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
  • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
  • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
  • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
  • C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
  • C11D17/045—Multi-compartment
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/50—Perfumes
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
  • C11D2111/10—Objects to be cleaned
  • C11D2111/12—Soft surfaces, e.g. textile

Definitions

• the present invention relates to improved unit dosed products comprising solid particles.
• a laundry unit dose product comprising at first and a second chamber formed between a pair of water-soluble films, said first chamber comprising a laundry liquid composition and said second chamber comprising a solid particle, and wherein said particle comprises from 0.1 to 30% by weight of benefit agent, wherein the average film thickness is from 0.15 to 0.18mm.
• said water-soluble film comprises maleic acid copolymerised with polyvinyl alcohol.
• the solid particle comprises at least 50% wt. of the solid laundry particle a carrier.
• the solid particle comprises at least 90% wt. of the solid laundry particle a carrier.
• the solid particle comprises from 5 to 15% by weight of an anionic surfactant selected from alkyl sulfate, alkyl ether sulfate, soap, and mixtures thereof.
• an anionic surfactant selected from alkyl sulfate, alkyl ether sulfate, soap, and mixtures thereof.
• the solid particle comprises less than 1.5% by weight of alkylbenzene sulfonates.
• the benefit agent is dispersed within the carrier.
• the water-soluble carrier comprises sugar selected from dextrose, sucrose, fructose, glucose, isoglucose, rhamnose, fucose, deoxyribose, ribose, trehalose, xylose, mannose, arabinose, galactose, cellobiose, lactose, maltose, isomaltose, melibiose, gentobiose, maltotriose, raffinose, panose, and mixtures thereof, preferably the water-soluble carrier comprises sugar selected from dextrose, sucrose, fructose, glucose, isoglucose, galactose, raffinose, and mixtures thereof.
• the carrier comprises PEG.
• the anionic surfactant is present in the solid particle in an amount of from 6 to 12% by weight of the composition, preferably from 7 to 10%.
• the benefit agent is selected from perfume, malodor agents, fabric softener actives, cationic polymers, dye transfer inhibitors, shading dyes, insect repellents, organic sunscreen actives, antimicrobial agents, ester solvents, lipids and lipid like substances, hydrocarbons, fish and vegetable oils, hydrophobic plant extracts, waxes, pigments, sugar-esters, silicone oils, resins and modifications thereof, and mixtures thereof.
• the benefit agent is perfume, preferably a combination of free perfume and perfume microcapsules.
• the particles comprise from 0.1% to 30% by weight of perfume, preferably from 0.5 to 20%.
• the solid particle comprises a disintegrant selected from polyvinylpyrrolidone, crospovidone, starch, starch derivatives, cellulose, cellulose derivatives, clays, gums, non-carbonate salt and mixtures thereof.
• a disintegrant selected from polyvinylpyrrolidone, crospovidone, starch, starch derivatives, cellulose, cellulose derivatives, clays, gums, non-carbonate salt and mixtures thereof.
• the solid particle has a maximum linear dimension in any direction of less than 10 mm, preferably 1 to 8 mm.
• the liquid unit dose product comprises at least two chambers, preferably, three chambers and more preferably four chambers. At least one chamber contains a liquid laundry detergent composition and at least one chamber contains a solid particle composition.
• each chamber is defined by water-soluble film in preferably each chamber is formed between two opposing sheets of film which are sealed at the edges to define the chambers.
• the product is from 10 to 50g in weight to represent a unit dose.
• Water-soluble film compositions optional ingredients for use therein, and methods of making the same are well known in the art, whether being used for making relatively thin water-soluble films (e.g., as capsule materials) or otherwise.
• Polyvinyl alcohol is a synthetic resin generally prepared by the alcoholysis, usually termed hydrolysis or saponification, of polyvinyl acetate. Fully hydrolyzed PVA, wherein virtually all the acetate groups have been converted to alcohol groups, is a strongly hydrogen-bonded, highly crystalline polymer which dissolves only in hot water- greater than about 140 degrees Fahrenheit (60 degrees C). If a sufficient number of acetate groups are allowed to remain after the hydrolysis of polyvinyl acetate, the PVA polymer then being known as partially hydrolyzed, it is more weakly hydrogen-bonded and less crystalline and is soluble in cold water- less than about 10 degrees C.
• An intermediate cold or hot water-soluble film can include, for example, intermediate partially- hydrolyzed PVA (e.g., with degrees of hydrolysis of about 94 percent to about 98 percent), and is readily soluble only in warm water- e.g., rapid dissolution at temperatures of about 40 degrees centigrade and greater.
• PVA intermediate partially- hydrolyzed polyvinyl acetate copolymer
• Both fully and partially hydrolyzed PVA types are commonly referred to as PVA homopolymers although the partially hydrolyzed type is technically a vinyl alcohol- vinyl acetate copolymer.
• water soluble polymers for use in addition to the PVA polymers and PVA copolymers in the blend can include, but are not limited to modified polyvinyl alcohols, polyacrylates, water-soluble acrylate copolymers, polyvinyl pyrrolidone, polyethyleneimine, pullulan, water-soluble natural polymers including, but not limited to, guar gum, gum Acacia, xanthan gum, carrageenan, and starch, water-soluble polymer derivatives including, but not limited to, modified starches, ethoxylated starch, and hydroxypropylated starch, copolymers of the forgoing and combinations of any of the foregoing.
• water-soluble polymers can include polyalkylene oxides, polyacrylamides, polyacrylic acids and salts thereof, celluloses, cellulose ethers, cellulose esters, cellulose amides, polyvinyl acetates, polycarboxylic acids and salts thereof, polyaminoacids, polyamides, gelatines, methylcelluloses, carboxymethylcelluloses and salts thereof, dextrins, ethylcelluloses, hydroxyethyl celluloses, hydroxypropyl methylcelluloses, maltodextrins, and polymethacrylates.
• Such water-soluble polymers, whether PVOH or otherwise are commercially available from a variety of sources.
• any of the foregoing water-soluble polymers are generally suitable for use as film-forming polymers.
• the water- soluble film can include copolymers and/or blends of the foregoing resins.
• the weight ratio of the amount of all water-soluble polymers as compared to the combined amount of all plasticizers, compatibilizing agents, and secondary additives can be in a range of about 0.5 to about 18, about 0.5 to about 15, about 0.5 to about 9, about 0.5 to about 5, about 1 to 3, or about 1 to 2, for example.
• the specific amounts of plasticizers and other non-polymer component can be selected in a particular embodiment based on an intended application of the water-soluble film to adjust film flexibility and to impart processing benefits in view of desired mechanical film properties.
• the viscosity of a water-soluble polymer is correlated with the weight- average molecular weight (W) of the same polymer, and often the viscosity is used as a proxy for Mw.
• W weight-average molecular weight of the water-soluble polymers
• the weight-average molecular weight of the water-soluble polymers, including the first PVA copolymer and second PVA polymer can be in a range of about 30,000 to about 175,000, or about 30,000 to about 100,000, or about 55,000 to about 80,000, for example.
• the water-soluble film can contain other auxiliary agents and processing agents, such as, but not limited to, plasticizers, plasticizer compatibilizers, surfactants, lubricants, release agents, fillers, extenders, cross-linking agents, antiblocking agents, antioxidants, detackifying agents, antifoams, nanoparticles such as layered silicate-type nanoclays (e.g., sodium montmorillonite), bleaching agents (e.g., sodium metabisulfite, sodium bisulfite or others), aversive agents such as bitterants (e.g., denatonium salts such as denatonium benzoate, denatonium saccharide, and denatonium chloride; sucrose octaacetate; quinine; flavonoids such as quercetin and naringen; and quassinoids such as quassin and brucine) and pungents (e.g., capsaicin, piperine, allyl isothiocyanate, and resinferatoxi
• Embodiments including plasticizers are preferred.
• the amount of such agents can be up to about 50 wt., 20 wt percent, 15 wt percent, 10 wt percent, 5 weight percent, 4 wt percent and/or at least 0.01 weight percent, 0.1 wt percent, 1 wt percent, or 5 wt, individually or collectively.
• the plasticizer can include, but is not limited to, glycerin, diglycerin, sorbitol, ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, tetraethylene glycol, propylene glycol, polyethylene glycols up to 400 MW, neopentyl glycol, trimethylolpropane, polyether polyols, sorbitol, 2-methyl-l,3-propanediol, ethanolamines, and a mixture thereof.
• a preferred plasticizer is glycerin, sorbitol, triethyleneglycol, propylene glycol, diproyplene glycol, 2-methyl-l,3-propanediol, trimethylolpropane, or a combination thereof.
• the total amount of the plasticizer can be in a range of about 10 weight percent to about 40 wt., or about 15 weight percent to about 35 wt., or about 20 weight percent to about 30 wt., for example about 25 wt., based on total film weight.
• Combinations of glycerin, dipropylene glycol, and sorbitol can be used.
• glycerin can be used in an amount of about 5 wt percent to about 30 wt, or 5 wt percent to about 20 wt, e.g., about 13 wt percent.
• dipropylene glycol can be used in an amount of about 1 weight percent to about 20 wt., or about 3 weight percent to about 10 wt., for example 6 weight percent.
• sorbitol can be used in an amount of about 1 wt percent to about 20 wt, or about 2 wt percent to about 10 wt, e.g., about 5 wt percent.
• the specific amounts of plasticizers can be selected in a particular embodiment based on desired film flexibility and processability features of the water-soluble film. At low plasticizer levels, films may become brittle, difficult to process, or prone to breaking. At elevated plasticizer levels, films may be too soft, weak, or difficult to process for a desired use.
• the composition comprises a taste aversive such as denatonium benzoate and/or a pungent agent such as capsaicin.
• Maleic acid copolymerised with polyvinyl alcohol is well known in the field and is commercially available from a number of water-soluble film manufacturers.
• the maleic acid copolymerised PVA comprises from 10 to 70% wt. and more preferably from 30 to 60% wt. of the water-soluble film.
• the film comprises a phthalocyanine based pigment.
• the film comprises less than 10% wt. acrylic acid copolymerised PVA.
• the pH of the laundry liquid composition is from 6.1 to 8.2. More preferably, the pH of the composition is from 6.5 to 7.5.
• water-soluble means that a material is soluble or otherwise dispersible in water at a level of at least 90% by weight at 25°C under ambient condition, preferably at least 95% by weight and more preferably at least 98% by weight at 25°C under ambient condition.
• the particles of the present invention comprise no less than 20% by weight of a water-soluble carrier, preferably no less than 30%, more preferably no less than 35% and most preferably no less than 40% by weight of a water-soluble carrier.
• the particles of the present invention comprise no more than 95% by weight of water-soluble carrier, preferably no more than 85%, more preferably no more than 75% and most preferably no more than 70% by weight of a water-soluble carrier.
• the particle of the present invention comprises from 20 to 95% by weight of a water-soluble carrier, preferably from 30 to 85%, more preferably from 35 to 75% and most preferably from 40 to 70% by weight of a water-soluble carrier.
• the water-soluble carrier comprises a carbohydrate selected from sugar, sugar alcohol and mixtures thereof, which may reduce the corrosion of the internal parts of the washing machine compared with using salts as the carrier. More preferably the water-soluble carrier comprises sugar. Suitable sugar may be selected from dextrose, sucrose, fructose, glucose, isoglucose, rhamnose, fucose, deoxyribose, ribose, trehalose, xylose, mannose, arabinose, galactose, cellobiose, lactose, maltose, isomaltose, melibiose, gentobiose, maltotriose, raffinose, panose, and mixtures thereof.
• the sugar is selected from dextrose, sucrose, fructose, glucose, isoglucose, galactose, raffinose, and mixtures thereof. More preferably the sugar comprises or is sucrose.
• a sugar alcohol is an organic compound having more than two hydroxyl groups.
• the sugar alcohol can have from 4 to 12 carbon atoms.
• Suitable sugar alcohol may be selected from sorbitol, mannitol, isomalt, maltitol, lactitol, xylitol, erythritol, and mixtures thereof.
• the sugar alcohol is selected from mannitol, sorbitol and mixtures thereof.
• a bittering agent if the water-soluble carrier comprises sugar.
• Preferred bettering agent is selected from the group consisting of denatonium benzoate, denatonium saccharide, quinine or a salt of quinine.
• the chemical name of denatonium is phenylmethyl-[2-[(2,6-dimethylphenyl)amino]-2-oxoethyl]-diethylammonium.
• Denatonium benzoate is particularly preferred.
• An example is Bitrex ® from Johnson Matthey Fine Chemicals.
• bittering agent is present in an amount from 0.001 to 0.01 % by weight of the particles.
• the particles of the present invention may comprise an additional carrier (in addition to the water-soluble carrier).
• the additional carrier material may provide various benefits such as stability benefits.
• the additional carrier materials may be selected from the group consisting of polymers (e.g, polyethylene glycol, ethylene oxide/propylene oxide block copolymers, polyvinyl alcohol, polyvinyl acetate, and derivatives thereof), proteins (e.g., gelatin, albumin, casein), polysaccharides (e.g., starch, xanthan gum, cellulose, or derivatives thereof), water dispersible fillers (e. g., zeolite, silica, clay), vegetable soap (e.g.
• the additional carrier comprises polysaccharide.
• a polysaccharide is a saccharide polymer comprising more than 10 monosaccharides units, preferably 15 to 1000 monosaccharides units and more preferably 25 to 500 monosaccharides units.
• Suitable polysaccharides may be selected from starch, glycogen, chitin, gum Arabic, xanthan gum, cellulose, callose, dextran, tunicin, inulin, alginic acid, gellan, guar, carob flour, carrageenan, and derivatives of these compounds, and mixtures thereof.
• the polysaccharide comprises starch and/or its derivatives.
• the polysaccharide comprises or is starch.
• Suitable starch may be selected from wheat starch, rice starch, potato starch, corn starch, tapioca starch and mixtures thereof.
• the particles of the present invention comprise from 0.1 to 50% by weight of the additional carrier, more preferably from 1 to 35%, even more preferably from 2 to 25%, and most preferably from 5 to 20% by weight of the additional carrier.
• the particles of the present invention preferably comprise no less than 5% by weight of an anionic surfactant, preferably no less than 6% by weight of an anionic surfactant, more preferably no less than 7% by weight of an anionic surfactant.
• the particles of the present invention comprise no more than 15% by weight of an anionic surfactant, preferably no more than 12% by weight of an anionic surfactant, more preferably no more than 10% by weight of an anionic surfactant.
• the particles of the present invention comprise from 5 to 15% by weight of an anionic surfactant, preferably from 6 to 12% by weight of an anionic surfactant, more preferably from 7 to 10% by weight of an anionic surfactant.
• the anionic surfactant may serve as binder to bind the carrier material and other constituent ingredients of the composition together thereby helping to provide for a processable composition in production.
• the use of 5 to 15% by weight of an anionic surfactant was surprisingly found to provide improved processability of the composition.
• the anionic surfactant may also improve the appearance of the particles and make the surface of the particles look smoother. Consumers are sensitive to visual cues when using a laundry product. A laundry product containing particles with rough surfaces are often regarded as quality problems and not liked by consumers.
• the anionic surfactant is selected from alkyl sulfate, alkyl ether sulfate, soap and mixtures thereof.
• the anionic surfactant is selected from alkyl sulfate, alkyl ether sulfate and mixtures thereof. More preferably the anionic surfactant comprises or is alkyl sulfate.
• Alkyl sulfates are anionic surfactants which are water soluble salts containing a hydrocarbon hydrophobic group and a hydrophilic sulfate group.
• the alkyl sulfate has an alkyl group having 8 to 18 carbon atoms, more preferably from 10 to 18 carbon atoms, even more preferably from 10 to 16 carbon atoms. It will be appreciated that both branched and linear alkyl groups are encompassed.
• the alkyl group is preferably linear, i.e. normal alkyl, however, branched chain alkyl sulfates can be employed, although they are less preferred from a biodegradability perspective.
• the alkyl sulfate comprises a salt of an alkyl sulfate.
• the alkyl sulfate comprises a positively charged ion and a negatively alkyl sulfate moiety.
• the positively charged ion may be a metal ion such as sodium, potassium or magnesium; or an ammoniacal ion such as ammonium, monoethanolamine, diethanolamine or triethanolamine. Mixtures of such ions may also be employed. Sodium and potassium are preferred.
• alkyl sulfate comprises sodium, potassium, calcium, magnesium, ammonium or ethanolamine salts of alkyl sulfate having 8 to 18 carbon atoms, more preferably 10 to 18 carbon atoms, even more preferably from 10 to 16 carbon atoms.
• alkyl sulfates include sodium lauryl sulfate (also known as sodium dodecyl sulfate), ammonium lauryl sulfate, diethanolamine (DEA) lauryl sulfate.
• Suitable examples also include alkyl sulfates commercially available from natural source with trade names Galaxy 689, Galaxy 780, Galaxy 789, Galaxy 799 SP, and Ufarol TCL 92N and from synthetic origin with trade names Safol 23, Dobanol 23A or 23S, Lial 123 S, Alfol 1412S, Empicol LC3, Empicol 075SR.
• Sodium lauryl sulfate also known as sodium dodecyl sulfate, is particularly preferred as the alkyl sulfate.
• SLS sodium lauryl sulfate
• An example of sodium lauryl sulfate is commercially available from Dongming Jujin Chemical Co., Ltd.
• Alkyl ether sulfate is an anionic surfactant having a formula RO(CH 2 CH 2 O) n SO 3 M, wherein R is a linear or branched, alkyl or alkenyl group having 8 to 18 carbon atoms, preferably 10 to 18 carbon atoms, more preferably 12 to 14 carbon atoms; M is a positively charged ion comprising sodium, potassium, calcium, magnesium, ammonium, monoethanolamine, diethanolamine, triethanolamine or mixtures thereof, preferably sodium, potassium or mixtures thereof; n is the degree of ethoxylation of from 0.5 to 3, preferably from 1 to 3.
• a preferred example is sodium lauryl ether sulfate (SLES) in which the predominantly C 12 lauryl alkyl group has been ethoxylated with an average of 2EO units per molecule.
• synap means the alkali metal or alkanol ammonium salts of aliphatic, alkanes, or alkene monocarboxylic acids.
• Preferred monocarboxylic acids are fatty acids with 6 to 22 carbon atoms, more preferably from 12 to 18 carbon atoms.
• soap examples include, but not limited to, sodium, potassium, calcium, magnesium, ammonium, monoethanolamine, diethanolamine, triethanolamine salts of lauric acid, myristic acid, palmitic acid, stearic acid, (hydrogenated) erucic acid, behenic acid, coconut oil fatty acid, palm oil fatty acid, palm kernel oil fatty acid, olive oil fatty acid, tallow fatty acid or mixtures thereof.
• the fatty acids may be saturated or unsaturated, linear or branched. It is particularly preferred that the soap comprises sodium or potassium salts of coconut fatty acid, palm kernel oil fatty acid or mixtures thereof.
• the particles of the present invention may comprise other anionic surfactants in addition to the anionic surfactants described above.
• suitable anionic surfactants include, but not limited to, alkyl sulfonates, alkaryl sulfonates, alpha-olefin sulfonates, alkyl isethionates, alkanoyl isethionates, alkyl succinates, alkyl sulphosuccinates, alkyl ether sulphosuccinates, N-alkyl sarcosinates, alkyl phosphates, alkyl ether phosphates, alkyl ether carboxylic acids and salts thereof, especially their sodium, potassium, calcium, magnesium, ammonium and mono-, di-, and triethanolamine salts.
• the alkyl radicals preferably contain from 10 to 18 carbon atoms and may be unsaturated.
• the alkyl ether sulphosuccinates, alkyl ether phosphates and alkyl ether carboxylic acids and salts thereof may contain from one to twenty ethylene oxide or propylene oxide units per molecule.
• the particles of the present invention may comprise alkylbenezene sulfonates, particularly linear alkylbenzene sulfonates (LAS) with an alkyl chain length of from 10 to 18 carbon atoms.
• LAS linear alkylbenzene sulfonates
• Commercial LAS is a mixture of closely related isomers and homologues alkyl chain homologues, each containing an aromatic ring sulfonated at the "para" position and attached to a linear alkyl chain at any position except the terminal carbons.
• the linear alkyl chain typically has a chain length of from 11 to 15 carbon atoms, with the predominant materials having a chain length of about C12.
• Each alkyl chain homologue consists of a mixture of all the possible sulfophenyl isomers except for the 1-phenyl isomer.
• LAS is normally formulated into compositions in acid (i.e. HLAS) form and then at least partially neutralized in-situ.
• alkylbenzene sulfonates include sodium salt of linear alkylbenzene sulphonate, alkyl toluene sulphonate, alkyl xylene sulphonate, alkyl phenol sulphonate, alkyl naphthalene-sulphonate, ammonium diamylnaphthalene-sulphonate and sodium dinonylnaphthalene-sulphonate and mixtures with olefin sulphonates.
• the particles of the present invention are substantially free of alkylbenezene sulfonates.
• substantially free of means less than 1.5%, preferably less than 1.0%, more preferably less than 0.75%, more preferably still less than 0.5% and even more preferably less than 0.1% and most preferably from 0 to 0.01% by weight, based on total weight of the composition, including all ranges subsumed therein. It is preferred that the particles of the present invention do not comprise any alkylbenezene sulfonates.
• Benefit agent as used herein means an active typically delivered to laundered fabrics to enhance or improve a characteristic of those fabrics.
• the benefit agents are dispersed within the carrier materials.
• the benefit agents may be free in the carrier material or they may be encapsulated.
• the particles of the present invention comprise from 0.1 to 30% by weight of the benefit agents, preferably from 1 to 30%, more preferably from 2 to 30%, even more preferably from 5 to 30%, even more preferably from 5 to 20%, and most preferably from 5 to 15% by weight of the benefit agents.
• suitable benefit agents include, but not limited to, perfume; malodor agents (e.g., uncomplexed cyclodextrin, odor blockers, reactive aldehydes, flavonoids, zeolites, activated carbon, or mixtures thereof); fabric softener actives; cationic polymers; dye transfer inhibitors; shading dyes; insect repellents; organic sunscreen actives (e.g., octylmethoxy cinnamate); antimicrobial agents (e.g., 2-hydroxy-4, 2,4-trichlorodiphenylether); ester solvents (e.g., isopropyl myristate); lipids and lipid like substances (e.g.
• hydrocarbons e.g., paraffins, petrolatum, and mineral oil
• fish and vegetable oils hydrophobic plant extracts
• waxes e.g., pigments (e.g., inorganic compounds with hydrophobically- modified surface and/ or dispersed in an oil or a hydrophobic liquid); sugar-esters (e.g., sucrose polyester); silicone oils, resins and modifications thereof (e.g., linear and cyclic polydimethylsiloxanes, amino-modified, allcyl, aryl, and alkylaryl silicone oils, which preferably have a viscosity of greater than 50,000 cst); or mixtures thereof.
• silicone oils, resins and modifications thereof e.g., linear and cyclic polydimethylsiloxanes, amino-modified, allcyl, aryl, and alkylaryl silicone oils, which preferably have a viscosity of greater than 50,000 cst); or mixtures thereof.
• the benefit agent is perfume.
• the particles preferably comprise from 0.1 to 30% by weight of perfume materials i.e. free perfume and/or perfume microcapsules.
• free perfumes and perfume microcapsules provide the consumer with perfume hits at different points during the wash cycle. It is particularly preferred that the particles of the present invention comprise a combination of both free perfume and perfume microcapsules.
• the particles of the present invention comprise 0.5 to 20% perfume materials, more preferably 1 to 15% perfume materials, most preferably 2 to 10% perfume materials.
• Useful perfume components may include materials of both natural and synthetic origin. They include single compounds and mixtures. Specific examples of such components may be found in the current literature, e.g., in Fenaroli's Handbook of Flavor Ingredients, 1975, CRC Press ; Synthetic Food Adjuncts, 1947 by M. B. Jacobs, edited by Van Nostr and; or Perfume and Flavor Chemicals by S. Arctander 1969, Montclair, N.J. (USA ). These substances are well known to the person skilled in the art of perfuming, flavouring, and/or aromatizing consumer products.
• the particles of the invention preferably comprise 0.1 to 15% free perfume, more preferably 0.5 to 8% of free perfume by weight of the particles.
• Particularly preferred perfume components are blooming perfume components and substantive perfume components.
• Blooming perfume components are defined by a boiling point less than 250°C and a LogP greater than 2.5.
• Substantive perfume components are defined by a boiling point greater than 250°C and a LogP greater than 2.5. Boiling point is measured at standard pressure (760 mm Hg).
• a perfume composition will comprise a mixture of blooming and substantive perfume components.
• the perfume composition may comprise other perfume components.
• perfume components it is commonplace for a plurality of perfume components to be present in a free oil perfume composition.
• compositions for use in the present invention it is envisaged that there will be three or more, preferably four or more, more preferably five or more, most preferably six or more different perfume components.
• An upper limit of 300 perfume components may be applied.
• the particles of the present invention preferably comprise 0.1 to 15% of perfume microcapsules, more preferably 0.5 to 8% of perfume microcapsules by weight of the particles.
• the weight of microcapsules is of the material as supplied.
• suitable encapsulating materials may comprise, but are not limited to; aminoplasts, proteins, polyurethanes, polyacrylates, polymethacrylates, polysaccharides, polyamides, polyolefins, gums, silicones, lipids, modified cellulose, polyphosphate, polystyrene, polyesters or mixtures thereof.
• Particularly preferred materials are aminoplast microcapsules, such as melamine formaldehyde or urea formaldehyde microcapsules.
• Perfume microcapsules of the present invention can be friable microcapsules and/or moisture activated microcapsules.
• friable it is meant that the perfume microcapsule will rupture when a force is exerted.
• moisture activated it is meant that the perfume is released in the presence of water.
• the particles of the present invention preferably comprise friable microcapsules. Moisture activated microcapsules may additionally be present. Examples of a microcapsules which can be friable include aminoplast microcapsules.
• Perfume components contained in a microcapsule may comprise odiferous materials and/or pro-fragrance materials.
• Particularly preferred perfume components contained in a microcapsule are blooming perfume components and substantive perfume components. Blooming perfume components are defined by a boiling point less than 250°C and a LogP greater than 2.5. Substantive perfume components are defined by a boiling point greater than 250°C and a LogP greater than 2.5. Boiling point is measured at standard pressure (760 mm Hg).
• a perfume composition will comprise a mixture of blooming and substantive perfume components.
• the perfume composition may comprise other perfume components.
• perfume components it is commonplace for a plurality of perfume components to be present in a microcapsule.
• compositions for use in the present invention it is envisaged that there will be three or more, preferably four or more, more preferably five or more, most preferably six or more different perfume components in a microcapsule.
• An upper limit of 300 perfume components may be applied.
• the microcapsules may comprise perfume components and a carrier for the perfume ingredients, such as zeolites or cyclodextrins.
• fabric softener active 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 or mixtures thereof.
• the fabric softening actives may preferably be cationic or non-ionic materials.
• the fabric softening actives of the present invention are cationic materials. Suitable cationic fabric softening actives are described herein.
• the preferred softening actives for use in the particles of the invention are quaternary ammonium compounds (QAC).
• the QAC 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 A preferred class of quaternary ammonium compound are so called "ester quats". Particularly preferred materials are the ester-linked triethanolamine (TEA) quaternary ammonium compounds comprising a mixture of mono-, di- and tri-ester linked components.
• TAA ester-linked 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 present invention is represented by formula (I): wherein 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.
• Suitable actives include soft quaternary ammonium actives such as Stepantex VT90, Rewoquat WE18 (ex-Evonik) and Tetranyl L1/90N, Tetranyl L190 SP and Tetranyl L190 S (all ex-Kao).
• TEA ester quats actives rich in the di-esters of triethanolammonium methylsulfate, otherwise referred to as "TEA ester quats".
• Preapagen TM TQL Ex-Clariant
• Tetranyl TM AHT-1 Ex-Kao
• AT-1 di-[hardened tallow ester] of triethanolammonium methylsulfate
• L5/90 di-[palm ester] of triethanolammonium methylsulfate
• Rewoquat TM WE15 a di-ester of triethanolammonium methylsulfate having fatty acyl residues deriving from C10-C20 and C16-C18 unsaturated fatty acids
• 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 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 mono-ester.
• a third group of QACs suitable for use in the invention is 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 fourth group of QACs suitable for use in the invention are represented by formula (IV)
• R 1 and R 2 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 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 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 softening compound may be a non-ester quaternary ammonium material represented by formula (V): wherein each R 1 group is independently selected from C1 to C4 alkyl, hydroxyalkyl or C2 to C4 alkenyl groups; each R 2 group is independently selected from C8 to C28 alkyl or alkenyl groups, and X - is as defined above.
• V non-ester quaternary ammonium material represented by formula (V): wherein each R 1 group is independently selected from C1 to C4 alkyl, hydroxyalkyl or C2 to C4 alkenyl groups; each R 2 group is independently selected from C8 to C28 alkyl or alkenyl groups, and X - is as defined above.
• the particles of the present invention preferably comprise from 0.1 to 50% by weight of the fabric softening active, more preferably from 1 to 40%, even more preferably from 5 to 35% and most preferably from 10 to 30% by weight of the fabric softening active.
• the particles of the present invention may comprise silicates.
• Silicate may act as a process aid to improve the processibility of the composition in production by giving the composition hardness.
• silicates examples include, but not limited to, sodium silicate, potassium silicate, magnesium silicate, calcium silicate or mixtures thereof.
• Sodium silicate is particularly preferred.
• An example is sodium silicate commercially available from Tianjin Sailicheng Technology Co., Ltd.
• the particles of the present invention comprise from 0.01 to 10% by weight of the silicates, more preferably from 0.05 to 5%, even more preferably from 0.1 to 3% and most preferably from 0.4 to 0.9% by weight of the silicates. It is not preferable to use a high level of silicates in the particles. More silicates may result in particles which are brittle and tended to break up into undesirable small pieces. Furthermore, the dissolution time of the particles in the laundry process may also be increased when a high level of silicates is present in the particles.
• the particles of the present invention comprise a disintegrant.
• Disintegrant refers to materials which are added to the particles to make them disintegrate and thus release the benefit agents upon contact with water.
• the particles of the present invention preferably comprise from 0.1 to 20% by weight of the disintegrant, more preferably from 0.5 to 15%, even more preferably 1 to 10%, more preferably still from 1 to 5%, and most preferably from 1.5 to 3% by weight of the disintegrant.
• the disintegrant is a non-effervescent disintegrant.
• suitable non-effervescent disintegrant include, but not limited to, polyvinylpyrrolidone, crospovidone (cross-linked polyvinylpyrrolidone), starch derivatives, cellulose, cellulose derivatives, clays (e.g. bentonite, alginates), gums (e.g., agar, Arabic, xanthan, guar, locust bean, karaya, pectin, tragacanth), non-carbonate salt (e.g. sodium chloride, potassium chloride, magnesium sulfate, calcium silicate, magnesium aluminum silicate) or mixtures thereof.
• non-carbonate salt e.g. sodium chloride, potassium chloride, magnesium sulfate, calcium silicate, magnesium aluminum silicate
• the disintegrant is a cellulose or a cellulose derivative.
• suitable cellulose derivatives include, but not limited to, methyl cellulose, ethyl cellulose, propyl cellulose, methyl ethyl cellulose, carboxymethyl cellulose, ethyl carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethyl hydroxyethyl cellulose, methyl hydroxyethyl cellulose, hydroxypropyl methyl cellulose, ethyl hydroxyethyl cellulose, methyl ethyl hydroxyethyl cellulose, calcium carboxymethyl cellulose, sodium carboxymethyl cellulose, microcrystalline cellulose, croscarmellose sodium (cross-linked sodium carboxymethyl cellulose) or mixtures thereof.
• the disintegrant is selected from calcium carboxymethyl cellulose, sodium carboxymethyl cellulose, microcrystalline cellulose, croscarmellose sodium and mixtures thereof.
• the disintegrant is a starch derivative, which is also known as modified starch.
• suitable starch derivatives include, but not limited to, sodium starch glycolate, carboxymethyl starch, sodium carboxymethyl starch, hydroxypropyl starch, pre-gelatinized starch or mixtures thereof.
• the disintegrant is selected from croscarmellose sodium (cross-linked sodium carboxymethyl cellulose), sodium carboxymethyl starch, sodium starch glycolate and mixtures thereof.
• Croscarmellose sodium is particularly preferred.
• Croscarmellose sodium is particularly preferred.
• An example is croscarmellose sodium commercially available under Anhuisunhere Pharmaceutical Excipients Co., Ltd.
• the particles of the present invention comprise from 0.1 to 20% by weight of croscarmellose sodium, more preferably from 0.5 to 15%, even more preferably from 1 to 10%, more preferably still from 1 to 5% and most preferably from 1.5 to 3% by weight of croscarmellose sodium.
• the disintegrant may be an effervescent disintegrant.
• Suitable effervescent disintegrant includes a carbonate salt and an acid.
• the acid is selected from an organic acid, a salt of organic acid, a salt of inorganic acid and mixtures thereof. More preferably the acid is organic acids.
• the organic acid suitable for use in the composition of the present invention can be any organic acid. Particularly good results were achieved with organic acids being polyacids (i.e. acids having more than one carboxylic acid group), and more particularly with di- or tricarboxylic organic acids.
• the organic acid used in the invention has a weight average molecular mass of at most 500 Dalton, more preferably of at most 400 Dalton and most preferably of at most 300 Dalton, the molecular mass being based on the free acid equivalent. In any case, preferably the organic acid is not a polymer-based acid.
• the organic acid employed in accordance with the invention preferably comprises 3 to 25 carbon atoms, more preferably 4 to 15 carbon atoms.
• the organic acids preferably are those which are also found naturally occurring, such as in plants.
• suitable organic acids include acetic acid, citric acid, aspartic acid, lactic acid, adipic acid, succinic acid, glutaric acid, gluconic acid, malic acid, tartaric acid, maleic acid, fumaric acid, saccharic acid, their salts or mixtures thereof.
• the organic acid is citric acid, succinic acid, their salts or a mixture thereof.
• the carbonate salt comprises sodium carbonate, sodium bicarbonate, sodium glycine carbonate, potassium carbonate, potassium bicarbonate, potassium glycine carbonate, calcium carbonate, calcium bicarbonate, magnesium carbonate or mixtures thereof. More preferably the carbonate salt comprises sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate or mixtures thereof. Most preferably the carbonate salt comprises sodium carbonate, sodium bicarbonate or mixtures thereof.
• the effervescent disintegrant is a combination of sodium bicarbonate, citric acid and succinic acid.
• the amount of carbonate salt is related to the amount of acid. More specifically it is desired that the weight ratio of the carbonate salt to the acid is from 1:10 to 10:1, more preferably from 1:5 to 5:1, even more preferably from 1:3 to 3:1.
• the particles of the invention may comprise a colourant.
• the colourant may be a dye or a pigment or a mixture thereof.
• the colourant has the purpose to impart colour to the particles, it is not intended to be a shading dye or to impart colour to the laundered fabrics.
• a single colourant or a mixture of colourants may be used.
• the colourant is a dye, more preferably a polymeric dye.
• suitable dyes include the LIQUITINET range of dyes ex Milliken Chemical.
• the particles of the present invention comprise 0.001 to 2%, more preferably 0.005 to 1%, most preferably 0.005 to 0.6% of by weight of the colourant.
• Water may be included to enhance the processibility of the composition in production.
• the particles comprise from 0.1 to 10% by weight of water, more preferably from 0.5 to 8% by weight of water, even more preferably from 1 to 6% by weight of water, and most preferably from 2% to 5% by weight of water.
• the particles preferably comprise more than about 40 percent by weight polyethylene glycol having a weight average molecular weight from about 2000 to about 13000.
• Polyethylene glycol (PEG) has a relatively low cost, may be formed into many different shapes and sizes, minimizes unencapsulated perfume diffusion, and dissolves well in water. PEG comes in various weight average molecular weights.
• a suitable weight average molecular weight range of PEG includes from about 2,000 to about 13,000, from about 4,000 to about 12,000, alternatively from about 5,000 to about 11,000, alternatively from about 6,000 to about 10,000, alternatively from about 7,000 to about 9,000, alternatively combinations thereof.
• PEG is available from BASF, for example PLURIOL E 8000.
• the particles preferably comprise more than about 40 percent by weight of the particles of PEG.
• the particles can comprise more than about 50 percent by weight of the particles of PEG.
• the particles can comprise more than about 60 percent by weight of the particles of PEG.
• the particles may comprise from about 65 percent to about 99 percent by weight of the composition of PEG.
• the particles may comprise from about 40 percent to about 99 percent by weight of the composition of PEG.
• the particles can comprise from about 40 percent to less than about 90 percent, alternatively from about 45 percent to about 75 percent, alternatively from about 50 percent to about 70 percent, alternatively combinations thereof and any whole percentages or ranges of whole percentages within any of the aforementioned ranges, of PEG by weight of the particles.
• the particles can comprise from about 0.5 percent to about 5 percent by weight of the particles of a balancing agent selected from the group consisting of glycerin, polypropylene glycol, isopropyl myristate, dipropylene glycol, 1,2 propanediol, PEG having a weight average molecular weight less than 2,000, and mixtures thereof.
• a balancing agent selected from the group consisting of glycerin, polypropylene glycol, isopropyl myristate, dipropylene glycol, 1,2 propanediol, PEG having a weight average molecular weight less than 2,000, and mixtures thereof.
• the particles can further comprise 0.1 percent to about 20 percent by weight perfume.
• the perfume can be unencapsulated perfume, encapsulated perfume, perfume provided by a perfume delivery technology, or a perfume provided in some other manner.
• Perfumes are generally described in U.S. Patent No. 7,186,680 at column 10, line 56, to column 25, line 22.
• the particles can comprise unencapsulated perfume and are essentially free of perfume carriers, such as a perfume microcapsules.
• the precursor material, and there by particles can comprise perfume carrier materials (and perfume contained therein). Examples of perfume carrier materials are described in U.S. Patent No. 7,186,680 , column 25, line 23, to column 31, line 7. Specific examples of perfume carrier materials may include cyclodextrin and zeolites.
• the particles can comprise about 0.1 percent to about 20 percent, alternatively about 1 percent to about 15 percent, alternatively 2 percent to about 10 percent, alternatively combinations thereof and any whole percentages within any of the aforementioned ranges, of perfume by weight of the precursor material or particles.
• the perfume can be unencapsulated perfume and or encapsulated perfume.
• the particle can be free or essentially free of a perfume carrier.
• the particles may comprise about 0.1 percent to about 20 percent, alternatively about 1 percent to about 15 percent, alternatively 2 percent to about 10 percent, alternatively combinations thereof and any whole percentages within any of the aforementioned ranges, of unencapsulated perfume by weight of the particles.
• the particles can comprise unencapsulated perfume and perfume microcapsules.
• the particles may comprise about 0.1 percent to about 20 percent, alternatively about 1 percent to about 15 percent, alternatively from about 2 percent to about 10 percent, alternatively combinations thereof and any whole percentages or ranges of whole percentages within any of the aforementioned ranges, of the unencapsulated perfume by weight of the particles.
• Such levels of unencapsulated perfume can be appropriate for any of the precursor materials 20, and thereby particles, disclosed herein that have unencapsulated perfume.
• the particles can comprise unencapsulated perfume and a perfume microcapsule but be free or essentially free of other perfume carriers.
• the particles can comprise unencapsulated perfume and perfume microcapsules and be free of other perfume carriers.
• the particles can comprise encapsulated perfume.
• Encapsulated perfume can be provided as plurality of perfume microcapsules.
• a perfume microcapsule is perfume oil enclosed within a shell.
• the shell can have an average shell thickness less than the maximum dimension of the perfume core.
• the perfume microcapsules can be friable perfume microcapsules.
• the perfume microcapsules can be moisture activated perfume microcapsules.
• the perfume microcapsules can comprise a melamine/formaldehyde shell.
• Perfume microcapsules may be obtained from Appleton, Quest International, or International Flavor and Fragrances, or other suitable source.
• the perfume microcapsule shell can be coated with polymer to enhance the ability of the perfume microcapsule to adhere to fabric. This can be desirable if the particles are designed to be a fabric treatment composition.
• the perfume microcapsules can be those described in U.S. Patent Pub. 2008/0305982 .
• the particles can comprise about 0.1 percent to about 20 percent, alternatively about 1 percent to about 15 percent, alternatively 2 percent to about 10 percent, alternatively combinations thereof and any whole percentages within any of the aforementioned ranges, of encapsulated perfume by weight of the precursor material, or particles.
• the particles can comprise perfume microcapsules but be free of or essentially free of unencapsulated perfume.
• the particles may comprise about 0.1 percent to about 20 percent, alternatively about 1 percent to about 15 percent, alternatively about 2 percent to about 10 percent, alternatively combinations thereof and any whole percentages within any of the aforementioned ranges, of encapsulated perfume by weight of the precursor material or particles.
• the precursor material can be prepared by providing molten PEG into the batch mixer. The batch mixer can be heated so as to help prepare the precursor material at the desired temperature. Perfume is added to the molten PEG. Dye, if present, can be added to the batch mixer. Other adjunct materials can be added to the precursor material if desired.
• the precursor material and particles may comprise dye.
• the particles may comprise less than about 0.1 percent, alternatively about 0.001 percent to about 0.1 percent, alternatively about 0.01 percent to about 0.02 percent, alternatively combinations thereof and any hundredths of percent or ranges of hundredths of percent within any of the aforementioned ranges, of dye by weight of the precursor material or particles.
• suitable dyes include, but are not limited to, LIQUITINT PINK AM, AQUA AS CYAN 15, and VIOLET FL, available from Milliken Chemical.
• the particles may have a variety of shapes.
• the particles may be formed into different shapes include tablets, pills, spheres, and the like.
• a particle can have a shape selected from the group consisting of spherical, hemispherical, compressed hemispherical, lentil shaped, and oblong.
• Lentil shaped refers to the shape of a lentil bean.
• Compressed hemispherical refers to a shape corresponding to a hemisphere that is at least partially flattened such that the curvature of the curved surface is less, on average, than the curvature of a hemisphere having the same radius.
• a compressed hemispherical particle can have a ratio of height to maximum based dimension of from about 0.01 to about 0.4, alternatively from about 0.1 to about 0.4, alternatively from about 0.2 to about 0.3.
• Oblong shaped refers to a shape having a maximum dimension and a maximum secondary dimension orthogonal to the maximum dimension, wherein the ratio of maximum dimension to the maximum secondary dimension is greater than about 1.2.
• An oblong shape can have a ratio of maximum base dimension to maximum minor base dimension greater than about 1.5.
• An oblong shape can have a ratio of maximum base dimension to maximum minor base dimension greater than about 2.
• Oblong shaped particles can have a maximum base dimension from about 2 mm to about 6 mm, a maximum minor base dimension of from about 2 mm to about 6 mm.
• Individual particles can have a mass from about 0.1 mg to about 5 g, alternatively from about 10 mg to about 1 g, alternatively from about 10 mg to about 500 mg, alternatively from about 10 mg to about 250 mg, alternatively from about 0.95 mg to about 125 mg, alternatively combinations thereof and any whole numbers or ranges of whole numbers of mg within any of the aforementioned ranges.
• individual particles can have a shape selected from the group consisting of spherical, hemispherical, compressed hemispherical, lentil shaped, and oblong.
• An individual particle may have a volume from about 0.003 cm 3 to about 0.15 cm 3 .
• a number of particles may collectively comprise a dose for dosing to a laundry washing machine or laundry wash basin.
• a single dose of the particles may comprise from about 1 g to about 27 g.
• a single dose of the particles may comprise from about 5 g to about 27 g, alternatively from about 13 g to about 27 g, alternatively from about 14 g to about 20 g, alternatively from about 15 g to about 19 g, alternatively from about 18 g to about 19 g, alternatively combinations thereof and any whole numbers of grams or ranges of whole numbers of grams within any of the aforementioned ranges.
• the individual particles forming the dose of particles that can make up the dose can have a mass from about 0.95 mg to about 2 g.
• the plurality of particles can be made up of particles having different size, shape, and/or mass.
• the particles in a dose can have a maximum dimension less than about 1 centimeter.
• the particle can have a substantially flat base and a height H.
• the height H of a particle is measured as the maximum extent of the particle in a direction orthogonal to the substantially flat base.
• the height H can be measured conveniently using image analysis software to analyze a profile view of the particle.
• the base can have a maximum base dimension MBD.
• the maximum base dimension MBD is the length of the maximum extent of the base in the plane of the base. If the base has the shape of an ellipse, the maximum base dimension MBD is the length of the major axis of the ellipse.
• the particles can be considered to have a major axis MA in line with the maximum base dimension MBD.
• the base can further have a maximum minor base dimension MMBD.
• the maximum minor base dimension MMBD is measured orthogonal to the major axis MA and in plane with the base.
• a packaged composition comprising a plurality of particles in a package is shown in Fig. 8.
• Substantially all of the particles in the package can have a substantially flat base and a height H measured orthogonal to the base and together the particles can have distribution of heights H, wherein the distribution of heights H has a mean height between about 1 mm and about 5 mm and a height H standard deviation of less than about 0.3.
• More than about 90 percent, or even more than about 95 percent, or even more than about 99 percent of the particles in the package can have a substantially flat base and a height H measured orthogonal to the base and together the particles can have distribution of heights H, wherein the distribution of heights H has a mean height between about 1 mm and about 5 mm and a height H standard deviation of less than about 0.3 or even less than about 0.2 or even less than about 0.15 or even less than about 0.13, any combinations of the fractions of particles in the package having a substantially flat base as set forth herein and the height H standard deviations set forth herein being contemplated.
• more than about 95 percent of the particles in the package can have a substantially flat base and a height H measured orthogonal to the base and together the particles can have distribution of heights H, wherein the distribution of heights H has a mean height between about 1 mm and about 5 mm and a height H standard deviation of less than about 0.15.
• Packages containing particles as described herein are thought to provide for relatively uniform fill heights amongst different packages having substantially the same filled weight.
• Substantially all of the particles in the package can have a substantially flat base and a maximum base dimension MBD and the particles together can have a distribution of maximum base dimensions MBD wherein the distribution of maximum base dimensions MBD can have a mean maximum base dimension MBD between about 2 mm and about 7 mm and a maximum base dimension MBD standard deviation less than about 0.5.
• Packages containing particles as such are thought to provide for relatively uniform fill heights amongst different packages having substantially the same filled weight.
• Substantially all of the particles in the package can have a substantially flat base and a maximum base dimension MBD and the particles together can have a distribution of maximum base dimensions MBD wherein the distribution of maximum base dimensions MBD can have a mean maximum base dimension MBD between about 2 mm and about 7 mm and a maximum base dimension MBD standard deviation less than about 0.3 or even less than about 0.25.
• Substantially all of the particles in the package can have a substantially flat base and have a major axis MA in line with the maximum base dimension MBD and maximum minor base dimension MMBD measured orthogonal to the major axis MA and in plane with the base. Together such particles can have a distribution of maximum minor base dimensions MMBD wherein the distribution of maximum minor base dimensions MMBD has a mean maximum minor base dimension MMBD standard deviation less than about 0.5 or even less than about 0.3 or even less than about 0.25. Packages containing particles as such are thought to provide for relatively uniform fill heights amongst different packages having approximately the same filled weight.
• Particles having one or more of a tight distribution of heights H, maximum base dimension MBD, and or maximum minor base dimensions MMBD, as disclosed herein, are thought to provide for packages containing particles that have relatively uniform fill heights amongst different packages having substantially the same filled weight.
• substantially all of the particles in the package can have a substantially flat base and a height H measured orthogonal to the base and together the particles can have distribution of heights H, wherein the distribution of heights H has a mean height between about 1 mm and about 5 mm and a height H standard deviation of less than about 0.3 and substantially all of the particles in the package can have a substantially flat base and a maximum base dimension MBD and the particles together can have a distribution of maximum base dimensions MBD wherein the distribution of maximum base dimensions MBD can have a mean maximum base dimension MBD between about 2 mm and about 7 mm and a maximum base dimension MBD standard deviation less than about 0.5.
• Substantially all or more than about 90 percent by weight or more than 95 percent by weight or more than 99 percent by weight can have a height H wherein the distribution of heights H has a mean height between about 1 mm and about 5 mm and a height H standard deviation of less than about 0.3 or less than about 0.2 or less than about 0.15 or less than about 0.13, a maximum base dimension MBD wherein the distribution of maximum base dimensions MBD has a mean maximum base dimension MBD between about 2 mm and about 7 mm and a maximum base dimension MBD standard deviation less than about 0.5 or less than about 0.3 or less than about 0.25, a maximum minor base dimension MMBD wherein the distribution of maximum minor base dimensions MMBD has a mean maximum minor base dimension MMBD between about 2 mm and about 7 mm and a maximum minor base dimension MMBD standard deviation less than about 0.5 or less than about 0.3 or less than about 0.25. Any combinations of the aforesaid ranges, and ranges within such ranges, for each property and other ranges disclosed
• substantially all of the particles in the package can have a substantially flat base and a height H measured orthogonal to the base and together the particles can have a distribution of heights H, wherein the distribution of heights H has a mean height between about 1 mm and about 5 mm and a height H standard deviation of less than about 0.3 and substantially all of the particles in the package can have a substantially flat base and a maximum base dimension MBD and the particles together can have a distribution of maximum base dimensions MBD wherein the distribution of maximum base dimensions MBD can have a mean maximum base dimension MBD between about 2 mm and about 7 mm and a maximum base dimension MBD standard deviation less than about 0.5 and substantially all of the particles in the package can have a substantially flat base and have a major axis MA in line with the maximum base dimension MBD and maximum minor base dimension MMBD measured orthogonal to the major axis MA and in plane with the base wherein the distribution of maximum minor base dimensions MMBD has a mean maximum minor base dimension MMBD between about 2 mm and about 7
• a 50 kg batch of precursor material was prepared in a mixer.
• Molten PEG8000 was added to a jacketed mixer held at 70 degrees centigrade and agitated with a pitch blade agitator at 125 rpm.
• Butylated hydroxy toluene was added to the mixer at a level of 0.01 by weight of the precursor material.
• Dipropylene glycol was added to the mixer at a level of 1.08 percent by weight of the precursor material.
• a water based slurry of perfume microcapsules was added to the mixer at a level of 4.04 percent by weight of the precursor material.
• Unencapsulated perfume was added to the mixer at a level of 7.50 percent by weight of the precursor material.
• Dye was added to the mixer at a level of 0.0095 percent by weight of the precursor material.
• the PEG accounted for 87.36 percent by weight of the precursor material.
• the precursor material was mixed for 30 minutes.
• the precursor material was formed into particles on a Sandvik Rotoform 3000 having a 750 mm wide 10 m long belt.
• the cylinder 110 had 2 mm diameter apertures 60 set at a 10 mm pitch in the cross machine direction CD and 9.35 mm pitch in the machine direction MD.
• the cylinder was set at approximately 3 mm above the belt.
• the belt speed and rotational speed of the cylinder 110 was set at 10 m/min.
• the particles of the present invention may be in any solid form, for example: powder, pellet, tablet, prill, pastille or extrudate.
• the particles are in the form of an extruded particle.
• each individual particle may be any shape or size suitable for dissolution in the laundry process.
• each individual particle has a mass of between 0.95 mg to 5 grams, more preferably 0.005 to 1 gram, even more preferably 0.005 to 0.5 gram and most preferably 0.01 to 0.1 gram.
• each individual particle has a maximum linear dimension in any direction of less than 10 mm, more preferably 1 to 8 mm and most preferably of 4 to 6 mm.
• each particle has a substantially flat base and a height perpendicular to the base.
• each particle has a maximum base dimension of less than 10 mm, more preferably 1 to 8 mm and most preferably of 4 to 6 mm.
• each particle has a height of from 0.05 to 5 mm, more preferably from 0.1 to 3 mm, and most preferably from 0.2 to 2.5 mm. It is preferred that each individual particle has a maximum base dimension of less than 10 mm and a height of from 0.05 to 5 mm.
• the shape of the particles may be selected from hemispherical, compressed hemispherical, lentil-shaped, oblong, cubical, rectangular, circular, cylindrical, disc, flower-shaped, star-shaped, petal-shaped, heart-shaped and mixtures thereof.
• the shape of the particles is selected from disc, flower-shaped, star-shaped, petal-shaped, heart-shaped and mixtures thereof, which can be more visually attractive to consumers.
• the particles of the present invention are formed using an extrusion apparatus.
• the extrusion apparatus may be a single screw extruder or a twin screw extruder, preferably a twin screw extruder having co-rotating or contra-rotating screws.
• the present invention also relates to a method of forming the particles comprising the steps of:
• the method is carried out at a temperature from 10 to 50°C, more preferably from 15 to 40°C and even more preferably from 20 to 30°C. It is preferred that the method is carried out at room temperature (25°C) and one atmospheric pressure.
• the mixture of step (i) is homogeneous.
• homogeneous it means that the mixture prior to extrusion has a uniform texture so that extrudates obtained from the mixture have an even quality.
• constituent ingredients of the composition include perfume microcapsules, it is preferred that the perfume microcapsules are added to the mixture as the last ingredient for mixing, which may reduce the breakage of perfume microcapsules during mixing.
• step (i) is extruded from the extruder through a die having an orifice with a predetermined diameter.
• the extruder is equipped with a cutter-knife allowing to cut the extrudate at the die exit to form particles.
• the desired height of the particles may be achieved by varying the speed that the extrudate is fed into the cutter and the rate at which the extrudate is cut.
• the drying step (iv) may be carried out before, during or after step (iii).
• the drying is carried out at room temperature (25°C), relative humidity (RH) ⁇ 50% and one atmospheric pressure, which may reduce the evaporative loss of benefit agents such as perfume.
• the method may comprise a step (v) of dusting the particles with an anti-caking agent.
• the anti-caking agent may be applied to the exterior surface of the particles to reduce the potential for particles to stick together.
• suitable anti-caking agent include, but not limited to, silica, zeolite, unmodified starch, cellulose, rock flour, clay, stearates of calcium and magnesium, silica, silicates, talc, flour, starch, tricalcium phosphate, powdered cellulose, sodium bicarbonate, sodium ferrocyanide, potassium ferrocyanide, calcium ferrocyanide, calcium phosphate, sodium silicate, calcium silicate, magnesium trisilicate, talcum powder, sodium aluminosilicate, potassium aluminum silicate, calcium aluminosilicate, bentonite, aluminum silicate, stearic acid, polydimethylsiloxane or mixtures thereof.
• the method does not require to heat up the mixture above a melting temperature to shape it into a desired form and cool it down again, which greatly simplifies the production process and reduces the loss of benefit agents such as perfume in production.
• the particles of the present invention may also be made using roller compacting.
• the constituent ingredients of the composition are introduced between two rollers and rolled under pressure between the two rollers to form a sheet of compactate.
• the sheet of compactate is broken up into small pieces by cutting. The small pieces can be further shaped into particles.
• the particles of the present invention are preferably homogeneously structured.
• homogeneously structured it is meant that there is a continuous phase throughout the particle. There is not a core and shell type structure.
• the constituent ingredients of the particles such as the benefit agents will be distributed or dispersed within the continuous phase.
• the benefit agent is perfume, it may improve the perfume stability against oxidation and evaporative loss during storage.
• the continuous phase is provided predominately by the carrier material.
• the particles of the present invention need to dissolve in a typically wash cycle time, preferably no more than 20 minutes, more preferably no more than 15 minutes, even more preferably no more than 10 minutes. If the dissolution rate of the particles is too slow, there may be un-dissolved residues formed from constituent ingredients of the particles remaining on the laundered fabrics when the wash is complete which is undesirable for consumers.
• the particles preferably have a dissolution rate of no less than 1 minutes, more preferably no less than 2 minutes, and even more preferably no less than 3 minutes. If the dissolution rate of the particles is too fast, most of the benefit agents may be released early and washed away before they can be delivered to laundered fabrics to provide various benefits.
• the particles Preferably have a dissolution rate from 1 minutes to 20 minutes, more preferably from 2 minutes to 15 minutes, even more preferably from 3 minutes to 10 minutes.
• the laundry liquid composition is described below.
• the anionic surfactant is preferably added to the detergent composition in the form of a salt.
• Preferred cations are alkali metal ions, such as sodium and potassium.
• the salt form of the anionic surfactant may be formed in situ by neutralization of the acid form of the surfactant with alkali such as sodium hydroxide or an amine, such as mono-, di-, or tri-ethanolamine. Weight ratios are calculated for the protonated form of the surfactant.
• Nonionic surfactant are discussed in Non-ionic Surfactants: Organic Chemistry edited by Nico M. van Os (Marcel Dekker 1998), Surfactant Science Series published by CRC press .
• the C16 alcohol ethoxylate surfactant comprises at least 2% wt. and more preferably, from 4% of the total C16 and C18 alcohol ethoxylate surfactant.
• the saturated C18 alcohol ethoxylate surfactant comprises up to 20% wt. and more preferably, up to 11% of the total C16 and C18 alcohol ethoxylate surfactant.
• the saturated C18 content is at least 2% wt. of the total C16 and C18 alcohol ethoxylate content.
• Linear saturated or mono-unsaturated C20 and C22 alcohol ethoxylate may also be present.
• the weight fraction of sum of 'C18 alcohol ethoxylate' /'C20 and C22 alcohol ethoxylate' is greater than 10.
• the C16/18 alcohol ethoxylate contains less than 15wt%, more preferably less than 8wt%, most preferably less than 5wt% of the alcohol ethoxylate polyunsaturated alcohol ethoxylates.
• a polyunsaturated alcohol ethoxylate contains a hydrocarbon chains with two or more double bonds.
• these narrower distribution catalysts involve a Group II base such as Ba dodecanoate; Group II metal alkoxides; Group II hyrodrotalcite as described in WO2007/147866 . Lanthanides may also be used.
• Group II base such as Ba dodecanoate
• Group II metal alkoxides Group II hyrodrotalcite as described in WO2007/147866 .
• Lanthanides may also be used.
• Such narrower distribution alcohol ethoxylates are available from Azo Nobel and Sasol.
• R 2 is selected from saturated, monounsaturated and polyunsaturated linear C16 and C18 alkyl chains and where p is from 3 to 20, preferably 4 to 12, more preferably 5 to 10.
• the mono-unsaturation is preferably in the 9 position of the chain, where the carbons are counted from the ethoxylate bound chain end.
• the double bond may be in a cis or trans configuration (oleyl or elaidyl), but is preferably cis.
• the proportion of monounsaturated C18 constitutes at least 60% wt., most preferably at least 75 of the total C16 and C18 alkyl ether sulphate surfactant.
• the C16 alcohol ethoxylate surfactant comprises at least 2% wt. and more preferably, from 4% of the total C16 and C18 alkyl ether sulphate surfactant.
• the saturated C18 content is at least 2% wt. of the total C16 and C18 alkyl ether sulphate content.
• the C16 and C18 ether sulfate contains less than 15 wt.%, more preferably less than 8 wt.%, most preferably less than 4wt% and most preferably less than 2% wt. of the ether sulfate polyunsaturated ether sulfate.
• a polyunsaturated ether sulfate contains a hydrocarbon chains with two or more double bonds.
• the ether sulfate weight is calculated as the protonated form: R 2 -O-(CH 2 CH 2 O) p SO 3 H.
• R 2 -O-(CH 2 CH 2 O) p SO 3 H In the formulation it will be present as the ionic form R 2 -O-(CH 2 CH 2 O) p SO 3 - with a corresponding counter ion, preferred counter ions are group I and II metals, amines, most preferably sodium.
• R 3 COO is a fatty acid moiety, such as oleic, stearic, palmitic.
• Fatty acid nomenclature is to describe the fatty acid by 2 numbers A:B where A is the number of carbons in the fatty acid and B is the number of double bonds it contains.
• A is the number of carbons in the fatty acid
• B is the number of double bonds it contains.
• oleic is 18:1
• stearic 18:0
• palmitic 16:0 The position of the double bond on the chain may be given in brackets, 18:1(9) for oleic, 18:2 (9,12) for linoleic where 9 if the number of carbons from the COOH end.
• n is the mole average number of ethoxylates.
• Methyl Ester Ethoxylates are described in chapter 8 of Biobased Surfactants (Second Edition) Synthesis, Properties, and Applications Pages 287-301 (AOCS press 2019) by G.A. Smith ; J.Am.Oil. Chem.Soc. vol 74 (1997) page 847-859 by Cox M.E. and Weerasooriva U ; Tenside Surf.Det. vol 28 (2001) page by 72-80 by Hreczuch et al; by C. Kolano. Household and Personal Care Today (2012) page 52-55 ; J.Am.Oil. Chem.Soc. vol 72 (1995) page 781-784 by A.Hama et al.
• MEE may be produced the reaction of methyl ester with ethylene oxide, using catalysts based on calcium or magnesium. The catalyst may be removed or left in the MEE.
• An alternative route to preparation is transesterification reaction of a methyl ester or esterification reaction of a carboxylic acid with a polyethylene glycol that is methyl terminated at one end of the chain.
• Triglycerides occur naturally in plant fats or oils, preferred sources are rapeseed oil, castor oil, maize oil, cottonseed oil, olive oil, palm oil, safflower oil, sesame oil, soybean oil, high steric/high oleic sunflower oil, high oleic sunflower oil, non-edible vegetable oils, tall oil and any mixture thereof and any derivative thereof.
• the oil from trees is called tall oil.
• Used food cooking oils may be utilised.
• Triglycerides may also be obtained from algae, fungi, yeast or bacteria. Plant sources are preferred.
• Distillation and fractionation process may be used in the production of the methyl ester or carboxylic acid to produce the desired carbon chain distribution.
• Preferred sources of triglyceride are those which contain less than 35%wt polyunsaturated fatty acids in the oil before distillation, fractionation, or hydrogenation.
• Fatty acid and methyl ester may be obtained from Oleochemical suppliers such as Wilmar, KLK Oleo, Unilever oleochemical Indonesia. Biodiesel is methyl ester and these sources may be used.
• ESB is MEE preferably has a mole average of from 8 to 30 ethoxylate groups (EO), more preferably from 10 to 20.
• the most preferred ethoxylate comprises 12 to 18EO.
• at least 10% wt., more preferably at least 30% wt. of the total C18:1 MEE in the composition has from 9 to 11EO, even more preferably at least 10wt% is exactly 10EO.
• at least 10 wt.% of the MEE should consist of ethoxylate with 9, 10 and 11 ethoxylate groups.
• the methyl ester ethoxylate preferably has a mole average of from 8 to 13 ethoxylate groups (EO).
• EO ethoxylate groups
• the most preferred ethoxylate has a mol average of from 9 to 11EO, even more preferably 10EO.
• the MEE has a mole average of 10EO then at least 10 wt.% of the MEE should consist of ethoxylate with 9, 10 and 11 ethoxylate groups.
• At least 40wt% of the total MEE in the composition is C18:1.
• the MEE component also comprises some C16 MEE.
• the total MEE component comprises from 5 to 50% wt. total MEE, C16 MEE.
• the C16 MEE is greater than 90wt%, more preferably greater than 95wt% C16:0.
• the total MEE component comprises less than 15% wt, more preferably less than 10wt%, most preferably less than 5wt% total MEE of polyunsaturated C18, i.e. C18:2 and C18:3.
• C18:3 is present at less than 1 wt%, more preferably less than 0.5wt%, most preferably essentially absent.
• the levels of polyunsaturation may be controlled by distillation, fractionation or partial hydrogenation of the raw materials (triglyceride or methyl ester) or of the MEE.
• the C18:0 component is less than 10wt% by weight of the total MEE present.
• the components with carbon chains of 15 or shorter comprise less than 4wt% by weight of the total MEE present.
• a particularly preferred MEE has 2 to 26 wt.% of the MEE C16:0 chains, 1 to 10 wt.% C18:0 chains, 50 to 85 wt.% C18:1 chains and 1 to 12 wt.% C18:2 chains.
• Preferred sources for the alkyl groups for the MEE include methyl ester derived from distilled palm oil and distilled high oleic methyl ester derived from palm kernel oil, partially hydrogenated methyl ester of low euric rapeseed oil, methyl ester of high oleic sunflower oil, methyl ester of high oleic safflower oil and methyl ester of high oleic soybean oil.
• High Oleic oils are available from DuPont (Plenish high oleice soybean oil), Monsanto (Visitive Gold Soybean oil), Dow (Omega-9 Canola oil, Omega-9 sunflower oil), the National Sunflower Association and Oilseeds International.
• the double bonds in the MEE are greater than 80wt% in the cis configuration.
• the 18:1 component is oleic.
• the 18:2 component is linoleic.
• the methyl group of the methyl ester may be replace by an ethyl or propyl group. Methyl is most preferred.
• the methyl ester ethoxylate comprises from 0.1 to 95% wt. of the composition methyl ester ethoxylate. More preferably the composition comprises from 2 to 40% MEE and most preferably from 4 to 30% wt. MEE.
• the composition comprises at least 50% wt. water but this depends on the level of total surfactant and is adjusted accordingly.
• the methyl ester ethoxylate surfactant is used in combination with anionic surfactant.
• the weight fraction of methyl ester ethoxylate surfactant/total anionic surfactant is from 0.1 to 9, more preferably 0.15 to 2, most preferably 0.2 to 1.
• total anionic surfactant means the total content of any of the classes of anionic surfactant preferably ether sulfates, linear alkyl benzene sulfonates, alkyl ether carboxylates, alkyl sulfates, rhamnolipids and mixtures thereof.
• Anionic surfactant weights are calculated as the protonated form.
• the alkyl chain of C16/18 surfactant is preferably obtained from a renewable source, preferably from a triglyceride.
• a renewable source is one where the material is produced by natural ecological cycle of a living species, preferably by a plant, algae, fungi, yeast or bacteria, more preferably plants, algae or yeasts.
• Preferred plant sources of oils are rapeseed, sunflower, maze, soy, cottonseed, olive oil and trees.
• the oil from trees is called tall oil.
• Palm and Rapeseed oils are the source.
• Algal oils are discussed in Energy Environ. Sci., 2019,12, 2717 A sustainable, high-performance process for the economic production of waste-free microbial oils that can replace plant-based equivalents by Masri M.A. et al.
• Non edible plant oils may be used and are preferably selected from the fruit and seeds of Jatropha curcas, Calophyllum inophyllum, Sterculia feotida, Madhuca indica (mahua), Pongamia glabra (koroch seed), Linseed, Pongamia pinnata (karanja), Hevea brasiliensis (Rubber seed), Azadirachta indica (neem), Camelina sativa, Lesquerella fendleri, Nicotiana tabacum (tobacco), Deccan hemp, Ricinus communis L.(castor), Simmondsia chinensis (Jojoba), Eruca sativa.
• SLES and other such alkali metal alkyl ether sulphate anionic surfactants are typically obtainable by sulphating alcohol ethoxylates. These alcohol ethoxylates are typically obtainable by ethoxylating linear alcohols.
• primary alkyl sulphate surfactants (PAS) can be obtained from linear alcohols directly by sulphating the linear alcohol. Accordingly, forming the linear alcohol is a central step in obtaining both PAS and alkalimetal alkyl ether sulphate surfactants.
• linear alcohols which are suitable as an intermediate step in the manufacture of alcohol ethoxylates and therefore anionic surfactants such as sodium lauryl ether sulphate ca be obtained from many different sustainable sources. These include:
• Primary sugars are obtained from cane sugar or sugar beet, etc., and may be fermented to form bioethanol.
• the bioethanol is then dehydrated to form bio-ethylene which then undergoes olefin methathesis to form alkenes.
• These alkenes are then processed into linear alcohols either by hydroformylation or oxidation.
• An alternative process also using primary sugars to form linear alcohols can be used and where the primary sugar undergoes microbial conversion by algae to form triglycerides.
• triglycerides are then hydrolysed to linear fatty acids and which are then reduced to form the linear alcohols.
• Biomass for example forestry products, rice husks and straw to name a few may be processed into syngas by gasification. Through a Fischer Tropsch reaction these are processed into alkanes, which in turn are dehydrogenated to form olefins. These olefins may be processed in the same manner as the alkenes described above [primary sugars].
• An alternative process turns the same biomass into polysaccharides by steam explosion which may be enzymatically degraded into secondary sugars. These secondary sugars are then fermented to form bioethanol which in turn is dehydrated to form bio-ethylene. This bio-ethylene is then processed into linear alcohols as described above [primary sugars].
• Waste plastic is pyrolyzed to form pyrolysed oils. This is then fractioned to form linear alkanes which are dehydrogenated to form alkenes. These alkenes are processed as described above [primary sugars].
• the pyrolyzed oils are cracked to form ethylene which is then processed to form the required alkenes by olefin metathesis. These are then processed into linear alcohols as described above [primary sugars].
• MSW is turned into syngas by gasification. From syngas it may be processed as described above [primary sugars] or it may be turned into ethanol by enzymatic processes before being dehydrogenated into ethylene. The ethylene may then be turned into linear alcohols by the Ziegler Process.
• the MSW may also be turned into pyrolysis oil by gasification and then fractioned to form alkanes. These alkanes are then dehydrogenated to form olefins and then linear alcohols.
• the raw material can be separated into polysaccharides which are enzymatically degraded to form secondary sugars. These may be fermented to form bioethanol and then processed as described above [Primary Sugars].
• Waste oils such as used cooking oil can be physically separated into the triglycerides which are split to form linear fatty acids and then linear alcohols as described above.
• the used cooking oil may be subjected to the Neste Process whereby the oil is catalytically cracked to form bio-ethylene. This is then processed as described above.
• Methane capture methods capture methane from landfill sites or from fossil fuel production.
• the methane may be formed into syngas by gasification.
• the syngas may be processed as described above whereby the syngas is turned into methanol ( Fischer Tropsch reaction) and then olefins before being turned into linear alcohols by hydroformylation oxidation.
• the syngas may be turned into alkanes and then olefins by Fischer Tropsch and then dehydrogenation.
• Carbon dioxide may be captured by any of a variety of processes which are all well known.
• the carbon dioxide may be turned into carbon monoxide by a reverse water gas shift reaction and which in turn may be turned into syngas using hydrogen gas in an electrolytic reaction.
• the syngas is then processed as described above and is either turned into methanol and/or alkanes before being reacted to form olefins.
• the captured carbon dioxide is mixed with hydrogen gas before being enzymatically processed to form ethanol.
• This is a process which has been developed by Lanzatech. From here the ethanol is turned into ethylene and then processed into olefins and then linear alcohols as described above.
• the above processes may also be used to obtain the C16/18 chains of the C16/18 alcohol ethoxylate and/or the C16/18 ether sulfates.
• LAS linear alkyl benzene sulphonate
• alkenes may be produced by any of the methods described above and may be formed from primary sugars, biomass, waste plastic, MSW, carbon capture, methane capture, marine carbon to name a few.
• the olefin is processed to form linear alcohols by hydroformylation and oxidation instead, the olefin is reacted with benzene and then sulphonate to form the LAS.
• Commercial LAS is a mixture of closely related isomers and homologues alkyl chain homologues, each containing an aromatic ring sulfonated at the "para" position and attached to a linear alkyl chain at any position except the terminal carbons.
• the linear alkyl chain preferably has a chain length of from 11 to 15 carbon atoms, with the predominant materials having a chain length of about C12.
• Each alkyl chain homologue consists of a mixture of all the possible sulfophenyl isomers except for the 1-phenyl isomer.
• LAS is normally formulated into compositions in acid (i.e.
• HLAS HLAS
• linear alkyl benzene sulphonate surfactant is present at from 1 to 20% wt., more preferably from 2 to 15% wt. of the composition, most preferably 8 to 12 wt.%.
• the liquid composition comprises an aminocarboxylate sequestrant.
• the aminocarboxylate sequestrant is selected from GLDA and MGDA.
• the aminocarboxylate is present in the composition at from 0.1 to 15%wt., more preferably 0.1 to 10% wt., even more preferably 0.3 to 5 % wt., still more preferably 0.8 to 3% wt., and most preferably 1 to 2.5 % wt. (by weight of the composition).
• GLDA may be present as a salt or a mixture of GDLA and a GDLA salt.
• Preferred salt forms include mono-, di-, tri- or tetraalkali metal and mono-, di-, tri- or tetraammonium salts of GLDA.
• Alkali metal salts of glutamic acid diacetic acid GDLA are preferably selected from lithium salts, potassium salts and more preferably sodium salts of GLDA.
• Glutamic acid diacetic acid can be partially or preferably fully neutralized with the respective alkali.
• an average of from 3.5 to 4 COOH groups of GLDA is neutralized with alkali metal, preferably with sodium.
• the composition comprises a tetrasodium salt of GLDA.
• GLDA is at least partially neutralized with alkali metal, more preferably with sodium or potassium, most preferred with sodium.
• the GLDA salt may be an alkali metal salt of L-GLDA, an alkali metal salt of D-GLDA, or enantiomerically enriched mixtures of isomers.
• the composition comprises a mixture of L- and D- enantiomers of glutamic acid diacetic acid (GLDA) or its respective mono-, di-, tri-, or tetraalkali metal or mono-, di-, tri- or tetraammonium salt or mixtures thereof, said mixtures containing predominantly the respective L-isomer with an enantiomeric excess in the range of from 10 to 95%.
• GLDA glutamic acid diacetic acid
• the GLDA salt is essentially L-glutamic acid diacetic acid that is at least partially neutralized with alkali metal.
• Sodium salts of GLDA are preferred.
• a suitable commercial source of GLDA in the form of the tetrasodium salt is DISSOLVINE ® GL available from Nouryon.
• the GLDA is present in the composition at from 0.1 to 15% wt., more preferably 0.1 to 10% wt., even more preferably 0.3 to 5 % wt., still more preferably 0.8 to 3% wt., and most preferably 1 to 2.5 % wt. (by weight of the composition).
• Preferred salt forms include mono-, di-, tri- or tetraalkali metal and mono-, di-, tri- or tetraammonium salts of MGDA.
• Alkali metal salts are preferably selected from lithium salts, potassium salts and more preferably sodium salts of MGDA.
• the sodium salt of methyl glycine diacetic acid is preferred. Especially preferred is the trisodium salt of MGDA.
• MGDA can be partially or preferably fully neutralized with the respective alkali metal.
• an average of from 2.7 to 3 COOH groups per molecule of MGDA is neutralized with alkali metal, preferably with sodium.
• MGDA can be selected from racemic mixtures of alkali metal salts of MGDA and of the pure enantiomers such as alkali metal salts of L-MGDA, alkali metal salts of D-MGDA and of mixtures of enantiomerically enriched isomers.
• Suitable commercial sources of MGDA in the form of the trisodium salt are TRILONO M available from BASF and Dissolvine ® M-40 from Nouryon.
• the MGDA is present in the composition at from 0.1 to 15%wt., more preferably 0.1 to 10% wt., even more preferably 0.3 to 5 % wt., still more preferably 0.8 to 3% wt., and most preferably 1 to 2.5 % wt. (by weight of the composition).
• Minor amounts of the aminocarboxylate may bear a cation other than alkali metal. It is thus possible that minor amounts, such as 0.01 to 5 mol-% bear alkali earth metal cations such as Mg2+ or Ca2+, or an Fe(ll) or Fe(lll) cation.
• GLDA may contain minor amounts of impurities stemming from its synthesis, such as lactic acid, alanine, propionic acid or the like.
• “Minor amounts” in this context refer to a total of 0.1 to 1% by weight, referring to sequestering agent aminocarboxylate.
• the liquid composition preferably comprises an organic acid.
• the organic acid has the general structure R-CH(OH)-COOH where R is a linear C1-C5, more preferably C2-C4, most preferably C4 alky group.
• At least two, more preferably all carbon atoms in the linear C1-4 are substituted with an OH group.
• R comprises a terminal COOH group.
• Preferred examples are lactic acid, tartaric acid, gluconic acid, mucic acid, glucoheptonic acid. Most preferably the organic acid is gluconic acid.
• the organic acid may be in their D or L form.
• Gluconic acid can be selected from racemic mixtures of salts of gluconic acid (gluconates) and of the pure enantiomers such as alkali metal salts of L-gluconic acid, alkali metal salts of D-gluconic acid and of mixtures of enantiomerically enriched isomers. D-isomeric forms are preferred.
• the organic acid is present in the range of from 0.1 to 15%wt, more preferably 0.1 to 10wt%, even more preferably 0.2 to 4%wt, still more preferably 0.5 to 3 %wt., and most preferably 0.8 to 2%wt (by weight of the composition). Measured with regard to its protonated form.
• the composition comprises GLDA and/or MGDA and gluconic acid, more preferably GLDA and gluconic acid.
• the liquid composition preferably comprises a crystallizable glyceride.
• the crystallizable glyceride is useful in forming an external structuring system as described in WO2011/031940 , the contents of which, in particular as regards manufacture of the ESS are incorporated by reference.
• the ESS of the present invention preferably comprises: (a) crystallizable glyceride(s); (b) alkanolamine; (c) anionic surfactant; (d) additional components; and (e) optional components. Each of these components is discussed in detail below.
• Crystallizable glyceride(s) of use herein preferably include "Hydrogenated castor oil” or "HCO".
• HCO as used herein most generally can be any hydrogenated castor oil, provided that it is capable of crystallizing in the ESS premix.
• Castor oils may include glycerides, especially triglycerides, comprising C10 to C22 alkyl or alkenyl moieties which incorporate a hydroxyl group. Hydrogenation of castor oil to make HCO converts double bonds, which may be present in the starting oil as ricinoleyl moieties, to convert ricinoleyl moieties to saturated hydroxyalkyl moieties, e.g., hydroxystearyl.
• the HCO herein may, in some embodiments, be selected from: trihydroxystearin; dihydroxystearin; and mixtures thereof.
• the HCO may be processed in any suitable starting form, including, but not limited those selected from solid, molten and mixtures thereof.
• HCO is typically present in the ESS of the present invention at a level of from about 2 percent to about 10 percent, from about 3 percent to about 8 percent, or from about 4 percent to about 6 percent by weight of the structuring system.
• the corresponding percentage of hydrogenated castor oil delivered into a finished laundry detergent product is below about 1.0 percent, typically from 0.1 percent to 0.8 percent.
• Useful HCO may have the following characteristics: a melting point of from about 40 degrees centigrade to about 100 degrees centigrade, or from about 65 degrees centigrade to about 95 degrees C; and/or Iodine value ranges of from 0 to about 5, from 0 to about 4, or from 0 to about 2.6.
• the melting point of HCO can measured using either ASTM D3418 or ISO 11357; both tests utilize DSC: Differential Scanning Calorimetry.
• HCO of use in the present invention includes those that are commercially available. Non-limiting examples of commercially available HCO of use in the present invention include: THIXCIN(R) from Rheox, Inc. Further examples of useful HCO may be found in U.S. Patent 5,340,390 .
• the source of the castor oil for hydrogenation to form HCO can be of any suitable origin, such as from Brazil or India.
• castor oil is hydrogenated using a precious metal, e.g., palladium catalyst, and the hydrogenation temperature and pressure are controlled to optimize hydrogenation of the double bonds of the native castor oil while avoiding unacceptable levels of dehydroxylation.
• the invention is not intended to be directed only to the use of hydrogenated castor oil.
• Any other suitable crystallizable glyceride(s) may be used.
• the structurant is substantially pure triglyceride of 12-hydroxystearic acid. This molecule represents the pure form of a fully hydrogenated triglyceride of 12-hydrox-9-cis-octadecenoic acid.
• the composition of castor oil is rather constant, but may vary somewhat. Likewise hydrogenation procedures may vary.
• Any other suitable equivalent materials, such as mixtures of triglycerides wherein at least 80 percent wt. is from castor oil, may be used.
• Exemplary equivalent materials comprise primarily, or consist essentially of, triglycerides; or comprise primarily, or consist essentially of, mixtures of diglycerides and triglycerides; or comprise primarily, or consist essentially of, mixtures of triglyerides with diglycerides and limited amounts, e.g., less than about 20 percent wt. of the glyceride mixtures, of monoglyerides; or comprise primarily, or consist essentially of, any of the foregoing glycerides with limited amounts, e.g., less than about 20 percent wt., of the corresponding acid hydrolysis product of any of said glycerides.
• a proviso in the above is that the major proportion, typically at least 80 percent wt, of any of said glycerides is chemically identical to glyceride of fully hydrogenated ricinoleic acid, i.e., glyceride of 12- hydroxystearic acid. It is for example well known in the art to modify hydrogenated castor oil such that in a given triglyceride, there will be two 12-hydroxystearic- moieties and one stearic moiety. Likewise it is envisioned that the hydrogenated castor oil may not be fully hydrogenated. In contrast, the invention excludes poly(oxyalkylated) castor oils when these fail the melting criteria.
• Crystallizable glyceride(s) of use in the present invention may have a melting point of from about 40 degrees centigrade to about 100 degrees centigrade.
• fatty acid is present at from 4 to 20% wt. of the composition (as measured with reference to the acid added to the composition), more preferably from 5 to 12% wt. and most preferably 6 to 8% wt.
• Suitable fatty acids in the context of this invention include aliphatic carboxylic acids of formula RCOOH, where R is a linear or branched alkyl or alkenyl chain containing from 6 to 24, more preferably 10 to 22, most preferably from 12 to 18 carbon atoms and 0 or 1 double bond.
• R is a linear or branched alkyl or alkenyl chain containing from 6 to 24, more preferably 10 to 22, most preferably from 12 to 18 carbon atoms and 0 or 1 double bond.
• saturated C12-18 fatty acids such as lauric acid, myristic acid, palmitic acid or stearic acid
• fatty acid mixtures in which 50 to 100% (by weight based on the total weight of the mixture) consists of saturated C12-18 fatty acids.
• Such mixtures may typically be derived from natural fats and/or optionally hydrogenated natural oils (such as coconut oil, palm kernel oil or tallow).
• the fatty acids may be present in the form of their sodium, potassium or ammonium salts and/or in the form of soluble salts of organic bases, such as mono-, di- or triethanolamine.
• fatty acids and/or their salts are not included in the level of surfactant or in the level of builder.
• the liquid detergent compositions may also preferably comprise a sequestrant material.
• a sequestrant material examples include the alkali metal citrates, succinates, malonates, carboxymethyl succinates, carboxylates, polycarboxylates and polyacetyl carboxylates. Specific examples include sodium, potassium and lithium salts of oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids, and citric acid.
• Other examples are DEQUEST TM , organic phosphonate type sequestering agents sold by Monsanto and alkanehydroxy phosphonates.
• a preferred sequestrant is Dequest(R) 2066 (Diethylenetriamine penta(methylene phosphonic acid or Heptasodium DTPMP).
• HEDP 1-Hydroxyethylidene-1,1,-diphosphonic acid
• composition comprises fatty acid and sequestrant.
• composition according to the invention is a low aqueous composition.
• the composition comprises less than 15% wt. water, more preferably less than 10% wt. water.
• the composition comprises an alkoxylated cationic or zwitterionic di or polyamine polymer, wherein the positive charge is provided by quaternisation of the nitrogen atoms of the amines, and the anionic groups (where present) by sulphation or sulphonation of the alkoxylated group.
• the alkoxylate is selected from propoxy and ethoxy, most preferably ethoxy.
• nitrogen amines are quaternised, preferably with a methyl group.
• the polymer contains 3 to 10, more preferably 3 to 6, most preferably 3 to 5 quaternised nitrogen amines.
• the alkoxylate groups are selected from ethoxy and propoxy groups, most preferably ethoxy.
• the polymer contains ester (COO) or acid amide (CONH) groups within the structure, preferably these groups are placed, so that when all the ester or acid amide groups are hydrolysed, at least one, preferably all of the hydrolysed fragments has a molecular weight of less than 4000, preferably less than 2000, most preferably less than 1000.
• the polymer is of the form:
• R 1 is a C3 to C8 alkyl group
• X is an a (C2H4O)nY group where n is from 15 to 30, where m is from 2 to 10, preferably 2, 3, 4 or 5 and where Y is selected from OH and SO 3 - and preferably the number of SO 3 - groups is greater than the number of OH groups. Preferably there are from 0, 1 or 2 OH groups.
• X and R 1 may contain ester groups within them.
• X may contain a carbonyl group, preferably an ester group.
• Such polymers are described in WO2021239547 (Unilever ), An example polymer is sulphated ethoxylated hexamethylene diamine and examples P1, P2, P3, P4, P5 and P6 of WO2021239547 . Ester groups may be included using lactones or sodium chloroacetate (Modified Williamson synthesis), addition to an OH or NH group, then subsequent ethoxylation.
• Soil release polymers help to improve the detachment of soils from fabric by modifying the fabric surface during washing.
• the adsorption of a SRP over the fabric surface is promoted by an affinity between the chemical structure of the SRP and the target fibre.
• SRPs for use in the invention may include a variety of charged (e.g. anionic) as well as non-charged monomer units and structures may be linear, branched or star-shaped.
• the SRP structure may also include capping groups to control molecular weight or to alter polymer properties such as surface activity.
• the weight average molecular weight (M w ) of the SRP may suitably range from about 1000 to about 20,000 and preferably ranges from about 1500 to about 10,000.
• SRPs for use in the invention may suitably be selected from copolyesters of dicarboxylic acids (for example adipic acid, phthalic acid or terephthalic acid), diols (for example ethylene glycol or propylene glycol) and polydiols (for example polyethylene glycol or polypropylene glycol).
• the copolyester may also include monomeric units substituted with anionic groups, such as for example sulfonated isophthaloyl units.
• oligomeric esters produced by transesterification/oligomerization of poly(ethyleneglycol) methyl ether, dimethyl terephthalate (“DMT”), propylene glycol (“PG”) and poly(ethyleneglycol) (“PEG”); partly- and fully-anionic-endcapped oligomeric esters such as oligomers from ethylene glycol ("EG”), PG, DMT and Na-3,6-dioxa-8-hydroxyoctanesulfonate; non-ionic-capped block polyester oligomeric compounds such as those produced from DMT, Me-capped PEG and EG and/or PG, or a combination of DMT, EG and/or PG, Me-capped PEG and Na-dimethyl-5-sulfoisophthalate, and copolymeric blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate.
• DMT dimethyl terephthalate
• PG propylene glyco
• cellulosic derivatives such as hydroxyether cellulosic polymers, C 1 -C 4 alkylcelluloses and C 4 hydroxyalkyl celluloses
• Preferred SRPs for use in the invention include copolyesters formed by condensation of terephthalic acid ester and diol, preferably 1,2 propanediol, and further comprising an end cap formed from repeat units of alkylene oxide capped with an alkyl group. Examples of such materials have a structure corresponding to general formula (I):
• n, n and a are not necessarily whole numbers for the polymer in bulk.
• the overall level of SRP when included, may range from 0.1 to 10%, depending on the level of polymer intended for use in the final diluted composition and which is desirably from 0.3 to 7%, more preferably from 0.5 to 5% (by weight based on the total weight of the diluted composition).
• Suitable soil release polymers are described in greater detail in U. S. Patent Nos. 5,574,179 ; 4,956,447 ; 4,861,512 ; 4,702,857 , WO 2007/079850 and WO2016/005271 . If employed, soil release polymers will typically be incorporated into the liquid laundry detergent compositions herein in concentrations ranging from 0.01 percent to 10 percent, more preferably from 0.1 percent to 5 percent, by weight of the composition.
• a composition of the invention may incorporate non-aqueous carriers such as hydrotropes, cosolvents and phase stabilizers.
• non-aqueous carriers such as hydrotropes, cosolvents and phase stabilizers.
• Such materials are typically low molecular weight, water-soluble or water-miscible organic liquids such as C1 to C5 monohydric alcohols (such as ethanol and n- or i-propanol); C2 to C6 diols (such as monopropylene glycol and dipropylene glycol); C3 to C9 triols (such as glycerol); polyethylene glycols having a weight average molecular weight (M w ) ranging from about 200 to 600; C1 to C3 alkanolamines such as mono-, di- and triethanolamines; and alkyl aryl sulfonates having up to 3 carbon atoms in the lower alkyl group (such as the sodium and potassium xylene, toluene, eth
• Non-aqueous carriers are preferably included, may be present in an amount ranging from 1 to 50%, preferably from 10 to 30%, and more preferably from 15 to 25% (by weight based on the total weight of the composition).
• the level of hydrotrope used is linked to the level of surfactant and it is desirable to use hydrotrope level to manage the viscosity in such compositions.
• the preferred hydrotropes are monopropylene glycol and glycerol.
• a liquid composition of the invention may contain one or more cosurfactants (such as amphoteric (zwitterionic) and/or cationic surfactants) in addition to the non-soap anionic and/or nonionic detersive surfactants described above.
• cosurfactants such as amphoteric (zwitterionic) and/or cationic surfactants
• Specific cationic surfactants include C8 to C18 alkyl dimethyl ammonium halides and derivatives thereof in which one or two hydroxyethyl groups replace one or two of the methyl groups, and mixtures thereof.
• Cationic surfactant when included, may be present in an amount ranging from 0.1 to 5% (by weight based on the total weight of the composition).
• amphoteric (zwitterionic) surfactants include alkyl amine oxides, alkyl betaines, alkyl amidopropyl betaines, alkyl sulfobetaines (sultaines), alkyl glycinates, alkyl carboxyglycinates, alkyl amphoacetates, alkyl amphopropionates, alkylamphoglycinates, alkyl amidopropyl hydroxysultaines, acyl taurates and acyl glutamates, having alkyl radicals containing from about 8 to about 22 carbon atoms preferably selected from C12, C14, C16 ,C18 and C18:1, the term "alkyl” being used to include the alkyl portion of higher acyl radicals.
• Amphoteric (zwitterionic) surfactant, when included, may be present in an amount ranging from 0.1 to 5% (by weight based on the total weight of the composition).
• fluorescer in the liquid compositions.
• these fluorescent agents are supplied and used in the form of their alkali metal salts, for example, the sodium salts.
• the total amount of the fluorescent agent or agents used in the composition is generally from 0.005 to 2 wt %, more preferably 0.01 to 0.5 wt % the composition.
• Preferred classes of fluorescer are: Di-styryl biphenyl compounds, e.g. Tinopal ® CBS-X, Di-amine stilbene di-sulphonic acid compounds, e.g. Tinopal DMS pure Xtra, Tinopal 5BMGX, and Blankophor ® HRH, and Pyrazoline compounds, e.g. Blankophor SN.
• Di-styryl biphenyl compounds e.g. Tinopal ® CBS-X
• Di-amine stilbene di-sulphonic acid compounds e.g. Tinopal DMS pure Xtra, Tinopal 5BMGX, and Blankophor ® HRH
• Pyrazoline compounds e.g. Blankophor SN.
• Preferred fluorescers are: sodium 2 (4-styryl-3-sulfophenyl)-2H-napthol[1,2-d]triazole, disodium 4,4'-bis ⁇ [(4-anilino-6-(N methyl-N-2 hydroxyethyl) amino 1,3,5-triazin-2-yl)]amino ⁇ stilbene-2-2' disulfonate, disodium 4,4'-bis ⁇ [(4-anilino-6-morpholino-1,3,5-triazin-2-yl)]amino ⁇ stilbene-2-2' disulfonate, and disodium 4,4'-bis(2-sulfoslyryl)biphenyl.
• the fluoescer is a di-styryl biphenyl compound, preferably sodium 2,2'-([1,1'-biphenyl]-4,4'-diylbis(ethene-2,1-diyl))dibenzenesulfonate ( CAS-No 27344-41-8 ).
• Shading dye can be used to improve the performance of the liquid compositions.
• Preferred dyes are violet or blue. It is believed that the deposition on fabrics of a low level of a dye of these shades, masks yellowing of fabrics.
• a further advantage of shading dyes is that they can be used to mask any yellow tint in the composition itself.
• Shading dyes are well known in the art of laundry liquid formulation.
• Suitable and preferred classes of dyes include direct dyes, acid dyes, hydrophobic dyes, basic dyes, reactive dyes and dye conjugates.
• Preferred examples are Disperse Violet 28, Acid Violet 50, anthraquinone dyes covalently bound to ethoxylate or propoxylated polyethylene imine as described in WO2011/047987 and WO 2012/119859 alkoxylated mono-azo thiophenes, dye with CAS-No 72749-80-5 , acid blue 59, and the phenazine dye selected from: wherein:
• the shading dye is preferably present in the composition in range from 0.0001 to 0.1wt %. Depending upon the nature of the shading dye there are preferred ranges depending upon the efficacy of the shading dye which is dependent on class and particular efficacy within any particular class.
• Liquid compositions of the invention may have their rheology further modified by use of one or more external structurants which form a structuring network within the composition.
• external structurants include crystallizable glycerides such as hydrogenated castor oil; microfibrous cellulose and citrus pulp fibre.
• crystallizable glycerides such as hydrogenated castor oil; microfibrous cellulose and citrus pulp fibre.
• the presence of an external structurant may provide shear thinning rheology and may also enable materials such as encapsulates and visual cues to be suspended stably in the liquid.
• the composition preferably comprises a crystallizable glyceride.
• the crystallizable glyceride is useful in forming an external structuring system as described in WO2011/031940 , the contents of which, in particular as regards manufacture of the ESS are incorporated by reference.
• the ESS of the present invention preferably comprises: (a) crystallizable glyceride(s); (b) alkanolamine; (c) anionic surfactant; (d) additional components; and (e) optional components. Each of these components is discussed in detail below.
• Crystallizable glyceride(s) of use herein preferably include "Hydrogenated castor oil" or "HCO".
• HCO as used herein most generally can be any hydrogenated castor oil, provided that it is capable of crystallizing in the ESS premix.
• Castor oils may include glycerides, especially triglycerides, comprising C10 to C22 alkyl or alkenyl moieties which incorporate a hydroxyl group.
• Hydrogenation of castor oil to make HCO converts double bonds, which may be present in the starting oil as ricinoleyl moieties, to convert ricinoleyl moieties to saturated hydroxyalkyl moieties, e.g., hydroxystearyl.
• the HCO herein may, in some embodiments, be selected from: trihydroxystearin; dihydroxystearin; and mixtures thereof.
• the HCO may be processed in any suitable starting form, including, but not limited those selected from solid, molten and mixtures thereof.
• HCO is typically present in the ESS of the present invention at a level of from about 2 percent to about 10 percent, from about 3 percent to about 8 percent, or from about 4 percent to about 6 percent by weight of the structuring system.
• the corresponding percentage of hydrogenated castor oil delivered into a finished laundry detergent product is below about 1.0 percent, typically from 0.1 percent to 0.8 percent.
• Useful HCO may have the following characteristics: a melting point of from about 40 degrees centigrade to about 100 degrees centigrade, or from about 65 degrees centigrade to about 95 degrees C; and/or Iodine value ranges of from 0 to about 5, from 0 to about 4, or from 0 to about 2.6.
• the melting point of HCO can measured using either ASTM D3418 or ISO 11357; both tests utilize DSC: Differential Scanning Calorimetry.
• HCO of use in the present invention includes those that are commercially available. Nonlimiting examples of commercially available HCO of use in the present invention include: THIXCIN(R) from Rheox, Inc. Further examples of useful HCO may be found in U.S. Patent 5,340,390 .
• the source of the castor oil for hydrogenation to form HCO can be of any suitable origin, such as from Brazil or India.
• castor oil is hydrogenated using a precious metal, e.g., palladium catalyst, and the hydrogenation temperature and pressure are controlled to optimize hydrogenation of the double bonds of the native castor oil while avoiding unacceptable levels of dehydroxylation.
• the invention is not intended to be directed only to the use of hydrogenated castor oil.
• Any other suitable crystallizable glyceride(s) may be used.
• the structurant is substantially pure triglyceride of 12-hydroxystearic acid. This molecule represents the pure form of a fully hydrogenated triglyceride of 12-hydrox-9-cis-octadecenoic acid.
• the composition of castor oil is rather constant, but may vary somewhat. Likewise hydrogenation procedures may vary.
• Any other suitable equivalent materials, such as mixtures of triglycerides wherein at least 80 percent wt. is from castor oil, may be used.
• Exemplary equivalent materials comprise primarily, or consist essentially of, triglycerides; or comprise primarily, or consist essentially of, mixtures of diglycerides and triglycerides; or comprise primarily, or consist essentially of, mixtures of triglyerides with diglycerides and limited amounts, e.g., less than about 20 percent wt. of the glyceride mixtures, of monoglyerides; or comprise primarily, or consist essentially of, any of the foregoing glycerides with limited amounts, e.g., less than about 20 percent wt., of the corresponding acid hydrolysis product of any of said glycerides.
• a proviso in the above is that the major proportion, typically at least 80 percent wt, of any of said glycerides is chemically identical to glyceride of fully hydrogenated ricinoleic acid, i.e., glyceride of 12- hydroxystearic acid. It is for example well known in the art to modify hydrogenated castor oil such that in a given triglyceride, there will be two 12-hydroxystearic- moieties and one stearic moiety. Likewise it is envisioned that the hydrogenated castor oil may not be fully hydrogenated. In contrast, the invention excludes poly(oxyalkylated) castor oils when these fail the melting criteria.
• Crystallizable glyceride(s) of use in the present invention may have a melting point of from about 40 degrees centigrade to about 100 degrees centigrade.
• the composition preferably comprises an enzyme selected from cellulase, a protease and an amylase/mannase mixture.
• the composition may comprise an effective amount of one or more enzyme preferably selected from the group comprising lipases, hemicellulases, peroxidases, hemicellulases, xylanases, xantanase, lipases, phospholipases, esterases, cutinases, pectinases, carrageenases, pectate lyases, keratinases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, ⁇ -glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase, tannases, nucleases (such as deoxyribonuclease and/or ribonuclease), phosphodiesterases, or mixtures thereof.
• one or more enzyme preferably selected from the group comprising
• the level of an enzyme is from 0.1 to 100, more preferably from 0.5 to 50, most preferably from 5 to 30 mg active enzyme protein per 100g finished laundry liquid composition.
• Examples of preferred enzymes are sold under the following trade names Purafect Prime ® , Purafect ® , Preferenz ® (DuPont), Savinase ® , Pectawash ® , Mannaway ® , Lipex ® , Lipoclean ® , Whitzyme ® Stainzyme ® , Stainzyme Plus ® , Natalase ® , Mannaway ® , Amplify ® Xpect ® , Celluclean ® (Novozymes), Biotouch (AB Enzymes), Lavergy ® (BASF).
• Purafect Prime ® Purafect ®
• Purafect ® Purafect ®
• Preferenz ® DuPont
• Savinase ® Pectawash ®
• Mannaway ® Mannaway ®
• Lipex ® Lipoclean ®
• Whitzyme ® Stainzyme ® Stainzyme Plus ®
• Detergent enzymes are discussed in WO2020/186028(Procter and Gamble) , WO2020/200600 (Henkel) , WO2020/070249 (Novozymes) , WO2021/001244 (BASF) and WO2020/259949 (Unilever) .
• a nuclease enzyme is an enzyme capable of cleaving the phosphodiester bonds between the nucleotide sub-units of nucleic acids and is preferably a deoxyribonuclease or ribonuclease enzyme.
• proteases hydrolyse bonds within peptides and proteins, in the laundry context this leads to enhanced removal of protein or peptide containing stains.
• suitable proteases families include aspartic proteases; cysteine proteases; glutamic proteases; aspargine peptide lyase; serine proteases and threonine proteases. Such protease families are described in the MEROPS peptidase database (http://merops.sanger.ac.uk/). Serine proteases are preferred. Subtilase type serine proteases are more preferred.
• the term "subtilases" refers to a sub-group of serine protease according to Siezen et al. , Protein Engng.
• Serine proteases are a subgroup of proteases characterized by having a serine in the active site, which forms a covalent adduct with the substrate.
• the subtilases may be divided into 6 sub divisions, i.e. the Subtilisin family, the Thermitase family, the Proteinase K family, the Lantibiotic peptidase family, the Kexin family and the Pyrolysin family.
• subtilases are those derived from Bacillus such as Bacillus lentus, B. alkalophilus, B. subtilis, B. amyloliquefaciens, Bacillus pumilus and Bacillus gibsonii described in; US7262042 and WO09/021867 , and subtilisin lentus, subtilisin Novo, subtilisin Carlsberg, Bacillus licheniformis, subtilisin BPN', subtilisin 309, subtilisin 147 and subtilisin 168 described in WO 89/06279 and protease PD138 described in ( WO 93/18140 ).
• proteases may be those described in WO 92/175177 , WO 01/016285 , WO 02/026024 and WO 02/016547 .
• trypsin-like proteases are trypsin (e.g. of porcine or bovine origin) and the Fusarium protease described in WO 89/06270 , WO 94/25583 and WO 05/040372 , and the chymotrypsin proteases derived from Cellumonas described in WO 05/052161 and WO 05/052146 .
• protease is a subtilisins (EC 3.4.21.62).
• subtilases are those derived from Bacillus such as Bacillus lentus, B. alkalophilus, B. subtilis, B. amyloliquefaciens, Bacillus pumilus and Bacillus gibsonii described in; US7262042 and WO09/021867 , and subtilisin lentus, subtilisin Novo, subtilisin Carlsberg, Bacillus licheniformis, subtilisin BPN', subtilisin 309, subtilisin 147 and subtilisin 168 described in WO89/06279 and protease PD138 described in ( WO93/18140 ).
• the subsilisin is derived from Bacillus, preferably Bacillus lentus, B.
• subtilisin is derived from Bacillus gibsonii or Bacillus Lentus.
• Suitable commercially available protease enzymes include those sold under the trade names names Alcalase ® , Blaze ® ; DuralaseTm, DurazymTm, Relase ® , Relase ® Ultra, Savinase ® , Savinase ® Ultra, Primase ® , Polarzyme ® , Kannase ® , Liquanase ® , Liquanase ® Ultra, Ovozyme ® , Coronase ® , Coronase ® Ultra, Neutrase ® , Everlase ® and Esperase ® all could be sold as Ultra ® or Evity ® (Novozymes A/S).
• Suitable amylases include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Amylases include, for example, alpha-amylases obtained from Bacillus, e.g. a special strain of B. licheniformis, described in more detail in GB 1 ,296,839 , or the Bacillus sp. strains disclosed in WO 95/026397 or WO00/060060 .
• amylases are Duramyl TM , Termamyl TM , Termamyl Ultra TM , Natalase TM , Stainzyme TM , Fungamyl TM and BAN TM (Novozymes A/S), Rapidase TM and Purastar TM (from Genencor International Inc.).
• Suitable cellulases include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Suitable cellulases include cellulases from the genera Bacillus, Pseudomonas, Humicola, Fusarium, Thielavia, Acremonium, e.g. the fungal cellulases produced from Humicola insolens, Thielavia terrestris, Myceliophthora thermophila, and Fusarium oxysporum disclosed in US 4,435,307 , US 5,648,263 , US 5,691 ,178 , US 5,776,757 , WO 89/09259 , WO 96/029397 , and WO 98/012307 .
• Celluzyme TM Commercially available cellulases include Celluzyme TM , Carezyme TM , Celluclean TM , Endolase TM ,Renozyme TM (Novozymes A/S), Clazinase TM and Puradax HA TM (Genencor International Inc.), and KAC-500(B) TM (Kao Corporation). Celluclean TM is preferred.
• Lipases are lipid esterase enzymes and the terms lipid esterase and lipase are used herein synonymously.
• the composition preferably comprises from 0.0005 to 0.5 wt.%, preferably from 0.005 to 0.2 wt.% of a lipase.
• the lipid esterase may be selected from lipase enzymes in E.C. class 3.1 or 3.2 or a combination thereof.
• the cleaning lipid esterases is selected from:
• Triacylglycerol lipases (E.C. 3.1.1.3) are most preferred.
• Suitable triacylglycerol lipases can be selected from variants of the Humicola lanuginosa (Thermomyces lanuginosus) lipase.
• Other suitable triacylglycerol lipases can be selected from variants of Pseudomonas lipases, e.g., from P. alcaligenes or P. pseudoalcaligenes ( EP 218 272 ), P. cepacia ( EP 331 376 ), P. stutzeri ( GB 1,372,034 ), P. fluorescens, Pseudomonas sp. strain SD 705 ( WO 95/06720 and WO 96/27002 ), P.
• wisconsinensis ( WO 96/12012 ), Bacillus lipases, e.g., from B. subtilis ( Dartois et al. (1993), Biochemica et Biophysica Acta, 1131, 253-360), B . stearothermophilus ( JP 64/744992 ) or B. pumilus ( WO 91/16422 ).
• Suitable carboxylic ester hydrolases can be selected from wild-types or variants of carboxylic ester hydrolases endogenous to B. gladioli, P. fluorescens, P. putida, B. acidocaldarius, B. subtilis, B. stearothermophilus, Streptomyces chrysomallus, S. diastatochromogenes and Saccaromyces cerevisiae.
• Suitable cutinases can be selected from wild-types or variants of cutinases endogenous to strains of Aspergillus, in particular Aspergillus oryzae, a strain of Alternaria, in particular Alternaria brassiciola, a strain of Fusarium, in particular Fusarium solani, Fusarium solani pisi, Fusarium oxysporum, Fusarium oxysporum cepa, Fusarium roseum culmorum, or Fusarium roseum sambucium, a strain of Helminthosporum, in particular Helminthosporum sativum, a strain of Humicola, in particular Humicola insolens, a strain of Pseudomonas, in particular Pseudomonas mendocina, or Pseudomonas putida, a strain of Rhizoctonia, in particular Rhizoctonia solani, a strain of Streptomyces, in particular
• the cutinase is selected from variants of the Pseudomonas mendocina cutinase described in WO 2003/076580 (Genencor) , such as the variant with three substitutions at I178M, F180V, and S205G.
• the cutinase is a wild-type or variant of the six cutinases endogenous to Coprinopsis cinerea described in H. Kontkanen et al, App. Environ. Microbiology, 2009, p2148-2157 .
• the cutinase is a wild-type or variant of the two cutinases endogenous to Trichoderma reesei described in WO2009007510 (VTT) .
• the cutinase is derived from a strain of Humicola insolens, in particular the strain Humicola insolens DSM 1800. Humicola insolens cutinase is described in WO 96/13580 which is hereby incorporated by reference.
• the cutinase may be a variant, such as one of the variants disclosed in WO 00/34450 and WO 01/92502 .
• Preferred cutinase variants include variants listed in Example 2 of WO 01/92502 .
• Preferred commercial cutinases include Novozym 51032 (available from Novozymes, Bagsvaerd, Denmark).
• Suitable sterol esterases may be derived from a strain of Ophiostoma, for example Ophiostoma piceae, a strain of Pseudomonas, for example Pseudomonas aeruginosa, or a strain of Melanocarpus, for example Melanocarpus albomyces.
• the sterol esterase is the Melanocarpus albomyces sterol esterase described in H. Kontkanen et al, Enzyme Microb Technol., 39, (2006), 265-273 .
• Suitable wax-ester hydrolases may be derived from Simmondsia chinensis.
• the lipid esterase is preferably selected from lipase enzyme in E.C. class 3.1.1.1 or 3.1.1.3 or a combination thereof, most preferably E.C.3.1.1.3.
• Examples of EC 3.1.1.3 lipases include those described in WIPO publications WO 00/60063 , WO 99/42566 , WO 02/062973 , WO 97/04078 , WO 97/04079 and US 5,869,438 .
• Lipolase ® Lipolase Ultra ® , Lipoprime ® , Lipoclean ® and Lipex ® (registered tradenames of Novozymes) and LIPASE P "AMANO ® " available from Areario Pharmaceutical Co. Ltd., Nagoya, Japan, AMANO-CES ® , commercially available from Toyo Jozo Co., Tagata, Japan; and further Chromobacter viscosum lipases from Amersham Pharmacia Biotech., Piscataway, New Jersey, U.S.A. and Diosynth Co., Netherlands, and other lipases such as Pseudomonas gladioli.
• suitable lipases include the "first cycle lipases" described in WO 00/60063 and U.S. Patent 6,939,702 B1 , preferably a variant of SEQ ID No. 2, more preferably a variant of SEQ ID No. 2 having at least 90% homology to SEQ ID No.
• lipases can be used in combination (any mixture of lipases can be used). Suitable lipases can be purchased from Novozymes, Bagsvaerd, Denmark; Areario Pharmaceutical Co. Ltd., Nagoya, Japan; Toyo Jozo Co., Tagata, Japan; Amersham Pharmacia Biotech., Piscataway, New Jersey, U.S.A; Diosynth Co., Oss, Netherlands and/or made in accordance with the examples contained herein.
• Lipid esterase with reduced potential for odour generation and a good relative performance are particularly preferred, as described in WO 2007/087243 . These include lipoclean ® (Novozyme).
• Lipolase TM and Lipolase Ultra TM Lipex TM and Lipoclean TM (Novozymes A/S).
• the liquid composition comprises a fragrance and preferably, the fragrance is present at from 0.01 to 5% wt., more preferably 0.1 to 1wt% of the composition.
• the fragrance comprises a component selected from the group consisting of ethyl-2-methyl valerate (manzanate), limonene, (4Z)-cyclopentadec-4-en-1-one, dihyro myrcenol, dimethyl benzyl carbonate acetate, benzyl acetate, spiro[1,3-dioxolane-2,5'-(4',4',8',8'-tetramethyl-hexahydro-3',9'-methanonaphthalene)], benzyl acetate, Rose Oxide, geraniol, methyl nonyl acetaldehyde, decanal, octanal, undecanal, verdyl acetate, tert-butylcyclohexyl acetate, cyclamal, beta ionone, hexyl salicylate, tonalid, phenafleur, octahydro
• the fragrance comprises from 0.5 to 30% wt., more preferably from 2 to 15wt.% and especially preferably from 6 to 10% wt. of the fragrance component ethyl-2-methyl valerate (manzanate).
• the fragrance comprises from 0.5 to 30% wt., more preferably from 2 to 15 wt.% and especially preferably from 6 to 10% wt. of the fragrance component limonene.
• the fragrance comprises from 0.5 to 30% wt., more preferably from 2 to 15% and especially preferably from 6 to 10% wt. of the fragrance component (4Z)-cyclopentadec-4-en-1-one.
• the fragrance comprises from 0.5 to 30% wt., more preferably from 2 to 15% and especially preferably from 6 to 10% wt. of the fragrance component dimethyl benzyl carbonate acetate.
• the fragrance comprises from 0.5 to 30% wt., more preferably from 2 to 15% and especially preferably from 6 to 10% wt. of the fragrance component dihyromyrcenol.
• the fragrance comprises from 0.5 to 30% wt., more preferably from 2 to 15% and especially preferably from 6 to 10% wt. of the fragrance component rose oxide.
• the fragrance comprises from 0.5 to 30% wt., more preferably from 2 to 15% and especially preferably from 6 to 10% wt. of the fragrance component tert-butylcyclohexyl acetate.
• the fragrance comprises from 0.5 to 30% wt., more preferably from 2 to 15% and especially preferably from 6 to 10% wt. of the fragrance component verdyl acetate.
• the fragrance comprises from 0.5 to 30% wt., more preferably from 2 to 15% and especially preferably from 6 to 10% wt. of the fragrance component benzyl acetate.
• the fragrance comprises from 0.5 to 30% wt., more preferably from 2 to 15% and especially preferably from 6 to 10% wt. of the fragrance component spiro[1,3-dioxolane-2,5'-(4',4',8',8'-tetramethyl-hexahydro-3',9'-methanonaphthalene)].
• the fragrance comprises from 0.5 to 30% wt., more preferably from 2 to 15% and especially preferably from 6 to 10% wt. of the fragrance component geraniol.
• the fragrance comprises from 0.5 to 30% wt., more preferably from 2 to 15% and especially preferably from 6 to 10% wt. of the fragrance component methyl nonyl acetaldehyde.
• the fragrance comprises from 0.5 to 30% wt., more preferably from 2 to 15% and especially preferably from 6 to 10% wt. of the fragrance component cyclamal.
• the fragrance comprises from 0.5 to 30% wt., more preferably from 2 to 15wt.% and especially preferably from 6 to 10% wt. of the fragrance component beta ionone.
• the fragrance comprises from 0.5 to 30% wt., more preferably from 2 to 15wt.% and especially preferably from 6 to 10% wt. of the fragrance component hexyl salicylate.
• the fragrance comprises from 0.5 to 30% wt., more preferably from 2 to 15wt.% and especially preferably from 6 to 10% wt. of the fragrance component tonalid.
• the fragrance comprises from 0.5 to 30% wt., more preferably from 2 to 15wt.% and especially preferably from 6 to 10% wt. of the fragrance component phenafleur.
• the fragrance comprises a component selected from the benzene, toluene, xylene (BTX) feedstock class. More preferably, the fragrance component is selected from 2-phenyl ethanol, phenoxanol and mixtures thereof.
• the fragrance comprises a component selected from the cyclododecanone feedstock class. More preferably, the fragrance component is habolonolide.
• the fragrance comprises a component selected from the phenolics feedstock class. More preferably, the fragrance component is hexyl salicylate.
• the fragrance comprises a component selected from the C5 blocks or oxygen containing heterocycle moiety feedstock class. More preferably, the fragrance component is selected from gamma decalactone, methyl dihydrojasmonate and mixtures thereof.
• the fragrance comprises a component selected from the terpenes feedstock class. More preferably, the fragrance component is selected from, linalool, terpinolene, camphor, citronellol and mixtures thereof.
• the fragrance comprises a component selected from the alkyl alcohols feedstock class. More preferably, the fragrance component is ethyl-2-methylbutyrate.
• the fragrance comprises a component selected from the diacids feedstock class. More preferably, the fragrance component is ethylene brassylate.
• the fragrance component listed above is present in the final detergent composition at from 0.0001 to 1% by wt. of the composition.
• microencapsulation may be defined as the process of surrounding or enveloping one substance within another substance on a very small scale, yielding capsules ranging from less than one micron to several hundred microns in size.
• the material that is encapsulated may be called the core, the active ingredient or agent, fill, payload, nucleus, or internal phase.
• the material encapsulating the core may be referred to as the coating, membrane, shell, or wall material.
• Microcapsules typically have at least one generally spherical continuous shell surrounding the core.
• the shell may contain pores, vacancies or interstitial openings depending on the materials and encapsulation techniques employed.
• Multiple shells may be made of the same or different encapsulating materials, and may be arranged in strata of varying thicknesses around the core.
• the microcapsules may be asymmetrically and variably shaped with a quantity of smaller droplets of core material embedded throughout the microcapsule.
• the shell may have a barrier function protecting the core material from the environment external to the microcapsule, but it may also act as a means of modulating the release of core materials such as fragrance.
• a shell may be water soluble or water swellable and fragrance release may be actuated in response to exposure of the microcapsules to a moist environment.
• a microcapsule might release fragrance in response to elevated temperatures.
• Microcapsules may also release fragrance in response to shear forces applied to the surface of the microcapsules.
• a preferred type of polymeric microparticle suitable for use in the invention is a polymeric core-shell microcapsule in which at least one generally spherical continuous shell of polymeric material surrounds a core containing the fragrance formulation (f2).
• the shell will typically comprise at most 20% by weight based on the total weight of the microcapsule.
• the fragrance formulation (f2) will typically comprise from about 10 to about 60% and preferably from about 20 to about 40% by weight based on the total weight of the microcapsule.
• the amount of fragrance (f2) may be measured by taking a slurry of the microcapsules, extracting into ethanol and measuring by liquid chromatography.
• Polymeric core-shell microcapsules for use in the invention may be prepared using methods known to those skilled in the art such as coacervation, interfacial polymerization, and polycondensation.
• Coacervation typically involves encapsulation of a generally water-insoluble core material by the precipitation of colloidal material(s) onto the surface of droplets of the material.
• Coacervation may be simple e.g. using one colloid such as gelatin, or complex where two or possibly more colloids of opposite charge, such as gelatin and gum arabic or gelatin and carboxymethyl cellulose, are used under carefully controlled conditions of pH, temperature and concentration.
• Interfacial polymerisation typically proceeds with the formation of a fine dispersion of oil droplets (the oil droplets containing the core material) in an aqueous continuous phase.
• the dispersed droplets form the core of the future microcapsule and the dimensions of the dispersed droplets directly determine the size of the subsequent microcapsules.
• Microcapsule shell-forming materials are contained in both the dispersed phase (oil droplets) and the aqueous continuous phase and they react together at the phase interface to build a polymeric wall around the oil droplets thereby to encapsulate the droplets and form core-shell microcapsules.
• An example of a core-shell microcapsule produced by this method is a polyurea microcapsule with a shell formed by reaction of diisocyanates or polyisocyanates with diamines or polyamines.
• Polycondensation involves forming a dispersion or emulsion of the core material in an aqueous solution of precondensate of polymeric materials under appropriate conditions of agitation to produce capsules of a desired size, and adjusting the reaction conditions to cause condensation of the precondensate by acid catalysis, resulting in the condensate separating from solution and surrounding the dispersed core material to produce a coherent film and the desired microcapsules.
• An example of a core-shell microcapsule produced by this method is an aminoplast microcapsule with a shell formed from the polycondensation product of melamine (2,4,6-triamino-1,3,5-triazine) or urea with formaldehyde.
• Suitable cross-linking agents e.g. toluene diisocyanate, divinyl benzene, butanediol diacrylate
• secondary wall polymers may also be used as appropriate, e.g. anhydrides and their derivatives, particularly polymers and co-polymers of maleic anhydride.
• One example of a preferred polymeric core-shell microcapsule for use in the invention is an aminoplast microcapsule with an aminoplast shell surrounding a core containing the fragrance formulation (f2). More preferably such an aminoplast shell is formed from the polycondensation product of melamine with formaldehyde.
• Polymeric microparticles suitable for use in the invention will generally have an average particle size between 100 nanometers and 50 microns. Particles larger than this are entering the visible range.
• particles in the sub-micron range include latexes and mini-emulsions with a typical size range of 100 to 600 nanometers.
• the preferred particle size range is in the micron range.
• particles in the micron range include polymeric core-shell microcapsules (such as those further described above) with a typical size range of 1 to 50 microns, preferably 5 to 30 microns.
• the average particle size can be determined by light scattering using a Malvern Mastersizer with the average particle size being taken as the median particle size D (0.5) value.
• the particle size distribution can be narrow, broad or multimodal. If necessary, the microcapsules as initially produced may be filtered or screened to produce a product of greater size uniformity.
• Polymeric microparticles suitable for use in the invention may be provided with a deposition aid at the outer surface of the microparticle.
• Deposition aids serve to modify the properties of the exterior of the microparticle, for example to make the microparticle more substantive to a desired substrate.
• Desired substrates include cellulosics (including cotton) and polyesters (including those employed in the manufacture of polyester fabrics).
• the deposition aid may suitably be provided at the outer surface of the microparticle by means of covalent bonding, entanglement or strong adsorption.
• Examples include polymeric core-shell microcapsules (such as those further described above) in which a deposition aid is attached to the outside of the shell, preferably by means of covalent bonding. While it is preferred that the deposition aid is attached directly to the outside of the shell, it may also be attached via a linking species.
• Deposition aids for use in the invention may suitably be selected from polysaccharides having an affinity for cellulose.
• polysaccharides may be naturally occurring or synthetic and may have an intrinsic affinity for cellulose or may have been derivatised or otherwise modified to have an affinity for cellulose.
• Suitable polysaccharides have a 1-4 linked ⁇ glycan (generalised sugar) backbone structure with at least 4, and preferably at least 10 backbone residues which are ⁇ 1-4 linked, such as a glucan backbone (consisting of ⁇ 1-4 linked glucose residues), a mannan backbone (consisting of ⁇ 1-4 linked mannose residues) or a xylan backbone (consisting of ⁇ 1-4 linked xylose residues).
• ⁇ 1-4 linked polysaccharides examples include xyloglucans, glucomannans, mannans, galactomannans, ⁇ (1-3),(1-4) glucan and the xylan family incorporating glucurono-, arabino- and glucuronoarabinoxylans.
• Preferred ⁇ 1-4 linked polysaccharides for use in the invention may be selected from xyloglucans of plant origin, such as pea xyloglucan and tamarind seed xyloglucan (TXG) (which has a ⁇ 1-4 linked glucan backbone with side chains of ⁇ -D xylopyranose and ⁇ -D-galactopyranosyl-(1-2)- ⁇ -D-xylo-pyranose, both 1-6 linked to the backbone); and galactomannans of plant origin such as loc ust bean gum (LBG) (which has a mannan backbone of ⁇ 1-4 linked mannose residues, with single unit galactose side chains linked ⁇ 1-6 to the backbone).
• TXG pea xyloglucan and tamarind seed xyloglucan
• LBG loc ust bean gum
• polysaccharides which may gain an affinity for cellulose upon hydrolysis, such as cellulose mono-acetate; or modified polysaccharides with an affinity for cellulose such as hydroxypropyl cellulose, hydroxypropyl methylcellulose, hydroxyethyl methylcellulose, hydroxypropyl guar, hydroxyethyl ethylcellulose and methylcellulose.
• Deposition aids for use in the invention may also be selected from phthalate containing polymers having an affinity for polyester.
• phthalate containing polymers may have one or more nonionic hydrophilic segments comprising oxyalkylene groups (such as oxyethylene, polyoxyethylene, oxypropylene or polyoxypropylene groups), and one or more hydrophobic segments comprising terephthalate groups.
• the oxyalkylene groups will have a degree of polymerization of from 1 to about 400, preferably from 100 to about 350, more preferably from 200 to about 300.
• a suitable example of a phthalate containing polymer of this type is a copolymer having random blocks of ethylene terephthalate and polyethylene oxide terephthalate.
• Deposition aids for use in the invention will generally have a weight average molecular weight (M w ) in the range of from about 5 kDa to about 500 kDa, preferably from about 10 kDa to about 500 kDa and more preferably from about 20 kDa to about 300 kDa.
• M w weight average molecular weight
• One example of a particularly preferred polymeric core-shell microcapsule for use in the invention is an aminoplast microcapsule with a shell formed by the polycondensation of melamine with formaldehyde; surrounding a core containing the fragrance formulation (f2); in which a deposition aid is attached to the outside of the shell by means of covalent bonding.
• the preferred deposition aid is selected from ⁇ 1-4 linked polysaccharides, and in particular the xyloglucans of plant origin, as are further described above.
• the present inventors have surprisingly observed that it is possible to reduce the total level of fragrance included in the composition of the invention without sacrificing the overall fragrance experience delivered to the consumer at key stages in the laundry process. A reduction in the total level of fragrance is advantageous for cost and environmental reasons.
• the total amount of fragrance formulation (f1) and fragrance formulation (f2) in the composition of the invention suitably ranges from 0.5 to 1.4%, preferably from 0.5 to 1.2%, more preferably from 0.5 to 1% and most preferably from 0.6 to 0.9% (by weight based on the total weight of the composition).
• the weight ratio of fragrance formulation (f1) to fragrance formulation (f2) in the composition of the invention preferably ranges from 60:40 to 45:55. Particularly good results have been obtained at a weight ratio of fragrance formulation (f1) to fragrance formulation (f2) of around 50:50.
• fragrance (f1) and fragrance (f2) are typically incorporated at different stages of formation of the composition of the invention.
• the discrete polymeric microparticles (e.g. microcapsules) entrapping fragrance formulation (f2) are added in the form of a slurry to a warmed base formulation comprising other components of the composition (such as surfactants and solvents).
• Fragrance (f1) is typically post-dosed later after the base formulation has cooled.
• a liquid composition of the invention may contain further optional ingredients to enhance performance and/or consumer acceptability.
• additional optional ingredients include foam boosting agents, preservatives (e.g. bactericides), polyelectrolytes, anti-shrinking agents, anti-wrinkle agents, anti-oxidants, sunscreens, anti-corrosion agents, drape imparting agents, anti-static agents, ironing aids, colorants, pearlisers and/or opacifiers, and shading dye.
• foam boosting agents e.g. bactericides
• preservatives e.g. bactericides
• polyelectrolytes e.g. bactericides
• anti-shrinking agents e.g. bactericides
• anti-wrinkle agents e.g. bactericides
• anti-oxidants e.g. bactericides
• sunscreens e.g. bactericides
• anti-corrosion agents e.g. bactericides
• drape imparting agents e.g. bactericide
• ingredients used in embodiments of the invention may be obtained from so called black carbon sources or a more sustainable green source.
• black carbon sources or a more sustainable green source.
• the following provides a list of alternative sources for several of these ingredients and how they can be made into raw materials described herein.
• the unit dose detergent is packaged in a container such as a plastic tub.
• a container such as a plastic tub.
• plastic tubs are typically hermetically sealable and comprise child resistant closures.
• the laundry unit dose detergent is packaged within a container comprising at least 80% wt. biodegradable material.
• Suitable biodegradable materials include cardboard and other pulp based materials. Such biodegradable material may be virgin or recycled but it is preferred if it is recycled.
• the container comprises at least 90% wt biodegradable material.
• Preferred pulps include cardboard, in particular corrugated cardboard.
• compartment detergent capsules were produced.
• the capsule was 5.1cm by 5.1 cm and 2 compartments (A1 and A2) had a liquid fill volume of 5.9g and 2 compartments (B1 and B2) a fill volume of 4.1g.
• the compartments were arranged as a petal and between each compartment there was a sealed line of film.
• the film used was polyvinylalcohol-based ex Monosol.
• the capsules were made using a Formech vacuum former, film was place over the mould and clamped, the top film was thermoformed, and the formulation component added into the respective cavities. 5.9g of Liquid formulation was placed into A1; 4.1g of liquid formulation into both B1 and B2; 3g of beads was placed into A2.
• the liquid formulation had the following composition: INGREDIENT % propylene glycol 24 c12-16 pareth-9 20 dodecylbenzene sulfonic acid ethanol amine salt 20 trideceth-4 / alcohol c13 ethoxylated 11 c12-14 fatty acid 4 glycerin 7 sodium laureth sulfate 5 lauryl polyqlucose 1 Sodium citrate 1 Water + Minors (dyes, preservative, fluorescer, thickening polymer residual
• the beads were oval shaped (5 mm diameter 2.3 mm height). Beads were made using
• Binders were required in (b) to maintain structural integrity.
• Capsules were made with a measured capsule film thickness of 0.172mm (+/- 0.003mm) and 0.192mm (+/- 0.003mm). The film thickness was measured on the edge of the capsule. Different film thicknesses were achieved by using base films of different thickeness.
• the capsules were held at 35% RH and 290K for 24 hours to equilibrate.
• the capsules with the 2 bead types were shaken and a visibly rattling noise heard from the solid.
• the capsules were shaken by the ears of 11 human subjects, each subject was asked to assign the loudest. The results are given in the table below. 0.172mm loudest 0.192mm loudest No difference PEG bead 6/11 0/11 5/11 Sucrose bead 5/11 0/11 6/11
• the data shows that a thinner film provides the loudest capsule.

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  • 2024-06-13 EP EP24182113.1A patent/EP4663738A1/de active Pending

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