EP3234086B1 - Pourable liquid fabric conditioner compositions - Google Patents

Pourable liquid fabric conditioner compositions Download PDF

Info

Publication number
EP3234086B1
EP3234086B1 EP15798483.2A EP15798483A EP3234086B1 EP 3234086 B1 EP3234086 B1 EP 3234086B1 EP 15798483 A EP15798483 A EP 15798483A EP 3234086 B1 EP3234086 B1 EP 3234086B1
Authority
EP
European Patent Office
Prior art keywords
polymer
composition
water
composition according
particles
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Not-in-force
Application number
EP15798483.2A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP3234086A1 (en
Inventor
Christopher Boardman
Elizabeth Ann Clowes
Peter Graham
David Stephen Grainger
Robert Allan Hunter
Janette Perry
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Unilever PLC
Unilever NV
Original Assignee
Unilever PLC
Unilever NV
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 NV filed Critical Unilever PLC
Publication of EP3234086A1 publication Critical patent/EP3234086A1/en
Application granted granted Critical
Publication of EP3234086B1 publication Critical patent/EP3234086B1/en
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

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
    • C11D1/38—Cationic compounds
    • C11D1/62—Quaternary ammonium 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
    • C11D3/001—Softening compositions
    • C11D3/0015—Softening compositions liquid
    • 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
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C11D3/3773—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines in liquid compositions

Definitions

  • the present invention relates to pourable liquid fabric conditioner compositions comprising viscosity modifying polymers.
  • fabric conditioners to have a viscosity of at least 30 mPas at 25°C and 106s -1 .
  • concentration of conditioning active (cationic) and the lower the recommended dose the higher the inherent composition viscosity becomes and the more it becomes an issue for effective dispensing.
  • the viscosity of liquid compositions that would otherwise be too thin for consumer preference can be increased by addition of a thickening polymer.
  • a thickening polymer One such additive consists of polymer gels ⁇ 10 microns in diameter when swollen with water. These particles display strong colloidal interactions and increase viscosity at the expense of reduced dispersibility. This poor dispersibility leads to major problems if the product is to be dispensed from a washing machine drawer and is also perceived as unsatisfactory when hand washing. Poor dispersion leads to poor fabric conditioning.
  • a structured fabric conditioning liquid comprises multiple phases in which a cationic softening active (typically a quaternary ammonium compound) is suspended in water.
  • a cationic softening active typically a quaternary ammonium compound
  • Water and a dispersion of immiscible softening active typically exist as a structured bilayer microstructure, e.g. multilayer vesicles.
  • the resulting liquid exhibits complex flow behaviour (non Newtonian flow) and short to medium range ordering within the liquid.
  • GB1428062 discloses fabric softening compositions comprising a cationic softener compound and a water-insoluble particulate material having an average particle size of 1 to 50 microns. The addition of this insoluble particulate material is said to enhance the properties of the softened fabric. Glass beads and micro balloons, starch and other low swelling materials are exemplified. It is taught that particulate materials with high swelling power (>15) should be avoided as such swelling detracts from the benefits. Deposition of such a large mass of solid particles onto clothing is not desirable.
  • WO2010/079100 discloses fabric conditioner compositions comprising cationic polymeric thickeners exhibiting a low fraction of water soluble polymers and a relatively high level of cross-linking, which results in a markedly improved weight efficiency and reduction in the re-deposition of soil. These polymers comprise particles that are too small to provide the desired dispersion improvements.
  • a pourable liquid fabric conditioning composition comprising:
  • Also according to the invention there is a method of providing a liquor for the conditioning of fabrics comprising the step of dispersing a composition according to the invention in water.
  • the composition is a dispersible, pourable liquid fabric conditioner composition.
  • dispersible is meant that the particles separate throughout a liquid to form a dispersion on addition of water.
  • Good dispersion is characterised by good, uniform separation of the particles in the liquid, and by the speed of the separation.
  • DI Dispersion Index
  • the mixture may be stirred by performing 5 revolutions at a rate of one per second with a flat spatula before being re-assessed using the same rating scale.
  • Fabric conditioners of the present invention are dispersed in water prior to or during use.
  • compositions have a viscosity that is preferably in the range of from 80 to 1000 mPas, more preferably from 120 to 500, even more preferably from 180 to 350 mPas at 25°C and 106s -1 .
  • Any suitable viscometer can be used, for example, a Haake VT550, or a Thermo Fisher RS600.
  • the composition is preferably substantially free from conventional thickening polymers, meaning 0 to 1 wt% conventional thickening polymer may be used in the composition, preferably 0 to 0.05 wt %, more preferably 0 to 0.01 wt %, most preferably zero wt %.
  • conventional thickening polymers in the context of this invention is meant extended polymer molecules that reach across long-length scales within the solution phase (for example, modified cellulose materials such as hydroxyl-ethyl cellulose (HEC), sodium carboxy-methyl cellulose (SCMC), or Xanthan gum), associative thickeners which link between surfactant micelles or liquid crystal domains (e.g.
  • hydrophobically modified polyacrylates hydrophobic alkali swellable emulsions - HASE
  • small particle microgels which occupy sufficient phase-volume to increase the viscosity of the solution phase as described by the Krieger-Dougherty equation (e.g. polyacrylates (carbomers)).
  • the microgel particles of conventional thickeners are much smaller ( ⁇ 10 micron) in the composition than the particles used in the present invention, and display a strong colloidal interaction which further enhances their capacity to make viscous dispersions but has the disadvantage that dispersion gets worse as viscosity increases.
  • compositions of the current invention not only have the benefit of improved thickening and improved dispersion on dilution with water, but also have an environmental and sustainable benefit arising from the large viscosity increasing particles.
  • the majority of the mass of these particles is water, which allows the composition to deliver the desired consumer benefits without using unnecessary chemicals.
  • any particles deposit onto the fabric being conditioned then they will have a very low mass and impact when dried.
  • the particles are added to a base liquid with a low inherent viscosity and associated good dispersibility in order to provide it with a viscosity boost for as long as it remains undiluted.
  • the particles are formed from water swellable cross linked polymer and are swollen to some extent by having absorbed some of the water in the composition. Such swollen particles fill more space.
  • These viscosity increasing particles have an average dry size of 10 to 400 microns. However, in the presence of water the polymer swells so that the particles have a volume average size of from 25 to 5000 microns, preferably from 25 to 1000 microns and more preferably from 50 to 500 microns, even from 60 to 300 microns or from 100 to 225 and especially from 140 to 200 microns. Unless stated otherwise all size measurements will be stated as the size in the presence of water, i.e. swollen. In general the preferred polymers absorb approximately 50 times their own weight of water to form the viscosity increasing particles. This is lower than would be the case if the cationic were absent and the swelling took place in pure water. Then the same polymer might absorb up to 450 times its own weight. It is preferred that the amount of particles in the composition will absorb less than 50% of the available water in the composition.
  • the polymer in the particle is insoluble in water.
  • water-insoluble is defined as materials having a solubility of less than 1 x 10 -3 wt% in demineralised water at 20°C, preferably less than 1 x 10 -4 wt%, more preferably from less than 1 x 10 -8 to 1 x 10 -6 wt%.
  • the polymer material should be chosen so that the particle is not reactive with other materials within the composition; in other words it is inert in the context of the composition.
  • the polymer raw material may contain some soluble components, arising mainly from incomplete crosslinking.
  • the amount of soluble components is preferably less than 15 wt %, more preferably less than 10 wt %, and most preferably less than 7.5 wt %, by weight of polymer.
  • Preferred swellable polymer particles for use in the compositions of the invention are present in a crosslinked swellable polymer containing at least one cationic monomer and optionally non-ionic and or anionic monomers; wherein said polymer has an extractable (soluble) polymer content, as defined herein, lower than 15 %, and a cross-linking agent concentration of from 500 ppm to 10,000 ppm relative to the polymer, said polymer being obtained by gel polymerization.
  • the extractable content of the polymer is preferably below 10 percent, and more preferably below 7.5 percent based on the total weight of polymer before hydration.
  • a preferred crosslinked swellable polymer forms a polymer gel in the wet state, i.e. when combined with a suitable solvent such as water.
  • the polymers may be homopolymers or co-polymers.
  • gel polymerization it is advantageous to use gel polymerization to manufacture the polymer to be used to make the particles.
  • This type of polymerisation produces dry particles of the large size required.
  • the polymer mass produced by gel polymerisation may be broken into smaller fragments and, if necessary, classified to obtain three dimensional polymer particles in the required size range, e.g. by sieving.
  • the skilled worker will have access to other polymerisation methods that produce polymer particles within the required size range to obtain the large viscosity increasing particles when combined with water.
  • the crosslinked polymers for have a three dimensional network in which water can be absorbed. As the water penetrates in the network, the volume of the particle increases from 10 to 100 times the initial volume of the particle when a cationic material is present. The resulting particle is the viscosity increasing particle. Inclusion of these particles filled with water in the base composition leads to increased viscosity of the composition.
  • the overall performance of fabric softening compositions comprising the particles is improved versus the same base composition including conventional smaller size cationic polymeric thickeners. In particular they have been found to have higher stability upon aging and more desirable rheology.
  • Cationic crosslinked swellable polymers suitable for use in the compositions of the invention may be prepared by means of gel polymerization, by polymerizing:
  • the overall charge of the polymer is preferably cationic, although nonionic polymers may also be suitable.
  • a cationic polymer necessarily contains at least one cationic monomer. In other words, when the polymer contain anionic and/or non-ionic monomers, the amount of cationic charges is greater than the amount of anionic charges.
  • Gel polymerization is a well-known polymerization technique consisting of polymerizing water soluble monomers in an aqueous media in order to obtain a gel which is then generally cut or sliced, and dried so as to obtain a polymer in powder form.
  • the resulting polymer may be pre-added in water or in another solvent before use. It may also be used as a powder.
  • Crosslinked polymers may be prepared using a gel polymerization process comprising the following steps:
  • the resulting gel is converted to powder by conventional manner, for instance by cutting the mass of gel into pieces and/or by extruding a mass of gel through coarse orifices, optionally cutting the gel before or after the extrusion, and by drying the pieces of gel. Jet milling may also be used.
  • the crosslinked swellable polymer can be added to the softening composition as a powder, or as a liquid dispersion.
  • the added amount is preferably comprised between 0.1% and 10% in weight, more preferably between 0.2 and 7%. This amount corresponds to the polymer in dry powder form which has not yet absorbed water.
  • the polymerization is generally a radical polymerization generally induced by a redox couple, for instance sodium persulfate and sodium metabisulfite.
  • the crosslinking agent concentration is comprised in the range of 500 ppm to 10000 ppm in weight relative to the total amount of monomers.
  • crosslinking agents methylene bisacrylamide (MBA), ethylene glycol diacrylate, polyethylene glycol dimethacrylate, diacrylamide, triallylamine, glyoxal, compounds of the glycidyl ether type such as ethyleneglycol diglycidyl ether, allylpentaerythritol, trimethylolpropane diallylether, or any other means familiar to the expert permitting crosslinking.
  • MBA methylene bisacrylamide
  • ethylene glycol diacrylate polyethylene glycol dimethacrylate
  • diacrylamide diacrylamide
  • triallylamine glyoxal
  • compounds of the glycidyl ether type such as ethyleneglycol diglycidyl ether, allylpentaerythritol, trimethylolpropane diallylether, or any other means familiar to the expert permitting crosslinking.
  • Preferred crosslinking agents are methylene bisacrylamide (MBA), triallylamine and allylpentaerythritol.
  • the crosslinking agent used is the methylene bisacrylamide
  • its concentration is preferably between of 500 ppm and 5000 ppm by weight relative to the monomers.
  • the crosslinking agent used is the triallylamine
  • its concentration is preferably between of 1000 and 10000 ppm by weight relative to the monomers.
  • Suitable cationic monomers for use in the preparation of the crosslinked swellable polymer are preferably selected from the group consisting of the following monomers and quaternized or salified derivatives: dimethylaminopropylmethacrylamide, dimethylaminopropylacrylamide, diallylamine, methyldiallylamine, dialkylaminoalkyl-acrylate, dialkylaminoalkyl-methacrylate, dialkylaminoalkyl-acrylamide, and dialkylaminoalkyl-methacrylamide.
  • a preferred cationic monomer is selected from the group consisting of dimethylaminoethyl-methacrylate and its quaternized or salified derivatives and/or dimethylaminopropylmethacrylamide and its quaternized or salified derivatives.
  • the cationic monomer is dimethylaminoethyl methacrylate methyl chloride salt or dimethylaminoethyl methacrylate quaternary salt.
  • the crosslinked polymer for use in the composition of the invention may be prepared by polymerizing:
  • the amount of a crosslinking agent and the amount of chain transfer agent are in ppm in weight relative to the weight of total monomers i.e. relative to the above mentioned 100 mol% of monomers.
  • Chain transfer agents such as isopropyl alcohol, sodium hypophosphite, mercaptoethanol, may be used in the polymerization mixture in order to control the polymeric chain's length and the crosslinking density.
  • a chain transfer agent When a chain transfer agent is used, its concentration is in the range of 10 ppm to 1000 ppm in weight relative to the total amount of monomers.
  • Preferred non-ionic monomers for use in preparing the crosslinked polymer for use in the compositions of the invention are selected from the group consisting of acrylamide, methacrylamide, N-Alkyl acrylamide, N-vinyl pyrrolidone, N-vinyl formamide, N-vinyl acetamide, vinylacetate, vinyl alcohol, acrylate esters and allyl alcohol.
  • a preferred non-ionic monomer is acrylamide.
  • Preferred anionic monomers for use in preparing the crosslinked polymer for use in the compositions of the invention are selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, as well as monomers performing a sulfonic acid or phosphonic acid functions, such as 2-acrylamido-2-methyl propane sulfonic acid (ATBS) said anionic monomers being acid, or partially or totally salified. More preferred anionic monomers are acrylic acid and 2-acrylamido-2-methyl propane sulfonic acid (ATBS) said anionic monomers being acid, or partially or totally salified.
  • ATBS 2-acrylamido-2-methyl propane sulfonic acid
  • ATBS 2-acrylamido-2-methyl propane sulfonic acid
  • the crosslinked polymer may also contain monomers having hydrophobic character.
  • a preferred crosslinked water swellable cationic polymer is obtained by gel polymerization of dimethyl aminoethyl methacrylate quaternized with methyl chloride (cationic monomer), acrylamide (non-ionic monomer), and methylene bisacrylamide (crosslinking agent).
  • the water extractable polymer content is the ratio between the mass of the polymer which can be extracted when the polymer is submitted to dispersion in water and the total mass of the polymer.
  • the method for determining water extractable polymer content of the crosslinked polymer is based on the basic principle of colloidal titration which is well-known by the chemists and the skilled man of the art.
  • the method consists of separation of the water-soluble part ("extractable" polymer) from the water-insoluble part of the polymer to obtain a filtrate containing only the water-soluble part, and then measurement by colloidal titration of the water-soluble polymer content in the filtrate.
  • the water extractable polymer content is the ratio between the mass of the polymer in the filtrate and the total mass of the polymer.
  • This step consists in separating insoluble polymer (swollen particles) from water soluble polymer: 0.5 g ( m 0 in g) of polymer is added to a beaker containing 800 ml of deionised water. The mixture is gently stirred with a magnetic stirrer for 6 hours. Then, 8 g of NaCl are added to complete the extraction. The salt solution is stirred for a further 1 hour. The polymer mixture is then filtered over a 100 ⁇ m screen, and 15 minutes later the filtrate is then recovered in order to measure its weight ( M 0 in g). The "water extractables" polymer content in the filtrate is then titrated.
  • Step 2 Polymer titration
  • the titration principle is a well-known colloidal titration used to determine charge density of cationic polymers.
  • the colloidal titration is performed as follows: A potassium polyvinyl sulphate (PVSK) solution is prepared by dissolving in deionised water a PVSK polymer having a molecular weight of 243,300 g/mol, so as to obtain a solution having a concentration of 0.0025 N (N/400).
  • PVSK potassium polyvinyl sulphate
  • a 0,1 N solution of hydrochloric acid is prepared in deionised water.
  • the expert will know how to vary the amount of crosslinking in order to obtain a final polymer having a low enough fraction of water-soluble polymer and the desired rheology. It is known, for example, that an increase of the concentration of crosslinking agent, other parameters being identical, leads to a decrease the extractable polymer content. The reverse is also true.
  • compositions of the present invention contain a cationic fabric softening active.
  • the fabric conditioning compositions of the invention may be dilute or concentrated.
  • Dilute products typically contain up to about 8 wt%, preferably from 2 to 8 wt% softening active, whereas concentrated products may contain from about 8 to about 50 wt%, preferably from 8 to 25 wt% active.
  • Compositions of more than about 25 wt% of active are defined as "super concentrated", depending on the active system, and are also intended to be covered by the present invention.
  • the fabric softening active may, for example, be used in amounts of from 0.5 % to 35 wt%, preferably from 2 % to 30 wt% more preferably from 5 % to 25 wt% and most preferably from 8 % to 20 wt% of the composition.
  • the preferred softening active for use in rinse conditioner compositions of the invention is a quaternary ammonium compound (QAC).
  • the preferred quaternary ammonium compounds for use in compositions of the present invention are the so called "ester quats" comprising an ester link.
  • Particularly preferred materials are the ester-linked triethanolamine (TEA) quaternary ammonium compounds comprising a mixture of mono-, di- and tri-ester linked components.
  • TAA triethanolamine
  • Most preferably the ester-linked quaternary ammonium compound is an ester-linked triethanolamine quaternary ammonium compound comprising unsaturated fatty chains.
  • TEA-based fabric softening actives comprise a mixture of mono, di- and tri-ester forms of the compound where the di-ester linked component comprises no more than 70 % by weight of the fabric softening compound, preferably no more than 60 %, e.g. 55 %, or 45 % of the fabric softening compound and at least 10 % of the monoester linked component, for example 11 % monoester.
  • a preferred hardened type of active has a typical mono:di:tri ester distribution of from 18 to 22 monoester: from 58 to 62 diester: from 18 to 22 triester; for example 20:60:20.
  • a soft TEA quat may have a typical mono:di:tri ester distribution of from 25 to 45 %, preferably from 30 to 40 % monoester: from 45 to 60 %, preferably from 50 to 55 % diester: and from 5 to 25 %, preferably from 10 to 15 % triester; for example 40:50:10.
  • a first group of quaternary ammonium compounds (QACs) suitable for use in the present invention is represented by formula (I): wherein each R is independently selected from a C 5-35 alkyl or alkenyl group; R 1 represents a C 1-4 alkyl, C 2-4 alkenyl or a C 1-4 hydroxyalkyl group; T is generally O-CO. (i.e. an ester group bound to R via its carbon atom), but may alternatively be CO-O (i.e.
  • TEA ester quats preparations which are rich in the di-esters of triethanolammonium methylsulfate, otherwise referred to as "TEA ester quats".
  • StepantexTM UL85 Ex Stepan, PrapagenTM TQL, ex Clariant, and TetranylTM AHT-1
  • Ex Kao both di-[hardened tallow ester] of triethanolammonium methylsulphate
  • AT-1 di-[tallow ester] of triethanolammonium methylsulphate
  • L5/90 di-[palm ester] of triethanolammonium methylsulphate
  • Ex Kao and RewoquatTM WE15 (a di-ester of triethanolammonium methylsulphate having fatty acyl residues deriving from C 10 -C 20 and C 16 -C 18 unsaturated fatty acids), ex Evonik.
  • soft quaternary ammonium actives such as Stepantex VK90, Stepantex VT90, SP88 (ex-Stepan), Ceca Noramine, Prapagen TQ (ex-Clariant), Dehyquart AU-57 (ex-Cognis), Rewoquat WE18 (ex-Degussa) and Tetranyl L190 P, Tetranyl L190 SP and Tetranyl L190 S (all ex-Kao).
  • a second group of QACs suitable for use in the invention is represented by formula (II): wherein each R 1 group is independently selected from C 1-4 alkyl, hydroxyalkyl or C 2-4 alkenyl groups; and wherein each R 2 group is independently selected from C 8-28 alkyl or alkenyl groups; and wherein n, T, and X - are as defined above.
  • Preferred materials of this second group include 1,2 bis [tallowoyloxy]-3-trimethylammonium propane chloride, 1,2 bis [hardened tallowoyloxy]-3-trimethylammonium propane chloride, 1,2- bis [oleoyloxy]-3-trimethylammonium propane chloride, and 1,2 bis [stearoyloxy]-3-trimethylammonium propane chloride.
  • Such materials are described in US 4,137,180 (Lever Brothers ).
  • these materials also comprise an amount of the corresponding mono-ester.
  • a third group of QACs suitable for use in the invention is represented by formula (III): (R 1 ) 2 -N + -[(CH 2 ) n -T-R 2 ] 2 X - (III) wherein each R 1 group is independently selected from C 1-4 alkyl, or C 2-4 alkenyl groups; and wherein each R 2 group is independently selected from C 8-28 alkyl or alkenyl groups; and n, T, and X - are as defined above.
  • Preferred materials of this third group include bis(2-tallowoyloxyethyl)dimethyl ammonium chloride and hardened versions thereof.
  • the iodine value of the quaternary ammonium fabric conditioning material is preferably from 0 to 80, more preferably from 0 to 60, and most preferably from 0 to 45.
  • the iodine value may be chosen as appropriate.
  • Essentially saturated material having an iodine value of from 0 to 5, preferably from 0 to 1 may be used in the compositions of the invention. Such materials are known as "hardened" quaternary ammonium compounds.
  • a further preferred range of iodine values is from 20 to 60, preferably 25 to 50, more preferably from 30 to 45.
  • a material of this type is a "soft" triethanolamine quaternary ammonium compound, preferably triethanolamine di-alkylester methylsulphate. Such ester-linked triethanolamine quaternary ammonium compounds comprise unsaturated fatty chains.
  • Iodine value refers to the measurement of the degree of unsaturation present in a material by a method of nmr spectroscopy as described in Anal. Chem., 34, 1136 (1962) Johnson and Shoolery .
  • a further type of softening compound is a non-ester quaternary ammonium material represented by formula (IV): wherein each R 1 group is independently selected from C 1-4 alkyl, hydroxyalkyl or C 2-4 alkenyl groups; each R 2 group is independently selected from C 8-28 alkyl or alkenyl groups, and X - is as defined above.
  • compositions of the invention may optionally contain a non-cationic softening material, which is preferably an oily sugar derivative.
  • An oily sugar derivative is a liquid or soft solid derivative of a cyclic polyol (CPE) or of a reduced saccharide (RSE), said derivative resulting from 35 to 100 % of the hydroxyl groups in said polyol or in said saccharide being esterified or etherified.
  • the derivative has two or more ester or ether groups independently attached to a C 8 -C 22 alkyl or alkenyl chain.
  • the CPE or RSE does not have any substantial crystalline character at 20°C. Instead it is preferably in a liquid or soft solid state as herein defined at 20°C.
  • liquid or soft solid (as hereinafter defined) CPEs or RSEs suitable for use in the present invention result from 35 to 100% of the hydroxyl groups of the starting cyclic polyol or reduced saccharide being esterified or etherified with groups such that the CPEs or RSEs are in the required liquid or soft solid state.
  • These groups typically contain unsaturation, branching or mixed chain lengths.
  • the CPEs or RSEs have 3 or more ester or ether groups or mixtures thereof, for example 3 to 8, especially 3 to 5. It is preferred if two or more of the ester or ether groups of the CPE or RSE are independently of one another attached to a C 8 to C 22 alkyl or alkenyl chain.
  • the C 8 to C 22 alkyl or alkenyl groups may be branched or linear carbon chains.
  • the CPE or RSE contains at least 35 % tri or higher esters, e.g. at least 40 %.
  • the CPE or RSE has at least one of the chains independently attached to the ester or ether groups having at least one unsaturated bond. This provides a cost effective way of making the CPE or RSE a liquid or a soft solid. It is preferred if predominantly unsaturated fatty chains, derived from, for example, rape oil, cotton seed oil, soybean oil, oleic, tallow, palmitoleic, linoleic, erucic or other sources of unsaturated vegetable fatty acids, are attached to the ester/ether groups.
  • ester or ether chains of the CPE or RSE.
  • the ester or ether chains of the CPE or RSE are preferably predominantly unsaturated.
  • Preferred CPEs or RSEs include sucrose tetratallowate, sucrose tetrarapeate, sucrose tetraoleate, sucrose tetraesters of soybean oil or cotton seed oil, cellobiose tetraoleate, sucrose trioleate, sucrose triapeate, sucrose pentaoleate, sucrose pentarapeate, sucrose hexaoleate, sucrose hexarapeate, sucrose triesters, pentaesters and hexaesters of soybean oil or cotton seed oil, glucose tiroleate, glucose tetraoleate, xylose trioleate, or sucrose tetra-,tri-, penta- or hexa- esters with any mixture of predominantly unsaturated fatty acid chains.
  • CPEs or RSEs are those with monounsaturated fatty acid chains, i.e. where any polyunsaturation has been removed by partial hydrogenation.
  • CPEs or RSEs based on polyunsaturated fatty acid chains e.g. sucrose tetralinoleate, may be used provided most of the polyunsaturation has been removed by partial hydrogenation.
  • liquid CPEs or RSEs are any of the above but where the polyunsaturation has been removed through partial hydrogenation.
  • Preferably 40 % or more of the fatty acid chains contain an unsaturated bond, more preferably 50 % or more, most preferably 60% or more. In most cases 65 % to 100 %, e.g. 65 % to 95 % contain an unsaturated bond.
  • CPEs are preferred for use with the present invention.
  • Inositol is a preferred example of a cyclic polyol. Inositol derivatives are especially preferred.
  • cyclic polyol encompasses all forms of saccharides. Indeed saccharides are especially preferred for use with this invention. Examples of preferred saccharides for the CPEs or RSEs to be derived from are monosaccharides and disaccharides.
  • Examples of monosaccharides include xylose, arabinose, galactose, fructose, sorbose and glucose. Glucose is especially preferred.
  • Examples of disaccharides include maltose, lactose, cellobiose and sucrose. Sucrose is especially preferred.
  • An example of a reduced saccharide is sorbitan.
  • the liquid or soft solid CPEs can be prepared by methods well known to those skilled in the art. These include acylation of the cyclic polyol or reduced saccharide with an acid chloride; trans-esterification of the cyclic polyol or reduced saccharide fatty acid esters using a variety of catalysts; acylation of the cyclic polyol or reduced saccharide with an acid anhydride and acylation of the cyclic polyol or reduced saccharide with a fatty acid. See for instance US 4 386 213 and AU 14416/88 (both P&G).
  • the CPE or RSE has 3 or more, preferably 4 or more ester or ether groups. If the CPE is a disaccharide it is preferred if the disaccharide has 3 or more ester or ether groups. Particularly preferred CPEs are esters with a degree of esterification of 3 to 5, for example, sucrose tri, tetra and penta esters.
  • each ring of the CPE has one ether or ester group, preferably at the C 1 position.
  • Suitable examples of such compounds include methyl glucose derivatives.
  • CPEs examples include esters of alkyl(poly)glucosides, in particular alkyl glucoside esters having a degree of polymerisation from 1 to 2.
  • the length of the unsaturated (and saturated if present) chains in the CPE or RSE is Cs-C 22 , preferably C 12 -C 22 . It is possible to include one or more chains of C 1 -C 8 , however these are less preferred.
  • the liquid or soft solid CPEs or RSEs which are suitable for use in the present invention are characterised as materials having a solid:liquid ratio of between 50:50 and 0:100 at 20°C as determined by T 2 relaxation time NMR, preferably between 43:57 and 0:100, most preferably between 40:60 and 0:100, such as, 20:80 and 0:100.
  • the T 2 NMR relaxation time is commonly used for characterising solid:liquid ratios in soft solid products such as fats and margarines.
  • any component of the signal with a T 2 of less than 100 ⁇ s is considered to be a solid component and any component with T 2 ⁇ 100 ⁇ s is considered to be a liquid component.
  • the prefixes e.g. tetra and penta
  • the compounds exist as a mixture of materials ranging from the monoester to the fully esterified ester. It is the average degree of esterification which is used herein to define the CPEs and RSEs.
  • the HLB of the CPE or RSE is typically between 1 and 3.
  • the CPE or RSE is preferably present in the composition in an amount of 0.5-50% by weight, based upon the total weight of the composition, more preferably 1-30% by weight, such as 2-25%, e.g. 2-20%.
  • the CPEs and RSEs for use in the compositions of the invention include sucrose tetraoleate, sucrose pentaerucate, sucrose tetraerucate and sucrose pentaoleate.
  • Silicone based fabric softening agents (and other non quat softening compounds)
  • compositions of the invention may further contain a silicone based fabric softening agent.
  • a silicone based fabric softening agent Preferably the fabric softening silicone is a polydimethylsiloxane.
  • the fabric softening silicones include but are not limited to 1) non-functionalized silicones such as polydimethylsiloxane (PDMS) or alkyl (or alkoxy) functional silicones 2) functionalized silicones or copolymers with one or more different types of functional groups such as amino, phenyl, polyether, acrylate, siliconhydride, carboxylic acid, quaternized nitrogen, etc.
  • PDMS polydimethylsiloxane
  • alkyl (or alkoxy) functional silicones 2) functionalized silicones or copolymers with one or more different types of functional groups such as amino, phenyl, polyether, acrylate, siliconhydride, carboxylic acid, quaternized nitrogen, etc.
  • Suitable silicones may be selected from polydialkylsiloxanes, preferably polydimethylsiloxane more preferably amino functionalised silicones; anionic silicones and carboxyl functionalised silicone.
  • An amino silicone that may also be used, for example, Arristan 64, ex CHT or Wacker CT45E, ex Wacker.
  • the particle size can be in the range from about 1 nm to 100 microns and preferably from about 10 nm to about 10 microns including microemulsions ( ⁇ 150 nm), standard emulsions (about 200 nm to about 500 nm) and macroemulsions (about 1 micron to about 20 microns).
  • Polyalkyl wax emulsions for example polyethylene wax may also be used as softening agents in the composition of the invention.
  • Co-softeners may be used. When employed, they are typically present at from 0.1 to 20% and particularly at from 0.5 to 10%, based on the total weight of the composition.
  • Preferred co-softeners include fatty esters, and fatty N-oxides.
  • Fatty esters that may be employed include fatty monoesters, such as glycerol monostearate, fatty sugar esters, such as those disclosed WO 01/46361 (Unilever ).
  • compositions of the present invention may comprise a fatty complexing agent.
  • Suitable fatty complexing agents include fatty alcohols and fatty acids. Of these, fatty alcohols are most preferred.
  • the fatty complexing material improves the viscosity profile of the composition by complexing with mono-ester component of the fabric conditioner material thereby providing a composition which has relatively higher levels of di-ester and tri-ester linked components.
  • the di-ester and tri-ester linked components are more stable and do not affect initial viscosity as detrimentally as the mono-ester component.
  • compositions comprising quaternary ammonium materials based on TEA may destabilise the composition through depletion flocculation.
  • depletion flocculation is significantly reduced.
  • the fatty complexing agent at the increased levels as required by the present invention, "neutralises” the mono-ester linked component of the quaternary ammonium material. This in situ di-ester generation from mono-ester and fatty alcohol also improves the softening of the composition.
  • Preferred fatty acids include hardened tallow fatty acid (available under the trade name PristereneTM, ex Croda).
  • Preferred fatty alcohols include hardened tallow alcohol (available under the trade names StenolTM and HydrenolTM, ex BASF and LaurexTM CS, ex Huntsman).
  • the fatty complexing agent is preferably present in an amount greater than 0.3 to 5% by weight based on the total weight of the composition. More preferably, the fatty component is present in an amount of from 0.4 to 4%.
  • the weight ratio of the mono-ester component of the quaternary ammonium fabric softening material to the fatty complexing agent is preferably from 5:1 to 1:5, more preferably 4:1 to 1:4, most preferably 3:1 to 1:3, e.g. 2:1 to 1:2.
  • compositions may further comprise a nonionic surfactant.
  • a nonionic surfactant typically these can be included for the purpose of stabilising the compositions.
  • Suitable nonionic surfactants include addition products of ethylene oxide and/or propylene oxide with fatty alcohols, fatty acids and fatty amines. Any of the alkoxylated materials of the particular type described hereinafter can be used as the nonionic surfactant.
  • Suitable surfactants are substantially water soluble surfactants of the general formula (V): R-Y-(C 2 H 4 O),-CH 2 -CH 2 -OH (V) where R is selected from the group consisting of primary, secondary and branched chain alkyl and/or acyl hydrocarbyl groups; primary, secondary and branched chain alkenyl hydrocarbyl groups; and primary, secondary and branched chain alkenyl-substituted phenolic hydrocarbyl groups; the hydrocarbyl groups having a chain length of from 8 to about 25, preferably 10 to 20, e.g. 14 to 18 carbon atoms.
  • Y is typically: -O-, -C(O)O-, -C(O)N(R)- or -C(O)N(R)R- in which R has the meaning given above for formula (V), or can be hydrogen; and Z is at least about 8, preferably at least about 10 or 11.
  • the nonionic surfactant has an HLB of from about 7 to about 20, more preferably from 10 to 18, e.g. 12 to 16.
  • GenapolTM C200 (Clariant) based on coco chain and 20 EO groups is an example of a suitable nonionic surfactant.
  • the nonionic surfactant is present in an amount from 0.01 to 10%, more preferably 0.1 to 5 by weight, based on the total weight of the composition.
  • a class of preferred non-ionic surfactants include addition products of ethylene oxide and/or propylene oxide with fatty alcohols, fatty acids and fatty amines. These are preferably selected from addition products of (a) an alkoxide selected from ethylene oxide, propylene oxide and mixtures thereof with (b) a fatty material selected from fatty alcohols, fatty acids and fatty amines.
  • Y is typically: -O-, -C(O)O-, -C(O)N(R)- or -C(O)N(R)R- in which R has the meaning given above for formula (VI), or can be hydrogen; and Z is at least about 6, preferably at least about 10 or 11.
  • LutensolTM AT25 (BASF) based on coco chain and 25 EO groups is an example of a suitable non-ionic surfactant.
  • suitable surfactants include Renex 36 (Trideceth-6), ex Croda; Tergitol 15-S3, ex Dow Chemical Co.; Dihydrol LT7, ex Thai Ethoxylate ltd; Cremophor CO40, ex BASF and Neodol 91-8, ex Shell.
  • compositions may comprise other ingredients of fabric conditioner liquids as will be known to the person skilled in the art.
  • antifoams perfumes and fragrances (both free oil and encapsulated material), insect repellents, shading or hueing dyes, preservatives (e.g. bactericides), pH buffering agents, perfume carriers, hydrotropes, anti-redeposition agents, soil-release agents, polyelectrolytes, anti-shrinking agents, anti-wrinkle agents, anti-oxidants, dyes, colorants, sunscreens, anti-corrosion agents, drape imparting agents, anti-static agents, sequestrants and ironing aids.
  • the products of the invention may contain pearlisers and/or opacifiers.
  • a preferred sequestrant is HEDP, an abbreviation for Etidronic acid or 1-hydroxyethane 1,1-diphosphonic acid.
  • compositions are rinse-added softening compositions suitable for use in a laundry process.
  • the compositions are pourable liquids.
  • the liquid compositions have a pH ranging from about 2.0 to 6, preferably from about 2.2 to 4.5, most preferably about 2.5 to 2.8.
  • the compositions of the invention may also contain pH modifiers preferably hydrochloric acid or lactic acid.
  • the composition is preferably a ready-to-use liquid comprising an aqueous phase.
  • the aqueous phase may comprise water-soluble species, such as mineral salts or short chain (C 1-4 ) alcohols.
  • the composition is preferably for use in the rinse cycle of a home textile laundering operation, where, it may be added directly in an undiluted state to a washing machine, e.g. through a dispenser drawer or, for a top-loading washing machine, directly into the drum.
  • the compositions may also be used in a domestic hand-washing laundry operation.
  • compositions of the invention may be made by preparing a fabric conditioning composition and adding the particles.
  • the polymer may be added dry to the composition and allowed to hydrate in situ.
  • the functional compositions are preferably made in the conventional way, as known to the person skilled in the art, and then combined with preformed particles of the invention to form the composition of the invention.
  • the compositions of the invention are made by combining at least the cationic softener active ingredient in water, with the preformed particles.
  • compositions of the invention may typically be made by combining a melt comprising the fabric softening active with an aqueous phase.
  • the polymer may be combined with the water phase, or it may be post dosed into the composition after combination of the melt and water phase.
  • a preferred method of preparation is as follows:-
  • the formed particles may be post dosed or added in the batch water.
  • Examples of the invention are represented by a number. Comparative examples are represented by a letter.
  • Example 1 Synthesis of cationic polymer. Polymer 1, by gel polymerization
  • a monomer solution was prepared by adding and stirring the following ingredients in a glass beaker:
  • the polymer composition (monomer ratio) in weight was 92.0% of dimethyl aminoethyl methacrylate quaternized and 8.0% acrylamide. After 30 minutes of stirring, the monomer solution was cooled down to 10°C, transferred in a Dewar flask, and then sparged with nitrogen for 15 minutes to remove oxygen. The polymerization was run in an adiabatic manner by addition of a redox couple of sodium persulfate (20 ppm / Total weight of monomers) and Mohr salt (10 ppm / Total weight of monomers). The salt was pre-diluted in water at 25 g/L tether with addition of azobisisobutironitrile, dispersed at 500 ppm/ Total weight of monomers.
  • the temperature of the solution rose spontaneously to 75°C in 2 hours, and was then held for 2 additional hours at 75°C.
  • the resulting mixture was a sticky gel.
  • This gel was sliced into pieces of 2 to 5 mm and then dried in an oven for 24 hours at 80°C. The dried slices were then jet milled or ground to give a dry powder. This powder was then filtered to remove particles less than 10 micron diameter by passing them through a sieve. The residual moisture of this powder was ⁇ 10.0%, as determined by weight loss after 2 hours in a drying oven at 105°C.
  • the particle size of the dry powder was measured to fall between 10 and 60 microns using a Malvern Mastersizer Scirocco 2000 at 2.0 bar pressure (standard pressure).
  • Fabric conditioning compositions were made with the ingredients in Table 1.
  • Table 1 Material Example 1 Example A Example 2
  • Example B Stepantex SP88 12 12 12 12 Lutensol AT25 1 1 1 1 HEDP 0.005 0.005 0.005 0.005
  • Perfume 1.15 1.15 1.15 1.15 CaCl 2 0.0025% 0.0025% 0.0025% Polymer 1* 0.5 0 0.5 0 Flosoft 270LS 0 0.5 0 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Flosoft 270LS 0 0.5 0 0.5 0.5 0.5 0.5 0.5 0.5 0.5 HCl 0.04 0.04 0.04 0.04 Minors and water To 100% To 100% To 100% To 100% To 100% To 100% To 100% To 100% To 100% To 100% To 100% To 100% To 100% To 100% To 100% To 100% To 100% To 100% To 100% To 100% To 100% To 100%
  • Example Compositions 1 & 2 and A & B Dispersion properties of Example Compositions 1 & 2 and A & B
  • a concentric cylinder type system consisting of a rotor (cross bladed vane with square edged vertical blades) and stator (jacketed cylinder).
  • the cylinder had an internal diameter of 26 mm and an axial depth of 35 mm; the jacket was connected to an external circulating water bath to control the temperature to 25°C.
  • the blade diameter for the cross bladed vane was 20 mm while the blade height was 20 mm.
  • the T90 point (time taken to reach 90% dispersion) was taken as being the time at which the viscosity values from step (i) first exceed 90% of the final viscosity value obtained in step (iii). The times were adjusted to take account of the time before the water addition.
  • Particles size was characterised using a Malvern Mastersizer Scirocco 2000.
  • Figure 1 shows the particle size distribution for Example 1. The lower peak is due to the presence of the vesicles of cationic softener material. It can be seen that the swollen crosslinked polymer particles in the composition are mostly (by volume%) over 100 microns in diameter.
  • Figure 2 shows the corresponding data for Example A. Like Example 1 there is a first peak indicating small particles of cationic, then a second peak showing that most of the polymer is present in this composition as particles smaller than 12 microns.
  • Figure 3 shows the data for Example 2. The plot is an average of three measurements.
  • Figure 4 shows the data for Example B. Both the individual measurements and the average of the three are shown to show that there is little variation between the different measurements. As with Example A, the dominant peaks occur at 0.5 to 1 micron and 4 to 12microns.
  • Figure 5 shows a comparison of Polymer 1 and the comparative Flosoft 270LS thickening polymer in the absence of the cationic and other components of the fabric conditioning compositions.
  • the curve with the smaller peak below 1 micron is the prior art Flosoft polymer at 0.2 wt% in water and the one with the larger peak above 100 micron is Polymer 1 at 0.5 wt% in water.
  • the different concentrations do not affect the position of the peaks.
  • Comparative Example C with no polymer demonstrates that the low particle size peaks found in the inventive and comparative examples above are a result of other components in the composition, not the crosslinked polymer particles.
  • Example 3 Fabric conditioning Compositions 3 & D
  • An ester quat based fabric softener base formulation was prepared, which comprised 20 wt % partially hardened TEAQ (Stepantex SP88 (ex-Stepan)) by weight of the total base composition, the remainder being minors and water.
  • 50 % (by volume of the final composition) of the fabric softener base formulation was combined with 50 % by volume of a polymer gel comprising the large polymer viscosity increasing particles of the invention (Polymer 1) to produce Composition 3.
  • the concentration of Polymer 1 within the 50 % vol was 2 wt % by weight of the polymer as supplied.
  • Composition 1 comprised 50 % by volume of the fabric softener formulation and 50 % by volume of the polymer gel, by volume of the final composition.
  • Composition D was made in the same way, but using a pre-hydrated prior art thickening polymer (Flosoft 270LS ex SNF) instead of Polymer 1.
  • the thickening polymer portion made up 50 % by volume of the final composition.
  • the concentration of the polymer within the 50 % vol was 2 wt % by weight of the polymer as supplied.
  • Table 3 Compositions 3 & D, showing amount (wt %) of components Material Composition 3 Composition D Stepantex SP88 10 10 Flosoft 270LS - 1.0 Polymer 1 1.0 - Minors & Water Up to 100 wt % Up to 100 wt %
  • the mixture may be stirred by performing 5 revolutions at a rate of one per second with a flat spatula before being re-assessed using the same rating scale.
  • Table 4 Viscosity and dispersion scores for Example Compositions 3 & D Viscosity Dispersion score @ 106s -1 Pre stir Post stir D 694 4.5 3.5 3 682 3 1.5
  • composition 3 in accordance with the invention, has dramatically improved dispersion properties over the similar composition D comprising the conventional thickening polymer.
  • An ester quat based fabric softener base formulation was prepared with a conventional thickening polymer, which comprised 12 wt % partially hardened TEAQ (Stepantex SP88 (ex-Stepan)) by weight of the total base composition, the remainder being minors and water.
  • a conventional thickening polymer which comprised 12 wt % partially hardened TEAQ (Stepantex SP88 (ex-Stepan)) by weight of the total base composition, the remainder being minors and water.
  • compositions were made by combining the polymer with the water phase prior to adding the melt and minors.
  • the ingredient used for these Compositions are shown in Table 5.
  • Table 5 Compositions E to G, showing amount (wt %) of components Material Composition E Composition F Composition G Stepantex SP88 12 12 12 Flosoft 270LS 0.5 - - Luvigel Star - 0.1 0.07 Minors & Water Up to 100 wt % Up to 100 wt % Up to 100 wt % Up to 100 wt %
  • An ester quat based fabric softener base formulation was prepared, which comprised 20 wt % partially hardened TEAQ (Stepantex VT90 (ex-Stepan)) by weight of the total base composition, the remainder being minors and water.
  • compositions 4 to 6 60 % (by volume of the final composition) of the fabric softener base formulation, was combined with 40 % by volume of a cross linked polymer gel (Polymer 1, ex SNF) to produce Compositions 4 to 6.
  • concentration of the Polymer 1 within the 40 % vol was 2 wt % by weight of the polymer as supplied.
  • the amount of the 2 wt % polymer in composition was varied as shown in Table 7, as wt % of the compositions.
  • Table 7 Compositions 4 to 6 (wt %) Material Composition 4 Composition 5 Composition 6 Stepantex SP88 12 12 12 Polymer 1 0.4 0.5 0.6 Minors & Water Up to 100 wt % Up to 100 wt % Up to 100 wt % Up to 100 wt %
  • Table 8 Viscosity and dispersion scores for Compositions 4 to 6 Viscosity Dispersion score @ 106s -1 Pre stir Post stir 4 136.67 1.5 0.5 5 207.20 2.5 0.5 6 341.12 2.5 1
  • An ester quat based fabric softener base formulation was prepared, which comprised 20 wt % partially hardened TEAQ (Stepantex SP88 (ex-Stepan)) by weight of the total base composition, the remainder being minor ingredients and water.
  • Example Composition 7 50 % (by volume of the final composition) of the fabric softener base formulation, was combined with 50 % by volume of a polymer gel comprising the large polymer particles of the invention (Polymer 1, ex SNF) to produce Example Composition 7.
  • the concentration of the Polymer 1 within the 50 % vol was 1 wt % by weight of the polymer as supplied.
  • Composition 7 comprised 50 % by volume of the fabric softener formulation and 50 % by volume of the polymer gel, by volume of the final composition.
  • Composition H was a commercially available fabric conditioner, under the brand name Molto, ex Unilever, Indonesia containing a conventional thickening polymer instead of Polymer 1.
  • Composition 7 has dramatically improved dispensing properties over a similar product comprising conventional thickening polymer.

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)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
EP15798483.2A 2014-12-15 2015-11-25 Pourable liquid fabric conditioner compositions Not-in-force EP3234086B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP14197882 2014-12-15
PCT/EP2015/077633 WO2016096347A1 (en) 2014-12-15 2015-11-25 Pourable liquid fabric conditioner compositions

Publications (2)

Publication Number Publication Date
EP3234086A1 EP3234086A1 (en) 2017-10-25
EP3234086B1 true EP3234086B1 (en) 2018-09-26

Family

ID=52101154

Family Applications (1)

Application Number Title Priority Date Filing Date
EP15798483.2A Not-in-force EP3234086B1 (en) 2014-12-15 2015-11-25 Pourable liquid fabric conditioner compositions

Country Status (5)

Country Link
EP (1) EP3234086B1 (pt)
CN (1) CN107109297B (pt)
BR (1) BR112017012522A2 (pt)
TR (1) TR201815223T4 (pt)
WO (1) WO2016096347A1 (pt)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20220025298A1 (en) * 2018-12-11 2022-01-27 Conopco, Inc., D/B/A Unilever Fabric conditioner compositions
WO2023006384A1 (en) * 2021-07-26 2023-02-02 Unilever Ip Holdings B.V. Method of producing a fabric conditioner

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7150884B2 (ja) * 2018-06-04 2022-10-11 ザ プロクター アンド ギャンブル カンパニー 布地及び関連組成物の処理方法
WO2021239375A1 (en) * 2020-05-27 2021-12-02 Unilever Ip Holdings B.V. Method of preparing a liquid fabric conditioner
WO2022106322A1 (en) * 2020-11-18 2022-05-27 Unilever Ip Holdings B.V. Fabric conditioner

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3861870A (en) 1973-05-04 1975-01-21 Procter & Gamble Fabric softening compositions containing water-insoluble particulate material and method
GB1567947A (en) 1976-07-02 1980-05-21 Unilever Ltd Esters of quaternised amino-alcohols for treating fabrics
DE3027611A1 (de) 1980-07-21 1982-02-18 Bayer Ag, 5090 Leverkusen Di- und oligo-1,2,4-triazolidin-3,5-dione und verfahren zu ihrer herstellung
DE3887247T2 (de) 1987-04-10 1994-06-09 Procter & Gamble Feste unverdauliche fettähnliche Verbindungen.
GB8909069D0 (en) * 1989-04-21 1989-06-07 Bp Chem Int Ltd Fabric conditioners
GB9930435D0 (en) 1999-12-22 2000-02-16 Unilever Plc Fabric softening compositions
US6949500B2 (en) * 2002-12-16 2005-09-27 Colgate-Palmolive Company Fabric softener compositions containing a mixture of cationic polymers as rheology modifiers
WO2010079100A1 (en) 2009-01-06 2010-07-15 Unilever Plc Improvements relating to fabric conditioners
US9441188B2 (en) * 2012-12-11 2016-09-13 Colgate-Palmolive Company Fabric conditioning composition
CA2889164C (en) * 2012-12-11 2020-03-24 Colgate-Palmolive Company Fabric conditioning composition

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20220025298A1 (en) * 2018-12-11 2022-01-27 Conopco, Inc., D/B/A Unilever Fabric conditioner compositions
WO2023006384A1 (en) * 2021-07-26 2023-02-02 Unilever Ip Holdings B.V. Method of producing a fabric conditioner

Also Published As

Publication number Publication date
TR201815223T4 (tr) 2018-11-21
WO2016096347A1 (en) 2016-06-23
CN107109297A (zh) 2017-08-29
EP3234086A1 (en) 2017-10-25
CN107109297B (zh) 2019-08-16
BR112017012522A2 (pt) 2018-02-27

Similar Documents

Publication Publication Date Title
EP3234086B1 (en) Pourable liquid fabric conditioner compositions
CA2745628C (en) Improvements relating to fabric conditioners
EP1399533B1 (en) Thickened fabric conditioners
CA2021010C (en) Fabric softening composition
EP1765966B1 (en) Fabric softening composition
AU652429B2 (en) Fabric softening composition
EP2646533B1 (en) Fabric conditioners
CA2378114C (en) Fabric conditioning composition containing fatty acid-derived quaternary ammonium compounds and oils
EP1283859B1 (en) Process for preparing a fabric conditioning composition
US8168582B2 (en) Fabric softening composition comprising a polymeric viscosity modifier
US6436896B2 (en) Method for preparing fabric softening compositions
WO2012052349A1 (en) Improvements relating to fabric conditioners
WO2012072369A1 (en) Fabric conditioners
CA2533809C (en) Fabric conditioning compositions
WO2004104149A1 (en) Use of nonionic surfactant in a laundry treatment composition
EP2646536B1 (en) Fabric conditioners
EP2373774B1 (en) Improvements relating to fabric conditioners
AU2009336682B2 (en) Improvements relating to fabric conditioners

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

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

Free format text: ORIGINAL CODE: 0009012

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

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20170612

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

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

Free format text: STATUS: GRANT OF PATENT IS INTENDED

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
INTG Intention to grant announced

Effective date: 20180305

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAJ Information related to disapproval of communication of intention to grant by the applicant or resumption of examination proceedings by the epo deleted

Free format text: ORIGINAL CODE: EPIDOSDIGR1

GRAL Information related to payment of fee for publishing/printing deleted

Free format text: ORIGINAL CODE: EPIDOSDIGR3

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

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

INTC Intention to grant announced (deleted)
GRAR Information related to intention to grant a patent recorded

Free format text: ORIGINAL CODE: EPIDOSNIGR71

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

Free format text: STATUS: GRANT OF PATENT IS INTENDED

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

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

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

INTG Intention to grant announced

Effective date: 20180808

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 1046054

Country of ref document: AT

Kind code of ref document: T

Effective date: 20181015

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602015017213

Country of ref document: DE

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20180926

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

Ref country code: NO

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

Effective date: 20181226

Ref country code: GR

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

Effective date: 20181227

Ref country code: FI

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

Effective date: 20180926

Ref country code: SE

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

Effective date: 20180926

Ref country code: LT

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

Effective date: 20180926

Ref country code: RS

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

Effective date: 20180926

Ref country code: BG

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

Effective date: 20181226

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

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

Ref country code: AL

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

Effective date: 20180926

Ref country code: LV

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

Effective date: 20180926

Ref country code: HR

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

Effective date: 20180926

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 1046054

Country of ref document: AT

Kind code of ref document: T

Effective date: 20180926

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

Ref country code: IS

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

Effective date: 20190126

Ref country code: AT

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

Effective date: 20180926

Ref country code: PL

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

Effective date: 20180926

Ref country code: EE

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

Effective date: 20180926

Ref country code: ES

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

Effective date: 20180926

Ref country code: RO

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

Effective date: 20180926

Ref country code: NL

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

Effective date: 20180926

Ref country code: CZ

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

Effective date: 20180926

Ref country code: IT

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

Effective date: 20180926

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

Ref country code: PT

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

Effective date: 20190126

Ref country code: SM

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

Effective date: 20180926

Ref country code: SK

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

Effective date: 20180926

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602015017213

Country of ref document: DE

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

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

Ref country code: DK

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

Effective date: 20180926

Ref country code: MC

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

Effective date: 20180926

Ref country code: LU

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

Effective date: 20181125

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

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

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

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20181130

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

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

Ref country code: CH

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

Effective date: 20181130

Ref country code: LI

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

Effective date: 20181130

26N No opposition filed

Effective date: 20190627

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

Ref country code: SI

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

Effective date: 20180926

Ref country code: IE

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

Effective date: 20181125

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

Ref country code: BE

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

Effective date: 20181130

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

Ref country code: MT

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

Effective date: 20181125

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

Ref country code: DE

Payment date: 20191121

Year of fee payment: 5

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

Ref country code: FR

Payment date: 20191120

Year of fee payment: 5

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

Ref country code: TR

Payment date: 20191120

Year of fee payment: 5

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

Ref country code: GB

Payment date: 20191120

Year of fee payment: 5

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

Ref country code: CY

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

Effective date: 20180926

Ref country code: MK

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

Effective date: 20180926

Ref country code: HU

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

Effective date: 20151125

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 602015017213

Country of ref document: DE

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20201125

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

Ref country code: FR

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

Effective date: 20201130

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

Ref country code: DE

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

Effective date: 20210601

Ref country code: GB

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

Effective date: 20201125

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

Ref country code: TR

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

Effective date: 20201125