WO2016005271A1 - Laundry liquid composition - Google Patents

Laundry liquid composition Download PDF

Info

Publication number
WO2016005271A1
WO2016005271A1 PCT/EP2015/065136 EP2015065136W WO2016005271A1 WO 2016005271 A1 WO2016005271 A1 WO 2016005271A1 EP 2015065136 W EP2015065136 W EP 2015065136W WO 2016005271 A1 WO2016005271 A1 WO 2016005271A1
Authority
WO
WIPO (PCT)
Prior art keywords
component
molar average
composition according
polyesters
weight
Prior art date
Application number
PCT/EP2015/065136
Other languages
French (fr)
Inventor
Robert John Carswell
Carsten Cohrs
Richard Michael Craven
David Philip Jones
Peter Klug
Helen Elspeth LYON
Peter Naumann
Alyn James Parry
Henricus Peerlings
Alastair Richard Sanderson
Andrew WYNNE
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 PL15732008T priority Critical patent/PL3167033T3/en
Priority to CN201580036837.4A priority patent/CN106471111B/en
Priority to CA2953273A priority patent/CA2953273C/en
Priority to BR112017000306-6A priority patent/BR112017000306B1/en
Priority to US15/323,501 priority patent/US10336968B2/en
Priority to EP15732008.6A priority patent/EP3167033B1/en
Publication of WO2016005271A1 publication Critical patent/WO2016005271A1/en

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/26Organic compounds containing nitrogen
    • C11D3/30Amines; Substituted amines ; Quaternized amines
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D11/00Special methods for preparing compositions containing mixtures of detergents
    • C11D11/0094Process for making liquid detergent compositions, e.g. slurries, pastes or gels
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/2003Alcohols; Phenols
    • C11D3/2041Dihydric alcohols
    • C11D3/2044Dihydric alcohols linear
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/2068Ethers
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3703Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3715Polyesters or polycarbonates
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10Objects to be cleaned
    • C11D2111/12Soft surfaces, e.g. textile

Definitions

  • the invention relates to laundry liquid compositions comprising polyesters and methods for making compositions comprising polyesters.
  • DE 10 2007 013 217 A1 and WO 2007/079850 A1 disclose anionic polyesters that may be used as soil release components in washing and cleaning compositions.
  • DE 10 2007 005 532 A1 describes aqueous formulations of soil release oligo- and polyesters with a low viscosity.
  • R 1 and R 2 independently of one another are X-(OC2H4)n-(OC3H 6 ) m wherein X is C1-4 alkyl and preferably methyl, the -(OC2H4) groups and the -(OC3H6) groups are arranged blockwise and the block consisting of the -(OC3H6) groups is bound to a COO group or are HO-(C3H 6 ), and preferably are independently of one another X- n is based on a molar average a number of from 12 to 120 and preferably of from 40 to 50,
  • m is based on a molar average a number of from 1 to 10 and preferably of from 1 to
  • a is based on a molar average a number of from 4 to 9 and
  • active blend is meant that it is preformed and added to the remainder of the laundry liquid composition, or to components which ultimately form the laundry liquid composition.
  • butyl glycol has the following structure:
  • polyesters of component A) group "X" is C1-4 alkyl and preferably is methyl.
  • polyesters of component A) of the inventive compositions are according to the following formula (I) R— O -C C -O -C 8 H g -O -C C-O -R (I)
  • n is based on a molar average a number of from 40 to 50
  • m is based on a molar average a number of from 1 to 7, and
  • a is based on a molar average a number of from 4 to 9.
  • variable "a" based on a molar average preferably is a number of from 5 to 8 and more preferably is a number of from 6 to 7.
  • variable "m" based on a molar average preferably is a number of from 2 to 5.
  • variable "n" based on a molar average preferably is a number of from 43 to 47, more preferably is a number of from 44 to 46 and even more preferably is 45.
  • polyesters of component A) of the inventive compositions are according to the following formula (I)
  • R 1 and R 2 independently of one another are H 3 C-(OC2H4)n-(OC3l-l6)m wherein the -(OC2H4) groups and the -(OC3H6) groups are arranged blockwise and the block consisting of the -(OC3H6) groups is bound to a COO group,
  • n is based on a molar average a number of from 44 to 46
  • n based on a molar average
  • n is based on a molar average 45
  • n based on a molar average
  • a is based on a molar average a number of from 6 to 7
  • polyesters of component A) of the inventive compositions are according to the following formula (I)
  • R 1 and R 2 independently of one another are H 3 C-(OC2H4)n-(OC3l-l6)m wherein the -(OC2H4) groups and the -(OC3H6) groups are arranged blockwise and the block consisting of the -(OC3H6) groups is bound to a COO group,
  • n is based on a molar average a number of from 44 to 46
  • m is based on a molar average 5
  • a is based on a molar average a number of from 5 to 8.
  • n is based on a molar average 45
  • m is based on a molar average 5
  • a is based on a molar average a number of from 6 to 7
  • the groups -O-C2H4- in the structural units "X-(OC 2 H4)n-(OC 3 H6)m” or "H 3 C-(OC2H4)n-(OC3H 6 )m" are of the formula -O-CH2-CH2-.
  • the groups -O-C3H6- in the structural units indexed with "a”, in the structural units "X-(OC2H4) n - (OC 3 H 6 ) m " or "H 3 C-(OC2H4)n-(OC3H 6 )m” and in the structural units HO-(C 3 H 6 ) are of the formula -0-CH(CH 3 )-CH 2 - or -0-CH 2 -CH(CH 3 )-, i.e. are of the formula
  • the active blend compositions may advantageously be used in laundry detergent and fabric care products and in particular in liquid laundry detergent and fabric care products.
  • These laundry detergent and fabric care products may comprise one or more optional ingredients, e.g. they may comprise conventional ingredients commonly used in laundry detergent and fabric care products.
  • optional ingredients include, but are not limited to builders, surfactants, bleaching agents, bleach active compounds, bleach activators, bleach catalysts, photobleaches, dye transfer inhibitors, color protection agents, anti-redeposition agents, dispersing agents, fabric softening and antistatic agents, fluorescent whitening agents, enzymes, enzyme stabilizing agents, foam regulators, defoamers, malodour reducers, preservatives, disinfecting agents, hydrotopes, fibre lubricants, anti-shrinkage agents, buffers, fragrances, processing aids, colorants, dyes, pigments, anti-corrosion agents, fillers, stabilizers and other conventional ingredients for laundry detergent and fabric care products.
  • the active blend compositions have an advantageous stability in alkaline environment, possess a beneficial solubility and advantageously are clearly soluble in alkaline compositions such as heavy duty washing liquids and also possess advantageous soil release properties.
  • laundry detergent or fabric care products they result in a beneficial washing performance, in particular also after storage. Furthermore, they are storage stable at elevated temperature, i.e. they are clear solutions at elevated temperature also after a prolonged time of storage.
  • the active blend provides for:
  • the polyesters of component A) of the active blend compositions may advantageously be prepared by a process which comprises heating dimethyl terephthalate (DMT), 1 ,2-propylene glycol (PG), and X-(OC2H4)n-(OC3H 6 )m-OH, wherein X is C1-4 alkyl and preferably methyl, the -(OC2H4) groups and the -(OC3H6) groups are arranged blockwise and the block consisting of the -(OC3H6) groups is bound to the hydroxyl group -OH and n and m are as defined for the polyesters of component A) of the inventive compositions, with the addition of a catalyst, to temperatures of from 160 to 220 °C, firstly at atmospheric pressure, and then continuing the reaction under reduced pressure at temperatures of from 160 to 240 °C.
  • DMT dimethyl terephthalate
  • PG 1,2-propylene glycol
  • X-(OC2H4)n-(OC3H 6 )m-OH wherein X is
  • Reduced pressure preferably means a pressure of from 0.1 to 900 mbar and more preferably a pressure of from 0.5 to 500 mbar.
  • the process for the preparation of the polyesters of component A) of the inventive compositions is characterized in that a) dimethyl therephthalate, 1 ,2-propylene glycol, X-(OC2H4)n-(OC3H6)m-OH, wherein X is C1-4 alkyl and preferably methyl, and a catalyst are added to a reaction vessel, heated under inert gas, preferably nitrogen, to a temperature of from 160 °C to 220 °C to remove methanol and then pressure is reduced to below atmospheric pressure, preferably to a pressure of from 200 to 900 mbar and more preferably to a pressure of from 400 to 600 mbar for completion of the transesterification, and b) in a second step the reaction is continued at a temperature of from 210 °C to 240 °C and at a pressure of from 0.1 to 10 mbar and preferably of from 0.5 to 5 mbar to form the polyester.
  • inert gas preferably nitrogen
  • Sodium acetate (NaOAc) and tetraisopropyl orthotitanate (IPT) is preferably used as the catalyst system in the preparation of the polyesters of component A) of the inventive compositions.
  • the preparation of the polyesters of component A) of the active blend compositions is e.g. described in WO 2013/019658 A1.
  • the one or more alcohols of component B) of the inventive compositions are selected from the group consisting of 1 ,2-propylene glycol, 1 ,3-propylene glycol and butyl glycol.
  • the alcohol of component B) of the inventive compositions is 1 ,2-propylene glycol.
  • the active blend compositions preferably comprise
  • the active blend may preferably comprise from 0 to 10 % by weight, and more preferably from 0 to 5 % by weight, of one or more additives, that may generally be used in detergent applications.
  • Additives that may be used are e.g. sequestering agents, complexing agents, polymers different from the one or more polyesters of component A) of the inventive compositions, and surfactants.
  • the active blend preferably comprises one or more additives (component D)), and in this case the amount of water of component C) preferably is of from 24 to 39.95 % by weight, the amounts in each case being based on the total weight of the active blend.
  • component D additives
  • the amount of water of component C) preferably is of from 24 to 39.95 % by weight, the amounts in each case being based on the total weight of the active blend.
  • the one or more additives of component D) of the active blend are preferably selected from the group consisting of sequestering agents, complexing agents, polymers different from the one or more polyesters of component A) and surfactants.
  • Suitable sequestering agents e.g. are polyacrylic acid or acrylic acid / maleic acid copolymers (e.g. Sokalan CP 12S, BASF).
  • Suitable complexing agents e.g. are EDTA (ethylene diamine tetraactetate), diethylene triamine pentaacetate, nitrilotriacetic acid salts or iminodisuccinic acid salts.
  • Suitable polymers different from the one or more polyesters of component A) of the inventive compositions e.g. are dye transfer inhibitors such as e.g. vinyl pyrrolidone.
  • the one or more additives of component D) are present in the active blend compositions in an amount of up to 10 % by weight, and in this case the amount of water of component C) in the active blend compositions preferably is of from 24 to 39.95 % by weight, the amounts in each case being based on the total weight of the active blend.
  • the one or more additives of component D) are present in the active blend compositions in an amount of from 0.1 to 10 % by weight, and in this case the amount of water of component C) in the active blend compositions preferably is of from 24 to 39.9 % by weight, the amounts in each case being based on the total weight of the active blend.
  • the one or more additives of component D) are present in the active blend compositions in an amount of from 0.5 to 5 % by weight, and in this case the amount of water of component C) in the active blend compositions preferably is of from 24 to 39.5 % by weight, the amounts in each case being based on the total weight of the active blend compositions.
  • the active blend consists of the one or more polyesters of component A), the one or more alcohols of component B), and water of component C).
  • the viscosity of the active blend compositions is of from 200 to 5 000 mPa-s More preferably, the viscosity of the active blend compositions, measured at 25 °C, is of from 500 to 2 000 mPa-s
  • the viscosities are measured on the active blend compositions themselves using a Brookfield- viscosimeter, model DV II and the spindles of the set of spindles RV at 20 revolutions per minute and 25*C.
  • Spindle No. 1 is used for viscosities of up to 500 mPa*s
  • spindle No. 2 for viscosities of up to 1 000 mPa*s
  • spindle No. 3 for viscosities of up to 5 000 mPa*s
  • spindle No. 4 for viscosities of up to 10 000 mPa*s
  • spindle No. 5 for viscosities of up to 20 000 mPa*s
  • spindle No. 6 for viscosities of up to 50 000 mPa*s
  • spindle No. 7 for viscosities of up to 200 000 mPa « s.
  • a method for making a laundry liquid composition comprising adding an active blend as described above to a composition comprising cleansing surfactant selected from anionic surfactants and nonionic surfactants.
  • the method comprises adding the active blend as described herein and mixing before adding perfume, fragrance or preservative.
  • the temperature of the mixture of surfactants to which the active blend is added is not more than 50C and preferably from 10 to 40C.
  • Preferred preservatives include BIT (1 ,2-Benzoisothiazolin-3-one); MIT (Methylisothiazolinone); Phenoxyethanol, IPBC and mixtures thereof.
  • Preferred preservative systems include BIT (1 ,2-Benzoisothiazolin-3-one), BIT (1 ,2- Benzoisothiazolin-3-one) and MIT (Methylisothiazolinone); and Phenoxyethanol and BIT;
  • a laundry liquid composition obtainable by a process according to the second aspect.
  • the polyester synthesis is carried out by the reaction of dimethyl terephthalate (DMT), 1 ,2- propylene glycol (PG), and methyl polyalkyleneglycol using sodium acetate (NaOAc) and tetraisopropyl orthotitanate (IPT) as the catalyst system.
  • DMT dimethyl terephthalate
  • PG propylene glycol
  • IPT tetraisopropyl orthotitanate
  • the synthesis is a two-step procedure. The first step is a transesterification and the second step is a polycondensation.
  • Dimethyl terephthalate (DMT), 1 ,2-propylene glycol (PG), methyl polyalkyleneglycol, sodium acetate (anhydrous) (NaOAc) and tetraisopropyl orthotitanate (IPT) are weighed into a reaction vessel at room temperature.
  • the mixture is heated up to 170 °C for 1 h and then up to 210 °C for a further 1 h sparged by a nitrogen stream.
  • methanol is released from the reaction and is distilled out of the system (distillation temperature ⁇ 55 °C). After 2 h at 210 °C nitrogen is switched off and the pressure is reduced to 400 mbar over 3 h.
  • R 1 and R 2 are H 3 C-(OC2H4)n-(OC3H 6 )m wherein the -(OC 2 H 4 ) groups and the -(OC 3 H 6 ) groups are arranged blockwise and the block consisting of the -(OC3H6) groups is bound to a COO group,
  • n is based on a molar average 45
  • R 1 and R 2 are H 3 C-(OC2H4)n-(OC3H 6 )m wherein the -(OC 2 H 4 ) groups and the -(OC 3 H 6 ) groups are arranged blockwise and the block consisting of the -(OC3H6) groups is bound to a COO group,
  • n is based on a molar average 45
  • n based on a molar average
  • a is based on a molar average a number of from 6 to 7.
  • Optical brightener, salt, acids, alkalis & hydrotrope are added to water followed by the surfactants in order: nonionic, LAS then the fatty acid. SLES is then injected in line using a mill. Once SLES is dispersed Texcare SRN UL 50, ex. Clariant (the polyester active blend) is then added. In a separate vessel a pre-mix of dyes & water is made which is then added to the main mixer. After this point the minors are added (preservation & perfume & enzymes if applicable).

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)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)

Abstract

Storage-stable compositions comprising soil release polymers. Compositions are described comprising • A) of from 45 to 55 % by weight of one or more polyesters according to the following formula (I) wherein • R and R2 independently of one another are X-(OC 2 H 4) n-(OC 3H 6) m wherein X is C 1- 4alkyl, the -(OC 2H 4) groups and the -(OC 3H 6) groups are arranged blockwise and the block consisting of the -(OC 3H 6) groups is bound to a COO group or are HO-(C 3H 6), • n is based on a molar average a number of from 12 to 120, • m is based on a molar average a number of from 1 to 10, and • a is based on a molar average a number of from 4 to 9, and • B) of from 10 to 30 % by weight of one or more alcohols selected from the group consisting of ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 1,4- butylene glycol and butyl glycol and • C) of from 24 to 42 % by weight of water, the amounts in each case being based on the total weight of the composition. The compositions may advantageously be used in laundry detergent and fabric care products. Process for making laundry liquid compositions comprising said active blend.

Description

LAUNDRY LIQUID COMPOSITION
The invention relates to laundry liquid compositions comprising polyesters and methods for making compositions comprising polyesters.
DE 10 2007 013 217 A1 and WO 2007/079850 A1 disclose anionic polyesters that may be used as soil release components in washing and cleaning compositions. DE 10 2007 005 532 A1 describes aqueous formulations of soil release oligo- and polyesters with a low viscosity.
EP 0 964 015 A1 discloses soil release oligoesters that may be used as soil release polymers in detergents and that are prepared using polyols comprising 3 to 6 hydroxyl groups.
EP 1 661 933 A1 is directed to at room temperature flowable, amphiphilic and nonionic oligoesters prepared by reacting dicarboxylic acid compounds, polyol compounds and water- soluble alkylene oxide adducts and their use as additive in washing and cleaning compositions.
Accordingly and in regard to a first aspect there is provided an alkaline laundry liquid composition comprising at least 1 % by weight triethanolamine, at least 5% non-soap surfactant and at least 0.5% a polyester provided as an active blend comprising:
A) from 45 to 55 % by weight of the active blend of one or more polyesters according to the following formula (I)
Figure imgf000003_0001
wherein
R1 and R2 independently of one another are X-(OC2H4)n-(OC3H6)m wherein X is C1-4 alkyl and preferably methyl, the -(OC2H4) groups and the -(OC3H6) groups are arranged blockwise and the block consisting of the -(OC3H6) groups is bound to a COO group or are HO-(C3H6), and preferably are independently of one another X-
Figure imgf000003_0002
n is based on a molar average a number of from 12 to 120 and preferably of from 40 to 50,
m is based on a molar average a number of from 1 to 10 and preferably of from 1 to
7, and
a is based on a molar average a number of from 4 to 9 and
B) from 10 to 30 % by weight of the active blend of one or more alcohols selected from the group consisting of ethylene glycol, 1 ,2-propylene glycol, 1 ,3-propylene glycol, 1 ,2-butylene glycol, 1 ,3-butylene glycol, 1 ,4-butylene glycol and butyl glycol and
C) from 24 to 42 % by weight of the active blend of water..
By active blend is meant that it is preformed and added to the remainder of the laundry liquid composition, or to components which ultimately form the laundry liquid composition.
Preferably, butyl glycol has the following structure:
Figure imgf000004_0001
Surprisingly, the active blend is based on water and on solvents that are not easily flammable. Aqueous or aqueous-alcoholic solutions of the polyesters often possess a relatively good stability when stored at 5 °C. However, when stored at 25 °C for a longer period of time and even faster at elevated temperatures of from 30 to 50 °C, that may occur during transport or storage, non-inventive compositions of the polyesters at first show a turbidity during storage that later results in massive precipitations. These precipitations cannot be dissolved again at 80 °C, meaning that the respective products may not be regarded as being storage-stable, and their properties are changed irreversibly by storage at elevated temperature.
The active blend is sufficiently storage-stable, also at elevated temperatures. The active blend compositions preferably are solutions at 25 °C.
In the polyesters of component A) group "X" is C1-4 alkyl and preferably is methyl.
In a preferred embodiment of the invention the polyesters of component A) of the inventive compositions are according to the following formula (I) R— O -C C -O -C8Hg -O -C C-O -R (I)
Figure imgf000005_0001
wherein
R1 and R2 independently of one another are H3C-(OC2l-l4)n-(OC3l-l6)m wherein the -(OC2H4) groups and the -(OC3H6) groups are arranged blockwise and the block consisting of the -(OC3H6) groups is bound to a COO group or are HO-(C3H6), and preferably are independently of one another H3C-(OC2H4)n-(OC3H6)m,
n is based on a molar average a number of from 40 to 50,
m is based on a molar average a number of from 1 to 7, and
a is based on a molar average a number of from 4 to 9.
In the polyesters of component A) of the inventive compositions variable "a" based on a molar average preferably is a number of from 5 to 8 and more preferably is a number of from 6 to 7.
In the polyesters of component A) of the inventive compositions variable "m" based on a molar average preferably is a number of from 2 to 5.
In the polyesters of component A) of the inventive compositions variable "n" based on a molar average preferably is a number of from 43 to 47, more preferably is a number of from 44 to 46 and even more preferably is 45.
In one particularly preferred embodiment of the invention the polyesters of component A) of the inventive compositions are according to the following formula (I)
Figure imgf000005_0002
wherein
R1 and R2 independently of one another are H3C-(OC2H4)n-(OC3l-l6)m wherein the -(OC2H4) groups and the -(OC3H6) groups are arranged blockwise and the block consisting of the -(OC3H6) groups is bound to a COO group,
n is based on a molar average a number of from 44 to 46,
m is based on a molar average 2, and
a is based on a molar average a number of from 5 to 8. Among these polyesters the polyesters according to formula (I)
Figure imgf000006_0001
wherein
R1 and R2 independently of one another are H3C-(OC2l-l4)n-(OC3l-l6)m wherein the -(OC2H4) groups and the -(OC3H6) groups are arranged blockwise and the block consisting of the -(OC3H6) groups is bound to a COO group,
n is based on a molar average 45,
m is based on a molar average 2, and
a is based on a molar average a number of from 6 to 7
are especially preferred.
In another particularly preferred embodiment of the invention the polyesters of component A) of the inventive compositions are according to the following formula (I)
Figure imgf000006_0002
wherein
R1 and R2 independently of one another are H3C-(OC2H4)n-(OC3l-l6)m wherein the -(OC2H4) groups and the -(OC3H6) groups are arranged blockwise and the block consisting of the -(OC3H6) groups is bound to a COO group,
n is based on a molar average a number of from 44 to 46,
m is based on a molar average 5, and
a is based on a molar average a number of from 5 to 8.
Among these polyesters the polyesters according to formula (I)
Figure imgf000006_0003
wherein R1 and R2 independently of one another are H3C-(OC2H4)n-(OC3H6)m wherein the -(OC2H4) groups and the -(OC3H6) groups are arranged blockwise and the block consisting of the -(OC3H6) groups is bound to a COO group,
n is based on a molar average 45,
m is based on a molar average 5, and
a is based on a molar average a number of from 6 to 7
are especially preferred.
The groups -O-C2H4- in the structural units "X-(OC2H4)n-(OC3H6)m" or "H3C-(OC2H4)n-(OC3H6)m" are of the formula -O-CH2-CH2-.
The groups -O-C3H6- in the structural units indexed with "a", in the structural units "X-(OC2H4)n- (OC3H6)m" or "H3C-(OC2H4)n-(OC3H6)m" and in the structural units HO-(C3H6) are of the formula -0-CH(CH3)-CH2- or -0-CH2-CH(CH3)-, i.e. are of the formula
CH, CH3
I 3 I 3
— O— CH CH2 or — O— CH2 CH
REM: COMPOSITIONS
The active blend compositions may advantageously be used in laundry detergent and fabric care products and in particular in liquid laundry detergent and fabric care products. These laundry detergent and fabric care products may comprise one or more optional ingredients, e.g. they may comprise conventional ingredients commonly used in laundry detergent and fabric care products. Examples of optional ingredients include, but are not limited to builders, surfactants, bleaching agents, bleach active compounds, bleach activators, bleach catalysts, photobleaches, dye transfer inhibitors, color protection agents, anti-redeposition agents, dispersing agents, fabric softening and antistatic agents, fluorescent whitening agents, enzymes, enzyme stabilizing agents, foam regulators, defoamers, malodour reducers, preservatives, disinfecting agents, hydrotopes, fibre lubricants, anti-shrinkage agents, buffers, fragrances, processing aids, colorants, dyes, pigments, anti-corrosion agents, fillers, stabilizers and other conventional ingredients for laundry detergent and fabric care products.
The active blend compositions have an advantageous stability in alkaline environment, possess a beneficial solubility and advantageously are clearly soluble in alkaline compositions such as heavy duty washing liquids and also possess advantageous soil release properties. In laundry detergent or fabric care products they result in a beneficial washing performance, in particular also after storage. Furthermore, they are storage stable at elevated temperature, i.e. they are clear solutions at elevated temperature also after a prolonged time of storage. In the context of a laundry liquid composition the active blend provides for:
• ease of addition & potentially shorter batch cycle time
· better perfume, preservation & enzyme performance due to addition at lower
temperature
• improved polymer delivery.
The polyesters of component A) of the active blend compositions may advantageously be prepared by a process which comprises heating dimethyl terephthalate (DMT), 1 ,2-propylene glycol (PG), and X-(OC2H4)n-(OC3H6)m-OH, wherein X is C1-4 alkyl and preferably methyl, the -(OC2H4) groups and the -(OC3H6) groups are arranged blockwise and the block consisting of the -(OC3H6) groups is bound to the hydroxyl group -OH and n and m are as defined for the polyesters of component A) of the inventive compositions, with the addition of a catalyst, to temperatures of from 160 to 220 °C, firstly at atmospheric pressure, and then continuing the reaction under reduced pressure at temperatures of from 160 to 240 °C.
Reduced pressure preferably means a pressure of from 0.1 to 900 mbar and more preferably a pressure of from 0.5 to 500 mbar.
Preferably, the process for the preparation of the polyesters of component A) of the inventive compositions is characterized in that a) dimethyl therephthalate, 1 ,2-propylene glycol, X-(OC2H4)n-(OC3H6)m-OH, wherein X is C1-4 alkyl and preferably methyl, and a catalyst are added to a reaction vessel, heated under inert gas, preferably nitrogen, to a temperature of from 160 °C to 220 °C to remove methanol and then pressure is reduced to below atmospheric pressure, preferably to a pressure of from 200 to 900 mbar and more preferably to a pressure of from 400 to 600 mbar for completion of the transesterification, and b) in a second step the reaction is continued at a temperature of from 210 °C to 240 °C and at a pressure of from 0.1 to 10 mbar and preferably of from 0.5 to 5 mbar to form the polyester. Sodium acetate (NaOAc) and tetraisopropyl orthotitanate (IPT) is preferably used as the catalyst system in the preparation of the polyesters of component A) of the inventive compositions. The preparation of the polyesters of component A) of the active blend compositions is e.g. described in WO 2013/019658 A1. Preferably, the one or more alcohols of component B) of the inventive compositions are selected from the group consisting of 1 ,2-propylene glycol, 1 ,3-propylene glycol and butyl glycol.
More preferably, the alcohol of component B) of the inventive compositions is 1 ,2-propylene glycol.
The active blend compositions preferably comprise
of from 45 to 55 % by weight of the one or more polyesters of component A), of from 15 to 25 % by weight of the one or more alcohols of component B), and
- of from 24 to 40 % by weight of water of component C),
the amounts in each case being based on the total weight of the active blend.
The active blend may preferably comprise from 0 to 10 % by weight, and more preferably from 0 to 5 % by weight, of one or more additives, that may generally be used in detergent applications. Additives that may be used are e.g. sequestering agents, complexing agents, polymers different from the one or more polyesters of component A) of the inventive compositions, and surfactants.
Preferably, the active blend preferably comprises one or more additives (component D)), and in this case the amount of water of component C) preferably is of from 24 to 39.95 % by weight, the amounts in each case being based on the total weight of the active blend.
The one or more additives of component D) of the active blend are preferably selected from the group consisting of sequestering agents, complexing agents, polymers different from the one or more polyesters of component A) and surfactants.
Suitable sequestering agents e.g. are polyacrylic acid or acrylic acid / maleic acid copolymers (e.g. Sokalan CP 12S, BASF). Suitable complexing agents e.g. are EDTA (ethylene diamine tetraactetate), diethylene triamine pentaacetate, nitrilotriacetic acid salts or iminodisuccinic acid salts. Suitable polymers different from the one or more polyesters of component A) of the inventive compositions e.g. are dye transfer inhibitors such as e.g. vinyl pyrrolidone.
Suitable surfactants may be anionic surfactants such as lauryl sulfate, lauryl ether sulfate, alkane sulfonates, linear alkylbenzene sulfonates, methylester sulfonates, amine oxides or betaine surfactants.
Preferably, the one or more additives of component D) are present in the active blend compositions in an amount of up to 10 % by weight, and in this case the amount of water of component C) in the active blend compositions preferably is of from 24 to 39.95 % by weight, the amounts in each case being based on the total weight of the active blend.
More preferably, the one or more additives of component D) are present in the active blend compositions in an amount of from 0.1 to 10 % by weight, and in this case the amount of water of component C) in the active blend compositions preferably is of from 24 to 39.9 % by weight, the amounts in each case being based on the total weight of the active blend.
Even more preferably, the one or more additives of component D) are present in the active blend compositions in an amount of from 0.5 to 5 % by weight, and in this case the amount of water of component C) in the active blend compositions preferably is of from 24 to 39.5 % by weight, the amounts in each case being based on the total weight of the active blend compositions.
In a further preferred embodiment the active blend consists of the one or more polyesters of component A), the one or more alcohols of component B), and water of component C).
Preferably, the viscosity of the active blend compositions, measured at 25 °C, is of from 200 to 5 000 mPa-s More preferably, the viscosity of the active blend compositions, measured at 25 °C, is of from 500 to 2 000 mPa-s
The viscosities are measured on the active blend compositions themselves using a Brookfield- viscosimeter, model DV II and the spindles of the set of spindles RV at 20 revolutions per minute and 25*C. Spindle No. 1 is used for viscosities of up to 500 mPa*s, spindle No. 2 for viscosities of up to 1 000 mPa*s, spindle No. 3 for viscosities of up to 5 000 mPa*s, spindle No. 4 for viscosities of up to 10 000 mPa*s, spindle No. 5 for viscosities of up to 20 000 mPa*s, spindle No. 6 for viscosities of up to 50 000 mPa*s and spindle No. 7 for viscosities of up to 200 000 mPa«s.
In a second aspect there is provided a method for making a laundry liquid composition comprising adding an active blend as described above to a composition comprising cleansing surfactant selected from anionic surfactants and nonionic surfactants. Preferably, the method comprises adding the active blend as described herein and mixing before adding perfume, fragrance or preservative. Preferably, the temperature of the mixture of surfactants to which the active blend is added is not more than 50C and preferably from 10 to 40C.
Preferred preservatives include BIT (1 ,2-Benzoisothiazolin-3-one); MIT (Methylisothiazolinone); Phenoxyethanol, IPBC and mixtures thereof.
Preferred preservative systems include BIT (1 ,2-Benzoisothiazolin-3-one), BIT (1 ,2- Benzoisothiazolin-3-one) and MIT (Methylisothiazolinone); and Phenoxyethanol and BIT;
Phenoxyethanol and IPBC.
In a third aspect there is provided a laundry liquid composition obtainable by a process according to the second aspect.
The examples below are intended to illustrate the invention in detail without, however, limiting it thereto. Unless explicitly stated otherwise, all percentages given are percentages by weight (% by wt. or wt.-%). General procedure for the preparation of the polyesters
The polyester synthesis is carried out by the reaction of dimethyl terephthalate (DMT), 1 ,2- propylene glycol (PG), and methyl polyalkyleneglycol using sodium acetate (NaOAc) and tetraisopropyl orthotitanate (IPT) as the catalyst system. The synthesis is a two-step procedure. The first step is a transesterification and the second step is a polycondensation.
Transesterification
Dimethyl terephthalate (DMT), 1 ,2-propylene glycol (PG), methyl polyalkyleneglycol, sodium acetate (anhydrous) (NaOAc) and tetraisopropyl orthotitanate (IPT) are weighed into a reaction vessel at room temperature. For the melting process and homogenization, the mixture is heated up to 170 °C for 1 h and then up to 210 °C for a further 1 h sparged by a nitrogen stream. During the transesterification methanol is released from the reaction and is distilled out of the system (distillation temperature < 55 °C). After 2 h at 210 °C nitrogen is switched off and the pressure is reduced to 400 mbar over 3 h.
Polvcondensation
The mixture is heated up to 230 °C. At 230 °C the pressure is reduced to 1 mbar over 160 min. Once the polycondensation reaction has started, 1 ,2-propylene glycol is distilled out of the system. The mixture is stirred for 4 h at 230 °C and a pressure of 1 mbar. The reaction mixture is cooled down to 140 - 150 °C. Vacuum is released with nitrogen and the molten polymer is transferred into a glass bottle. Example I
Figure imgf000012_0001
A polyester according to formula (I) is obtained wherein
R1 and R2 are H3C-(OC2H4)n-(OC3H6)m wherein the -(OC2H4) groups and the -(OC3H6) groups are arranged blockwise and the block consisting of the -(OC3H6) groups is bound to a COO group,
n is based on a molar average 45,
m is based on a molar average 5, and
a is based on a molar average a number of from 6 to 7. Example II
Figure imgf000013_0001
A polyester according to formula (I) is obtained wherein
R1 and R2 are H3C-(OC2H4)n-(OC3H6)m wherein the -(OC2H4) groups and the -(OC3H6) groups are arranged blockwise and the block consisting of the -(OC3H6) groups is bound to a COO group,
n is based on a molar average 45,
m is based on a molar average 2, and
a is based on a molar average a number of from 6 to 7.
Stability tests
Solutions according to the compositions of the following table have been prepared by dissolving the polyester in the respective mixture of water and alcoholic solvent. The additive Sokalan CP 12S was dissolved in the final mixture. The mixtures were investigated with respect to their stability in a storage cabinet (+ = clear solution, o = turbidity, - = pronounced turbidity / precipitation). Freshly prepared samples are clear solutions. The polyester of Example I (Ex. I) has been used for the stability tests.
Sokalan CP 12S (acrylic acid / maleic acid copolymer, BASF) has been used as the additive. From the table it can be seen that solutions of the soil release polyesters in water (Examples 1 - 4) become turbid at 45°C already after two weeks of storage. Inventive compositions comprising 1 ,2-propylene glycol or butyl glycol are still clear after 4 weeks of storage at 45°C. EXAMPLE III
Process for making laundry liquid composition.
Optical brightener, salt, acids, alkalis & hydrotrope are added to water followed by the surfactants in order: nonionic, LAS then the fatty acid. SLES is then injected in line using a mill. Once SLES is dispersed Texcare SRN UL 50, ex. Clariant (the polyester active blend) is then added. In a separate vessel a pre-mix of dyes & water is made which is then added to the main mixer. After this point the minors are added (preservation & perfume & enzymes if applicable).
Example Polyester of Ex. I Water 1 ,2-Propy-lene Butyl glycol Glycerol
[wt.-%] glycol [wt.-%]
[wt.-%] [wt.-%] [wt.-%]
1 35 65
2 35 64
3 40 60
4 50 50
5 45 44 10
6 45 39 15
7 45 34 20
8 45 24 30
9 45 44 10
10 45 39 15
11 45 34 20
12 50 40 10
13 50 40 10
14 50 39 10
15 50 39 10
16 55 34 10
17 55 34 10
18 50 30 20
19 50 35 15
20 50 29 20
21 50 25 25
22 50 30 20
23 40 50 10
24 45 45 10
25 40 49 10
26 45 44 10
27 50 30 20
28 50 30 20 Example Additive clarity clarity Viscosity
[wt.-%] at 45 °C after 2 weeks at 45 °C after 4 weeks at 25 °C [mPa-s]
1 - - 250
2 1 - - 260
3 - - 850
4 - - 3300
5 1 - -
6 1 + +
7 1 + +
8 1 + +
9 1 - -
10 1 + +
11 1 + +
12 + +
13 + +
14 1 + +
15 1 + +
16 +
17 + +
18 + + 1170
19 + + 1260
20 1 + + 1 170
21 + + 870
22 + o 285
23 - -
24 - -
25 1 - -
26 1 - -
27 - -
28 - -

Claims

CLAIMS 1. An alkaline laundry liquid composition comprising at least 1 % wt. of the composition triethanolamine, at least 5% wt. of the composition non-soap surfactant and at least 0.5% wt. of the composition of a polyester, characterized in that the polyester is provided as an active blend comprising:
A) from 45 to 55 % by weight of the active blend one or more polyesters according to the following formula (I)
Figure imgf000017_0001
wherein
R1 and R2 independently of one another are X-(OC2H4)n-(OC3H6)m wherein X is C1-4 alkyl and preferably methyl, the -(OC2H4) groups and the -(OC3H6) groups are arranged blockwise and the block consisting of the -(OC3H6) groups is bound to a COO group or are HO-(C3H6), and preferably are independently of one another X-(OC2H4)n-(OC3H6)m,
is based on a molar average a number of from 12 to 120 and preferably of from 40 to 50,
m is based on a molar average a number of from 1 to 10 and preferably of from
1 to 7, and
is based on a molar average a number of from 4 to 9 and
B) from 10 to 30 % by weight of the active blend one or more alcohols selected from the group consisting of ethylene glycol, 1 ,2-propylene glycol, 1 ,3-propylene glycol, 1 ,2- butylene glycol, 1 ,3-butylene glycol, 1 ,4-butylene glycol and butyl glycol and C) from 24 to 42 % by weight of the active blend water.
2. Composition according to claim 1 , characterized in that in the one or more polyesters of component A) R1 and R2 independently of one another are H3C-(OC2H4)n-(OC3l-l6)m wherein the -(OC2H4) groups and the -(OC3H6) groups are arranged blockwise and the block consisting of the -(OC3H6) groups is bound to a COO group or are HO-(C3H6), and preferably are independently of one another H3C-(OC2H4)n-
Figure imgf000018_0001
n is based on a molar average a number of from 40 to 50,
m is based on a molar average a number of from 1 to 7, and
a is based on a molar average a number of from 4 to 9.
3. Composition according to claim 1 or 2, characterized in that in the one or more polyesters of component A) a based on a molar average is a number of from 5 to 8.
4. Composition according to claim 3, characterized in that in the one or more polyesters of component A) a based on a molar average is a number of from 6 to 7.
5. Composition according to one or more of claims 1 to 4, characterized in that in the one or more polyesters of component A) m based on a molar average is a number of from 2 to 5.
6. Composition according to one or more of claims 1 to 5, characterized in that in the one or more polyesters of component A) n based on a molar average is a number of from
43 to 47.
7. Composition according to claim 6, characterized in that in the one or more polyesters of component A) n based on a molar average is a number of from 44 to 46.
8. Composition according to claim 7, characterized in that in the one or more polyesters of component A) n based on a molar average is 45.
9. Composition according to one or more of claims 1 to 3 and 5 to 7, characterized in that in the one or more polyesters of component A)
R1 and R2 independently of one another are H3C-(OC2H4)n-(OC3l-l6)m wherein the
-(OC2H4) groups and the -(OC3H6) groups are arranged blockwise and the block consisting of the -(OC3H6) groups is bound to a COO group, n is based on a molar average a number of from 44 to 46, m is based on a molar average 2, and
a is based on a molar average a number of from 5 to 8.
10. Composition according to claim 9, characterized in that in the one or more polyesters of component A) n based on a molar average is 45, and a based on a molar average is a number of from 6 to 7.
1 1. Composition according to one or more of claims 1 to 3 and 5 to 7, characterized in that in the one or more polyesters of component A)
R1 and R2 independently of one another are H3C-(OC2H4)n-(OC3l-l6)m wherein the
-(OC2H4) groups and the -(OC3H6) groups are arranged blockwise and the block consisting of the -(OC3H6) groups is bound to a COO group, n is based on a molar average a number of from 44 to 46,
m is based on a molar average 5, and
a is based on a molar average a number of from 5 to 8.
12. Composition according to claim 1 1 , characterized in that in the one or more polyesters of component A) n based on a molar average is 45, and a based on a molar average is a number of from 6 to 7.
13. Composition according to one or more of claims 1 to 12, characterized in that the one or more alcohols of component B) are selected from the group consisting of
1 ,2-propylene glycol, 1 ,3-propylene glycol and butyl glycol.
14. Composition according to claim 13, characterized in that the alcohol of component B) is 1 ,2-propylene glycol.
15. Composition according to one or more of claims 1 to 14, characterized in that it comprises
- of from 45 to 55 % by weight of the active blend of the one or more polyesters of component A),
of from 15 to 25 % by weight of the active blend of the one or more alcohols of component B), and
of from 24 to 40 % by weight of the active blend water of component C).
16. Composition according to one or more of claims 1 to 15, characterized in that it comprises one or more additives (component D)), and in this case the amount of water preferably is of from 24 to 39.95 % by weight of the active blend.
17. Composition according to claim 16, characterized in that the one or more additives of component D) are selected from the group consisting of sequestering agents, complexing agents, polymers different from the one or more polyesters of component A) and surfactants.
18. Composition according to claim 16 or 17, characterized in that the one or more additives of component D) are present in the composition in an amount of up to 10 % by weight of the active blend, and in this case the amount of water preferably is of from 24 to 39.95 % by weight of the active blend.
19. Composition according to one or more of claims 16 to 18, characterized in that the one or more additives of component D) are present in the composition in an amount of from 0.1 to 10 % by weight, and in this case the amount of water preferably is of from 24 to 39.9 % by weight, the amounts in each case being based on the total weight of the active blend.
20. Composition according to one or more of claims 16 to 19, characterized in that the one or more additives of component D) are present in the composition in an amount of from 0.5 to 5 % by weight, and in this case the amount of water preferably is of from 24 to 39.5 % by weight, the amounts in each case being based on the total weight of the active blend.
21. Composition according to one or more of claims 1 to 15, characterized in that it consists of the one or more polyesters of component A), the one or more alcohols of component B), and water.
22. Composition according to one or more of claims 1 to 21 , characterized in that its viscosity of the active blend measured at 25 °C is of from 200 to 5 000 mPa-s.
23. Composition according to claim 22, characterized in that its viscosity of the active blend measured at 25 °C is of from 500 to 2 000 mPa-s.
24. Process for making a laundry liquid compositions comprising adding an active blend as described above to a composition comprising cleansing surfactant selected from anionic surfactants and nonionic surfactants.
25. Process according to claim 24 wherein the method comprises adding the active blend as described herein and mixing before adding perfume, fragrance or preservative.
26. Process according to claim 24 or 25 wherein the temperature of the mixture of surfactants to which the active blend is added is not more than 50°C and preferably from 10 to 40°C.
PCT/EP2015/065136 2014-07-09 2015-07-02 Laundry liquid composition WO2016005271A1 (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
PL15732008T PL3167033T3 (en) 2014-07-09 2015-07-02 Process for making a laundry liquid composition
CN201580036837.4A CN106471111B (en) 2014-07-09 2015-07-02 Laundry detergent composition
CA2953273A CA2953273C (en) 2014-07-09 2015-07-02 Alkaline laundry liquid composition comprising polyesters
BR112017000306-6A BR112017000306B1 (en) 2014-07-09 2015-07-02 Process for producing an alkaline liquid laundry composition
US15/323,501 US10336968B2 (en) 2014-07-09 2015-07-02 Laundry liquid composition comprising a polyester/butyl glycol/water active blend
EP15732008.6A EP3167033B1 (en) 2014-07-09 2015-07-02 Process for making a laundry liquid composition

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP14176406 2014-07-09
EPEP14176406.8 2014-07-09

Publications (1)

Publication Number Publication Date
WO2016005271A1 true WO2016005271A1 (en) 2016-01-14

Family

ID=51133946

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2015/065136 WO2016005271A1 (en) 2014-07-09 2015-07-02 Laundry liquid composition

Country Status (7)

Country Link
US (1) US10336968B2 (en)
EP (1) EP3167033B1 (en)
CN (1) CN106471111B (en)
BR (1) BR112017000306B1 (en)
CA (1) CA2953273C (en)
PL (1) PL3167033T3 (en)
WO (1) WO2016005271A1 (en)

Cited By (100)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018028936A1 (en) * 2016-08-08 2018-02-15 Henkel Ag & Co. Kgaa Stable liquid detergent comprising soil release polymer
WO2018028933A1 (en) * 2016-08-08 2018-02-15 Henkel Ag & Co. Kgaa Stable liquid detergent comprising soil release polymer
WO2018028935A1 (en) * 2016-08-08 2018-02-15 Henkel Ag & Co. Kgaa Stable liquid detergent comprising soil release polymer
WO2018028934A1 (en) * 2016-08-08 2018-02-15 Henkel Ag & Co. Kgaa Stable liquid detergent comprising soil release polymer
DE202019104451U1 (en) 2018-08-14 2019-08-30 Unilever N.V. composition
WO2019219477A1 (en) 2018-05-15 2019-11-21 Unilever Plc Composition
WO2020057844A1 (en) 2018-09-17 2020-03-26 Unilever Plc Composition
WO2020057845A1 (en) 2018-09-17 2020-03-26 Unilever Plc Composition
WO2020193561A1 (en) 2019-03-26 2020-10-01 Unilever Plc Composition
WO2020229158A1 (en) 2019-05-10 2020-11-19 Unilever Plc Compound and detergent composition
WO2020229160A1 (en) 2019-05-16 2020-11-19 Unilever Plc Laundry composition
WO2021099095A1 (en) 2019-11-20 2021-05-27 Unilever Ip Holdings B.V. Composition
WO2021151852A1 (en) 2020-01-29 2021-08-05 Unilever Ip Holdings B.V. A home care composition comprising dehydroacetic acid
WO2021204831A1 (en) 2020-04-09 2021-10-14 Unilever Ip Holdings B.V. Laundry detergent composition
WO2022008150A1 (en) 2020-07-06 2022-01-13 Unilever Ip Holdings B.V. Irritation mitigating surfactants
WO2022033884A1 (en) 2020-08-12 2022-02-17 Unilever Ip Holdings B.V. Laundry detergent composition
WO2022033855A1 (en) 2020-08-12 2022-02-17 Unilever Ip Holdings B.V. Laundry detergent composition
WO2022033857A1 (en) 2020-08-12 2022-02-17 Unilever Ip Holdings B.V. Laundry detergent composition
WO2022033853A1 (en) 2020-08-12 2022-02-17 Unilever Ip Holdings B.V. Laundry detergent composition
WO2022033986A1 (en) 2020-08-12 2022-02-17 Unilever Ip Holdings B.V. Laundry detergent composition
WO2022033848A1 (en) 2020-08-12 2022-02-17 Unilever Ip Holdings B.V. Laundry detergent composition
WO2022034150A1 (en) 2020-08-12 2022-02-17 Unilever Ip Holdings B.V. Process for making laundry liquid detergent composition
WO2022033846A1 (en) 2020-08-12 2022-02-17 Unilever Ip Holdings B.V. Laundry detergent composition
WO2022033851A1 (en) 2020-08-12 2022-02-17 Unilever Ip Holdings B.V. Laundry detergent composition
WO2022033997A1 (en) 2020-08-12 2022-02-17 Unilever Ip Holdings B.V. Process for making laundry liquid detergent composition
WO2022063708A1 (en) 2020-09-24 2022-03-31 Unilever Ip Holdings B.V. Composition
WO2022063707A1 (en) 2020-09-24 2022-03-31 Unilever Ip Holdings B.V. Composition
WO2022101005A1 (en) 2020-11-10 2022-05-19 Unilever Ip Holdings B.V. Laundry composition
WO2022106079A1 (en) 2020-11-17 2022-05-27 Unilever Ip Holdings B.V. Composition
WO2022122474A1 (en) 2020-12-07 2022-06-16 Unilever Ip Holdings B.V. Composition
WO2022122417A1 (en) 2020-12-07 2022-06-16 Unilever Ip Holdings B.V. Composition
WO2022122267A1 (en) 2020-12-08 2022-06-16 Unilever Ip Holdings B.V. Oleyl alcohol and process of production
WO2022122427A1 (en) 2020-12-07 2022-06-16 Unilever Ip Holdings B.V. Composition
WO2022122425A1 (en) 2020-12-07 2022-06-16 Unilever Ip Holdings B.V. Composition
WO2022122426A1 (en) 2020-12-07 2022-06-16 Unilever Ip Holdings B.V. Composition
WO2022129374A1 (en) 2020-12-18 2022-06-23 Unilever Ip Holdings B.V. Detergent composition
WO2022157232A1 (en) 2021-01-21 2022-07-28 Unilever Ip Holdings B.V. Composition
WO2022189059A1 (en) 2021-03-09 2022-09-15 Unilever Ip Holdings B.V. Composition
WO2022219118A1 (en) 2021-04-15 2022-10-20 Unilever Ip Holdings B.V. Composition
WO2022219130A1 (en) 2021-04-15 2022-10-20 Unilever Ip Holdings B.V. Composition
WO2022219132A1 (en) 2021-04-15 2022-10-20 Unilever Ip Holdings B.V. Composition
WO2022219114A1 (en) 2021-04-15 2022-10-20 Unilever Ip Holdings B.V. Composition
WO2022219112A1 (en) 2021-04-15 2022-10-20 Unilever Ip Holdings B.V. Composition
WO2022228951A1 (en) 2021-04-30 2022-11-03 Unilever Ip Holdings B.V. Composition
WO2022228832A1 (en) 2021-04-30 2022-11-03 Unilever Ip Holdings B.V. Composition
WO2022228950A1 (en) 2021-04-30 2022-11-03 Unilever Ip Holdings B.V. Composition
WO2022228949A1 (en) 2021-04-30 2022-11-03 Unilever Ip Holdings B.V. Composition
WO2022228903A1 (en) 2021-04-30 2022-11-03 Unilever Ip Holdings B.V. Composition
WO2022248108A1 (en) 2021-05-28 2022-12-01 Unilever Ip Holdings B.V. A liquid laundry detergent composition comprising c16 and c18 alcohol ethoxylate surfactant and/or c16 and c18 alkyl ether sulphate
WO2023012093A1 (en) 2021-08-05 2023-02-09 Unilever Ip Holdings B.V. Method
WO2023011892A1 (en) 2021-08-05 2023-02-09 Unilever Ip Holdings B.V. Composition
WO2023012098A1 (en) 2021-08-05 2023-02-09 Unilever Ip Holdings B.V. Method
WO2023051978A1 (en) 2021-09-29 2023-04-06 Unilever Ip Holdings B.V. Composition
WO2023057367A1 (en) 2021-10-08 2023-04-13 Unilever Ip Holdings B.V. Laundry composition
WO2023057323A2 (en) 2021-10-08 2023-04-13 Unilever Ip Holdings B.V. Composition
WO2023057531A2 (en) 2021-10-08 2023-04-13 Unilever Ip Holdings B.V. Composition
WO2023057526A1 (en) 2021-10-08 2023-04-13 Unilever Ip Holdings B.V. Composition
WO2023057604A2 (en) 2021-10-08 2023-04-13 Unilever Ip Holdings B.V. Laundry composition
WO2023057536A1 (en) 2021-10-08 2023-04-13 Unilever Ip Holdings B.V. Composition
WO2023057537A1 (en) 2021-10-08 2023-04-13 Unilever Ip Holdings B.V. Laundry composition
WO2023057322A1 (en) 2021-10-08 2023-04-13 Unilever Ip Holdings B.V. Composition
WO2023057532A2 (en) 2021-10-08 2023-04-13 Unilever Ip Holdings B.V. Composition
WO2023057530A2 (en) 2021-10-08 2023-04-13 Unilever Ip Holdings B.V. Composition
DE102022128399A1 (en) 2021-10-26 2023-04-27 Unilever Global Ip Limited COMPOSITION
WO2023138838A1 (en) 2022-01-20 2023-07-27 Unilever Ip Holdings B.V. Composition
WO2023138837A1 (en) 2022-01-20 2023-07-27 Unilever Ip Holdings B.V. Use
US11739286B2 (en) 2017-11-17 2023-08-29 Conopco, Inc. Soil release polymers and laundry detergent compositions containing them
WO2023227375A1 (en) 2022-05-27 2023-11-30 Unilever Ip Holdings B.V. Laundry liquid composition comprising a surfactant, an aminocarboxylate, an organic acid and a fragrance
WO2023227356A1 (en) 2022-05-27 2023-11-30 Unilever Ip Holdings B.V. Composition containing enzyme
WO2023227357A1 (en) 2022-05-27 2023-11-30 Unilever Ip Holdings B.V. Composition
WO2023227335A1 (en) 2022-05-27 2023-11-30 Unilever Ip Holdings B.V. Liquid composition comprising linear alkyl benzene sulphonate, methyl ester ethoxylate and alkoxylated zwitterionic polyamine polymer
WO2023227358A1 (en) 2022-05-27 2023-11-30 Unilever Ip Holdings B.V. Premix and composition and method of preparing the same
WO2023227421A1 (en) 2022-05-27 2023-11-30 Unilever Ip Holdings B.V. Laundry liquid composition comprising a surfactant, an alkoxylated zwitterionic polyamine polymer, and a fragrance
WO2023227331A1 (en) 2022-05-27 2023-11-30 Unilever Ip Holdings B.V. Composition comprising a specific methyl ester ethoxylate surfactant and a lipase
WO2023227332A1 (en) 2022-05-27 2023-11-30 Unilever Ip Holdings B.V. Laundry liquid composition comprising a surfactant, an alkoxylated zwitterionic polyamine polymer and a protease
WO2023233025A1 (en) 2022-06-03 2023-12-07 Unilever Ip Holdings B.V. Liquid detergent product
WO2024042179A1 (en) 2022-08-25 2024-02-29 Unilever Ip Holdings B.V. A cleaning composition
WO2024046757A1 (en) 2022-08-30 2024-03-07 Unilever Ip Holdings B.V. Detergent product
WO2024056331A1 (en) 2022-09-13 2024-03-21 Unilever Ip Holdings B.V. Washing machine and washing method
WO2024056334A1 (en) 2022-09-13 2024-03-21 Unilever Ip Holdings B.V. Washing machine and washing method
WO2024056278A1 (en) 2022-09-13 2024-03-21 Unilever Ip Holdings B.V. Washing machine and washing method
WO2024056333A1 (en) 2022-09-13 2024-03-21 Unilever Ip Holdings B.V. Washing machine and washing method
EP4349946A1 (en) 2022-10-05 2024-04-10 Unilever IP Holdings B.V. Unit dose fabric treatment product
EP4349944A1 (en) 2022-10-05 2024-04-10 Unilever IP Holdings B.V. Laundry liquid composition
EP4349943A1 (en) 2022-10-05 2024-04-10 Unilever IP Holdings B.V. Laundry liquid composition
EP4349948A1 (en) 2022-10-05 2024-04-10 Unilever IP Holdings B.V. Laundry liquid composition
EP4349947A1 (en) 2022-10-05 2024-04-10 Unilever IP Holdings B.V. Laundry liquid composition
EP4349942A1 (en) 2022-10-05 2024-04-10 Unilever IP Holdings B.V. Laundry liquid composition
EP4349945A1 (en) 2022-10-05 2024-04-10 Unilever IP Holdings B.V. Laundry liquid composition
WO2024074247A1 (en) 2022-10-06 2024-04-11 Unilever Ip Holdings B.V. Composition
EP4361239A1 (en) 2022-10-25 2024-05-01 Unilever IP Holdings B.V. Laundry liquid composition
WO2024088716A1 (en) 2022-10-25 2024-05-02 Unilever Ip Holdings B.V. Composition
WO2024088706A1 (en) 2022-10-25 2024-05-02 Unilever Ip Holdings B.V. Composition
EP4372071A1 (en) 2022-11-18 2024-05-22 Unilever IP Holdings B.V. Detergent composition
WO2024194098A1 (en) 2023-03-21 2024-09-26 Unilever Ip Holdings B.V. Detergent unit dose
WO2024213376A1 (en) 2023-04-11 2024-10-17 Unilever Ip Holdings B.V. Composition
WO2024213438A1 (en) 2023-04-11 2024-10-17 Unilever Ip Holdings B.V. Composition
WO2024213443A1 (en) 2023-04-11 2024-10-17 Unilever Ip Holdings B.V. Composition
WO2024213428A1 (en) 2023-04-11 2024-10-17 Unilever Ip Holdings B.V. Composition
WO2024213430A1 (en) 2023-04-11 2024-10-17 Unilever Ip Holdings B.V. Composition

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10808206B2 (en) 2017-11-14 2020-10-20 Henkel IP & Holding GmbH Detergent boosters, detergent systems that include a detergent booster, and methods of laundering fabric

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0964015A1 (en) 1998-06-12 1999-12-15 Clariant GmbH Soil release oligoester
EP1661933A1 (en) 2004-11-24 2006-05-31 SASOL Germany GmbH Liquid, amphiphilic and nonionic oligoesters
WO2007079850A1 (en) 2005-12-21 2007-07-19 Clariant Produkte (Deutschland) Gmbh Anionic soil release polymers
DE102007005532A1 (en) 2007-02-03 2008-08-07 Clariant International Limited Aqueous oligo- and polyester preparations
DE102007013217A1 (en) 2007-03-15 2008-09-18 Clariant International Ltd. Anionic Soil Release Polymers
WO2013019658A2 (en) 2011-07-29 2013-02-07 Selecta Biosciences, Inc. Synthetic nanocarriers comprising polymers comprising multiple immunomodulatory agents
EP2692842A1 (en) * 2012-07-31 2014-02-05 Unilever PLC Concentrated liquid detergent compositions
WO2014019903A1 (en) * 2012-07-31 2014-02-06 Unilever Plc Alkaline liquid laundry detergent compositions comprising polyesters
WO2014019658A1 (en) * 2012-07-31 2014-02-06 Clariant International Ltd Polyesters

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
MY163351A (en) 2011-01-31 2017-09-15 Unilever Plc Alkaline liquid detergent compositions
CN103347927B (en) 2011-01-31 2015-04-22 荷兰联合利华有限公司 Soil release polymers

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0964015A1 (en) 1998-06-12 1999-12-15 Clariant GmbH Soil release oligoester
EP1661933A1 (en) 2004-11-24 2006-05-31 SASOL Germany GmbH Liquid, amphiphilic and nonionic oligoesters
WO2007079850A1 (en) 2005-12-21 2007-07-19 Clariant Produkte (Deutschland) Gmbh Anionic soil release polymers
DE102007005532A1 (en) 2007-02-03 2008-08-07 Clariant International Limited Aqueous oligo- and polyester preparations
DE102007013217A1 (en) 2007-03-15 2008-09-18 Clariant International Ltd. Anionic Soil Release Polymers
WO2013019658A2 (en) 2011-07-29 2013-02-07 Selecta Biosciences, Inc. Synthetic nanocarriers comprising polymers comprising multiple immunomodulatory agents
EP2692842A1 (en) * 2012-07-31 2014-02-05 Unilever PLC Concentrated liquid detergent compositions
WO2014019903A1 (en) * 2012-07-31 2014-02-06 Unilever Plc Alkaline liquid laundry detergent compositions comprising polyesters
WO2014019658A1 (en) * 2012-07-31 2014-02-06 Clariant International Ltd Polyesters

Cited By (108)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018028936A1 (en) * 2016-08-08 2018-02-15 Henkel Ag & Co. Kgaa Stable liquid detergent comprising soil release polymer
WO2018028933A1 (en) * 2016-08-08 2018-02-15 Henkel Ag & Co. Kgaa Stable liquid detergent comprising soil release polymer
WO2018028935A1 (en) * 2016-08-08 2018-02-15 Henkel Ag & Co. Kgaa Stable liquid detergent comprising soil release polymer
WO2018028934A1 (en) * 2016-08-08 2018-02-15 Henkel Ag & Co. Kgaa Stable liquid detergent comprising soil release polymer
US11739286B2 (en) 2017-11-17 2023-08-29 Conopco, Inc. Soil release polymers and laundry detergent compositions containing them
WO2019219477A1 (en) 2018-05-15 2019-11-21 Unilever Plc Composition
DE202019104451U1 (en) 2018-08-14 2019-08-30 Unilever N.V. composition
WO2020057844A1 (en) 2018-09-17 2020-03-26 Unilever Plc Composition
WO2020057845A1 (en) 2018-09-17 2020-03-26 Unilever Plc Composition
WO2020193561A1 (en) 2019-03-26 2020-10-01 Unilever Plc Composition
WO2020229158A1 (en) 2019-05-10 2020-11-19 Unilever Plc Compound and detergent composition
WO2020229160A1 (en) 2019-05-16 2020-11-19 Unilever Plc Laundry composition
WO2021099095A1 (en) 2019-11-20 2021-05-27 Unilever Ip Holdings B.V. Composition
WO2021151852A1 (en) 2020-01-29 2021-08-05 Unilever Ip Holdings B.V. A home care composition comprising dehydroacetic acid
WO2021204831A1 (en) 2020-04-09 2021-10-14 Unilever Ip Holdings B.V. Laundry detergent composition
WO2021204636A1 (en) 2020-04-09 2021-10-14 Unilever Ip Holdings B.V. Laundry detergent composition
WO2022008150A1 (en) 2020-07-06 2022-01-13 Unilever Ip Holdings B.V. Irritation mitigating surfactants
WO2022033884A1 (en) 2020-08-12 2022-02-17 Unilever Ip Holdings B.V. Laundry detergent composition
WO2022033855A1 (en) 2020-08-12 2022-02-17 Unilever Ip Holdings B.V. Laundry detergent composition
WO2022033857A1 (en) 2020-08-12 2022-02-17 Unilever Ip Holdings B.V. Laundry detergent composition
WO2022033853A1 (en) 2020-08-12 2022-02-17 Unilever Ip Holdings B.V. Laundry detergent composition
WO2022033986A1 (en) 2020-08-12 2022-02-17 Unilever Ip Holdings B.V. Laundry detergent composition
WO2022033848A1 (en) 2020-08-12 2022-02-17 Unilever Ip Holdings B.V. Laundry detergent composition
WO2022034150A1 (en) 2020-08-12 2022-02-17 Unilever Ip Holdings B.V. Process for making laundry liquid detergent composition
WO2022033846A1 (en) 2020-08-12 2022-02-17 Unilever Ip Holdings B.V. Laundry detergent composition
WO2022033851A1 (en) 2020-08-12 2022-02-17 Unilever Ip Holdings B.V. Laundry detergent composition
WO2022033997A1 (en) 2020-08-12 2022-02-17 Unilever Ip Holdings B.V. Process for making laundry liquid detergent composition
WO2022063708A1 (en) 2020-09-24 2022-03-31 Unilever Ip Holdings B.V. Composition
WO2022063707A1 (en) 2020-09-24 2022-03-31 Unilever Ip Holdings B.V. Composition
WO2022101005A1 (en) 2020-11-10 2022-05-19 Unilever Ip Holdings B.V. Laundry composition
WO2022106079A1 (en) 2020-11-17 2022-05-27 Unilever Ip Holdings B.V. Composition
WO2022122474A1 (en) 2020-12-07 2022-06-16 Unilever Ip Holdings B.V. Composition
WO2022122417A1 (en) 2020-12-07 2022-06-16 Unilever Ip Holdings B.V. Composition
WO2022122427A1 (en) 2020-12-07 2022-06-16 Unilever Ip Holdings B.V. Composition
WO2022122425A1 (en) 2020-12-07 2022-06-16 Unilever Ip Holdings B.V. Composition
WO2022122426A1 (en) 2020-12-07 2022-06-16 Unilever Ip Holdings B.V. Composition
WO2022122267A1 (en) 2020-12-08 2022-06-16 Unilever Ip Holdings B.V. Oleyl alcohol and process of production
WO2022129374A1 (en) 2020-12-18 2022-06-23 Unilever Ip Holdings B.V. Detergent composition
WO2022157232A1 (en) 2021-01-21 2022-07-28 Unilever Ip Holdings B.V. Composition
WO2022189059A1 (en) 2021-03-09 2022-09-15 Unilever Ip Holdings B.V. Composition
WO2022219118A1 (en) 2021-04-15 2022-10-20 Unilever Ip Holdings B.V. Composition
WO2022219130A1 (en) 2021-04-15 2022-10-20 Unilever Ip Holdings B.V. Composition
WO2022219132A1 (en) 2021-04-15 2022-10-20 Unilever Ip Holdings B.V. Composition
WO2022219114A1 (en) 2021-04-15 2022-10-20 Unilever Ip Holdings B.V. Composition
WO2022219112A1 (en) 2021-04-15 2022-10-20 Unilever Ip Holdings B.V. Composition
WO2022228951A1 (en) 2021-04-30 2022-11-03 Unilever Ip Holdings B.V. Composition
WO2022228832A1 (en) 2021-04-30 2022-11-03 Unilever Ip Holdings B.V. Composition
WO2022228950A1 (en) 2021-04-30 2022-11-03 Unilever Ip Holdings B.V. Composition
WO2022228949A1 (en) 2021-04-30 2022-11-03 Unilever Ip Holdings B.V. Composition
WO2022228903A1 (en) 2021-04-30 2022-11-03 Unilever Ip Holdings B.V. Composition
WO2022248108A1 (en) 2021-05-28 2022-12-01 Unilever Ip Holdings B.V. A liquid laundry detergent composition comprising c16 and c18 alcohol ethoxylate surfactant and/or c16 and c18 alkyl ether sulphate
WO2023012093A1 (en) 2021-08-05 2023-02-09 Unilever Ip Holdings B.V. Method
WO2023011892A1 (en) 2021-08-05 2023-02-09 Unilever Ip Holdings B.V. Composition
WO2023012098A1 (en) 2021-08-05 2023-02-09 Unilever Ip Holdings B.V. Method
WO2023051978A1 (en) 2021-09-29 2023-04-06 Unilever Ip Holdings B.V. Composition
WO2023057367A1 (en) 2021-10-08 2023-04-13 Unilever Ip Holdings B.V. Laundry composition
WO2023057323A2 (en) 2021-10-08 2023-04-13 Unilever Ip Holdings B.V. Composition
WO2023057531A2 (en) 2021-10-08 2023-04-13 Unilever Ip Holdings B.V. Composition
WO2023057526A1 (en) 2021-10-08 2023-04-13 Unilever Ip Holdings B.V. Composition
WO2023057604A2 (en) 2021-10-08 2023-04-13 Unilever Ip Holdings B.V. Laundry composition
WO2023057536A1 (en) 2021-10-08 2023-04-13 Unilever Ip Holdings B.V. Composition
WO2023057537A1 (en) 2021-10-08 2023-04-13 Unilever Ip Holdings B.V. Laundry composition
WO2023057322A1 (en) 2021-10-08 2023-04-13 Unilever Ip Holdings B.V. Composition
WO2023057532A2 (en) 2021-10-08 2023-04-13 Unilever Ip Holdings B.V. Composition
WO2023057530A2 (en) 2021-10-08 2023-04-13 Unilever Ip Holdings B.V. Composition
DE102022128399A1 (en) 2021-10-26 2023-04-27 Unilever Global Ip Limited COMPOSITION
EP4174156A1 (en) 2021-10-26 2023-05-03 Unilever IP Holdings B.V. Composition
WO2023072507A1 (en) 2021-10-26 2023-05-04 Unilever Ip Holdings B.V. Composition
WO2023138838A1 (en) 2022-01-20 2023-07-27 Unilever Ip Holdings B.V. Composition
WO2023138837A1 (en) 2022-01-20 2023-07-27 Unilever Ip Holdings B.V. Use
WO2023227375A1 (en) 2022-05-27 2023-11-30 Unilever Ip Holdings B.V. Laundry liquid composition comprising a surfactant, an aminocarboxylate, an organic acid and a fragrance
WO2023227356A1 (en) 2022-05-27 2023-11-30 Unilever Ip Holdings B.V. Composition containing enzyme
WO2023227357A1 (en) 2022-05-27 2023-11-30 Unilever Ip Holdings B.V. Composition
WO2023227335A1 (en) 2022-05-27 2023-11-30 Unilever Ip Holdings B.V. Liquid composition comprising linear alkyl benzene sulphonate, methyl ester ethoxylate and alkoxylated zwitterionic polyamine polymer
WO2023227358A1 (en) 2022-05-27 2023-11-30 Unilever Ip Holdings B.V. Premix and composition and method of preparing the same
WO2023227421A1 (en) 2022-05-27 2023-11-30 Unilever Ip Holdings B.V. Laundry liquid composition comprising a surfactant, an alkoxylated zwitterionic polyamine polymer, and a fragrance
WO2023227331A1 (en) 2022-05-27 2023-11-30 Unilever Ip Holdings B.V. Composition comprising a specific methyl ester ethoxylate surfactant and a lipase
WO2023227332A1 (en) 2022-05-27 2023-11-30 Unilever Ip Holdings B.V. Laundry liquid composition comprising a surfactant, an alkoxylated zwitterionic polyamine polymer and a protease
WO2023233025A1 (en) 2022-06-03 2023-12-07 Unilever Ip Holdings B.V. Liquid detergent product
WO2023233028A1 (en) 2022-06-03 2023-12-07 Unilever Ip Holdings B.V. Laundry detergent product
WO2023233026A1 (en) 2022-06-03 2023-12-07 Unilever Ip Holdings B.V. Laundry detergent product
WO2024042179A1 (en) 2022-08-25 2024-02-29 Unilever Ip Holdings B.V. A cleaning composition
WO2024046757A1 (en) 2022-08-30 2024-03-07 Unilever Ip Holdings B.V. Detergent product
WO2024046743A1 (en) 2022-08-30 2024-03-07 Unilever Ip Holdings B.V. Detergent product
WO2024046756A1 (en) 2022-08-30 2024-03-07 Unilever Ip Holdings B.V. Detergent product
WO2024056331A1 (en) 2022-09-13 2024-03-21 Unilever Ip Holdings B.V. Washing machine and washing method
WO2024056334A1 (en) 2022-09-13 2024-03-21 Unilever Ip Holdings B.V. Washing machine and washing method
WO2024056278A1 (en) 2022-09-13 2024-03-21 Unilever Ip Holdings B.V. Washing machine and washing method
WO2024056333A1 (en) 2022-09-13 2024-03-21 Unilever Ip Holdings B.V. Washing machine and washing method
WO2024056332A1 (en) 2022-09-13 2024-03-21 Unilever Ip Holdings B.V. Washing machine and washing method
EP4349946A1 (en) 2022-10-05 2024-04-10 Unilever IP Holdings B.V. Unit dose fabric treatment product
EP4349944A1 (en) 2022-10-05 2024-04-10 Unilever IP Holdings B.V. Laundry liquid composition
EP4349943A1 (en) 2022-10-05 2024-04-10 Unilever IP Holdings B.V. Laundry liquid composition
EP4349948A1 (en) 2022-10-05 2024-04-10 Unilever IP Holdings B.V. Laundry liquid composition
EP4349947A1 (en) 2022-10-05 2024-04-10 Unilever IP Holdings B.V. Laundry liquid composition
EP4349942A1 (en) 2022-10-05 2024-04-10 Unilever IP Holdings B.V. Laundry liquid composition
EP4349945A1 (en) 2022-10-05 2024-04-10 Unilever IP Holdings B.V. Laundry liquid composition
WO2024074247A1 (en) 2022-10-06 2024-04-11 Unilever Ip Holdings B.V. Composition
EP4361239A1 (en) 2022-10-25 2024-05-01 Unilever IP Holdings B.V. Laundry liquid composition
WO2024088716A1 (en) 2022-10-25 2024-05-02 Unilever Ip Holdings B.V. Composition
WO2024088706A1 (en) 2022-10-25 2024-05-02 Unilever Ip Holdings B.V. Composition
EP4372071A1 (en) 2022-11-18 2024-05-22 Unilever IP Holdings B.V. Detergent composition
WO2024194098A1 (en) 2023-03-21 2024-09-26 Unilever Ip Holdings B.V. Detergent unit dose
WO2024213376A1 (en) 2023-04-11 2024-10-17 Unilever Ip Holdings B.V. Composition
WO2024213438A1 (en) 2023-04-11 2024-10-17 Unilever Ip Holdings B.V. Composition
WO2024213443A1 (en) 2023-04-11 2024-10-17 Unilever Ip Holdings B.V. Composition
WO2024213428A1 (en) 2023-04-11 2024-10-17 Unilever Ip Holdings B.V. Composition
WO2024213430A1 (en) 2023-04-11 2024-10-17 Unilever Ip Holdings B.V. Composition

Also Published As

Publication number Publication date
CA2953273A1 (en) 2016-01-14
EP3167033A1 (en) 2017-05-17
EP3167033B1 (en) 2020-04-29
US10336968B2 (en) 2019-07-02
CN106471111A (en) 2017-03-01
BR112017000306A2 (en) 2017-11-07
CN106471111B (en) 2020-04-07
CA2953273C (en) 2022-07-26
US20170137755A1 (en) 2017-05-18
BR112017000306B1 (en) 2022-06-07
PL3167033T3 (en) 2020-11-02

Similar Documents

Publication Publication Date Title
CA2953273C (en) Alkaline laundry liquid composition comprising polyesters
US10087400B2 (en) Storage-stable compositions comprising soil release polymers
JP6475617B2 (en) polyester
CN104603175B (en) Polyester
BR112015001754B1 (en) alkaline liquid detergent composition for washing
WO2019105939A1 (en) Detergent compositions containing renewably sourced soil release polyesters
JP2010265333A (en) Liquid detergent composition
AU2017245481A1 (en) Laundry liquid composition
AU2013298728B9 (en) Alkaline liquid laundry detergent compositions comprising polyesters

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 15732008

Country of ref document: EP

Kind code of ref document: A1

DPE1 Request for preliminary examination filed after expiration of 19th month from priority date (pct application filed from 20040101)
REEP Request for entry into the european phase

Ref document number: 2015732008

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 2015732008

Country of ref document: EP

ENP Entry into the national phase

Ref document number: 2953273

Country of ref document: CA

WWE Wipo information: entry into national phase

Ref document number: 15323501

Country of ref document: US

NENP Non-entry into the national phase

Ref country code: DE

REG Reference to national code

Ref country code: BR

Ref legal event code: B01A

Ref document number: 112017000306

Country of ref document: BR

ENP Entry into the national phase

Ref document number: 112017000306

Country of ref document: BR

Kind code of ref document: A2

Effective date: 20170106