WO2019008036A1 - Composition de blanchiment - Google Patents

Composition de blanchiment Download PDF

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Publication number
WO2019008036A1
WO2019008036A1 PCT/EP2018/068090 EP2018068090W WO2019008036A1 WO 2019008036 A1 WO2019008036 A1 WO 2019008036A1 EP 2018068090 W EP2018068090 W EP 2018068090W WO 2019008036 A1 WO2019008036 A1 WO 2019008036A1
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WO
WIPO (PCT)
Prior art keywords
cleaning composition
surfactant
composition according
laundry cleaning
alkyl
Prior art date
Application number
PCT/EP2018/068090
Other languages
English (en)
Inventor
Stephen Norman Batchelor
Catherine Breffa
Jan DIEDERICHS
Kevin James MUTCH
Steffen ROMANSKI
Carsten Schaefer
Original Assignee
Unilever Plc
Unilever N.V.
Conopco, Inc., D/B/A Unilever
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 Unilever Plc, Unilever N.V., Conopco, Inc., D/B/A Unilever filed Critical Unilever Plc
Priority to BR112020000201-1A priority Critical patent/BR112020000201B1/pt
Priority to EP18734831.3A priority patent/EP3649222B1/fr
Priority to CN201880045612.9A priority patent/CN110869480B/zh
Publication of WO2019008036A1 publication Critical patent/WO2019008036A1/fr
Priority to ZA2019/08604A priority patent/ZA201908604B/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/37—Mixtures of compounds all of which are anionic
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0036—Soil deposition preventing compositions; Antiredeposition agents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3707—Polyethers, e.g. polyalkyleneoxides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/40—Dyes ; Pigments
    • C11D3/42—Brightening agents ; Blueing agents
    • C—CHEMISTRY; METALLURGY
    • 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
    • C11D3/50—Perfumes
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/04—Carboxylic acids or salts thereof
    • C11D1/06—Ether- or thioether carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/34—Derivatives of acids of phosphorus
    • C11D1/345—Phosphates or phosphites
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/74—Carboxylates or sulfonates esters of polyoxyalkylene glycols

Definitions

  • the present invention concerns a laundry cleaning composition.
  • AD alkoxylated dispersants
  • the present invention provides a laundry cleaning composition
  • X is selected from: ethoxy; and mixtures of ethoxy and propoxy groups, wherein the number of ethoxy groups is greater than the number of propoxy groups, and wherein n is from 6 to 70;
  • n is selected from: 2 and 3;
  • Ri is selected from: uncharged C12 to C20 alkyl groups; uncharged aryl groups; and, uncharged alkyl-aryl groups wherein the alkyl group of the alkyl-aryl is a saturated linear or branched C1 to C3;
  • T is selected from: H; CH 3 ; S0 3 " ; ChbCOO-; PO3 2" ; C 2 H 5 ; n-propyl, i-propyl; n-butyl; t-butyl; and, sulfosuccinate; from 0 to 50 wt.% surfactant, other than the alkoxylated dispersant; and, an active selected from one or more of the following: from 0.001 to 3 wt.% perfume; from 0.0001 to 0.5 wt.% of fluorescent agent; and, from 0.0001 wt.% to 0.1 wt% of an enzyme.
  • Ri is an alkyl-aryl group in the alkoxylated dispersant structure.
  • T is not H in the alkoxylated dispersant structure.
  • X is ethoxy in the alkoxylated dispersant structure.
  • the mole average number of alkoxy groups is from 6 to 40, more preferably from 9 to 30, most preferably from 10 to 20 in the alkoxylated dispersant structure.
  • T is CH3 in the alkoxylated dispersant structure.
  • Ri is selected from: phenylethyl and benzyl. More preferably Ri is benzyl.
  • the alkoxylated dispersant is selected from:
  • a preferred laundry cleaning composition comprise surfactant, other than the alkoxylated dispersant, at a level of from 4 to 40 wt.%, more preferably from 4 to 35 wt.%, most preferably from 6 to 30 wt.%.
  • the surfactant, other than the alkoxylated dispersant comprises anionic and/or non-ionic surfactants.
  • the weight fraction of non-ionic surfactant to anionic surfactant is from 0 to 0.3. This means that non-ionic surfactant can be present (or it may be absent if the weight fraction is 0), but if non-ionic surfactant is present, then the weight fraction of the non-ionic surfactant is preferably at most 30% of the total weight of anionic surfactant + non-ionic surfactant, wherein the alkoxylated dispersant is not considered a surfactant as defined herein.
  • the anionic surfactant is selected from: linear alkyl benzene sulphonates; alkyl sulphates; alkyl ether sulphates; and mixtures thereof.
  • the non-ionic surfactant is an alcohol ethoxylate, more preferably an C10-C18 alcohol ethoxylate having an average of 3-10 moles of ethylene oxide, most preferably an C12-C15 alcohol ethoxylate having an average of 5-9 moles of ethylene oxide.
  • the laundry cleaning composition is preferably an aqueous laundry liquid detergent composition.
  • the pH of the aqueous liquid detergent composition is from 6 to 8.5, more preferably from 6.5 to 7.5, even more preferably from 6.8 to 7.2, most preferably 7.0.
  • the active ingredient is an enzyme and comprises one or more of the following: proteases, alpha-amylases, cellulases, lipases, peroxidases/oxidases, pectate lyases, and mannanases, or mixtures thereof. More preferably the enzyme is a protease, most preferably a subtilase type serine protease.
  • the invention provides a domestic method of treating a textile, the method comprising the steps of:
  • the aqueous solution comprising from 10 ppm to 5000 ppm, preferably from 100 ppm to 1000 ppm, of the alkoxylated dispersant as defined herein; and, 0 to 6 g/L, preferably from 0.5 to 6 g/L, more preferably from 1 to 5 g/L of a surfactant, other than the alkoxylated dispersant; and,
  • one or more of an active ingredient selected from perfume, fluorescent agent and enzyme is present in the aqueous solution of the alkoxylated dispersant,
  • the level of the perfume in the aqueous solution is from 0.1 to 100 ppm; preferably from 1 to 10ppm.
  • the level of the fluorescent agent in the aqueous solution is from 0.0001 g/l to 0.1 g/L, preferably from 0.001 to 0.02 g/L;
  • the level of the enzyme in the aqueous solution is from 0.01 to 10ppm, preferably 0.05 to 1 ppm.
  • the surfactant used is preferably as preferred for the composition aspects of the present invention.
  • domestic methods are preferably conducted in a domestic washing machine or by hand washing.
  • the temperature of the wash is preferably from 285 to 335 degrees Kelvin.
  • the textile is preferably an item of used clothing, bedding or table cloth.
  • Preferred items of clothing are worn cotton containing shirts, trousers, underwear and jumpers.
  • the alkoxylated dispersant has the following structure:-
  • X is selected from: ethoxy; and mixtures of ethoxy and propoxy groups where the number of ethoxy groups is greater than the number of propoxy groups, and wherein n is from 6 to 70;
  • Ri is selected from: uncharged C12 to C20 alkyl groups; uncharged aryl groups; and, uncharged alkyl-aryl groups wherein the alkyl group of the alkyl-aryl is a saturated linear or branched C1 to C3.
  • Ri is an alkyl-aryl group, most preferably benzyl.
  • T is selected from: H; CH 3 ; S0 3 " ; CH 2 COO " ; P0 3 2" ; C 2 H 5 ; n-propyl, i-propyl; n-butyl; t-butyl; and, sulfosuccinate; preferably T is not H, most preferably T is CH3.
  • the value m is selected from 2 and 3, and is preferably 2.
  • the alkoxylated dispersant is preferably formed as a reaction product of trimellitic anhydride or pyromellitic dianhydride with a polyether of the form T-(X) n -OH and alcohol of the form R1-OH, where Ri is selected from uncharged C12 to C20 alkyl groups;
  • uncharged aryl groups and, uncharged alkyl-aryl groups wherein the alkyl group of the alkyl-aryl is a saturated linear or branched C1 to C3.
  • R1-OH is selected from 2-phenylethanol and benzyl alcohol.
  • Ri may be substituted by further uncharged organic groups, for example when Ri contains a benzene ring the benzene ring may be substituted by methyl, ethyl, methoxy, ethoxy, CI, NO2.
  • R1-OH is an aromatic alcohol
  • phenol for example may be used in the reaction.
  • trimetalitc anhydride or pyrometallitic anhydride is reacted with the polyether then the R1-OH alcohol.
  • the trimetalitc anhydride or pyrometallitic anhydride is reacted with 1 mole equivalent of the polyether then the R1-OH alcohol.
  • X is selected from OCH2CH2 (ethoxy) and OCH(CH3)CH2 (propoxy) and mixtures thereof, wherein if a mixture, then the number of ethoxy groups is greater than the number of propoxy groups. If X comprises propoxy groups then preferably the mole ratio of ethoxy/propoxy is greater than 2, more preferably greater than 5.
  • X is a mixture of ethoxy and propoxy groups, then they may distributed blockwise, alternatively, periodically and/or statistically.
  • X is most preferably OCH2CH2 (ethoxy).
  • the value n is the mole average number of alkoxyl groups. The value of n may be measured using NMR. The value of n is from 6 to 70, preferably 6 to 40, more preferably 9 to 30. Indeed the value of n may be individually 9, 10, 1 1 , 12, 13, 14; 15; 16; 17; 18; 19; 20; 21 ; 22; 23; 24; 25; 26; 27; 28; 29, or 30. Most preferably the value of n may be from 10 to 20.
  • the alkoxylated dispersant may alternatively be formed by reaction of the anhydride with R1-OH then alkoxylation with an epoxide, however, this route is not preferred. Trimellitic anhydride chloride may also be used.
  • alkoxylated dispersant is not considered a surfactant and does not contribute numerically to the surfactant as defined herein.
  • Sulfoccinate has the structure:
  • the alkoxylated dispersant prevents the deposition of soil present in the wash liquor onto the fabric.
  • the alkoxylated dispersant can also increase stain removal.
  • the laundry cleaning composition comprises an active ingredient selected from one or more of the following: from 0.001 to 3 wt.% perfume; from 0.0001 to 0.5 wt.% of fluorescent agent; and, from 0.0001 wt.% to 0.1 wt.% of an enzyme.
  • Contemplated enzymes include proteases, alpha-amylases, cellulases, lipases, peroxidases/oxidases, pectate lyases, and mannanases, or mixtures thereof.
  • the enzyme is selected from: proteases, alpha-amylases; cellulases and lipases, or mixtures thereof. More preferably the enzyme is a protease, more preferably a subtilase type serine protease.
  • the laundry composition may comprise anionic and non-ionic surfactant (which includes a mixture of the same).
  • the surfactant is present at a level of from 0 to 50 wt.%. This means that surfactant need not be present, but it is preferred that it is present.
  • Preferred laundry cleaning compositions comprise surfactant at a level of from 4 to 40 wt.%, more preferably from 4 to 35 wt.%, most preferably from 6 to 30 wt.%.
  • the surfactant comprises anionic and/or non-ionic surfactants.
  • Suitable nonionic and anionic surfactants may be chosen from the surfactants described "Surface Active Agents" Vol. 1 , by Schwartz & Perry, Interscience 1949, Vol. 2 by
  • Suitable anionic detergent compounds which may be used are usually water-soluble alkali metal salts of organic sulphates and sulphonates having alkyl radicals containing from about 8 to about 22 carbon atoms, the term alkyl being used to include the alkyl portion of higher alkyl radicals.
  • suitable synthetic anionic detergent compounds are sodium and potassium alkyl sulphates, especially those obtained by sulphating higher Cs to Cie alcohols, produced for example from tallow or coconut oil, Alkyl ether carboxylic acids; sodium and potassium alkyl Cg to C20 benzene sulphonates, particularly sodium linear secondary alkyl C10 to Ci5 benzene sulphonates; and sodium alkyl glyceryl ether sulphates, especially those ethers of the higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum.
  • the anionic surfactant is preferably selected from: linear alkyi benzene sulphonate; alkyi sulphates; alkyi ether sulphates; alkyi ether carboxylates; soaps; alkyi (preferably methyl) ester sulphonates, and mixtures thereof. More preferred anionic surfactants are selected from: linear alkyi benzene sulphonate; alkyi sulphates; alkyi ether sulphates and mixtures thereof.
  • the alkyi ether sulphate is a C12-C14 n-alkyl ether sulphate with an average of 1 to 3EO (ethoxylate) units.
  • Sodium lauryl ether sulphate is particularly preferred (SLES).
  • the linear alkyi benzene sulphonate is a sodium Cn to C15 alkyi benzene sulphonates.
  • the alkyi sulphates is a linear or branched sodium C12 to C18 alkyi sulphates.
  • Sodium dodecyl sulphate is particularly preferred, (SDS, also known as primary alkyi sulphate).
  • two or more anionic surfactant are present, for example linear alkyi benzene sulphonate together with an alkyi ether sulphate.
  • anionic surfactant is selected from: linear alkyi benzene sulphonates; alkyi sulphates; alkyi ether sulphates; and mixtures thereof.
  • composition may comprise anionic and/or non-ionic surfactants.
  • the weight fraction of non-ionic surfactant to anionic surfactant is from 0 to 0.3. This means that non-ionic surfactant can be present (or it may be absent if the weight fraction is 0), but if non-ionic surfactant is present, then the weight fraction of the non- ionic surfactant is preferably at most 30% of the total weight of anionic surfactant + non- ionic surfactant.
  • Suitable nonionic detergent compounds which may be used include, in particular, the reaction products of compounds having an aliphatic hydrophobic group and a reactive hydrogen atom, for example, aliphatic alcohols, acids or amides, especially ethylene oxide either alone or with propylene oxide.
  • Specific nonionic detergent compounds are the condensation products of aliphatic Cs to C18 primary or secondary linear or branched alcohols with ethylene oxide.
  • the non-ionic surfactant is an alcohol ethoxylate, more preferably a C10-C18 alcohol ethoxylate having an average of 3- 10 moles of ethylene oxide, most preferably an C12-C15 alcohol ethoxylate having an average of 5-9 moles of ethylene oxide.
  • surfactants used are saturated.
  • surfactants such as those described in EP-A-328 177 (Unilever), which show resistance to salting-out, the alkyl polyglycoside surfactants described in A-070 074, and alkyl monoglycosides.
  • the surfactant may comprise a cationic surfactant
  • quaternary ammonium compounds Most preferred are quaternary ammonium compounds. It is advantageous if the quaternary ammonium compound is a quaternary ammonium compound having at least one C12 to C22 alkyl chain.
  • the quaternary ammonium compound has the following formula:
  • a preferred compound of this type is the quaternary ammonium compound cetyl trimethyl quaternary ammonium bromide.
  • a second class of materials for use with the present invention are the quaternary ammonium of the above structure in which R 1 and R 2 are independently selected from C12 to C22 alkyl or alkenyl chain; R 3 and R 4 are independently selected from Ci to C 4 alkyl chains and X " is a compatible anion.
  • composition optionally comprises a silicone.
  • One or more perfumes may be present as whole or part of the active ingredient of the laundry cleaning composition.
  • the composition preferably comprises a perfume.
  • the perfume is preferably present in the range from 0.001 to 3 wt.%, more preferably 0.05 to 0.5 wt.%, most preferably 0.1 to 1 wt.%.
  • CTFA Cosmetic, Toiletry and Fragrance Association
  • Many suitable examples of perfumes are provided in the CTFA (Cosmetic, Toiletry and Fragrance Association) 1992 International Buyers Guide, published by CFTA Publications and OPD 1993 Chemicals Buyers Directory 80th Annual Edition, published by Schnell Publishing Co.
  • the perfume comprises at least one note (compound) from: alpha-isomethyl ionone, benzyl salicylate; citronellol; coumarin; hexyl cinnamal; linalool; Pentanoic acid, 2- methyl-, ethyl ester; octanal; benzyl acetate; 1 ,6-octadien-3-ol, 3,7-dimethyl-, 3-acetate; cyclohexanol, 2-(1 , 1 -dimethylethyl)-, 1 -acetate; delta-damascone; beta-ionone; verdyl acetate; dodecanal; hexyl cinnamic aldehyde; cyclopentadecanolide; benzeneacetic acid, 2-phenylethyl ester;amyl salicylate; beta-caryophyllene; ethyl undecyl
  • Useful components of the perfume include materials of both natural and synthetic origin. They include single compounds and mixtures. Specific examples of such components may be found in the current literature, e.g., in Fenaroli's Handbook of Flavor Ingredients, 1975, CRC Press; Synthetic Food Adjuncts, 1947 by M. B. Jacobs, edited by Van
  • compositions of the present invention it is envisaged that there will be four or more, preferably five or more, more preferably six or more or even seven or more different perfume components.
  • top notes are defined by Poucher (Journal of the Society of Cosmetic Chemists 6(2):80 [1955]).
  • Preferred top- notes are selected from citrus oils, linalool, linalyl acetate, lavender, dihydromyrcenol, rose oxide and cis-3-hexanol.
  • perfume components which it is advantageous to encapsulate include those with a relatively low boiling point, preferably those with a boiling point of less than 300, preferably 100-250 Celsius. It is also advantageous to encapsulate perfume components which have a low CLog P (i.e., those which will have a greater tendency to be partitioned into water), preferably with a CLog P of less than 3.0.
  • these materials have been called the "delayed blooming" perfume ingredients and include one or more of the following materials: allyl caproate, amyl acetate, amyl propionate, anisic aldehyde, anisole, benzaldehyde, benzyl acetate, benzyl acetone, benzyl alcohol, benzyl formate, benzyl iso valerate, benzyl propionate, beta gamma hexenol, camphor gum, laevo-carvone, d-carvone, cinnamic alcohol, cinamyl formate, cis-jasmone, cis-3-hexenyl acetate, cuminic alcohol, cyclal c, dimethyl benzyl carbinol, dimethyl benzyl carbinol acetate, ethyl acetate, ethyl aceto acetate, ethy
  • anthranilate methyl benzoate, methyl benyl acetate, methyl eugenol, methyl heptenone, methyl heptine carbonate, methyl heptyl ketone, methyl hexyl ketone, methyl phenyl carbinyl acetate, methyl salicylate, methyl-n-methyl anthranilate, nerol, octalactone, octyl alcohol, p-cresol, p-cresol methyl ether, p-methoxy acetophenone, p-methyl acetophenone, phenoxy ethanol, phenyl acetaldehyde, phenyl ethyl acetate, phenyl ethyl alcohol, phenyl ethyl dimethyl carbinol, prenyl acetate, propyl bornate, pulegone, rose oxide, safrole, 4-terpinenol, alpha
  • perfume components it is commonplace for a plurality of perfume components to be present in a formulation. It is envisaged that there will be four or more, preferably five or more, more preferably six or more or even seven or more different perfume components from the list given of delayed blooming perfumes given above present in the perfume.
  • perfumes with which the present invention can be applied are the so-called aromatherapy' materials. These include many components also used in perfumery, including components of essential oils such as Clary Sage, Eucalyptus, Geranium, Lavender, Mace Extract, Neroli, Nutmeg, Spearmint, Sweet Violet Leaf and Valerian. It is preferred that the laundry treatment composition does not contain a peroxygen bleach, e.g., sodium percarbonate, sodium perborate, and peracid.
  • a peroxygen bleach e.g., sodium percarbonate, sodium perborate, and peracid.
  • One or more fluorescent agents may be present as whole or part of the active ingredient of the laundry cleaning composition.
  • the composition preferably comprises a fluorescent agent (optical brightener).
  • Fluorescent agents are well known and many such fluorescent agents are available commercially. Usually, these fluorescent agents are supplied and used in the form of their alkali metal salts, for example, the sodium salts.
  • Preferred classes of fluorescer are: Di-styryl biphenyl compounds, e.g. Tinopal (Trade Mark) CBS-X, Di-amine stilbene di-sulphonic acid compounds, e.g. Tinopal DMS pure Xtra and Blankophor (Trade Mark) HRH, and Pyrazoline compounds, e.g. Blankophor SN.
  • Preferred fluorescers are: sodium 2 (4-styryl-3-sulphophenyl)-2H-napthol[1 ,2-d]triazole, disodium 4,4'-bis ⁇ [(4-anilino-6-(N methyl-N-2 hydroxyethyl) amino 1 ,3,5-triazin-2- yl)]amino ⁇ stilbene-2-2' disulophonate, disodium 4,4'-bis ⁇ [(4-anilino-6-morpholino-1 ,3,5- triazin-2-yl)]amino ⁇ stilbene-2-2' disulphonate, and disodium 4,4'-bis(2- sulphostyryl)biphenyl.
  • the total amount of the fluorescent agent or agents used in the composition is preferably from 0.0001 to 0.5 wt.%, more preferably 0.005 to 2 wt.%, most preferably 0.05 to 0.25 wt.%.
  • the aqueous solution used in the method preferably has a fluorescer present.
  • the fluorescer is preferably present in the aqueous solution used in the method in the range from 0.0001 g/l to 0.1 g/l, more preferably 0.001 to 0.02 g/l.
  • Enzymes may be present as whole or part of the active ingredient of the laundry cleaning composition.
  • One or more enzymes are preferably present in the laundry composition of the invention and when practicing a method of the invention.
  • the level of each enzyme in the laundry composition of the invention is from 0.0001 wt.% to 0.1 wt.%.
  • Levels of enzyme present in the composition preferably relate to the level of enzyme as pure protein.
  • Contemplated enzymes include proteases, alpha-amylases, cellulases, lipases, peroxidases/oxidases, pectate lyases, and mannanases, or mixtures thereof.
  • the enzyme is selected from: proteases, alpha-amylases; cellulases and lipases.
  • Suitable lipases include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Examples of useful lipases include lipases from Humicola (synonym Thermomyces), e.g. from H. lanuginosa (T. lanuginosus) as described in EP 258 068 and EP 305 216 or from H. insolens as described in Humicola (synonym Thermomyces), e.g. from H. lanuginosa (T. lanuginosus) as described in EP 258 068 and EP 305 216 or from H. insolens as described in
  • WO 96/13580 a Pseudomonas lipase, e.g. from P. alcaligenes or
  • lipase variants such as those described in WO 92/05249,
  • Preferred commercially available lipase enzymes include LipolaseTM and Lipolase UltraTM, LipexTM and LipocleanTM(Novozymes A/S).
  • the method of the invention may be carried out in the presence of phospholipase classified as EC 3.1.1 .4 and/or EC 3.1.1 .32.
  • phospholipase is an enzyme which has activity towards phospholipids.
  • Phospholipids such as lecithin or phosphatidylcholine, consist of glycerol esterified with two fatty acids in an outer (sn-1 ) and the middle (sn-2) positions and esterified with phosphoric acid in the third position; the phosphoric acid, in turn, may be esterified to an amino-alcohol.
  • Phospholipases are enzymes which participate in the hydrolysis of phospholipids.
  • phospholipases Ai and A2 which hydrolyze one fatty acyl group (in the sn-1 and sn-2 position, respectively) to form lysophospholipid
  • lysophospholipase or phospholipase B which can hydrolyze the remaining fatty acyl group in lysophospholipid.
  • Phospholipase C and phospholipase D release diacyl glycerol or phosphatidic acid respectively.
  • proteases hydrolyse bonds within peptides and proteins, in the laundry context this leads to enhanced removal of protein or peptide containing stains.
  • suitable proteases families include aspartic proteases; cysteine proteases; glutamic proteases; aspargine peptide lyase; serine proteases and threonine proteases. Such protease families are described in the MEROPS peptidase database
  • Serine proteases are preferred. Subtilase type serine proteases are more preferred.
  • the term "subtilases” refers to a sub-group of serine protease according to Siezen et al., Protein Engng. 4 (1991 ) 719-737 and Siezen et al. Protein Science 6 (1997) 501 -523.
  • Serine proteases are a subgroup of proteases characterized by having a serine in the active site, which forms a covalent adduct with the substrate.
  • the subtilases may be divided into 6 sub-divisions, i.e.
  • subtilases are those derived from Bacillus such as Bacillus lentus, B.
  • trypsin-like proteases are trypsin (e.g. of porcine or bovine origin) and the Fusarium protease described in WO 89/06270, WO 94/25583 and WO 05/040372, and the chymotrypsin proteases derived from Cellumonas described in WO 05/052161 and WO 05/052146.
  • protease is a subtilisins (EC 3.4.21.62).
  • subtilases are those derived from Bacillus such as Bacillus lentus, B.
  • the subsilisin is derived from Bacillus, preferably Bacillus lentus, B. alkalophilus, B. subtilis, B. amyloliquefaciens, Bacillus pumilus and Bacillus gibsonii as described in US 6,312,936 Bl, US 5,679,630, US 4,760,025, US7,262,042 and WO 09/021867.
  • Bacillus gibsonii or Bacillus Lentus.
  • Suitable commercially available protease enzymes include those sold under the trade names names Alcalase®, Blaze®; DuralaseTm, DurazymTm, Relase®, Relase® Ultra, Savinase®, Savinase® Ultra, Primase®, Polarzyme®, Kannase®, Liquanase®,
  • the invention may be use cutinase, classified in EC 3.1 .1.74.
  • the cutinase used according to the invention may be of any origin.
  • Preferably cutinases are of microbial origin, in particular of bacterial, of fungal or of yeast origin.
  • Suitable amylases (alpha and/or beta) include those of bacterial or fungal origin.
  • Amylases include, for example, alpha-amylases obtained from Bacillus, e.g. a special strain of Bacillus, e.g. a special strain of Bacillus, e.g. a special strain of Bacillus, e.g. a special strain of Bacillus, e.g. a special strain of Bacillus, e.g. a special strain of Bacillus, e.g. a special strain of Bacillus, e.g. a special strain of Bacillus, e.g. a special strain of Bacillus, e.g. a special strain of Bacillus, e.g. a special strain of Bacillus, e.g. a special strain of Bacillus, e.g. a special strain of Bacillus, e.g. a special strain of Bacillus, e.g. a special strain of Bacillus, e.g. a special strain of Bacillus, e.g. a special strain
  • B. lichen iformis described in more detail in GB 1 ,296,839, or the Bacillus sp. strains disclosed in WO 95/026397 or WO 00/060060.
  • Commercially available amylases are DuramylTM, TermamylTM, Termamyl UltraTM, NatalaseTM, StainzymeTM, FungamylTM and BANTM (Novozymes A/S), RapidaseTM and PurastarTM (from Genencor International Inc.).
  • Suitable cellulases include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Suitable cellulases include cellulases from the genera Bacillus, Pseudomonas, Humicola, Fusarium, Thielavia, Acremonium, e.g. the fungal cellulases produced from Humicola insolens, Thielavia terrestris, Myceliophthora thermophila, and Fusarium oxysporum disclosed in US 4,435,307, US 5,648,263, US 5,691 ,178, US 5,776,757, WO 89/09259, WO 96/029397, and WO 98/012307.
  • CelluzymeTM Commercially available cellulases include CelluzymeTM, CarezymeTM, CellucleanTM, EndolaseTM, RenozymeTM (Novozymes A/S), ClazinaseTM and Puradax HATM (Genencor International Inc.), and KAC-500(B)TM (Kao Corporation). CellucleanTM is preferred.
  • Suitable peroxidases/oxidases include those of plant, bacterial or fungal origin.
  • peroxidases Chemically modified or protein engineered mutants are included.
  • useful peroxidases include peroxidases from Coprinus, e.g. from C. cinereus, and variants thereof as those described in WO 93/24618, WO 95/10602, and WO 98/15257.
  • peroxidases include GuardzymeTM and NovozymTM 51004 (Novozymes A/S). Further enzymes suitable for use are discussed in WO 2009/087524, WO 2009/090576, WO 2009/107091 , WO 2009/1 1 1258 and WO 2009/148983.
  • the aqueous solution used in the method preferably has an enzyme present.
  • the enzyme is preferably present in the aqueous solution used in the method at a
  • Any enzyme present in the composition may be stabilized using conventional stabilizing agents, e.g., a polyol such as propylene glycol or glycerol, a sugar or sugar alcohol, lactic acid, boric acid, or a boric acid derivative, e.g., an aromatic borate ester, or a phenyl boronic acid derivative such as 4-formylphenyl boronic acid, and the composition may be formulated as described in e.g. WO 92/19709 and WO 92/19708.
  • a polyol such as propylene glycol or glycerol
  • a sugar or sugar alcohol lactic acid, boric acid, or a boric acid derivative, e.g., an aromatic borate ester, or a phenyl boronic acid derivative such as 4-formylphenyl boronic acid
  • Builder materials may be present. If present then they are generally selected from 1 ) calcium sequestrant materials, 2) precipitating materials, 3) calcium ion-exchange materials and 4) mixtures thereof.
  • calcium sequestrant builder materials examples include alkali metal polyphosphates, such as sodium tripolyphosphate and organic sequestrants, such as ethylene diamine tetra-acetic acid.
  • precipitating builder materials examples include sodium orthophosphate and sodium carbonate.
  • Examples of calcium ion-exchange builder materials include the various types of water- insoluble crystalline or amorphous aluminosilicates, of which zeolites are well known representatives, e.g. zeolite A, zeolite B (also known as zeolite P), zeolite C, zeolite X, zeolite Y and also the zeolite P-type as described in EP-A-0,384,070.
  • zeolites are well known representatives, e.g. zeolite A, zeolite B (also known as zeolite P), zeolite C, zeolite X, zeolite Y and also the zeolite P-type as described in EP-A-0,384,070.
  • the composition may also contain 0-65 % of a builder or complexing agent such as ethylenediaminetetraacetic acid, diethylenetriamine-pentaacetic acid, alkyl- or alkenylsuccinic acid, nitrilotriacetic acid or the other builders mentioned below.
  • a builder or complexing agent such as ethylenediaminetetraacetic acid, diethylenetriamine-pentaacetic acid, alkyl- or alkenylsuccinic acid, nitrilotriacetic acid or the other builders mentioned below.
  • the laundry cleaning formulation is a non-phosphate built laundry detergent formulation, i.e., contains less than 1 wt.% of phosphate.
  • the laundry cleaning formulation is most preferably an aqueous liquid laundry detergent.
  • aqueous liquid laundry detergent it is preferred that mono propylene glycol is present at a level from 1 to 30 wt.%, most preferably 2 to 18 wt.%.
  • composition may preferably comprise one or more polymers.
  • Example polymers are carboxymethylcellulose, poly(ethylene glycol), polyvinyl alcohol), polycarboxylates such as polyacrylates, maleic/acrylic acid copolymers and lauryl methacrylate/acrylic acid copolymers.
  • Polymers present to prevent dye deposition may be present, for example
  • Shading Dyes for use in laundry compositions preferably have an extinction coefficient at the maximum absorption in the visible range (400 to 700nm) of greater than
  • the dyes are blue or violet in colour.
  • the composition comprises a shading dye.
  • the shading dye is present at from 0.0001 to 0.1 wt.% of the composition.
  • Preferred shading dye chromophores are azo, azine, anthraquinone, and
  • Azo, anthraquinone, phthalocyanine and triphenylmethane dyes preferably carry a net anionic charged or are uncharged.
  • Azine preferably carry a net anionic or cationic charge.
  • Blue or violet shading dyes deposit to fabric during the wash or rinse step of the washing process providing a visible hue to the fabric. In this regard the dye gives a blue or violet colour to a white cloth with a hue angle of 240 to 345, more preferably 250 to 320, most preferably 250 to 280.
  • the white cloth used in this test is bleached non- mercerised woven cotton sheeting.
  • Shading dyes are discussed in WO 2005/003274, WO 2006/032327(Unilever), WO 2006/032397(Unilever), WO 2006/045275(Unilever), WO 2006/027086(Unilever), WO 2008/017570(Unilever), WO 2008/141880 (Unilever), WO 2009/132870(Unilever), WO 2009/141 173 (Unilever), WO 2010/099997(Unilever), WO 2010/102861 (Unilever), WO 2010/148624(Unilever), WO 2008/087497 (P&G), WO 201 1/01 1799 (P&G), WO 2012/054820 (P&G), WO 2013/142495 (P&G) and WO 2013/151970 (P&G).
  • Mono-azo dyes preferably contain a heterocyclic ring and are most preferably thiophene dyes.
  • Bis-azo dyes are preferably sulphonated bis-azo dyes.
  • Preferred examples of sulphonated bis-azo compounds are direct violet 7, direct violet 9, direct violet 1 1 , direct violet 26, direct violet 31 , direct violet 35, direct violet 40, direct violet 41 , direct violet 51 , Direct Violet 66, direct violet 99 and alkoxylated versions thereof.
  • Alkoxylated bis-azo dyes are discussed in WO2012/054058 and WO2010/151906.
  • An example of an alkoxylated bis-azo dye is :
  • Thiophene dyes are available from Milliken under the tradenames of Liquitint Violet DD and Liquitint Violet ION.
  • Azine dye are preferably selected from sulphonated phenazine dyes and cationic phenazine dyes. Preferred examples are acid blue 98, acid violet 50, dye with CAS- No 72749-80-5, acid blue 59, and the phenazine dye selected from:
  • X 3 is selected from: -H; -F; -CH 3 ; -C 2 H 5 ; -OCH 3 ; and, -OC 2 H 5 ;
  • X 4 is selected from: -H; -CH 3 ; -C 2 H 5 ; -OCH 3 ; and, -OC 2 H 5 ;
  • Y 2 is selected from: -OH; -OCH 2 CH 2 OH; -CH(OH)CH 2 OH; -OC(0)CH 3 ; and, C(0)OCH 3 .
  • the shading dye is present is present in the composition in range from 0.0001 to
  • the shading dye is a blue or violet shading dye.
  • a mixture of shading dyes may be used.
  • the shading dye is most preferably a reactive blue anthraquinone dye covalently linked to an alkoxylated polyethyleneimine.
  • the alkoxylation is preferably selected from ethoxylation and propoxylation, most preferably propoxylation.
  • 80 to 95 mol% of the N-H groups in the polyethylene imine are replaced with iso-propyl alcohol groups by propoxylation.
  • the polyethylene imine before reaction with the dye and the propoxylation has a molecular weight of 600 to 1800.
  • An example structure of a preferred reactive anthraquinone covalently attached to a propoxylated polyethylene imine is:
  • alkyl groups are sufficiently long to form branched or cyclic chains, the alkyl groups encompass branched, cyclic and linear alkyl chains.
  • the alkyl groups are preferably linear or branched, most preferably linear.
  • the indefinite article “a” or “an” and its corresponding definite article “the” as used herein means at least one, or one or more, unless specified otherwise.
  • Trimellitic acid was used as purchased from ACROS Organics. Trimellitic anhydride and pyromellitic acid was used as purchased from Alfa Aesar. Phenoxyethanol, para-toluene sulfonic acid and titanium isopropoxide were used as purchased from Merck.
  • Methanesulfonic acid, 4-dodecylbenzenesulfonic acid mixture of isomers and benzyl alcohol were used as purchased from Sigma Aldrich. Lauryl/myristyl alcohol and cetearyl alcohol were used in technical grade quality and their molecular masses were determined prior to use by measuring the hydroxyl value (OH- value) and subsequently calculating the molecular weight (per hydroxyl function, "Gebrauchsmol"). In this case the OH-value may be measured according to DIN 53240. The acid number (acid value) may be measured according to DIN EN ISO 21 14.
  • Polyglykols M are mono hydroxy-functional polyethylene glycol monomethyl ethers (M- PEG, CAS-Nr. 9004-74-4).
  • Polyglykol M 500 is a linear, mono hydroxy-functional polyethylene glycol monomethyl ether (M-PEG) that has a molecular weight of 470-530 g/mol.
  • Polyglykol M 750 is a linear, mono hydroxy-functional polyethylene glycol monomethyl ether (M-PEG) that has a molecular weight of 720-780 g/mol.
  • Polyglykol M 1000 is a linear, mono hydroxy-functional polyethylene glycol monomethyl ether (M-PEG) that has a molecular weight of 970 - 1060 g/mol.
  • Polyglykol M 1250 is a linear, mono hydroxy-functional polyethylene glycol monomethyl ether (M-PEG) that has a molecular weight of 1 125-1375 g/mol.
  • Polyglykol M 2000 is a linear, mono hydroxy-functional polyethylene glycol monomethyl ether (M-PEG) that has a molecular weight of 1800 - 2200 g/mol.
  • the degree of alkoxylation of the used methyl polyglykols may be checked using NMR spectroscopy, for example using 1 H-NMR spectroscopy in analogy to the method described in R. Stevanova, D. Rankoff, S. Panayotova, S.L. Spassov, J. Am. Oil Chem. Soc, 65, 1516-1518 (1988).
  • NMR spectroscopy for example using 1 H-NMR spectroscopy in analogy to the method described in R. Stevanova, D. Rankoff, S. Panayotova, S.L. Spassov, J. Am. Oil Chem. Soc, 65, 1516-1518 (1988).
  • the samples are derivatised by reacting them with trichloro acetyl isocyanate and measured as solutions in deuterated chloroform containing 1 weight-% (1 wt.-%) of tetramethyl silane as an internal standard.
  • esterification reactions were controlled by determining the residual content of alcohol (e.g. benzyl alcohol, phenoxyethanol, lauryl myristyl alcohol and cetearyl alcohol) by GC- FID. Calibration was performed with pure starting materials. Gas chromatography (GC) was performed using a Hewlett Packard GC 6890 with autosampler, coupled with a flame-ionisation detector (FID).
  • alcohol e.g. benzyl alcohol, phenoxyethanol, lauryl myristyl alcohol and cetearyl alcohol
  • FID flame-ionisation detector
  • samples were separated on a 50 m x 0.2 mm, 0.33 ⁇ film column.
  • the column temperature was initially held at 50°C, then the temperature was raised to 175°C at a rate of 5°C per minute and from 175°C to 300°C at a rate of 25°C per minute.
  • the injector temperature was maintained at 250°C and the injection volume was 1.0 ⁇ _ in the split mode.
  • Helium was used as a carrier gas with a constant pressure of 1 .8 bar.
  • the samples were prepared by diluting 500 mg of sample (duplicate analysis) with 5 ml of methanol.
  • samples were separated on a 25 m x 0.32 mm, 0.52 ⁇ film column.
  • the column temperature was initially held at 50°C, then the temperature was raised to 250°C at a rate of 10°C per minute and held for 6.5 minutes.
  • the injector temperature was maintained at 250°C and the injection volume was 1 .0 ⁇ _ in the split mode.
  • Helium was used as a carrier gas with a constant pressure of 0.9 bar.
  • the samples were prepared by diluting 500 mg of sample (duplicate analysis) with 5 ml of methanol.
  • TLC Thin layer chromatography
  • the alcohol alkoxylate of choice was heated to 80°C with stirring under nitrogen.
  • the polycarboxylic acid or acid anhydride of choice was then added in portions over 5 minutes.
  • the reaction mixture was then stirred for 2.5 hours at 80°C.
  • the product, henceforth termed precursor was isolated and the acid number determined - these are listed in Table I in the column AN1 .
  • Some amount of the precursor (listed in the column "PC" of Table I) was mixed with the alcohol and catalyst of choice and heated to the temperature listed in Table I while stirring under nitrogen.
  • the reaction mixture was stirred at the temperature listed for the time denoted in Table I and water was distilled off. For all examples except examples 1 , 2, 10 and 1 1 , the product was then isolated after cooling and the acid number of the final product determined - listed as AN2 in Table I.
  • sample C1 from Table I was isolated after the first synth step and no reaction with alcohol was performed.
  • the formulation was used to wash eight 5x5 cm knitted cotton cloth pieces in a
  • the inventive dispersants enhance anti-redeposition.

Abstract

L'invention concerne une composition de nettoyage du linge comprenant : i) de 0,2 à 20 % en poids d'un dispersant alcoxylé de structure (F1) suivante : dans laquelle : X est choisi parmi : un éthoxy ; et des mélanges de groupes éthoxy et propoxy, le nombre de groupes éthoxy étant supérieur au nombre de groupes propoxy, et n étant compris entre 6 et 70 ; m est choisi parmi : 2 et 3 ; R1 est choisi parmi : des groupes alkyle en C12 à C20 non chargés ; des groupes aryle non chargés ; et des groupes alkyle-aryle non chargés, le groupe alkyle de l'alkyle-aryle étant un groupe alkyle linéaire ou ramifié saturé en C1 à C3 ; T est choisi parmi : H ; CH3 ; SO3- ; CH2COO- ; PO3 2- ; C2H5 ; un n-propyle, un i-propyle ; un n-butyle ; un t-butyle ; et un sulfosuccinate ; (ii) de 0 à 50 % en poids d'un tensioactif, autre que le dispersant alcoxylé ; (iii) un principe actif choisi parmi un ou plusieurs des éléments suivants : de 0,001 à 3 % en poids d'un parfum ; de 0,0001 à 0,5 % en poids d'un agent fluorescent ; et, de 0,0001 % en poids à 0,1 % en poids d'une enzyme. L'invention concerne en outre un procédé domestique de traitement d'un textile comprenant le traitement du textile avec une liqueur aqueuse comprenant ledit dispersant alcoxylé.
PCT/EP2018/068090 2017-07-07 2018-07-04 Composition de blanchiment WO2019008036A1 (fr)

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BR112020000201-1A BR112020000201B1 (pt) 2017-07-07 2018-07-04 Composição de limpeza para lavagem de tecidos e método doméstico de tratamento de um tecido
EP18734831.3A EP3649222B1 (fr) 2017-07-07 2018-07-04 Composition de blanchiment
CN201880045612.9A CN110869480B (zh) 2017-07-07 2018-07-04 增白组合物
ZA2019/08604A ZA201908604B (en) 2017-07-07 2019-12-23 Whitening composition

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