unilever Plc Composition détergente
WO2020104157A1 (fr) 2018-11-20 2020-05-28 Unilever Plc Composition détergente
CN113166689A (zh) 2018-11-20 2021-07-23 联合利华知识产权控股有限公司 洗涤剂组合物
WO2020109227A1 (fr) 2018-11-28 2020-06-04 Unilever N.V. Grosses particules
WO2020123889A1 (fr) 2018-12-14 2020-06-18 The Procter & Gamble Company Structures fibreuses moussantes comprenant des particules et leurs procédés de production
US20220098525A1 (en) 2019-01-22 2022-03-31 Conopco, Inc., D/B/A Unilever Laundry detergent
US20220098520A1 (en) * 2019-01-22 2022-03-31 Conopco, Inc., D/B/A Unilever Laundry detergent
WO2020222996A1 (fr) 2019-04-29 2020-11-05 The Procter & Gamble Company Procédé de fabrication d'une composition de détergent destiné au lavage du linge
EP3750978A1 (fr) 2019-06-12 2020-12-16 Unilever N.V. Composition de détergent pour lessive
EP3750979A1 (fr) 2019-06-12 2020-12-16 Unilever N.V. Utilisation d'une composition de détergent à lessive
EP3754010A1 (fr) 2019-06-17 2020-12-23 The Procter & Gamble Company Composition de détergent pour lessive solide particulaire à écoulement libre comprenant un tensioactif détersif et un sel de polyamine linéaire
EP3990604B1 (fr) 2019-06-28 2022-12-14 Unilever Global IP Limited Composition de détergent
US20220372400A1 (en) 2019-06-28 2022-11-24 Conopco, Inc., D/B/A Unilever Detergent composition
BR112021023398A2 (pt) 2019-06-28 2022-01-04 Unilever Ip Holdings B V Composição detergente, método doméstico de tratamento de um têxtil e uso de um álcool de sulfato de éter
WO2020260038A1 (fr) 2019-06-28 2020-12-30 Unilever Plc Composition détergente
WO2020260006A1 (fr) 2019-06-28 2020-12-30 Unilever Plc Compositions détergentes
EP3990599B1 (fr) 2019-06-28 2023-01-18 Unilever Global Ip Limited Composition de détergent
CN114207123A (zh) 2019-07-02 2022-03-18 诺维信公司 脂肪酶变体及其组合物
US11485934B2 (en) 2019-08-02 2022-11-01 The Procter & Gamble Company Foaming compositions for producing a stable foam and methods for making same
CN114286854A (zh) 2019-08-21 2022-04-05 联合利华知识产权控股有限公司 洗涤剂固体组合物
WO2021037878A1 (fr) 2019-08-27 2021-03-04 Novozymes A/S Composition comprenant une lipase
AR119874A1 (es) 2019-09-02 2022-01-19 Unilever Nv Composición detergente con un derivado de éster de ácido cítrico de un monoglicérido
EP3798290B1 (fr) 2019-09-30 2022-08-17 The Procter & Gamble Company Utilisation d'un polymère cellulosique anioniquement modifié en tant qu'inhibiteurs de transfert pigmentaire pendant un processus de blanchissage de textile
AR120142A1 (es) 2019-10-07 2022-02-02 Unilever Nv Composición detergente
US20210148044A1 (en) 2019-11-15 2021-05-20 The Procter & Gamble Company Graphic-Containing Soluble Articles and Methods for Making Same
US20210269747A1 (en) * 2020-03-02 2021-09-02 Milliken & Company Composition Comprising Hueing Agent
US11718814B2 (en) 2020-03-02 2023-08-08 Milliken & Company Composition comprising hueing agent
WO2021185956A1 (fr) 2020-03-19 2021-09-23 Unilever Ip Holdings B.V. Composition détergente
BR112022018393A2 (pt) 2020-03-19 2022-11-08 Unilever Ip Holdings B V Método e uso de saponina para inibir a atividade de lipase em uma composição detergente
US11807829B2 (en) 2020-06-05 2023-11-07 The Procter & Gamble Company Detergent compositions containing a branched surfactant
EP4162018B1 (fr) 2020-06-08 2024-01-31 Unilever IP Holdings B.V. Composition de détergent
HUE062018T2 (hu) 2020-07-06 2023-09-28 Procter & Gamble Eljárás szemcsés mosószerkészítmény elõállítására
EP4189051B1 (fr) 2020-07-27 2024-02-28 Unilever IP Holdings B.V. Utilisation d'une enzyme et d'un tensioactif pour inhiber les microorganismes
EP4204530A1 (fr) 2020-08-28 2023-07-05 Unilever IP Holdings B.V. Composition détergente
US20230287300A1 (en) 2020-08-28 2023-09-14 Conopco, Inc., D/B/A Unilever Surfactant and detergent composition
WO2022043042A1 (fr) 2020-08-28 2022-03-03 Unilever Ip Holdings B.V. Composition détergente
US20230303949A1 (en) 2020-08-28 2023-09-28 Conopco, Inc., D/B/A Unilever Surfactant and detergent composition
EP4204531A1 (fr) 2020-08-28 2023-07-05 Unilever IP Holdings B.V. Composition détergente
WO2022063707A1 (fr) 2020-09-24 2022-03-31 Unilever Ip Holdings B.V. Composition
EP4217455B1 (fr) 2020-09-24 2024-05-01 Unilever IP Holdings B.V. Composition
EP3978589A1 (fr) 2020-10-01 2022-04-06 The Procter & Gamble Company Alcoxylates d'alcool à gamme étroite et dérivés associés
WO2022077022A1 (fr) 2020-10-09 2022-04-14 The Procter & Gamble Company Produit détergent de blanchisserie emballé
WO2022093189A1 (fr) 2020-10-27 2022-05-05 Milliken & Company Compositions comprenant des composés leuco et des colorants
WO2022090361A2 (fr) 2020-10-29 2022-05-05 Novozymes A/S Variants de lipase et compositions comprenant de tels variants de lipase
WO2022103725A1 (fr) 2020-11-13 2022-05-19 Novozymes A/S Composition détergente comprenant une lipase
WO2022122474A1 (fr) 2020-12-07 2022-06-16 Unilever Ip Holdings B.V. Composition
US20240124800A1 (en) 2020-12-07 2024-04-18 Conopco, Inc., D/B/A Unilever Composition
WO2022122425A1 (fr) 2020-12-07 2022-06-16 Unilever Ip Holdings B.V. Composition
AU2021398306A1 (en) 2020-12-07 2023-06-15 Unilever Global Ip Limited Composition
CN116568787A (zh) 2020-12-08 2023-08-08 联合利华知识产权控股有限公司 油醇和产生方法
EP4263773A1 (fr) 2020-12-17 2023-10-25 Unilever IP Holdings B.V. Composition de nettoyage
WO2022128786A1 (fr) 2020-12-17 2022-06-23 Unilever Ip Holdings B.V. Utilisation et composition de nettoyage
WO2022129374A1 (fr) 2020-12-18 2022-06-23 Unilever Ip Holdings B.V. Composition détergente
EP4305140A1 (fr) 2021-03-09 2024-01-17 Unilever IP Holdings B.V. Composition
EP4323493A1 (fr) 2021-04-15 2024-02-21 Unilever IP Holdings B.V. Composition
CN117222730A (zh) 2021-04-15 2023-12-12 联合利华知识产权控股有限公司 组合物
CN117177913A (zh) 2021-04-15 2023-12-05 联合利华知识产权控股有限公司 组合物
WO2022219132A1 (fr) 2021-04-15 2022-10-20 Unilever Ip Holdings B.V. Composition
EP4323482A1 (fr) 2021-04-15 2024-02-21 Unilever IP Holdings B.V. Composition
WO2022228903A1 (fr) 2021-04-30 2022-11-03 Unilever Ip Holdings B.V. Composition
WO2022228949A1 (fr) 2021-04-30 2022-11-03 Unilever Ip Holdings B.V. Composition
CN116964184A (zh) 2021-04-30 2023-10-27 联合利华知识产权控股有限公司 组合物
CN116848224A (zh) 2021-04-30 2023-10-03 联合利华知识产权控股有限公司 组合物
WO2022228950A1 (fr) 2021-04-30 2022-11-03 Unilever Ip Holdings B.V. Composition
CN117043401A (zh) 2021-05-28 2023-11-10 宝洁公司 包含表面活性剂的基于天然聚合物的纤维元件及其制备方法
WO2022248108A1 (fr) 2021-05-28 2022-12-01 Unilever Ip Holdings B.V. Composition de détergent à lessive liquide comprenant un tensioactif d'éthoxylate d'alcool en c16 et c18 et/ou un sulfate d'éther alkylique en c16 à c18
BR112023026713A2 (pt) 2021-06-24 2024-03-12 Unilever Ip Holdings B V Composição de limpeza em dose unitária
EP4108754A1 (fr) 2021-06-25 2022-12-28 The Procter & Gamble Company Procédé de fabrication d'une poudre de détergent à lessive emballée
EP4108756A1 (fr) 2021-06-25 2022-12-28 The Procter & Gamble Company Poudre de détergent pour le linge
EP4112707A1 (fr) 2021-06-30 2023-01-04 The Procter & Gamble Company Traitement des tissus
EP4123005B1 (fr) 2021-07-19 2024-03-06 The Procter & Gamble Company Composition de nettoyage comprenant des spores bactériennes
WO2023011892A1 (fr) 2021-08-05 2023-02-09 Unilever Ip Holdings B.V. Composition
AU2022321954A1 (en) 2021-08-05 2024-02-01 Unilever Global Ip Limited Method
WO2023012093A1 (fr) 2021-08-05 2023-02-09 Unilever Ip Holdings B.V. Procédé
JPWO2023017794A1 (fr) 2021-08-10 2023-02-16
WO2023041694A1 (fr) 2021-09-20 2023-03-23 Unilever Ip Holdings B.V. Composition détergente
WO2023051978A1 (fr) 2021-09-29 2023-04-06 Unilever Ip Holdings B.V. Composition
WO2023057532A2 (fr) 2021-10-08 2023-04-13 Unilever Ip Holdings B.V. Composition
WO2023057537A1 (fr) 2021-10-08 2023-04-13 Unilever Ip Holdings B.V. Composition de lessive
WO2023057367A1 (fr) 2021-10-08 2023-04-13 Unilever Ip Holdings B.V. Composition de lessive
WO2023057604A2 (fr) 2021-10-08 2023-04-13 Unilever Ip Holdings B.V. Composition de lessive
WO2023057531A2 (fr) 2021-10-08 2023-04-13 Unilever Ip Holdings B.V. Composition
WO2023057323A2 (fr) 2021-10-08 2023-04-13 Unilever Ip Holdings B.V. Composition
WO2023057322A1 (fr) 2021-10-08 2023-04-13 Unilever Ip Holdings B.V. Composition
WO2023057530A2 (fr) 2021-10-08 2023-04-13 Unilever Ip Holdings B.V. Composition
WO2023067075A1 (fr) 2021-10-21 2023-04-27 Unilever Ip Holdings B.V. Compositions détergentes
US20230129953A1 (en) 2021-10-26 2023-04-27 Conopco, Inc., D/B/A Unilever Composition
WO2023116569A1 (fr) 2021-12-21 2023-06-29 Novozymes A/S Composition comprenant une lipase et un renforçateur
EP4212608A1 (fr) 2022-01-14 2023-07-19 The Procter & Gamble Company Procédé de fabrication d'une particule de détergent à lessive séchée par pulvérisation
WO2023144071A1 (fr) 2022-01-28 2023-08-03 Unilever Ip Holdings B.V. Composition de lessive
WO2023150903A1 (fr) 2022-02-08 2023-08-17 The Procter & Gamble Company Procédé de blanchissage de tissus
WO2023150905A1 (fr) 2022-02-08 2023-08-17 The Procter & Gamble Company Procédé de blanchissage de tissus
EP4234666A1 (fr) 2022-02-24 2023-08-30 The Procter & Gamble Company Article de dose unitaire soluble dans l'eau comprenant une feuille fibreuse non tissée et un système tensioactif
EP4234672A1 (fr) 2022-02-24 2023-08-30 The Procter & Gamble Company Article de dose unitaire soluble dans l'eau comprenant une feuille fibreuse non-tissée et une particule de colorant de nuançage
US20230348817A1 (en) 2022-04-27 2023-11-02 The Procter & Gamble Company Liquid detergent formulation
EP4279570A1 (fr) 2022-05-19 2023-11-22 The Procter & Gamble Company Procédé de fabrication d'une composition détergente de blanchisserie particulaire
WO2023227375A1 (fr) 2022-05-27 2023-11-30 Unilever Ip Holdings B.V. Composition liquide pour le linge comprenant un tensioactif, un aminocarboxylate, un acide organique et un parfum
WO2023227335A1 (fr) 2022-05-27 2023-11-30 Unilever Ip Holdings B.V. Composition liquide comprenant un sulfonate d'alkylbenzène linéaire, un éthoxylate d'ester de méthyle et un polymère de polyamine zwitterionique alcoxylé
WO2023227421A1 (fr) 2022-05-27 2023-11-30 Unilever Ip Holdings B.V. Composition liquide pour la lessive comprenant un tensioactif, un polymère de polyamine zwitterionique alcoxylé et un parfum
WO2023227331A1 (fr) 2022-05-27 2023-11-30 Unilever Ip Holdings B.V. Composition comprenant un tensioactif éthoxylate d'ester de méthyle spécifique et une lipase
WO2023227332A1 (fr) 2022-05-27 2023-11-30 Unilever Ip Holdings B.V. Composition liquide de blanchisserie comprenant un tensioactif, un polymère de polyamine zwitterionique alcoxylé et une protéase
WO2023247664A2 (fr) 2022-06-24 2023-12-28 Novozymes A/S Variants de lipase et compositions comprenant de tels variants de lipase
EP4299701A1 (fr) 2022-06-27 2024-01-03 The Procter & Gamble Company Composition de détergent de blanchisserie particulaire solide à écoulement libre
EP4299702A1 (fr) 2022-06-27 2024-01-03 The Procter & Gamble Company Composition de détergent de blanchisserie particulaire solide à écoulement libre
EP4299703A1 (fr) 2022-06-27 2024-01-03 The Procter & Gamble Company Composition de détergent de blanchisserie particulaire solide à écoulement libre
EP4299704A1 (fr) 2022-06-27 2024-01-03 The Procter & Gamble Company Procédé de lavage et de séchage de tissus
EP4321604A1 (fr) 2022-08-08 2024-02-14 The Procter & Gamble Company Tissu et composition de soins à domicile comprenant un tensioactif et un polyester
WO2024037918A1 (fr) 2022-08-16 2024-02-22 Unilever Ip Holdings B.V. Procédé pour produire une composition de blanchisserie
WO2024037921A1 (fr) 2022-08-16 2024-02-22 Unilever Ip Holdings B.V. Composition de lessive comprenant du carraghénane, un agent bénéfique et du chlorure de sodium
WO2024037920A1 (fr) 2022-08-16 2024-02-22 Unilever Ip Holdings B.V. Procédé de production d'une composition de lessive
WO2024056334A1 (fr) 2022-09-13 2024-03-21 Unilever Ip Holdings B.V. Machine à laver et procédé de lavage
WO2024056278A1 (fr) 2022-09-13 2024-03-21 Unilever Ip Holdings B.V. Machine à laver et procédé de lavage
WO2024056333A1 (fr) 2022-09-13 2024-03-21 Unilever Ip Holdings B.V. Machine à laver et procédé de lavage
WO2024056332A1 (fr) 2022-09-13 2024-03-21 Unilever Ip Holdings B.V. Machine à laver et procédé de lavage
EP4342970A1 (fr) 2022-09-21 2024-03-27 Milliken & Company Particules colorées d'agent colorant teintant
EP4342969A1 (fr) 2022-09-21 2024-03-27 The Procter & Gamble Company Composition de nettoyage de détergent solide
EP4349948A1 (fr) 2022-10-05 2024-04-10 Unilever IP Holdings B.V. Composition liquide pour la lessive
EP4349942A1 (fr) 2022-10-05 2024-04-10 Unilever IP Holdings B.V. Composition liquide pour la lessive
EP4349944A1 (fr) 2022-10-05 2024-04-10 Unilever IP Holdings B.V. Composition liquide pour la lessive
EP4349946A1 (fr) 2022-10-05 2024-04-10 Unilever IP Holdings B.V. Produit de traitement de tissu en dose unitaire
EP4349947A1 (fr) 2022-10-05 2024-04-10 Unilever IP Holdings B.V. Composition liquide pour la lessive
EP4349945A1 (fr) 2022-10-05 2024-04-10 Unilever IP Holdings B.V. Composition liquide pour la lessive
EP4349943A1 (fr) 2022-10-05 2024-04-10 Unilever IP Holdings B.V. Composition liquide pour la lessive
WO2024074247A1 (fr) 2022-10-06 2024-04-11 Unilever Ip Holdings B.V. Composition
WO2024088706A1 (fr) 2022-10-25 2024-05-02 Unilever Ip Holdings B.V. Composition
EP4361239A1 (fr) 2022-10-25 2024-05-01 Unilever IP Holdings B.V. Composition liquide pour la lessive
WO2024088716A1 (fr) 2022-10-25 2024-05-02 Unilever Ip Holdings B.V. Composition
EP4364930A1 (fr) 2022-11-01 2024-05-08 The Procter & Gamble Company Mâchoires de scellage et article de dose unitaire soluble dans l'eau comprenant une feuille fibreuse non tissée
EP4364929A1 (fr) 2022-11-01 2024-05-08 The Procter & Gamble Company Mâchoires de scellage et article de dose unitaire soluble dans l'eau comprenant une feuille fibreuse non tissée
WO2024094802A1 (fr) 2022-11-04 2024-05-10 The Procter & Gamble Company Tissu et composition d'entretien ménager
WO2024094790A1 (fr) 2022-11-04 2024-05-10 Clariant International Ltd Polyesters
WO2024094803A1 (fr) 2022-11-04 2024-05-10 The Procter & Gamble Company Composition d'entretien textile et ménager

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4137243A (en) * 1976-08-24 1979-01-30 Milliken Research Corporation Polymeric anthraquinone derived colorants
DE2962387D1 (en) * 1978-06-20 1982-05-06 Procter & Gamble Washing and softening compositions containing nonionic brightener
CA1243669A (fr) * 1984-06-25 1988-10-25 Edward W. Kluger Colorants reactifs
SE8504661L (sv) * 1984-10-17 1986-04-18 Colgate Palmolive Co Mjukgorande och antistatisk vetskeformig detergentkomposition
DE3911950A1 (de) * 1989-04-12 1990-10-18 Basf Ag Marineblaue und schwarze farbstoffmischungen
US5039782A (en) * 1990-12-11 1991-08-13 Lever Brothers Company, Division Of Conopco, Inc. Polymeric whitening agent
SG88788A1 (en) * 2000-08-31 2002-05-21 Milliken Asia Pte Ltd Laundry bars comprising non-staining high molecular weight water soluble polymeric colorants
GB0212995D0 (en) * 2002-06-06 2002-07-17 Unilever Plc Ligand and complex for catalytically bleaching a substrate
AR049538A1 (es) * 2004-06-29 2006-08-09 Procter & Gamble Composiciones de detergentes para lavanderia con colorante entonador eficiente
BRPI0515042A (pt) * 2004-09-23 2008-07-01 Unilever Nv composição de tratamento para a lavagem de roupas, e, método de tratamento de um têxtil
US7342113B2 (en) * 2004-11-18 2008-03-11 Milliken & Company Colorant compositions

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2008087497A1 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2118256B2 (fr) † 2007-01-26 2020-02-12 Unilever PLC Composition de nuançage

Also Published As

Publication number Publication date
PL2192169T3 (pl) 2012-10-31
ATE486927T1 (de) 2010-11-15
ES2355763T3 (es) 2011-03-30
BRPI0720944A2 (pt) 2013-03-26
JP2010515838A (ja) 2010-05-13
DE602007010350D1 (de) 2010-12-16
ATE557080T1 (de) 2012-05-15
CN101583704A (zh) 2009-11-18
EP2104729B1 (fr) 2010-11-03
CA2673239A1 (fr) 2008-07-24
PL2104729T3 (pl) 2011-04-29
JP5122583B2 (ja) 2013-01-16
BRPI0720944B1 (pt) 2017-05-30
CN101583704B (zh) 2013-05-15
WO2008087497A1 (fr) 2008-07-24
ES2386873T3 (es) 2012-09-04
CA2673239C (fr) 2012-07-24
MX2009007746A (es) 2009-07-27
EP2192169B1 (fr) 2012-05-09
EP2192169A1 (fr) 2010-06-02

Similar Documents

Publication Publication Date Title
US11946025B2 (en) Whitening agents for cellulosic substrates
CA2673239C (fr) Composition pour lavage de linge comprenant un agent blanchissant ayant une entite colorante d'azothiophene ou de triphenylmethane et une entite de polyoxyalkylene
EP2104709B1 (fr) Nouveaux agents de blanchiment pour des substrats cellulosiques
EP3362542B1 (fr) Compositions d'entretien du linge comprenant des agents de blanchiment pour substrats cellulosiques
WO2017066337A1 (fr) Nouveaux agents de blanchiment pour substrats cellulosiques
EP3362541B1 (fr) Compositions d'entretien du linge comprenant des agents de blanchiment pour substrats cellulosiques
EP3362543B1 (fr) Compositions d'entretien du linge comprenant des agents de blanchiment pour substrats cellulosiques
US9976035B2 (en) Whitening agents for cellulosic substrates
WO2017066334A1 (fr) Nouveaux agents de blanchiment pour substrats cellulosiques

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20090714

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

17Q First examination report despatched

Effective date: 20091204

DAX Request for extension of the european patent (deleted)
GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REF Corresponds to:

Ref document number: 602007010350

Country of ref document: DE

Date of ref document: 20101216

Kind code of ref document: P

REG Reference to a national code

Ref country code: NL

Ref legal event code: T3

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2355763

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20110330

LTIE Lt: invalidation of european patent or patent extension

Effective date: 20101103

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20101103

REG Reference to a national code

Ref country code: PL

Ref legal event code: T3

REG Reference to a national code

Ref country code: HU

Ref legal event code: AG4A

Ref document number: E010126

Country of ref document: HU

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110303

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20101103

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20101103

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20101103

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110303

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20101103

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20101103

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110203

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: PL

Payment date: 20101227

Year of fee payment: 5

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110204

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20101103

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20101103

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20101103

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20101103

Ref country code: MC

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20110131

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20110804

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20110131

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20110131

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602007010350

Country of ref document: DE

Effective date: 20110804

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20110119

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20110119

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20101103

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20101103

REG Reference to a national code

Ref country code: PL

Ref legal event code: LAPE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20130119

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 10

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 11

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20221213

Year of fee payment: 17

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230429

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20231130

Year of fee payment: 18

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20231215

Year of fee payment: 18

Ref country code: FR

Payment date: 20231212

Year of fee payment: 18

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20231219

Year of fee payment: 18

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20240205

Year of fee payment: 18

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: HU

Payment date: 20231213

Year of fee payment: 18

Ref country code: DE

Payment date: 20231205

Year of fee payment: 18

Ref country code: CZ

Payment date: 20240103

Year of fee payment: 18