Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/38—Cationic compounds
  • C11D1/62—Quaternary ammonium compounds
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/0005—Other compounding ingredients characterised by their effect
  • C11D3/001—Softening compositions
  • C11D3/0015—Softening compositions liquid
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/48—Medical, disinfecting agents, disinfecting, antibacterial, germicidal or antimicrobial compositions
• • 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
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/50—Perfumes
  • C11D3/502—Protected perfumes
  • C11D3/505—Protected perfumes encapsulated or adsorbed on a carrier, e.g. zeolite or clay

Definitions

• the present invention relates to dilute fabric conditioner compositions containing unsaturated TEA quaternary ammonium compounds which are stable and deliver both perfume and malodour benefits.
• Chlorinated phenyl ethers and in particular, "Diclosan” (4-4' dichloro-2-hydroxy diphenyl ether) are known for use in laundry products to give a persistent antimicrobial effect which resists exposure to high temperatures and therefore survives machine drying.
• Antimicrobials are known to have a secondary effect in the prevention of malodours through several microbial pathways. These may include (amongst others) odours generated by skin bacteria such as Staphylococcus epidermidis, decomposition of urine or growth of pathogenic bateria such as Proteus vulgaris, and the formation of foot odour by Micrococcus dermatophytes. Many anti-microbial materials are known or have been suggested for use in laundry products.
• compositions in reducing microbial growth can be measured by various tests.
• One well known and standard test is the AATCC100 test, which measures bacterial growth on fabrics. While industrial fabric treatments and modification of fibres (such as the incorporation of silver ions) give good results in this and other tests, it has proven difficult to achieve good scores in such tests for both gram positive and gram negative bacteria by treatments which can be used in the home under the diverse washing conditions which end users apply.
• Rinse conditioners are one type of laundry product and are essentially meta- stable dispersions of fabric softening actives in a solvent/water phase. The dispersions are formulated such that they are stable in storage and in transit, but in use they become unstable and the fabric softening active becomes deposited on the articles being treated.
• the stability of the formulation is dependent on the type of softening active being used and the levels of both that active and other softening components. Loss of stability can lead to changes in viscosity or even worse visible separation of formulation components. Changes in the micro- structure of a product can have unexpected effects on perfume behaviour and vice-versa. Even small changes in a formulation can have consequences as regards stability.
• an aqueous fabric conditioner composition comprising: (a) from 0.5 to 35%, by weight of the total composition, of a fabric softening active, wherein the fabric softening active comprises an ester-linked triethanolamine quaternary ammonium compound, (b) from 0.001 % to 2%, by weight of the total composition, of a non-ionic,
• antimicrobial which is not a perfume component
• compositions of the invention showed an unexpected
• the synergistic combination of the conditioner active with Diclosan enables economically sustainable fabric conditioner formulations capable of delivering persistent antimicrobial action for a wide range of domestic laundering practices.
• the fabric conditioning compositions of the invention may be dilute or
• Dilute products typically contain up to about 8 %, preferably from 2 to 8 % by weight of softening active, whereas concentrated products may contain from about 8 to about 50 %, preferably from 8 to 25 % by weight active.
• compositions of more than about 25 % by weight of active are defined as "super concentrated", depending on the active system, and are also intended to be covered by the present invention.
• the fabric conditioning agent may, for example, be used in amounts of preferably from 2 % to 30 % more preferably from 5 % to 25 % and most preferably from 8 % to 20 % by weight of the composition.
• 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 % by weight of the TEA-based fabric softening compound, preferably no more than 60 %, e.g. 55 %, or 45 % of the fabric softening compound and at least 10 % of the monoester linked component, for example 1 1 % monoester.
• Especially preferred agents are preparations which are rich in the di-esters of triethanolammonium methylsulphate,
• the triester content is preferably below 10 wt %, more preferably from 5 to 9 wt % by total weight of the quaternary active component.
• Preferred ester-linked triethanolamine quaternary ammonium compounds have a diester content of from 50 to 60 wt %, more preferably from 52 to 59 wt % by total weight of the quaternary active component.
• TEA quats having a monoester content of from 30 to 45 wt %, more preferably from 32 to 42 wt % by total weight of the quaternary active component.
• a preferred TEA quat of the present invention comprises from 32 to 42 wt % of monoester, from 52 to 59 wt % of diester and from 5 to 9 wt % of triester compounds, by total weight of the quaternary active; more preferably from 35 to 39 wt % of monoester, from 54 to 58 wt % of diester and from 7 to 8 wt % of triester compounds, by total weight of the quaternary active component.
• a preferred hardened type of TEA active has a typical mono:di:tri ester distribution of from 18 to 22 mono: from 58 to 62 di: from 18 to 22 tri; for example 20:60:20.
• a soft TEA quat may have a typical mono:di:tri ester distribution of from 25 to 45 %, preferably from 30 to 40 % mono: from 45 to 60 %, preferably from 50 to 55 % di: and from 5 to 25 %, preferably from 10 to 15 % tri; for example 40:60: 10.
• a further aspect of the invention provides a method of preparing a rinse water, which comprises adding to water a composition as defined in the first aspect.
• a yet further aspect of the invention subsists in the use of the rinse water of the second aspect to treat fabrics such that microbial growth on the fabrics is inhibited.
• the aqueous fabric conditioner composition has a viscosity of greater than 50 cps, preferably from 55 to 200 cps more preferably from 60 to 175, even more preferably from 80 to 150 and most preferably from 100 to 140 cps as measured on a "cup and bob" viscometer; the viscosity being continuously measured under shear at 106s "1 for 60 seconds, at 25°C.
• Any suitable viscometer can be used to make this measurement, for example, the Haake VT550 with a MV1 cup and bob geometry and the Thermo Fisher RS600 viscometer.
• the Fabric Softening Active for example, the Haake VT550 with a MV1 cup and bob geometry and the Thermo Fisher RS600 viscometer.
• the fabric softening active is present in an amount of from 0.5 to 35 wt %, based on the total weight of the composition, preferably from 6 to 35 wt %.
• the QAC is derived from palm or tallow feed stocks. These feed stocks may be pure or predominantly palm or tallow based. Blends of different feed stocks may be used.
• the fatty acid chains of the QAC preferably comprise from 20 to 35 wt % of saturated C18 chains and from 20 to 35 wt % of monounsaturated C18 chains by weight of total fatty acid chains.
• the fatty acid chains of the QAC comprise from 25 to 30 wt %, preferably from 26 to 28 wt % of saturated C18 chains and from 25 to 30 wt %, preferably from 26 to 28 wt % of monounsaturated C18 chains, by weight of total fatty acid chains.
• the fatty acid chains of the QAC comprise from 30 to 35 wt %, preferably from 33 to 35 wt % of saturated C18 chains and from 24 to 35 wt %, preferably from 27 to 32 wt % of monounsaturated C18 chains, by weight of total fatty acid chains.
• Iodine value as used in the context of the present invention refers to the
• the preferred quaternary ammonium materials for use in the present invention can be derived from feedstock having an overall iodine value of from 30 to 45, preferably from 30 to 42 and most preferably 36.
• StepantexTM UL85 Ex Stepan, PrapagenTM TQL, ex Clariant, and TetranylTM AHT-1 , ex Kao, (both di-[hardened tallow ester] of triethanolammonium methylsulphate), AT-1 (di-[tallow ester] of triethanolammonium methylsulphate), and L5/90 (di-[palm ester] of triethanolammonium methylsulphate), both ex Kao, and RewoquatTM WE15 (a di-ester of triethanolammonium methylsulphate having fatty acyl residues deriving from C10-C20 and C16-C18 unsaturated fatty acids), ex Witco Corporation.
• quaternary ammonium actives such as Stepantex VK90, Stepantex VT90, SP88 (ex-Stepan), Ceca Noramine, Prapagen TQ (ex-Clariant), Dehyquart AU-57 (ex-Cognis), Rewoquat WE18 (ex-Degussa) and Tetranyl L190 P, Tetranyl L190 SP and Tetranyl L190 S (all ex-Kao) are suitable.
• the Nonionic Antimicrobial is a halogenated material. Suitable materials include 5-chloro-2-(2,4-dichlorophenoxy)phenol, o-Benzyl-p-chloro- phenol, and 4-chloro-3-methylphenol.
• the material may be non-halogenated.
• suitable materials include 2-Phenylphenol and 2-(1 -Hydroxy-1 -methylethyl)-5- methylcyclohexanol.
• Phenyl ethers are one preferred sub-set of the non-ionic antimicrobials. More preferably the non-ionic antimicrobial is a bi-halogenated compound. Most preferably this comprises 4-4' dichloro-2-hydroxy diphenyl ether, and /or 2,2- dibromo-3-nitrilopropionamide (DBNPA). If the latter is used the pH of the composition needs to be in the acidic range where DBNPA is stable. This presents no difficulty with rinse conditioner compositions as they are usually formulated in that range.
• the non-ionic microbial active is present in an amount of from 0.001 to 2 wt %, by weight of the total composition.
• the preferred inclusion range for the non-ionic antimicrobial active is from 0.001 to 2 wt %, more preferably from 0.002 to 0.4 wt % and most preferably from 0.025 to 0.1 wt %, by weight of the total composition.
• Suitable materials are known in the marketplace as “Diclosan” and available as products such as TinosanTM HP 100 ex BASF.
• non-ionic antimicrobial In addition to the non-ionic antimicrobial other antimicrobial agents may also be present, provided that these are not present at a level which causes instability in the formulation.
• further antimicrobial agents are chelating agents, which are particularly useful in reducing the resistance of gram negative microbes in hard water.
• Acid biocides may also be present.
• the perfume is preferably present in an amount from 0.05 to 5 % by weight, even more preferably from 0.05 to 2 %, most preferably from 0.05 to 1.5 % by weight, based on the total weight of the composition.
• the perfume is an at least partially encapsulated perfume. That is, some, if not all, of the perfume material present is encapsulated in perfume particles. Encapsulating materials are not included in the weight of perfume present given above. It is believed that encapsulation of at least part of the perfume has a beneficial effect on the stability of the product. Encapsulation also provides for better perfume delivery especially where a deposition aid is linked to the encapsulate. ln one aspect of the invention the process for the preparation of the perfume particles is preferably a two step process in which the first step forms a particle comprising the benefit agent and the second step applies a coating to the capsule which includes a deposition aid.
• the first step can either be step-growth or addition polymerisation and the second step is preferably addition polymerisation.
• a particle can be formed which does not contain the perfume but which is capable of adsorbing it at some later time.
• This particle is then optionally decorated with the deposition aid thereby performing a two-step process analogous to that described above.
• the particle is subsequently exposed to the perfume, which diffuses into the particle.
• this may be done in- product, for example by adding the particles with deposition aid to a partly or fully formulated product which contains the perfume.
• the perfume is then adsorbed by the particle and retained within the particle during use of the product, so that at least some of the perfume is released from the particles after the fabric treatment process, when the particles have become deposited on the fabric.
• Single step encapsulation can also be used. In general, single step encapsulate particles do possess a deposition aid.
• Single step perfume particles can be formed either by step-growth polymerisation or addition polymerisation.
• Suitable classes of monomers for step-growth polymerization are given in the group consisting of the melamine/urea formaldehyde class, the isocyanate/diol class (preferably the polyurethanes) and polyesters.
• Suitable classes of monomers for addition/free radical polymerization are given in the group consisting of olefins, ethylene, vinylaromatic monomers, esters of vinyl alcohol with mono- and di- carboxylic acids, esters of ⁇ , ⁇ -monoethylenically unsaturated mono- and dicarboxylic acids with alcohols, nitriles of ⁇ , ⁇ - monoethylenically unsaturated carboxylic acids, conjugated dienes, ⁇ , ⁇ - monoethylenically unsaturated monocarboxylic and dicarboxylic acids and their amides, methacrylic acid and its esters with alcohols and diols, acrylic acid and its esters with alcohols and diols, dimethyl or di-n-butyl maleate, and vinyl-sulfonic acid and its water-soluble salts, and mixtures thereof.
• the polymer particle may comprise mixtures of monomer units.
• the polymer particle may optionally comprise monomers which are cross-linkers.
• Such cross-linkers may have at least two non-conjugated ethylenically
• alkylene glycol diacrylates and dimethacrylates examples are alkylene glycol diacrylates and dimethacrylates.
• a further type of suitable cross-linking monomers are those that are conjugated, such as divinyl benzene. If present, these monomers constitute from 0.1 to 10 % by weight, based on the total amount of monomers to be polymerised.
• the monomers are preferably selected from: styrene; a-methylstyrene;
• o-chlorostyrene vinyl acetate; vinyl propionate; vinyl n-butyrate; esters of acrylic, methacrylic, maleic, fumaric or itaconic acid with methyl, ethyl, n- butyl, isobutyl, n-hexyl and 2-ethylhexyl alcohol; 1 ,3-butadiene; 2,3 dimethyl butadiene; and isoprene.
• the preferred monomers are vinyl acetate and methyl acrylate.
• the monomers are used as co-monomers with one or more of acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, poly (alkylene oxide) monoacrylates and monomethacrylates, N-vinyl-pyrrolidone, methacrylic and acrylic acid, 2-hydroxyethyl acrylates and methacrylates, glycerol acrylates and methacrylates, poly(ethylene glycol) methacrylates and acrylates, n-vinyl pyrrolidone, acryloyl morpholine, vinyl formamide, n-vinyl acetamide and vinyl caprolactone, acrylonitrile (71 g/l), acrylamide, and methacrylamide at levels of less than 10 % by weight of the monomer unit content of the particle; 2- (dimethylamino) ethyl methacrylate, 2-(diethylamino) ethyl methacrylate, 2-(tert- butyla
• Optional cross linkers include vinyltoluenes, divinyl benzene, ethylene glycol diacrylate, 1 ,2-propylene glycol diacrylate, 1 ,3-propylene glycol diacrylate, 1 ,3- butylene glycol diacrylate, 1 ,4-butylene glycol diacrylates, ethylene glycol dimethacrylate, 1 ,2-propylene glycol dimethacrylate, 1 ,3-propylene glycol dimethacrylate, 1 ,3-butylene glycol dimethacrylate, 1 ,4-butylene glycol dimethacrylate, divinylbenzene, vinyl methacrylate, vinyl acrylate, allyl methacrylate, allyl acrylate, diallyl maleate, diallyl fumarate,
• the ratio of the monomers used in the overall shell formation and those used in deposition aid attachment are the ratio of 100: 1 to 5: 1 (as bulk shell former: deposition linker). Preferably, the ratio is 100: 1 - 50: 1 .
• the process for the preparation of the particles is preferably a two step process in which the first step forms a capsule around the benefit agent and the second step applies a coating to the capsule which includes the deposition aid.
• the first step can either be step-growth or addition polymerization and the second step is preferably addition polymerization.
• the first step uses monomers selected from melamine/urea-formaldehyde or methyl-methacrylate or isocyanate/diol
• the second step uses monomers selected from vinyl acetate and/or methyl acyrlate. It is particularly preferred that the deposition aid is not added until the second step.
• the initiator is preferably a chemical or chemicals capable of forming free radicals.
• free radicals can be formed either by homolytic scission (i.e. homolysis) of a single bond or by single electron transfer to or from an ion or molecule (e.g. redox reactions).
• homolysis may be achieved by the application of heat (typically in the range of from 50 to 100°C).
• Homolysis may also be achieved by the action of radiation (usually ultraviolet), in which case it is termed photolysis.
• radiation usually ultraviolet
• examples are the dissociation of 2,2'-azobis (2-cyanopropane) and the formation of free radicals from benzophenone and benzoin.
• Redox reactions can also be used to generate free radicals.
• an oxidising agent is paired with a reducing agent which then undergo a redox reaction.
• Some examples of appropriate pairs in the context of the invention are ammonium persulphate/sodium metabisulphite, cumyl hydroperoxide/ferrous ion and hydrogen peroxide/ascorbic acid.
• Preferred initiators are selected from the following:
• Redox ammonium persulphate/sodium metabisulphite mixture, cumyl
• hydroperoxide/ferrous ion mixture and/or hydrogen peroxide/ascorbic acid mixture.
• Preferred initiators are ammonium persulphate and hydrogen peroxide/ascorbic acid mixture.
• the preferred level of initiator is in the range of from 0.1 to
• the level is in the range of from 1 .0 to 3.0 % w/w by weight of monomer.
• Chain transfer agents can optionally be used.
• a chain transfer agent contains very labile hydrogen atoms that are easily abstracted by a propagating polymer chain. This terminates the polymerization of the growing polymer, but generates a new reactive site on the chain transfer agent that can then proceed to initiate further polymerization of the remaining monomer.
• Chain transfer agents in the context of the invention typically contain thiol (mercaptan) functionality and can be represented by the general chemical formula RS-H, such as n-dodecyl mercaptan and 2-mercaptoethanol.
• Preferred chain transfer agents are monothioglycerol and n-dodecyl mercaptan, used at levels of, preferably from 0 to 5 % w/w based on the weight of the monomer and more preferably at a level of 0.25 % w/w based on the weight of the monomer.
• Zeolites A, X and Y are taught for use in these compositions.
• Other perfume delivery systems are taught by WO 97/34982 and WO 98/41607, published by The Procter & Gamble.
• WO 97/34982 discloses particles comprising perfume loaded zeolite and a release barrier, which is an agent derived from a wax and having a size (i.e., a cross-sectional area) larger than the size of the pore openings of the zeolite carrier.
• WO 98/41607 discloses glassy particles comprising agents useful for laundry or cleaning compositions and a glass derived from one or more of at least partially-water-soluble hydroxylic compounds.
• PVP polyvinyl pyrrolidone
• PVA polyvinyl alcohol
• cellulose ethers polystyrene
• polyacrylates polymethacrylates
• Polymer particles are however preferred, especially polymer particles which comprise a water-insoluble shell comprising an aminoplast polymer.
• These include core shell encapsulates of which the water-insoluble shell comprises the reaction product of an amine selected from urea and melamine, or mixtures thereof, and an aldehyde selected from formaldehyde, acetaldehyde,
• the perfume carrying particles are typically of a size (measured as D 3 ) between 100 nanometers and 50 microns. Particles larger than this are entering the visible range.
• the preferred particle size range is either in the sub-micron range or the micron range.
• Suitable particles in the sub-micron range include nanoparticles, latexes, and mini-emulsion products with a typical size range of 100-600 nanometers.
• Suitable particles in the micron range include known types of aminoplast encapsulates, silica, clays starch and zeolite particles and coacervates with a typical size range of 1 -50 microns, preferably 5-30 microns.
• the particles may be provided with a deposition aid.
• Suitable deposition aids include natural or modified polysaccharides which are substantive to cotton and/or polyester, or phthalate containing species which are substantive to cotton and/or polyester.
• Useful components of the perfume include materials of both natural and synthetic origin. They include single compounds and mixtures. Specific examples of such components may be found in the current literature, e.g., in Fenaroli's Handbook of Flavor Ingredients, 1975, CRC Press; Synthetic Food Adjuncts, 1947 by M. B. Jacobs, edited by Van Nostrand; or Perfume and Flavor Chemicals by S.
• top notes are defined by Poucher (Journal of the Society of Cosmetic Chemists 6(2):80 [1955]). Examples of well known top-notes include citrus oils, linalool, linalyl acetate, lavender, dihydromyrcenol, rose oxide and cis-3-hexanol. Top notes typically comprise 15-25%wt of a perfume composition and in those embodiments of the invention which contain an increased level of top-notes it is envisaged at that least 20%wt would be present in an encapsulated form.
• Typical perfume components which it is advantageous to encapsulate include those with a relatively low boiling point, preferably those with a boiling point of less than 300, preferably 100-250 Celsius and pro-fragrances which can produce such components. It is also advantageous to encapsulate perfume components which have a low Clog P (i.e. those which will be partitioned into water), preferably with a Clog P of less than 3.0. These materials, of relatively low boiling point and relatively low Clog P have been called the "delayed blooming" perfume ingredients and include the following materials:
• Preferred non-encapsulated perfume ingredients are those hydrophobic perfume components with a ClogP above 3.
• ClogP means the calculated logarithm to base 10 of the octanol/water partition coefficient (P).
• the octanol/water partition coefficient of a PRM is the ratio between its equilibrium concentrations in octanol and water. Given that this measure is a ratio of the equilibrium concentration of a PRM in a non-polar solvent (octanol) with its concentration in a polar solvent (water), ClogP is also a measure of the
• ClogP values can be readily calculated from a program called "CLOGP" which is available from Daylight Chemical Information Systems Inc., Irvine Calif., USA. Octanol/water partition coefficients are described in more detail in U.S. Pat. No. 5,578,563.
• Perfume components with a ClogP above 3 comprise: Iso E super, citronellol, Ethyl cinnamate, Bangalol, 2,4,6-Trimethylbenzaldehyde, Hexyl cinnamic aldehyde, 2,6-Dimethyl-2-heptanol, Diisobutylcarbinol, Ethyl salicylate, Phenethyl isobutyrate, Ethyl hexyl ketone, Propyl amyl ketone, Dibutyl ketone, Heptyl methyl ketone, 4,5-Dihydrotoluene, Caprylic aldehyde, Citral, Geranial, Isopropyl benzoate, Cyclohexanepropionic acid, Campholene aldehyde, Caprylic acid, Caprylic alcohol, Cuminaldehyde, 1 -Ethyl-4-nitrobenzene, Heptyl formate,
• perfumes it is envisaged that there will be four or more, preferably five or more, more preferably six or more or even seven or more different perfume components present in the perfume.
• Another group of perfumes with which the present invention can be applied are the so-called 'aromatherapy' materials. These include many components also used in perfumery, including components of essential oils such as Clary Sage, Eucalyptus, Geranium, Lavender, Mace Extract, Neroli, Nutmeg, Spearmint, Sweet Violet Leaf and Valerian.
• antimicrobial perfume oils in addition to the non-ionic antimicrobial which is not a perfume oil. Examples of these include eucalyptol, thymol and tea-tree oil. Other antimicrobial perfume components are identified in WO 2000/024367.
• a further preferred feature is the inclusion of an insect repellent. Many suitable insect repellents are related to perfume species (many fall into both classes). The most commonly used insect repellents include: DEET (N,N-diethyl-m-toluamide), essential oil of the lemon eucalyptus (Corymbia citriodora) and its active compound p-menthane-3,8-diol (PMD), lcaridin, also known as Picaridin,
• D-Limonene, Bayrepel, and KBR 3023 Nepetalactone, also known as "catnip oil", Citronella oil, Permethrin, Neem oil and Bog Myrtle.
• Known insect repellents derived from natural sources include: Achillea alpina, alpha-terpinene, Basil oil (Ocimum basilicum), Callicarpa americana
• aqueous fabric conditioner composition comprising: (a) from 0.5 to 35%, by weight of the total composition, of a fabric softening active, wherein the fabric softening active includes an ester-linked triethanolamine quaternary ammonium compound, (b) from 0.01 % to 2%, by weight of the total composition, a non-ionic
• antimicrobial which is not a perfume component, preferably including a chlorinated phenyl ether, and/or 2, 2-dibromo-3-nitrilopropionamide, from 0.01 to 10%, by weight of the total composition, of a perfume, of which at least a part is encapsulated.
• compositions of the invention preferably comprise a floe prevention agent, which is a non-ionic alkoxylated material having an HLB value of from 8 to 18, preferably from 1 1 to 16, more preferably from 12 to 16 and most preferably 16.
• the flocculation prevention agent enables the formation of a thick "dilute" fabric conditioner composition, which does not flocculate upon use.
• the non-ionic alkoxylated material can be linear or branched, preferably linear.
• the floe prevention agent is preferably present in an amount of from 0.01 to 0.5 wt %, preferably from 0.02 to 0.4 wt %, more preferably from 0.05 to 0.25 wt % and most preferably 0.1 wt % by total weight of the composition.
• Suitable floe prevention agents include nonionic surfactants.
• Suitable non-ionic surfactants include addition products of ethylene oxide and/or propylene oxide with fatty alcohols, fatty acids and fatty amines.
• the floe prevention agent is preferably selected from addition products of (a) an alkoxide selected from ethylene oxide, propylene oxide and mixtures thereof with (b) a fatty material selected from fatty alcohols, fatty acids and fatty amines.
• Suitable surfactants are substantially water soluble surfactants of the general formula:
• Y is typically: -O- , -C(0)0- , -C(0)N(R)- or -C(0)N(R)R- in which R has the meaning given above or can be hydrogen; and Z is at least about 6, preferably at least about 10 or 1 1 .
• LutensolTM AT25 (BASF) based on coco chain and 25 EO groups is an example of a suitable nonoionic surfactant.
• Suitable surfactants include Renex 36 (Trideceth-6), ex Uniqema; Tergitol 15-S3, ex Dow Chemical Co.; Dihydrol LT7, ex Thai Ethoxylate ltd; Cremophor CO40, ex BASF and Neodol 91 -8, ex Shell.
• Polymeric Thickening Agent include Renex 36 (Trideceth-6), ex Uniqema; Tergitol 15-S3, ex Dow Chemical Co.; Dihydrol LT7, ex Thai Ethoxylate ltd; Cremophor CO40, ex BASF and Neodol 91 -8, ex Shell.
• Thickening polymers may be added to the compositions of the invention for further thickening. Any suitable thickener polymer may be used.
• Suitable polymers are water soluble or dispersable.
• the polymer is cationic.
• Polymers particularly useful in the compositions of the invention include those described in WO2010/078959 (SNF S.A.S.). These are crosslinked water swellable cationic copolymers having at least one cationic monomer and optionally other non-ionic and/or anionic monomers.
• Preferred polymers of this type are copolymers of acrylamide and trimethylaminoethylacrylate chloride.
• Preferred polymers comprise less than 25 % of water soluble polymers by weight of the total polymer, preferably less than 20 %, and most preferably less than 15%, and a cross-linking agent concentration of from 500 ppm to 5000 ppm relative to the polymer, preferably from 750 ppm to 5000 ppm, more preferably from 1000 to 4500 ppm (as determined by a suitable metering method such as that described on page 8 of patent EP 343840).
• the cross-linking agent concentration must be higher than about 500 ppm relative to the polymer, and preferably higher than about 750 ppm when the crosslinking agent used is the methylene bisacrylamide, or other cross-linking agents at concentrations that lead to equivalent cross-linking levels of from 10 to 10,000 ppm.
• Suitable cationic monomers are selected from the group consisting of the following monomers and derivatives and their quaternary or acid salts:
• dimethylaminopropylmethacrylamide dimethylaminopropylmethacrylamide, dimethylaminopropylacrylamide, diallylamine, methyldiallylamine, dialkylaminoalkyl-acrylates and methacrylates, dialkylaminoalkyl-acrylamides or -methacrylamides.
• the monomers may also contain hydrophobic groups.
• cross-linking agents methylene bisacrylamide (MBA), ethylene glycol diacrylate, polyethylene glycol dimethacrylate,
• the cross-linking rate preferably ranges from 800 to 5000 ppm (on the basis of methylene bisacrylamide) relative to the polymer or equivalent cross-linking with a cross-linking agent of different efficiency.
• the degree of non-linearity can additionally be controlled by the inclusion of chain transfer agents (such as isopropyl alcohol, sodium hypophosphite, mercaptoethanol) in the polymerisation mixture in order to control the polymeric chain's length and the cross-linking density.
• chain transfer agents such as isopropyl alcohol, sodium hypophosphite, mercaptoethanol
• the amount of polymer used in the compositions of the invention is suitably from 0.001 to 0.5 wt %, preferably from 0.005 to 0.4 wt %, more preferably from 0.05 to 0.35 wt % and most preferably from 0.1 to 0.25 wt %, by weight of the total composition.
• compositions of the invention may contain a non-cationic softening material, which is preferably an oil and more preferably an oily sugar derivative.
• perfume materials as used in this specification are distinguished from perfume materials in that perfume materials are listed as odiferous materials in Arctander's "Perfume and Flavor Materials of Natural Origin” ( ISBN-10: 0-931710-36-7), or listed as odiferous materials in various databases including Flavourbase 2010, ESO 2000 (2006 update) and PMP 2001 .
• Perfume materials are generally present as part of a complex mixture of components where each odiferous component is present at a level of below 0.5%wt of the composition as a whole. Oils present for other purposes are present at levels above 0.5%wt of the composition as a whole.
• An oily sugar derivative is a liquid or soft solid derivative of a cyclic polyol (CPE) or of a reduced saccharide (RSE), said derivative resulting from 35 to 100% of the hydroxyl groups in said polyol or in said saccharide being esterified or etherified.
• the derivative has two or more ester or ether groups independently attached to a C8-C22 alkyl or alkenyl chain.
• the CPE or RSE does not have any substantial crystalline character at 20°C. Instead it is preferably in a liquid or soft solid state as herein defined at 20°C.
• the liquid or soft solid (as hereinafter defined) CPEs or RSEs suitable for use in the present invention result from 35 to 100% of the hydroxyl groups of the starting cyclic polyol or reduced saccharide being esterified or etherified with groups such that the CPEs or RSEs are in the required liquid or soft solid state. These groups typically contain unsaturation, branching or mixed chain lengths.
• the CPEs or RSEs have 3 or more ester or ether groups or mixtures thereof, for example 3 to 8, especially 3 to 5. It is preferred if two or more of the ester or ether groups of the CPE or RSE are independently of one another attached to a Ce to C22 alkyl or alkenyl chain.
• the Ce to C22 alkyl or alkenyl groups may be branched or linear carbon chains.
• 35 to 85% of the hydroxyl groups most preferably 40-80%, even more preferably 45-75%, such as 45-70% are esterified or etherified.
• the CPE or RSE contains at least 35% tri or higher esters, e.g. at least 40%.
• the CPE or RSE has at least one of the chains independently attached to the ester or ether groups having at least one unsaturated bond. This provides a cost effective way of making the CPE or RSE a liquid or a soft solid. It is preferred if predominantly unsaturated fatty chains, derived from, for example, rape oil, cotton seed oil, soybean oil, oleic, tallow, palmitoleic, linoleic, erucic or other sources of unsaturated vegetable fatty acids, are attached to the ester/ether groups.
• the ester or ether chains of the CPE or RSE are preferably predominantly unsaturated.
• Preferred CPEs or RSEs include sucrose tetratallowate, sucrose tetrarapeate, sucrose tetraoleate, sucrose tetraesters of soybean oil or cotton seed oil, cellobiose tetraoleate, sucrose trioleate, sucrose triapeate, sucrose pentaoleate, sucrose pentarapeate, sucrose hexaoleate, sucrose hexarapeate, sucrose triesters, pentaesters and hexaesters of soybean oil or cotton seed oil, glucose tiroleate, glucose tetraoleate, xylose trioleate, or sucrose tetra-,tri-, penta- or hexa- esters with any mixture of predominantly unsaturated fatty acid chains.
• CPEs or RSEs based on polyunsaturated fatty acid chains e.g. sucrose tetralinoleate
• sucrose tetralinoleate may be used provided most of the polyunsaturation has been removed by partial hydrogenation.
• liquid CPEs or RSEs are any of the above but where the polyunsaturation has been removed through partial hydrogenation.
• the fatty acid chains Preferably 40% or more of the fatty acid chains contain an unsaturated bond, more preferably 50% or more, most preferably 60% or more. In most cases 65% to 100%, e.g. 65% to 95% contain an unsaturated bond.
• CPEs are preferred for use with the present invention.
• Inositol is a preferred example of a cyclic polyol. Inositol derivatives are especially preferred.
• the term cyclic polyol encompasses all forms of saccharides. Indeed saccharides are especially preferred for use with this invention.
• Examples of preferred saccharides for the CPEs or RSEs to be derived from are monosaccharides and disaccharides. Examples of monosaccharides include xylose, arabinose, galactose, fructose, sorbose and glucose. Glucose is especially preferred. Examples of
• disaccharides include maltose, lactose, cellobiose and sucrose. Sucrose is especially preferred.
• An example of a reduced saccharide is sorbitan.
• liquid or soft solid CPEs can be prepared by methods well known to those skilled in the art. These include acylation of the cyclic polyol or reduced
• the CPE or RSE has 3 or more, preferably 4 or more ester or ether groups. If the CPE is a disaccharide it is preferred if the disaccharide has 3 or more ester or ether groups. Particularly preferred CPEs are esters with a degree of esterification of 3 to 5, for example, sucrose tri, tetra and penta esters.
• each ring of the CPE has one ether or ester group, preferably at the Ci position.
• Suitable examples of such compounds include methyl glucose derivatives.
• CPEs examples include esters of alkyl(poly)glucosides, in particular alkyl glucoside esters having a degree of polymerisation from 1 to 2.
• the length of the unsaturated (and saturated if present) chains in the CPE or RSE is C8-C22, preferably Ci2-C22- It is possible to include one or more chains of Ci-Cs, however these are less preferred.
• the liquid or soft solid CPEs or RSEs which are suitable for use in the present invention are characterised as materials having a solid: liquid ratio of between 50:50 and 0: 100 at 20°C as determined by T 2 relaxation time NMR, preferably between 43:57 and 0: 100, most preferably between 40:60 and 0: 100, such as, 20:80 and 0: 100.
• the T 2 NMR relaxation time is commonly used for
• any component of the signal with a T 2 of less than 100 ⁇ is considered to be a solid component and any component with T 2 > 100 ⁇ is considered to be a liquid component.
• the prefixes e.g. tetra and penta
• the compounds exist as a mixture of materials ranging from the monoester to the fully esterified ester. It is the average degree of esterification which is used herein to define the CPEs and RSEs.
• the HLB of the CPE or RSE is typically between 1 and 3.
• the CPE or RSE is preferably present in the composition in an amount of 0.5-50% by weight, based upon the total weight of the composition, more preferably 1 -30% by weight, such as 2-25%, e.g. 2-20%.
• the CPEs and RSEs for use in the compositions of the invention include sucrose tetraoleate, sucrose pentaerucate, sucrose tetraerucate and sucrose pentaoleate.
• Optional shading dyes can be used. Preferred dyes appear violet or blue.
• the unsaturated quaternary ammonium compounds are subject to some degree of UV light and/or transition metal ion catalysed radical auto-oxidation, with an attendant risk of yellowing of fabric.
• the present of shading dye also reduces the risk of yellowing from this source.
• Different shading dyes give different levels of colouring.
• the level of shading dye present in the compositions of the present invention depends, therefore, on the type of shading dye.
• Preferred overall ranges, suitable for the present invention are from 0.00001 to 0.1 wt %, more preferably 0.0001 to 0.01 wt %, most preferably 0.0005 to 0.005 wt % by weight of the total composition.
• Direct Dyes Direct dyes (otherwise known as substantive dyes) are the class of water soluble dyes which have a affinity for fibres and are taken up directly. Direct violet and direct blue dyes are preferred.
• the dye are bis-azo or tris-azo dyes are used.
• the direct dye is a direct violet of the following structures:
• ring D and E may be independently naphthyl or phenyl as shown;
• Ri is selected from: hydrogen and C1 -C4-alkyl, preferably hydrogen;
• R 2 is selected from: hydrogen, C1 -C4-alkyl, substituted or unsubstituted phenyl and substituted or unsubstituted naphthyl, preferably phenyl;
• R 5 and R are independently selected from: hydrogen and C1 -C4-alkyl, preferably hydrogen or methyl;
• Preferred dyes are direct violet 7, direct violet 9, direct violet 1 1 , direct violet 26, direct violet 31 , direct violet 35, direct violet 40, direct violet 41 , direct violet 51 , and direct violet 99.
• Bis-azo copper containing dyes such as direct violet 66 may be used.
• the benzidene based dyes are less preferred.
• the direct dye is present at 0.00001 wt% to 0.0010 wt% of the formulation.
• the direct dye may be covalently linked to the photo- bleach, for example as described in WO2006/024612.
• Acid Dyes Cotton substantive acid dyes give benefits to cotton containing garments. Preferred dyes and mixes of dyes are blue or violet. Preferred acid dyes are: (i) azine dyes, wherein the dye is of the following core structure:
• R a , R b , R c and R d are selected from: H, an branched or linear C1 to C7- alkyl chain, benzyl a phenyl, and a naphthyl;
• the dye is substituted with at least one SO3 " or -COO " group
• the B ring does not carry a negatively charged group or salt thereof
• a ring may further substituted to form a naphthyl
• the dye is optionally substituted by groups selected from: amine, methyl, ethyl, hydroxyl, methoxy, ethoxy, phenoxy, CI, Br, I, F, and NO2.
• Preferred azine dyes are: acid blue 98, acid violet 50, and acid blue 59, more preferably acid violet 50 and acid blue 98.
• Other preferred non-azine acid dyes are acid violet 17, acid black 1 and acid blue 29.
• the composition may comprise one or more hydrophobic dyes selected from benzodifuranes, methine, triphenylmethanes, napthalimides, pyrazole, napthoquinone, anthraquinone and mono-azo or di-azo dye
• Hydrophobic dyes are dyes which do not contain any charged water solubilising group. Hydrophobic dyes may be selected from the groups of disperse and solvent dyes. Blue and violet anthraquinone and mono-azo dye are preferred.
• Preferred dyes include solvent violet 13, disperse violet 27 disperse violet 26, disperse violet 28, disperse violet 63 and disperse violet 77.
• the hydrophobic dye is present at 0.0001 wt% to 0.005 wt% of the formulation.
• Basic Dyes are organic dyes which carry a net positive charge. They deposit onto cotton. They are of particular utility for used in composition that contain predominantly cationic surfactants. Dyes may be selected from the basic violet and basic blue dyes listed in the Colour Index International.
• Preferred examples include triarylmethane basic dyes, methane basic dye, anthraquinone basic dyes, basic blue 16, basic blue 65, basic blue 66, basic blue 67, basic blue 71 , basic blue 159, basic violet 19, basic violet 35, basic violet 38, basic violet 48; basic blue 3, basic blue 75, basic blue 95, basic blue 122, basic blue 124, basic blue 141 .
• Reactive dyes are dyes which contain an organic group capable of reacting with cellulose and linking the dye to cellulose with a covalent bond. They deposit onto cotton. Preferably the reactive group is hydrolysed or reactive group of the dyes has been reacted with an organic species such as a polymer, so as to the link the dye to this species. Dyes may be selected from the reactive violet and reactive blue dyes listed in the Colour Index International.
• Preferred examples include reactive blue 19, reactive blue 163, reactive blue 182 and reactive blue, reactive blue 96.
• Dye conjugates are formed by binding direct, acid or basic dyes to polymers or particles via physical forces.
• Particularly preferred dyes are: direct violet 7, direct violet 9, direct violet 1 1 , direct violet 26, direct violet 31 , direct violet 35, direct violet 40, direct violet 41 , direct violet 51 , direct violet 99, acid blue 98, acid violet 50, acid blue 59, acid violet 17, acid black 1 , acid blue 29, solvent violet 13, disperse violet 27 disperse violet 26, disperse violet 28, disperse violet 63, disperse violet 77 and mixtures thereof.
• Co-softeners may be used. Suitable co-softeners include fatty acids. When employed, they are typically present at from 0.1 to 20% and particularly at from 0.5 to 10%, based on the total weight of the composition. Preferred co-softeners include fatty esters, and fatty N-oxides. Fatty esters that may be employed include fatty monoesters, such as glycerol monostearate, fatty sugar esters, such as those disclosed WO 01/46361 (Unilever). Preferred fatty acids include hardened tallow fatty acid (available under the tradename PristereneTM, ex Uniqema). Preferred fatty alcohols include hardened tallow alcohol (available under the tradenames StenolTM and HydrenolTM, ex Cognis and LaurexTM CS, ex Albright and Wilson).
• compositions for use in the present invention may comprise a fatty acid
• Especially suitable fatty complexing agents include fatty alcohols.
• Fatty complexing material may be used to improve the viscosity profile of the composition.
• the fatty complexing agent is preferably present in an amount greater than 0.3 to 5% by weight based on the total weight of the composition. More preferably, the fatty component is present in an amount of from 0.4 to 4%.
• the weight ratio of the mono-ester component of the quaternary ammonium fabric softening material to the fatty complexing agent is preferably from 5: 1 to 1 :5, more preferably 4: 1 to 1 :4, most preferably 3: 1 to 1 :3, e.g. 2: 1 to 1 :2.
• compositions of the invention may contain one or more other ingredients.
• Such ingredients include further preservatives (e.g. further bactericides and fungicides), pH buffering agents, hydrotropes, anti-redeposition agents, soil- release agents, polyelectrolytes, anti-shrinking agents, anti-wrinkle agents, anti- oxidants, sunscreens, anti-corrosion agents, drape imparting agents, anti-static agents, ironing aids pearlisers and/or opacifiers, natural oils/extracts, processing aids, e.g. electrolytes, and skin benefit agents.
• a particularly preferred optional ingredient is a suitable polyoxyalkylene material at a level effective to give a rinse aid benefit.
• a suitable material is polypropylene glycol at 0.15-5.0%wt.
• a preferred method of preparation for a dilute is as follows:-
• compositions of the present invention are aqueous fabric conditioning compositions suitable for use in a laundry process.
• compositions of the invention may also contain pH modifiers such as hydrochloric acid or lactic acid.
• pH modifiers such as hydrochloric acid or lactic acid.
• the liquid compositions preferably have a pH of about 2.5 to 3.0.
• composition is preferably for use in the rinse cycle of a home textile
• Examples of the invention are represented by a number following the point.
• TinosanTM HP 100 is a 30% solution of Diclosan (4,4'-Dichloro-2-hydroxy diphenyl ether) in a solvent (polypropylene glycol). It was used at various effective levels from 0.1 -0.025% In these examples this is compared with Benzalkonium chloride (BKC - Barquat MB50), which was used at an effective level of 0.4%.
• Example 1 Comparison of TEA base with 2HT base:
• Arquad is a di(hydrogenated tallow)dimethylammonium chloride based cationic fabric softening active.
• This base was processed by mixing water, preservative, peralescer citric acid and antimicrobial in a mixer at 28 rpm, 55 Celsius for 12 minutes before starting recirculation and milling. Agitator speed was then increased to 38 rpm and a premix of the active and the fatty acid were added together with the salt with mixing for 10 min. Dyes were added over 10 min with further stirring and milling. The mill was then stopped and the mixture cooled with recirculation to 45 Celsius, perfume was added and further recirculation and cooling was continued until the temperature reached 41 Celsius, at which point the antifoam was added.
• 2) TEA-base
• This base was processed by mixing water and the polymer in a mixer at 74 rpm, 50 Celsius for 12 minutes before slowing to 65 rpm. Preservative, sequestrant, acid and antimicrobial are then added with further mixing over 2 minutes. A premix of the active and non-ionic are added over 7 minutes. Salt and peariescer are added with a further 6 minutes mixing. Perfume added (encapsulates first) and the mix is cooled to 35 Celcius with recirculation before adding free perfume oil and antifoam mixing for a further 5 minutes after the target temperature is reached.
• Example 1 .B formed rust-coloured precipitates within 3 weeks using all processes and concentrations.
• Lonzabac 12 N,N'-Bis(3-aminopropyl)dodecylamine) .
• Antimicrobial effects were determined in the TEA base of example #1 using the EN1276 suspension method (with a 5 minute contact time at 20 Celsius) and by the AATCC TM100 surface method.
• the first of these tests (which is the standard EU test method) looks at hygiene in wash, while the second looks at hygiene in wear. Results are shown in the tables below:
• TM100 Bacterial Number (log cfu) (S. aureus)
• Treated textile ( ⁇ 10g) was quantitatively extracted by repeated reflux and concentration into ethanol (Soxhlet extraction). Following fifteen extraction cycles the volume of ethanol was reduced to 5 to 10 mis, allowed to cool and accurately weighed.
• the TEA base 2 with and without 0.05wt% Diclosan was prepared as given in the table below.
• TEA base 2 To 100% TEA base 2 was used in the final rinse at 35g dose using European wash conditions i.e. a Zanusi FLA machine on 40°C, cotton cycle, with a wash load comprising 1.5Kg knitted cotton and 1 .5Kg polyester in which the main wash was conducted using an 85gm dose of Persil non bio washing powder in 26°FH water. Following line-drying the knitted cotton from these washes was tested using the AATCC TM100 surface method.
• European wash conditions i.e. a Zanusi FLA machine on 40°C, cotton cycle
• a wash load comprising 1.5Kg knitted cotton and 1 .5Kg polyester
• Persil non bio washing powder Following line-drying the knitted cotton from these washes was tested using the AATCC TM100 surface method.
• Diclosan treated fabrics were also prepared by evenly wetting the fabric with diclosan solutions (in 90: 10 water: ethanol) and then evaporating to dryness. The levels of Diclosan retained on fabric were extracted and quantified as described previously. These Diclosan treated fabrics were tested using the AATCC TM100 surface method. This method provides a dose response indication of the level of Diclosan needed to achieve a reduction in bacterial growth. The results from the AATCC TM100 testing and the levels of Diclosan recovered are presented in the following table. Examples 5.B-5.G below provide data for the dried-own solutions, and examples 5.A and 5.1 provide data for the fully formulated products. TM100: bacterial Number (Log cfu; S. aureus)

Landscapes

• Chemical & Material Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Wood Science & Technology (AREA)
• Organic Chemistry (AREA)
• Dispersion Chemistry (AREA)
• Detergent Compositions (AREA)
• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Priority Applications (7)

Applications Claiming Priority (2)

Publications (1)

Family

ID=48095842

Family Applications (1)

Country Status (8)

Cited By (11)

Families Citing this family (4)

Citations (20)

Family Cites Families (12)

• 2013
  • 2013-04-10 BR BR112014025932A patent/BR112014025932A2/pt not_active Application Discontinuation
  • 2013-04-10 IN IN2042MUN2014 patent/IN2014MN02042A/en unknown
  • 2013-04-10 ES ES13716273.1T patent/ES2550989T3/es active Active
  • 2013-04-10 EP EP13716273.1A patent/EP2838982B9/en not_active Revoked
  • 2013-04-10 CN CN201380020539.7A patent/CN104220577B/zh active Active
  • 2013-04-10 WO PCT/EP2013/057512 patent/WO2013156371A1/en active Application Filing
• 2014
  • 2014-10-03 ZA ZA2014/07180A patent/ZA201407180B/en unknown
  • 2014-10-10 PH PH12014502291A patent/PH12014502291A1/en unknown

Patent Citations (21)

Non-Patent Citations (6)

Also Published As

Similar Documents

Legal Events