EP4634351A1 - Solid laundry composition - Google Patents

Solid laundry composition

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Publication number
EP4634351A1
EP4634351A1 EP23821292.2A EP23821292A EP4634351A1 EP 4634351 A1 EP4634351 A1 EP 4634351A1 EP 23821292 A EP23821292 A EP 23821292A EP 4634351 A1 EP4634351 A1 EP 4634351A1
Authority
EP
European Patent Office
Prior art keywords
water
cellulose
conditioning composition
fabric conditioning
solid
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.)
Pending
Application number
EP23821292.2A
Other languages
German (de)
French (fr)
Inventor
Girish Muralidharan
Vishal Mohan UDMALE
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 Global IP Ltd
Unilever IP Holdings BV
Original Assignee
Unilever Global IP Ltd
Unilever IP Holdings BV
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 Global IP Ltd, Unilever IP Holdings BV filed Critical Unilever Global IP Ltd
Publication of EP4634351A1 publication Critical patent/EP4634351A1/en
Pending legal-status Critical Current

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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
    • C11D3/0005Other compounding ingredients characterised by their effect
    • C11D3/001Softening compositions
    • 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
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047Detergents in the form of bars or tablets
    • C11D17/0052Cast detergent compositions
    • 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
    • C11D3/22Carbohydrates or derivatives thereof
    • C11D3/222Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin

Definitions

  • the present invention relates to solid fabric conditioning compositions.
  • Solid fabric conditioners provide consumers with an easy-to-use concentrated fabric conditioner composition. These compositions have various benefits including that they can contain high levels of active ingredient and have very low water content, leading to easier storage and transportation.
  • a solid fabric conditioning composition comprising: a 5 to 80 wt.% Fabric softening active; b 3 to 12 wt.% crosslinked cellulose; and c 2 to 80 wt.% Water soluble carrier selected from polysaccharides.
  • the invention further relates to a method of preparing a solid fabric conditioning composition comprising the steps of; a. Preparing a premix of a water-soluble carrier and water; b. Adding fabric softening active, crosslinked cellulose and any remaining ingredients to the premix; c. Casting the mixture on a surface or in a mold; and d. Removing the water, preferably by evaporation.
  • compositions described herein comprise a fabric softening active.
  • the fabric softening actives may be any material known to soften fabrics. These may be polymeric materials or compounds known to soften materials. Examples of suitable fabric softening actives include: quaternary ammonium compounds, silicone polymers, polysaccharides, clays, amines, fatty esters, dispersible polyolefins, polymer latexes and mixtures thereof.
  • the fabric softening actives may preferably be cationic or non-ionic materials.
  • the fabric softening actives are cationic materials. More preferably the fabric softening active comprises quaternary ammonium compounds.
  • the quaternary ammonium compound preferably comprises at least one chain derived from fatty acids, more preferably at least two chains derived from a fatty acid.
  • fatty acids are defined as aliphatic monocarboxylic acids having a chain of 4 to 28 carbons.
  • Fatty acids may be derived from various sources such as tallow or plant sources.
  • the fatty acid chains are derived from plants.
  • the fatty acid chains of the QAC comprise from 10 to 50 wt. % of saturated C18 chains and from 5 to 40 wt. % of monounsaturated C18 chains by weight of total fatty acid chains.
  • the fatty acid chains of the QAC comprise from 20 to 40 wt. %, preferably from 25 to 35 wt. % of saturated C18 chains and from 10 to 35 wt. %, preferably from 15 to 30 wt. % of monounsaturated C18 chains, by weight of total fatty acid chains.
  • ester quats or ester-linked quaternary ammonium compounds.
  • 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
  • TEA-based fabric softening compounds comprise a mixture of mono, di- and tri ester forms of the compound where the di-ester linked component comprises no more than 70 wt.% of the fabric softening compound, preferably no more than 60 wt.% e.g., no more than 55%, or even no more that 45% of the fabric softening compound and at least 10 wt.% of the monoester linked component.
  • a first group of quaternary ammonium compounds (QACs) suitable for use in the compositions are represented by formula (I):
  • each R is independently selected from a C5 to C35 alkyl or alkenyl group;
  • R 1 represents a C1 to C4 alkyl, C2 to C4 alkenyl or a C1 to C4 hydroxyalkyl group;
  • T may be either O-CO. (i.e. an ester group bound to R via its carbon atom), or may alternatively be CO-O (i.e. an ester group bound to R via its oxygen atom);
  • n is a number selected from 1 to 4;
  • m is a number selected from 1, 2, or 3; and
  • X- is an anionic counter-ion, such as a halide or alkyl sulphate, e.g.
  • a second group of QACs suitable for use in the compositions described herein is represented by formula (II): wherein each R 1 group is independently selected from C1 to C4 alkyl, hydroxyalkyl or C2 to C4 alkenyl groups; and wherein each R 2 group is independently selected from C8 to C28 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 monoester.
  • a third group of QACs suitable for use in the composition are represented by formula (III): wherein each R 1 group is independently selected from C1 to C4 alkyl, or C2 to C4 alkenyl groups; and wherein each R 2 group is independently selected from C8 to C28 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, partially hardened and hardened versions thereof.
  • a fifth group of QACs suitable for use in the composition are represented by formula (V)
  • Ri and R2 are independently selected from C10 to C22 alkyl or alkenyl groups, preferably C14 to C20 alkyl or alkenyl groups.
  • X- is as defined above.
  • 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 described herein. 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 methylsulfate. Such ester-linked triethanolamine quaternary ammonium compounds comprise unsaturated fatty chains.
  • the iodine value represents the mean iodine value of the parent fatty acyl compounds or fatty acids of all the quaternary ammonium materials present.
  • the iodine value represents the mean iodine value of the parent acyl compounds of fatty acids of all of the quaternary ammonium materials present.
  • Iodine value refers to, the fatty acid used to produce the QAC, 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 quaternary ammonium compound may be a non-ester quaternary ammonium material represented by formula (VI): wherein each R 1 group is independently selected from C1 to C4 alkyl, hydroxyalkyl or C2 to C4 alkenyl groups; R 2 group is independently selected from C8 to C28 alkyl or alkenyl groups, and X- is as defined above.
  • the fabric softening active comprises a mixture of cationic quaternary ammonium compound having more than one long carbon chain in combination with a secondary surfactant selected from a single chain cationic surfactant and/or a non-ionic surfactant.
  • a secondary surfactant selected from a single chain cationic surfactant and/or a non-ionic surfactant.
  • the cationic quaternary ammonium compound having more than one long carbon chain and secondary surfactant are present in a ratio of 1 :10 to 10:1 , more preferably 1 :5 to 5:1.
  • the combination of the cationic quaternary ammonium compound having more than one long carbon chain in combination with a secondary surfactant selected from a single chain cationic surfactant and/or a non-ionic surfactant provide a solid composition which can be diluted with water to form a stable liquid fabric softener and provides superior softening.
  • Cationic quaternary ammonium compound having more than one long carbon chain are as described above.
  • Suitable single chain cationic surfactant preferably have the general formula:
  • each Ri independently comprises 1 to 6 carbon atoms, selected from alky, alkenyl, aryl or combinations thereof.
  • Each Ri may independently comprise hydroxy groups.
  • R 2 comprises at least 10 carbon atoms.
  • the carbon atoms may be in the form of an alky, alkenyl, aryl or combinations thereof.
  • the single chain cationic surfactant comprises at least 12 carbon atoms, preferably at least 14 and most preferably at least 16.
  • R 2 may further comprise additional functional groups such as ester groups or hydroxy groups.
  • X- is an anionic counter-ion, such as a halide or alkyl sulphate, e.g.
  • Preferred cationic surfactants include Hydroxyethyl laurdimonium chloride, cetyltrimethylammonium chloride (CTAC), Behentrimonium chloride (BTAC), a Alkyl dimethyl hydroxyethyl ammonium chloride such as Praepagen HY ex Clariant GmbH.
  • 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 (VII):
  • 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:
  • R has the meaning given above for formula (VII), 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 0200 (Clariant) based on coco chain and 20 EG groups is an example of a suitable nonionic surfactant.
  • 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.
  • a second class of preferred non-ionic surfactants are polyethylene glycol ethers of glycerine.
  • non-ionic surfactant is selected from addition products of ethylene oxide and/or propylene oxide with fatty alcohols, fatty acids and fatty amines and polyethylene glycol ethers of glycerine.
  • Suitable non-ionic surfactants are available commercially as LutensolTM AT25 ex. BASF based on C16:18 chain and 25 EO groups is an example of a suitable non-ionic surfactant.
  • Other 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; LEVENOL® F-200, LEVENOL® C-301 and LEVENOL® C-201 ex. Kao.
  • compositions described herein comprise more than 5 wt. % fabric softening active, more preferably more than 10 wt. % fabric softening active, most preferably more than 20 wt. % fabric softening active by weight of the composition.
  • the fabric conditioners of the described herein comprise less than 80 wt. % fabric softening active, more preferably less than 70 wt. % fabric softening active, most preferably less than 65 wt. % fabric softening active by weight of the composition.
  • the fabric conditioners comprise 5 to 80 wt. % fabric softening active, preferably 10 to 70 wt.% fabric softening active and more preferably 20 to 65 wt. % fabric softening active by weight of the composition.
  • compositions described herein comprise cross linked cellulose, preferably the crosslinked cellulose comprises microcrystalline cellulose, preferably the crosslinked cellulose is microcrystalline cellulose.
  • the cross linked cellulose has a Water Absorption Ratio (WAR) of greater than 1 , more preferably greater than 1.5.
  • WAR Water Absorption Ratio
  • WAR Water Absorption Ratio
  • the water absorption may be measured by: Procuring a dry sample of the material to be tested
  • the composition comprises from 3 to 12% by weight cross linked cellulose, more preferably from 4.5 to 12% by weight and most preferably from 6 to 11 % by weight cross linked cellulose.
  • compositions described herein comprise water-soluble carrier.
  • the water-soluble carrier provides solid structure to the solid fabric conditioner.
  • the composition my comprise one carrier material or a combination of different carrier materials.
  • Suitable water-soluble carrier materials are selected from polysaccharides (e.g., starch, xanthan gum, cellulose, or derivatives thereof).
  • Suitable carrier materials include: starch, xanthan gum, carboxymethyl cellulose.
  • the water-soluble carrier is selected from cellulose derivatives. Most preferably cellulose ether derivatives. Typically, cellulose ether derivatives are obtained by substituting one or more hydrogen atoms of hydroxyl groups in the anhydro-glucose units of cellulose with alkyl or substituted alkyl groups. Degree of substitution (DS) is one of the factors, that define the properties of cellulose ether derivatives, particularly, solubility in water. It is defined as the number of substituted hydroxyl groups for every glucose molecule ranging between zero and three. For example, cellulose ether derivatives with degree of substitution values between 1.2 to 2.4 are soluble in cold water.
  • cellulose ether derivatives suitable for the compostions described herein includes methyl cellulose (MC), hydroxyethyl cellulose (HEC), hydroxypropyl cellulose (HPC), hydroxypropyl methyl cellulose (HPMC), carboxymethyl cellulose (CMC) and sodium carboxymethyl cellulose (SCMC).
  • the cellulose ether derivative is selected form hydroxypropyl methyl cellulose, methyl cellulose, hydroxypropyl cellulose, and combinations thereof. Most preferred cellulose ether derivative is hydroxypropyl methyl cellulose.
  • the compositions described herein comprise 2 to 80 wt.% water-soluble carrier materials, preferably 5 to 70 wt.%, more preferably 7.5 to 50 wt.% and most preferably 10 to 40 wt.% water-soluble carrier materials, by weight of the composition.
  • the water-soluble carrier preferably has a solubility at least 0.5% by weight in distilled water at 25 °C.
  • a solubility at least 1.0 % by weight, more preferably at least 2 % by weight, and most preferably at least 3% by weight in distilled water at 25 °C.
  • compositions described herein preferably comprise carbonaceous materials.
  • the carbonaceous material leads to improved strength of the solid composition.
  • Carbonaceous materials refer to materials having a 2D carbon lattice nanostructure.
  • the 2D lattice may be flat for example graphene or may be shaped into a 3D shape such as carbon nanotubes.
  • the carbonaceous material may be part of a larger structure, such as a composite material e.g. clay-carbonaceous material composite.
  • the carbonaceous materials comprise a material selected from carbon nanotubes, graphene, activated carbon and combinations thereof. More preferably the carbonaceous materials comprise preferably graphene and/or derivatives thereof and most preferably graphene oxide.
  • Graphene is an allotrope, formed by a single layer carbon atoms arranged in hexagonal lattice structure. Graphene can be obtained in two manners. The first is by peeling layers from graphite until you achieve a graphene monolayer. The second is known as Chemical Vapor Deposition (CVD) and where large-scale uniformity can be obtained and controlled.
  • CVD Chemical Vapor Deposition
  • the graphene derivative suitable for the composition described herein is graphene oxide.
  • Graphene oxide can be manufactured through Hummer’s method.
  • Graphene oxide is also commercially available and may be procured from suppliers such as Platonic Nanotech.
  • compositions described herein preferably comprise 0.001 to 2 wt.% carbonaceous materials, more preferably 0.0025 to 1 wt.% carbonaceous materials, even more preferably 0.005 to 0.5 wt.% carbonaceous materials and most preferably 0.01 to 0.25 wt.% carbonaceous materials.
  • compositions described herein may comprise additional ingredients common in the field of solid fabric conditioners, for example perfumes, perfume microcapsules, dyes, antifoams, 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, colorants, sunscreens, anti-corrosion agents, drape imparting agents, anti-static agents, sequestrants and ironing aids.
  • 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, colorants, sunscreens, anti-corrosion agents, drape imparting agents, anti-static agents, sequestrants and ironing aids.
  • preservatives
  • compositions comprise perfume, more preferably comprises 0.1 to 25 wt.% perfume, even more preferably 1 to 20 wt. % perfume and most preferably 2 to 15 wt.% perfume.
  • the solid fabric conditioner described herein are preferably ‘free from water’ when manufactured, however they may absorb moisture on storage. Therefore, preferably the composition comprises 0 to 20 wt.% weight, more preferably 0 to 15 wt.% water, most preferably 0 to 12 wt.% water. Water content may be measured by thermogravimetry, like moisture balance.
  • the solid fabric conditioner composition described herein may be in any suitable form.
  • a single dose of the composition may be a single article (e.g. a tablet or sheet), a part of a single article (i.e. a part of a sheet separated by tearing a section off a larger sheet), or may consist of multiple articles, (e.g. multiple particles of the composition).
  • the solid composition is in the form of articles having a minimum linear dimension in any direction of more than 1 mm.
  • the solid fabric conditioner composition does not include powders.
  • the solid composition is in a form suitable for use as a single article for example a tablet or sheet. These may be referred to as a ‘unit dose’.
  • the solid fabric conditioner may be made by any suitable process.
  • a preferred method comprises the steps of; a) Preparing a premix of a water-soluble carrier and water; b) Adding fabric softening active, crosslinked cellulose and any remaining ingredients to the premix; c) Casting the mixture on a surface or in a mold; and d) Removing the water, preferably by evaporation.
  • Step a) preferably comprises mixing and/or heating.
  • Step b) preferably comprises mixing fabric softening active, carbonaceous material and any remaining ingredients with water prior to addition to the pre-mix.
  • step c) if casting is used, preferably the thickness is controlled using an applicator.
  • the mixture is preferably cast onto a Polytetrafluoroethylene (PTFE) surface, for example PTFE sheets, PTFE coated foils or PTFE coated fabrics.
  • PTFE Polytetrafluoroethylene
  • Step d) preferably takes place at a temperature above room temperature (above 25°C), preferably at less than 100 °C, and more preferably less than 95 °C. Most preferably water is removed at a temperature of 70 to 90 °C. Preferably water is removed to reach a composition water content of 0 to 20 wt.%, more preferably a water content of 0 to 15 wt.%, more preferably 0 to 10 wt.%, even more preferably 0 to 5 wt. % and most preferably 0 to 2 wt.%.
  • a homogenized premix of water and water-soluble carrier is prepared with mixing. Subsequently, fabric softening active, crosslinked cellulose and any remaining ingredients are mixed with water under high shear before being added to the premix. Thereon the premix is casted on a surface as a sheet or film with certain thickness.
  • Table 1 Example formulations Quaternary ammonium compound 1 - TEA palm quaternary ammonium compound Micro-crystalline cellulose 2 - KEVICEL PH 102 ex. Keval Exports Polyvynl propylene polymer particles 3 - Disintex 75 ex. Ashland
  • the formulations where prepared by dispersing the hydroxypropyl methyl cellulose in hot water to make a 10% polymer solution. Separately the quaternary ammonium compound and perfume were mixed in the remaining water under high shear to make an emulsion. The remaining ingredients were added to the emulsion and mixed. The final mix was added to the polymer solution at room temperature and mixed well at high shear until a stable foam was formed. The foam was cast on a smooth, hard surface and dried at 80-90°C for 2 hours. The dried sheet was detached from the substrate on cooling.
  • Microcrystalline cellulose provided the lowest coefficient of friction of the various materials tested.
  • Dissolution time was measured the following method. 300 ml of water was placed in a 500ml beaker at room temperature. The beaker was placed over a magnetic stirrer with 1.5 inch magnetic bead in it. Stirring was set at 300 RPM. 1 inch X 1 inch piece of sheet (as prepared above) were added to the stirring water & the timer started. The dissolution time is the at which no residue of the sheet remains visible. Table 4: Results
  • crosslinked cellulose provides an improved coefficient of friction while maintaining an improved dissolution time.

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Abstract

A solid fabric conditioning composition comprising: fabric softening active; 3 to 12 wt.% crosslinked cellulose; and water soluble carrier.

Description

SOLID LAUNDRY COMPOSITION
Field of the Invention
The present invention relates to solid fabric conditioning compositions.
Background of the Invention
Solid fabric conditioners provide consumers with an easy-to-use concentrated fabric conditioner composition. These compositions have various benefits including that they can contain high levels of active ingredient and have very low water content, leading to easier storage and transportation.
There is a need to improve the softening provided by solid fabric conditioners, while maintaining a good dissolution time.
Summary of the Invention
It has been found that the addition of 3 to 12 wt.% crosslinked cellulose to a solid fabric conditioner improves the fabric softening while maintaining a suitable dissolution time.
Accordingly, is a first aspect of the present invention is provided a solid fabric conditioning composition comprising: a 5 to 80 wt.% Fabric softening active; b 3 to 12 wt.% crosslinked cellulose; and c 2 to 80 wt.% Water soluble carrier selected from polysaccharides.
The invention further relates to a method of preparing a solid fabric conditioning composition comprising the steps of; a. Preparing a premix of a water-soluble carrier and water; b. Adding fabric softening active, crosslinked cellulose and any remaining ingredients to the premix; c. Casting the mixture on a surface or in a mold; and d. Removing the water, preferably by evaporation.
Detailed Description of the Invention
These and other aspects, features and advantages will become apparent to those of ordinary skill in the art from a reading of the following detailed description and the appended claims. For the avoidance of doubt, any feature of one aspect of the present invention may be utilised in any other aspect of the invention. The word “comprising” is intended to mean “including” but not necessarily “consisting of” or “composed of.” In other words, the listed steps or options need not be exhaustive. It is noted that the examples given in the description below are intended to clarify the invention and are not intended to limit the invention to those examples per se. Similarly, all percentages are weight/weight percentages unless otherwise indicated. Except in the operating and comparative examples, or where otherwise explicitly indicated, all numbers in this description indicating amounts of material or conditions of reaction, physical properties of materials and/or use are to be understood as modified by the word “about”. Numerical ranges expressed in the format "from x to y" are understood to include x and y. When for a specific feature multiple preferred ranges are described in the format "from x to y", it is understood that all ranges combining the different endpoints are also contemplated.
All ingredient inclusion levels are wt.% of the final solid fabric conditioner product.
Fabric softening active
The compositions described herein comprise a fabric softening active. The fabric softening actives may be any material known to soften fabrics. These may be polymeric materials or compounds known to soften materials. Examples of suitable fabric softening actives include: quaternary ammonium compounds, silicone polymers, polysaccharides, clays, amines, fatty esters, dispersible polyolefins, polymer latexes and mixtures thereof.
The fabric softening actives may preferably be cationic or non-ionic materials. Preferably, the fabric softening actives are cationic materials. More preferably the fabric softening active comprises quaternary ammonium compounds.
The quaternary ammonium compound (QAC) preferably comprises at least one chain derived from fatty acids, more preferably at least two chains derived from a fatty acid. Generally fatty acids are defined as aliphatic monocarboxylic acids having a chain of 4 to 28 carbons. Fatty acids may be derived from various sources such as tallow or plant sources. Preferably the fatty acid chains are derived from plants. Preferably the fatty acid chains of the QAC comprise from 10 to 50 wt. % of saturated C18 chains and from 5 to 40 wt. % of monounsaturated C18 chains by weight of total fatty acid chains. In a further preferred embodiment, the fatty acid chains of the QAC comprise from 20 to 40 wt. %, preferably from 25 to 35 wt. % of saturated C18 chains and from 10 to 35 wt. %, preferably from 15 to 30 wt. % of monounsaturated C18 chains, by weight of total fatty acid chains.
The preferred quaternary ammonium fabric softening actives for use in compositions described herein are so called "ester quats" or ester-linked quaternary ammonium compounds. Particularly preferred materials are the ester-linked triethanolamine (TEA) quaternary ammonium compounds comprising a mixture of mono-, di- and tri-ester linked components. Typically, TEA-based fabric softening compounds comprise a mixture of mono, di- and tri ester forms of the compound where the di-ester linked component comprises no more than 70 wt.% of the fabric softening compound, preferably no more than 60 wt.% e.g., no more than 55%, or even no more that 45% of the fabric softening compound and at least 10 wt.% of the monoester linked component.
A first group of quaternary ammonium compounds (QACs) suitable for use in the compositions are represented by formula (I):
[(CH2)n(TR)] wherein each R is independently selected from a C5 to C35 alkyl or alkenyl group; R1 represents a C1 to C4 alkyl, C2 to C4 alkenyl or a C1 to C4 hydroxyalkyl group; T may be either O-CO. (i.e. an ester group bound to R via its carbon atom), or may alternatively be CO-O (i.e. an ester group bound to R via its oxygen atom); n is a number selected from 1 to 4; m is a number selected from 1, 2, or 3; and X- is an anionic counter-ion, such as a halide or alkyl sulphate, e.g. chloride or methylsulfate. Di-esters variants of formula I (i.e., m = 2) are preferred and typically have mono- and tri-ester analogues associated with them. Such materials are particularly suitable for use in the compositions described herein. A second group of QACs suitable for use in the compositions described herein is represented by formula (II): wherein each R1 group is independently selected from C1 to C4 alkyl, hydroxyalkyl or C2 to C4 alkenyl groups; and wherein each R2 group is independently selected from C8 to C28 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). Preferably, these materials also comprise an amount of the corresponding monoester.
A third group of QACs suitable for use in the composition are represented by formula (III): wherein each R1 group is independently selected from C1 to C4 alkyl, or C2 to C4 alkenyl groups; and wherein each R2 group is independently selected from C8 to C28 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, partially hardened and hardened versions thereof.
A particular example of the fourth group of QACs is represented the by the formula (IV):
A fifth group of QACs suitable for use in the composition are represented by formula (V)
Ri and R2 are independently selected from C10 to C22 alkyl or alkenyl groups, preferably C14 to C20 alkyl or alkenyl groups. X- is as defined above.
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 described herein. 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 methylsulfate. Such ester-linked triethanolamine quaternary ammonium compounds comprise unsaturated fatty chains.
If there is a mixture of quaternary ammonium materials present in the composition, the iodine value, referred to above, represents the mean iodine value of the parent fatty acyl compounds or fatty acids of all the quaternary ammonium materials present. Likewise, if there are any saturated quaternary ammonium materials present in the composition, the iodine value represents the mean iodine value of the parent acyl compounds of fatty acids of all of the quaternary ammonium materials present.
Iodine value as used in the context of the compositions described herein refers to, the fatty acid used to produce the QAC, 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 quaternary ammonium compound may be a non-ester quaternary ammonium material represented by formula (VI): wherein each R1 group is independently selected from C1 to C4 alkyl, hydroxyalkyl or C2 to C4 alkenyl groups; R2 group is independently selected from C8 to C28 alkyl or alkenyl groups, and X- is as defined above.
In a preferred embodiment the fabric softening active comprises a mixture of cationic quaternary ammonium compound having more than one long carbon chain in combination with a secondary surfactant selected from a single chain cationic surfactant and/or a non-ionic surfactant. Preferably the cationic quaternary ammonium compound having more than one long carbon chain and secondary surfactant are present in a ratio of 1 :10 to 10:1 , more preferably 1 :5 to 5:1. The combination of the cationic quaternary ammonium compound having more than one long carbon chain in combination with a secondary surfactant selected from a single chain cationic surfactant and/or a non-ionic surfactant provide a solid composition which can be diluted with water to form a stable liquid fabric softener and provides superior softening. Cationic quaternary ammonium compound having more than one long carbon chain are as described above.
Suitable single chain cationic surfactant preferably have the general formula:
(RI)3 - N+ - R2 X-
Wherein each Ri independently comprises 1 to 6 carbon atoms, selected from alky, alkenyl, aryl or combinations thereof. Each Ri may independently comprise hydroxy groups. Preferably at least two of the Ri groups correspond to a methyl group.
Wherein R2 comprises at least 10 carbon atoms. The carbon atoms may be in the form of an alky, alkenyl, aryl or combinations thereof. Preferably the single chain cationic surfactant comprises at least 12 carbon atoms, preferably at least 14 and most preferably at least 16. R2 may further comprise additional functional groups such as ester groups or hydroxy groups. X- is an anionic counter-ion, such as a halide or alkyl sulphate, e.g. chloride or methylsulfate Preferred cationic surfactants include Hydroxyethyl laurdimonium chloride, cetyltrimethylammonium chloride (CTAC), Behentrimonium chloride (BTAC), a Alkyl dimethyl hydroxyethyl ammonium chloride such as Praepagen HY ex Clariant GmbH.
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 (VII):
R-Y-(C2H4O)z-CH2-CH2-OH (VII) 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.
In the general formula for the ethoxylated nonionic surfactant, 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 (VII), or can be hydrogen; and Z is at least about 8, preferably at least about 10 or 11.
Preferably the nonionic surfactant has an HLB of from about 7 to about 20, more preferably from 10 to 18, e.g. 12 to 16. Genapol™ 0200 (Clariant) based on coco chain and 20 EG groups is an example of a suitable nonionic surfactant.
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.
A second class of preferred non-ionic surfactants are polyethylene glycol ethers of glycerine.
Such as Glycereth-6 Cocoate, Glycereth-7 Cocoate and Glycereth-17 Cocoate. Preferably the non-ionic surfactant is selected from addition products of ethylene oxide and/or propylene oxide with fatty alcohols, fatty acids and fatty amines and polyethylene glycol ethers of glycerine.
Suitable non-ionic surfactants are available commercially as Lutensol™ AT25 ex. BASF based on C16:18 chain and 25 EO groups is an example of a suitable non-ionic surfactant. Other 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; LEVENOL® F-200, LEVENOL® C-301 and LEVENOL® C-201 ex. Kao.
The compositions described herein comprise more than 5 wt. % fabric softening active, more preferably more than 10 wt. % fabric softening active, most preferably more than 20 wt. % fabric softening active by weight of the composition. The fabric conditioners of the described herein comprise less than 80 wt. % fabric softening active, more preferably less than 70 wt. % fabric softening active, most preferably less than 65 wt. % fabric softening active by weight of the composition. The fabric conditioners comprise 5 to 80 wt. % fabric softening active, preferably 10 to 70 wt.% fabric softening active and more preferably 20 to 65 wt. % fabric softening active by weight of the composition.
Cross linked cellulose
The compositions described herein comprise cross linked cellulose, preferably the crosslinked cellulose comprises microcrystalline cellulose, preferably the crosslinked cellulose is microcrystalline cellulose.
Preferably the cross linked cellulose has a Water Absorption Ratio (WAR) of greater than 1 , more preferably greater than 1.5. Water Absorption Ratio (WAR) is a measure as to how much water a material absorbs under controlled and defined conditions. Water absorption is expressed as the increase in weight percent of a specimen:
Increase in weight, % = [(wet weight - conditioned weight) / conditioned weight] x 100
The process described in ASTM D570 is suitable for measuring water absorption ratios.
Specifically the water absorption may be measured by: Procuring a dry sample of the material to be tested
- Weighing the sample to be tested then, placing in a container of boiling distilled water for 120 minutes, ensuing it is entirely immersed
Removing the specimen and removing excess water with filter paper.
- Weighing the sample immediately (wet weight) Drying the sample at 105°C for 20 minutes Reweighing the sample (conditioned weight)
The composition comprises from 3 to 12% by weight cross linked cellulose, more preferably from 4.5 to 12% by weight and most preferably from 6 to 11 % by weight cross linked cellulose.
Water soluble carrier
The compositions described herein comprise water-soluble carrier. The water-soluble carrier provides solid structure to the solid fabric conditioner. The composition my comprise one carrier material or a combination of different carrier materials.
Suitable water-soluble carrier materials are selected from polysaccharides (e.g., starch, xanthan gum, cellulose, or derivatives thereof).
Examples of suitable carrier materials include: starch, xanthan gum, carboxymethyl cellulose.
More preferably the water-soluble carrier is selected from cellulose derivatives. Most preferably cellulose ether derivatives. Typically, cellulose ether derivatives are obtained by substituting one or more hydrogen atoms of hydroxyl groups in the anhydro-glucose units of cellulose with alkyl or substituted alkyl groups. Degree of substitution (DS) is one of the factors, that define the properties of cellulose ether derivatives, particularly, solubility in water. It is defined as the number of substituted hydroxyl groups for every glucose molecule ranging between zero and three. For example, cellulose ether derivatives with degree of substitution values between 1.2 to 2.4 are soluble in cold water. Examples of cellulose ether derivatives suitable for the compostions described herein includes methyl cellulose (MC), hydroxyethyl cellulose (HEC), hydroxypropyl cellulose (HPC), hydroxypropyl methyl cellulose (HPMC), carboxymethyl cellulose (CMC) and sodium carboxymethyl cellulose (SCMC).
Preferably the cellulose ether derivative is selected form hydroxypropyl methyl cellulose, methyl cellulose, hydroxypropyl cellulose, and combinations thereof. Most preferred cellulose ether derivative is hydroxypropyl methyl cellulose. The compositions described herein comprise 2 to 80 wt.% water-soluble carrier materials, preferably 5 to 70 wt.%, more preferably 7.5 to 50 wt.% and most preferably 10 to 40 wt.% water-soluble carrier materials, by weight of the composition.
The water-soluble carrier preferably has a solubility at least 0.5% by weight in distilled water at 25 °C. Preferably a solubility at least 1.0 % by weight, more preferably at least 2 % by weight, and most preferably at least 3% by weight in distilled water at 25 °C. In other words, a solubility of at least 5 mg/ml of distilled water at 25°C, preferably at least 10 mg/ml of distilled water at 25°C, more preferably at least 20 mg/ml of distilled water at 25°C, most preferably 30 mg/ml of distilled water at 25°C.
Carbonaceous material
The compositions described herein preferably comprise carbonaceous materials. The carbonaceous material leads to improved strength of the solid composition. Carbonaceous materials refer to materials having a 2D carbon lattice nanostructure. The 2D lattice may be flat for example graphene or may be shaped into a 3D shape such as carbon nanotubes. The carbonaceous material may be part of a larger structure, such as a composite material e.g. clay-carbonaceous material composite. Preferably the carbonaceous materials comprise a material selected from carbon nanotubes, graphene, activated carbon and combinations thereof. More preferably the carbonaceous materials comprise preferably graphene and/or derivatives thereof and most preferably graphene oxide.
Graphene is an allotrope, formed by a single layer carbon atoms arranged in hexagonal lattice structure. Graphene can be obtained in two manners. The first is by peeling layers from graphite until you achieve a graphene monolayer. The second is known as Chemical Vapor Deposition (CVD) and where large-scale uniformity can be obtained and controlled.
Preferably the graphene derivative suitable for the composition described herein is graphene oxide. Graphene oxide can be manufactured through Hummer’s method. Graphene oxide is also commercially available and may be procured from suppliers such as Platonic Nanotech.
The compositions described herein preferably comprise 0.001 to 2 wt.% carbonaceous materials, more preferably 0.0025 to 1 wt.% carbonaceous materials, even more preferably 0.005 to 0.5 wt.% carbonaceous materials and most preferably 0.01 to 0.25 wt.% carbonaceous materials.
Other ingredients
The compositions described herein may comprise additional ingredients common in the field of solid fabric conditioners, for example perfumes, perfume microcapsules, dyes, antifoams, 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, colorants, sunscreens, anti-corrosion agents, drape imparting agents, anti-static agents, sequestrants and ironing aids. The compositions described herein may contain pearlisers and/or opacifiers.
Preferably the compositions comprise perfume, more preferably comprises 0.1 to 25 wt.% perfume, even more preferably 1 to 20 wt. % perfume and most preferably 2 to 15 wt.% perfume.
Water
The solid fabric conditioner described herein are preferably ‘free from water’ when manufactured, however they may absorb moisture on storage. Therefore, preferably the composition comprises 0 to 20 wt.% weight, more preferably 0 to 15 wt.% water, most preferably 0 to 12 wt.% water. Water content may be measured by thermogravimetry, like moisture balance.
Process of making and use of the compositions
The solid fabric conditioner composition described herein may be in any suitable form. A single dose of the composition may be a single article (e.g. a tablet or sheet), a part of a single article (i.e. a part of a sheet separated by tearing a section off a larger sheet), or may consist of multiple articles, (e.g. multiple particles of the composition). Preferably the solid composition is in the form of articles having a minimum linear dimension in any direction of more than 1 mm. The solid fabric conditioner composition does not include powders. Preferably the solid composition is in a form suitable for use as a single article for example a tablet or sheet. These may be referred to as a ‘unit dose’.
The solid fabric conditioner may be made by any suitable process. A preferred method comprises the steps of; a) Preparing a premix of a water-soluble carrier and water; b) Adding fabric softening active, crosslinked cellulose and any remaining ingredients to the premix; c) Casting the mixture on a surface or in a mold; and d) Removing the water, preferably by evaporation.
Step a) preferably comprises mixing and/or heating.
Step b) preferably comprises mixing fabric softening active, carbonaceous material and any remaining ingredients with water prior to addition to the pre-mix.
In step c) if casting is used, preferably the thickness is controlled using an applicator. The mixture is preferably cast onto a Polytetrafluoroethylene (PTFE) surface, for example PTFE sheets, PTFE coated foils or PTFE coated fabrics.
Step d) preferably takes place at a temperature above room temperature (above 25°C), preferably at less than 100 °C, and more preferably less than 95 °C. Most preferably water is removed at a temperature of 70 to 90 °C. Preferably water is removed to reach a composition water content of 0 to 20 wt.%, more preferably a water content of 0 to 15 wt.%, more preferably 0 to 10 wt.%, even more preferably 0 to 5 wt. % and most preferably 0 to 2 wt.%.
More specifically a homogenized premix of water and water-soluble carrier is prepared with mixing. Subsequently, fabric softening active, crosslinked cellulose and any remaining ingredients are mixed with water under high shear before being added to the premix. Thereon the premix is casted on a surface as a sheet or film with certain thickness.
Examples
Example 1 : Comparison with other materials
Table 1: Example formulations Quaternary ammonium compound1 - TEA palm quaternary ammonium compound Micro-crystalline cellulose2 - KEVICEL PH 102 ex. Keval Exports Polyvynl propylene polymer particles3 - Disintex 75 ex. Ashland
Calcite4 - Forcal II ex. Saurashtra Solid Private Ltd, India.
The formulations where prepared by dispersing the hydroxypropyl methyl cellulose in hot water to make a 10% polymer solution. Separately the quaternary ammonium compound and perfume were mixed in the remaining water under high shear to make an emulsion. The remaining ingredients were added to the emulsion and mixed. The final mix was added to the polymer solution at room temperature and mixed well at high shear until a stable foam was formed. The foam was cast on a smooth, hard surface and dried at 80-90°C for 2 hours. The dried sheet was detached from the substrate on cooling.
Terry knitted fabric monitors were washed in a 15 minute quick wash cycle. No detergent was added and 10g of the dried sheet (1, A, B, C or D) was added in the rinse cycle. The fabrics were then dried. The dynamic coefficient of friction of the dry fabric was measured using a Coefficient of Friction (COF) Tester ex. Packtest.
Table 2: Results
Microcrystalline cellulose provided the lowest coefficient of friction of the various materials tested.
Example 2: Dosing study
Table 3: Example formulations
Quaternary ammonium compound1 - TEA palm quaternary ammonium compound
Micro-crystalline cellulose2 - KEVICEL PH 102 ex. Keval Exports The formulations were prepared as in Example 1.
The coefficient of friction was measured as in Example 1.
Dissolution time was measured the following method. 300 ml of water was placed in a 500ml beaker at room temperature. The beaker was placed over a magnetic stirrer with 1.5 inch magnetic bead in it. Stirring was set at 300 RPM. 1 inch X 1 inch piece of sheet (as prepared above) were added to the stirring water & the timer started. The dissolution time is the at which no residue of the sheet remains visible. Table 4: Results
3 to 12 wt.% crosslinked cellulose provides an improved coefficient of friction while maintaining an improved dissolution time.

Claims

Claims
1. A solid fabric conditioning composition comprising: a 5 to 80 wt.% Fabric softening active; b 3 to 12 wt.% crosslinked cellulose; and c 2 to 80 wt.% Water soluble carrier selected from polysaccharides.
2. A solid fabric conditioning composition according to claim 1 , wherein the crosslinked cellulose has a Water Absorption Ratio (WAR) of greater than 1.
3. A solid fabric conditioning composition according to any preceding claim, wherein the crosslinked cellulose comprises microcrystalline cellulose.
4. A solid fabric conditioning composition according to any preceding claim, wherein the fabric softening active comprises a quaternary ammonium compound.
5. A solid fabric conditioning composition according to any preceding claim, wherein the fabric softening active comprises a mixture of cationic quaternary ammonium compound having more than one long carbon chain in combination with a secondary surfactant selected from a single chain cationic surfactant and/or a non-ionic surfactant.
6. A solid fabric conditioning composition according to any preceding claim, wherein the water-soluble carrier is selected from: cellulose derivatives and combinations thereof.
7. A solid fabric conditioning composition according to any preceding claim, wherein the composition further comprises a carbonaceous material having a 2D carbon lattice nanostructure.
8. A solid fabric conditioning composition according to any preceding claim, wherein the composition further comprises perfume.
9. A method of preparing a solid fabric conditioning composition comprising the steps of; a. Preparing a premix of a water-soluble carrier and water; b. Adding fabric softening active, crosslinked cellulose and any remaining ingredients to the premix; c. Casting the mixture on a surface or in a mold; and d. Removing the water, preferably by evaporation.
EP23821292.2A 2022-12-14 2023-12-08 Solid laundry composition Pending EP4634351A1 (en)

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WO2021239375A1 (en) * 2020-05-27 2021-12-02 Unilever Ip Holdings B.V. Method of preparing a liquid fabric conditioner

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GB1567947A (en) 1976-07-02 1980-05-21 Unilever Ltd Esters of quaternised amino-alcohols for treating fabrics
DE10059340A1 (en) * 2000-11-29 2002-06-20 Henkel Kgaa Particulate textile aftertreatment agent
CN107714493A (en) * 2017-11-28 2018-02-23 拜东辰 A kind of application of antibacterial ultraviolet-resistannanofiber line anti-corrosion material in daily cosmetics
WO2021239373A1 (en) * 2020-05-27 2021-12-02 Unilever Ip Holdings B.V. Dilutable fabric conditioner composition
WO2021239374A1 (en) * 2020-05-27 2021-12-02 Unilever Ip Holdings B.V. Fabric softener composition

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Publication number Priority date Publication date Assignee Title
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