EP2748295B1 - Verkapselter pflegestoff - Google Patents

Verkapselter pflegestoff Download PDF

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Publication number
EP2748295B1
EP2748295B1 EP12734951.2A EP12734951A EP2748295B1 EP 2748295 B1 EP2748295 B1 EP 2748295B1 EP 12734951 A EP12734951 A EP 12734951A EP 2748295 B1 EP2748295 B1 EP 2748295B1
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EP
European Patent Office
Prior art keywords
fabric conditioner
capsule
group
fabric
hydrophobic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Not-in-force
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EP12734951.2A
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English (en)
French (fr)
Other versions
EP2748295A1 (de
Inventor
Stuart Anthony Barnett
Robert Allan Hunter
Christopher Clarkson Jones
Craig Warren Jones
Xiaoyun Pan
Jinfang Wang
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Unilever PLC
Unilever NV
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Unilever PLC
Unilever NV
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Publication of EP2748295A1 publication Critical patent/EP2748295A1/de
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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
    • 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
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C11D3/3773—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines in liquid compositions
    • 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 encapsulated benefit agents, particularly one or more perfume components, and their use in the formulation of fabric conditioning compositions.
  • Compositions containing particles according to the invention provide superior viscostability and compatibility benefits as well as perfume longevity.
  • Perfume is one of the most expensive components in laundry products and its fragrance is one of the most important attributes and reasons for purchase across laundry brands.
  • a known technology for the provision of long-lasting perfume performance is the use of melamine-formaldehyde perfume capsules. The capsules have a high loading amount of perfume and are able to release perfume upon rubbing.
  • WO2004/031271 discloses modified PVOH films with a preferred average thickness of from 50 to 500 microns, used to make capsules.
  • the capsules preferably contain from 0.5 ml to 100 ml of a material such as a laundry conditioner.
  • WO2009/103576 relates to a particle having a diameter of less than 2 mm comprising a benefit agent, such as a perfume, and a water soluble polymeric film-forming material modified with a charged derivatising group; whereby the film remains substantially intact in the presence of a surfactant and disintegrates when the concentration of the surfactant reduces sufficiently, thereby releasing the benefit agent.
  • a benefit agent such as a perfume
  • WO 2005/103215 discloses storage stable liquid fabric conditioners comprising quaternary softening compounds and a polymer encapsulates article, further coated with a cationic polymer.
  • compositions comprising microcapsules which are further coated with a PVOH -copolymer.
  • WO2009/103615 relates to a fabric conditioning composition of pH of less than 7, comprising a quaternary ammonium conditioning agent, an encapsulated benefit agent, which is made, at least in part, from a formaldehyde-based polymer, and at least in part from a non-formaldehyde based polymer, and a formaldehyde scavenger.
  • perfume encaps with a coating technology based upon modified PVOH can solve the problem.
  • the coated capsules have superior compatibility with fabric conditioners so that the viscosity of the formulation is maintained at an appropriate level. Thus perfume longevity can be achieved without the need to sacrifice the quality of the product itself.
  • liquid fabric conditioner composition comprising:-
  • a method of improving the viscostability of a liquid fabric conditioner comprising a particle comprising a core comprising a benefit agent and a shell; comprising the step of providing the particle with a coating comprising a modified polyvinyl alcohol as defined in the first aspect of the invention, and wherein the particle has a weight ratio of the capsule to the coating in the range of from 1:1 to 4:1; and the modified polyvinyl alcohol has a level of hydrophobic modification of from 2.0 to 15.0 mole %, with the proviso that at a weight ratio of capsule to coating from 1:1 to 1.25:1 , the level of hydrophobic modification is from 2 to 10 mol %, and wherein the liquid fabric conditioner comprises a quaternary ammonium compound.
  • a process for conditioning fabrics comprising the step of contacting a composition as defined by the first aspect of the invention.
  • the fabric conditioning base comprises a fabric conditioning active and has a pH of from 2.0 to 5.0, preferably from 2.5 to 4.5, most preferably from 2.5 to 4.0.
  • the fabric conditioning active (also referred to herein as the fabric softening active) is a quaternary ammonium compound.
  • Fabric conditioning compositions of the invention may be dilute or concentrated.
  • Products of the invention comprise from 2 to about 50 % of fabric conditioning active.
  • Dilute products typically contain up to about 8 %, generally about 2 to 8 % by weight of softening active, whereas concentrated products may contain up to about 50 wt %, preferably from about 8.5 to about 50 %, more preferably from 8 to 25 % by weight active.
  • the softening active for use in rinse conditioner compositions of the invention is a quaternary ammonium compound (QAC).
  • QAC quaternary ammonium compound
  • the preferred quaternary ammonium fabric conditioner for use in compositions of the present invention are the 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 % by weight of the fabric softening compound, preferably no more than 60 wt % of the fabric softening compound and at least 10 % of the monoester linked component.
  • a preferred hardened type of active has a typical mono:di:tri ester distribution in the range of from 12 to 25 mono: from 55 to 65 di: from 15 to 27 tri.
  • 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 first group of quaternary ammonium compounds (QACs) suitable for use in the present invention is represented by formula (I): wherein each R is independently selected from a C 5-35 alkyl or alkenyl group; R 1 represents a C 1-4 alkyl, C 2-4 alkenyl or a C 1-4 hydroxyalkyl group; T is generally O-CO. (i.e. an ester group bound to R via its carbon atom), but may alternatively be CO-O (i.e.
  • TEA ester quats preparations which are rich in the di-esters of triethanolammonium methylsulphate, otherwise referred to as "TEA ester quats".
  • StepantexTM UL85 Ex Stepan, PrapagenTM TQL, ex Clariant, and TetranylTM AHT-1
  • Ex Kao both di-[hardened tallow ester] of triethanolammonium methylsulphate
  • AT-1 di-[tallow ester] of triethanolammonium methylsulphate
  • L5/90 di-[palm ester] of triethanolammonium methylsulphate
  • Ex Kao and RewoquatTM WE15 (a di-ester of triethanolammonium methylsulphate having fatty acyl residues deriving from C 10 -C 20 and C 16 -C 18 unsaturated fatty acids), ex Witco Corporation.
  • soft quaternary ammonium actives such as Stepantex VK90, Stepantex VT90, SP88 (ex-Stepan), 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.
  • a second group of QACs suitable for use in the invention is represented by formula (II): wherein each R 1 group is independently selected from C 1-4 alkyl, hydroxyalkyl or C 2-4 alkenyl groups; and wherein each R 2 group is independently selected from C 8-28 alkyl or alkenyl groups; and wherein n, T, and X- are as defined above.
  • Preferred materials of this second group include 1,2 bis [tallowoyloxy]-3-trimethylammonium propane chloride, 1,2 bis [hardened tallowoyloxy]-3-trimethylammonium propane chloride, 1,2- bis [oleoyloxy]-3-trimethylammonium propane chloride, and 1,2 bis [stearoyloxy]-3-trimethylammonium propane chloride.
  • Such materials are described in US 4,137,180 (Lever Brothers).
  • these materials also comprise an amount of the corresponding mono-ester.
  • a third group of QACs suitable for use in the invention is represented by formula (III): (R 1 ) 2 -N + -[(CH 2 ) n -T-R 2 ] 2 X- (III) wherein each R 1 group is independently selected from C 1-4 alkyl, or C 2-4 alkenyl groups; and wherein each R 2 group is independently selected from C 8-28 alkyl or alkenyl groups; and n, T, and X- are as defined above.
  • Preferred materials of this third group include bis(2-tallowoyloxyethyl)dimethyl ammonium chloride, partially hardened and hardened versions thereof.
  • the iodine value of the quaternary ammonium fabric conditioning material is preferably from 0 to 80, more preferably from 0 to 60, and most preferably from 0 to 45.
  • the iodine value may be chosen as appropriate.
  • Essentially saturated material having an iodine value of from 0 to 5, preferably from 0 to 1 may be used in the compositions of the invention. Such materials are known as "hardened" quaternary ammonium compounds.
  • a further preferred range of iodine values is from 20 to 60, preferably 25 to 50, more preferably from 30 to 45.
  • a material of this type is a "soft" triethanolamine quaternary ammonium compound, preferably triethanolamine di-alkylester methylsulphate. Such ester-linked triethanolamine quaternary ammonium compound comprise unsaturated fatty chains.
  • Iodine value refers to the measurement of the degree of unsaturation present in a material by a method of nmr spectroscopy as described in Anal. Chem., 34, 1136 (1962) Johnson and Shoolery .
  • a further type of softening compound is a non-ester quaternary ammonium material represented by formula (IV):- wherein each R 1 group is independently selected from C 1-4 alkyl, hydroxyalkyl or C 2-4 alkenyl groups; R 2 group is independently selected from C 8-28 alkyl or alkenyl groups, and X- is as defined above.
  • compositions of the invention may contain a non-cationic softening material, which is preferably an oily sugar derivative.
  • An oily sugar derivative is a liquid or soft solid derivative of a cyclic polyol (CPE) or of a reduced saccharide (RSE), said derivative resulting from 35 to 100 % of the hydroxyl groups in said polyol or in said saccharide being esterified or etherified.
  • the derivative has two or more ester or ether groups independently attached to a C 8 -C 22 alkyl or alkenyl chain.
  • the CPE or RSE does not have any substantial crystalline character at 20°C. Instead it is preferably in a liquid or soft solid state as herein defined at 20°C.
  • liquid or soft solid (as hereinafter defined) CPEs or RSEs suitable for use in the present invention result from 35 to 100% of the hydroxyl groups of the starting cyclic polyol or reduced saccharide being esterified or etherified with groups such that the CPEs or RSEs are in the required liquid or soft solid state.
  • These groups typically contain unsaturation, branching or mixed chain lengths.
  • the CPEs or RSEs have 3 or more ester or ether groups or mixtures thereof, for example 3 to 8, especially 3 to 5. It is preferred if two or more of the ester or ether groups of the CPE or RSE are independently of one another attached to a C 8 to C 22 alkyl or alkenyl chain.
  • the C 8 to C 22 alkyl or alkenyl groups may be branched or linear carbon chains.
  • the CPE or RSE contains at least 35 % tri or higher esters, e.g. at least 40 %.
  • the CPE or RSE has at least one of the chains independently attached to the ester or ether groups having at least one unsaturated bond. This provides a cost effective way of making the CPE or RSE a liquid or a soft solid. It is preferred if predominantly unsaturated fatty chains, derived from, for example, rape oil, cotton seed oil, soybean oil, oleic, tallow, palmitoleic, linoleic, erucic or other sources of unsaturated vegetable fatty acids, are attached to the ester/ether groups.
  • ester or ether chains of the CPE or RSE.
  • the ester or ether chains of the CPE or RSE are preferably predominantly unsaturated.
  • Preferred CPEs or RSEs include sucrose tetratallowate, sucrose tetrarapeate, sucrose tetraoleate, sucrose tetraesters of soybean oil or cotton seed oil, cellobiose tetraoleate, sucrose trioleate, sucrose triapeate, sucrose pentaoleate, sucrose pentarapeate, sucrose hexaoleate, sucrose hexarapeate, sucrose triesters, pentaesters and hexaesters of soybean oil or cotton seed oil, glucose tiroleate, glucose tetraoleate, xylose trioleate, or sucrose tetra-,tri-, penta-or hexa- esters with any mixture of predominantly unsaturated fatty acid chains.
  • CPEs or RSEs are those with monounsaturated fatty acid chains, i.e. where any polyunsaturation has been removed by partial hydrogenation.
  • CPEs or RSEs based on polyunsaturated fatty acid chains e.g. sucrose tetralinoleate, may be used provided most of the polyunsaturation has been removed by partial hydrogenation.
  • liquid CPEs or RSEs are any of the above but where the polyunsaturation has been removed through partial hydrogenation.
  • Preferably 40 % or more of the fatty acid chains contain an unsaturated bond, more preferably 50 % or more, most preferably 60% or more. In most cases 65 % to 100 %, e.g. 65 % to 95 % contain an unsaturated bond.
  • CPEs are preferred for use with the present invention.
  • Inositol is a preferred example of a cyclic polyol. Inositol derivatives are especially preferred.
  • cyclic polyol encompasses all forms of saccharides. Indeed saccharides are especially preferred for use with this invention. Examples of preferred saccharides for the CPEs or RSEs to be derived from are monosaccharides and disaccharides.
  • Examples of monosaccharides include xylose, arabinose, galactose, fructose, sorbose and glucose. Glucose is especially preferred.
  • Examples of disaccharides include maltose, lactose, cellobiose and sucrose. Sucrose is especially preferred.
  • An example of a reduced saccharide is sorbitan.
  • the liquid or soft solid CPEs can be prepared by methods well known to those skilled in the art. These include acylation of the cyclic polyol or reduced saccharide with an acid chloride; trans-esterification of the cyclic polyol or reduced saccharide fatty acid esters using a variety of catalysts; acylation of the cyclic polyol or reduced saccharide with an acid anhydride and acylation of the cyclic polyol or reduced saccharide with a fatty acid. See for instance US 4 386 213 and AU 14416/88 (both P&G).
  • the CPE or RSE has 3 or more, preferably 4 or more ester or ether groups. If the CPE is a disaccharide it is preferred if the disaccharide has 3 or more ester or ether groups. Particularly preferred CPEs are esters with a degree of esterification of 3 to 5, for example, sucrose tri, tetra and penta esters.
  • each ring of the CPE has one ether or ester group, preferably at the C 1 position.
  • Suitable examples of such compounds include methyl glucose derivatives.
  • CPEs examples include esters of alkyl(poly)glucosides, in particular alkyl glucoside esters having a degree of polymerisation of 2.
  • the length of the unsaturated (and saturated if present) chains in the CPE or RSE is C 8 -C 22 , preferably C 12 -C 22 . It is possible to include one or more chains of C 1 -C 8 , however these are less preferred.
  • the liquid or soft solid CPEs or RSEs which are suitable for use in the present invention are characterised as materials having a solid:liquid ratio of between 50:50 and 0:100 at 20°C as determined by T 2 relaxation time NMR, preferably between 43:57 and 0:100, most preferably between 40:60 and 0:100, such as, 20:80 and 0:100.
  • the T 2 NMR relaxation time is commonly used for characterising solid:liquid ratios in soft solid products such as fats and margarines.
  • any component of the signal with a T 2 of less than 100 ⁇ s is considered to be a solid component and any component with T 2 ⁇ 100 ⁇ s is considered to be a liquid component.
  • the prefixes e.g. tetra and penta
  • the compounds exist as a mixture of materials ranging from the monoester to the fully esterified ester. It is the average degree of esterification which is used herein to define the CPEs and RSEs.
  • the HLB of the CPE or RSE is typically between 1 and 3.
  • the CPE or RSE is preferably present in the composition in an amount of 0.5-50% by weight, based upon the total weight of the composition, more preferably 1-30% by weight, such as 2-25%, e.g. 2-20%.
  • the CPEs and RSEs for use in the compositions of the invention include sucrose tetraoleate, sucrose pentaerucate, sucrose tetraerucate and sucrose pentaoleate.
  • the particle comprises a capsule and a coating.
  • the capsule comprises a core comprising a benefit agent; and a shell; and the coating comprises a modified polyvinyl alcohol.
  • the particle preferably has a particle size of from 0.2 to 50 microns, more preferably from 2 to 50 microns.
  • the capsule (which is also referred to herein as a "microcapsule”) comprises a core and a shell.
  • the shell comprises a suitable encapsulating material, examples of which include aminoplasts, proteins, polyurethanes, polyacrylates, polymethacrylates, polysaccharides and gums.
  • Preferred encapsulating polymers include those formed from melamine formaldehyde or urea formaldehyde condensates, as well as similar types of aminoplasts. Most preferably the shell comprises melamine formaldehyde.
  • microcapsules made via the simple or complex coacervation of gelatin may also be used.
  • Microcapsules having shells comprised of polyurethane, polyamide, polyolefin, polysaccaharide, protein, silicone, lipid, gums, polyacrylate, polystyrene, and polyesters or combinations of these materials are also possible.
  • a representative process used for aminoplast encapsulation is disclosed in U.S. Patent No. 3,516,941 though it is recognized that many variations with regard to materials and process steps are possible.
  • a representative process used for gelatin encapsulation is disclosed in U.S. Patent No, 2,800,457 though it is recognized that many variations with regard to materials and process steps are possible. Both of these processes are discussed in the context of fragrance encapsulation for use in consumer products in U.S. Patent Nos. 4,145,184 and 5,112,688 respectively.
  • Encapsulation can provide pore vacancies or interstitial openings depending on the encapsulation techniques employed.
  • Fragrance capsules known in the art and suitable for use in the present invention comprise a shell comprising a three-dimensional cross-linked network of an aminoplast resin, more specifically a substituted or un-substituted acrylic acid polymer or co-polymer cross-linked with a urea-formaldehyde pre-condensate or a melamine-formaldehyde pre-condensate.
  • Microcapsule formation using mechanisms similar to the foregoing mechanism, using (i) melamine-formaldehyde or urea-formaldehyde pre-condensates and (ii) polymers containing substituted vinyl monomeric units having proton-donating functional group moieties (e.g. sulfonic acid groups or carboxylic acid anhydride groups) bonded thereto is disclosed in 44068162 USB U.S.
  • Patent 4,406,816 (2-acrylamido-2-methyl-propane sulfonic acid groups), 2062570 GBA UK published Patent Application GB 2,062,570 A (styrene sulfonic acid groups) and 2006709 GBA UK published Patent Application GB 2,006,709 A (carboxylic acid anhydride groups).
  • the capsules may be used in the form of a slurry, which preferably comprises about 40% solids.
  • the amount of such a 40% capsule slurry to be used in a composition is up to 10 %, preferably from 0.1 to 5 %, more preferably from 0.5 to 2 % by weight of the total composition.
  • Particle size and average diameter of the capsules can vary from about 10 nanometers to about 1000 microns, preferably from about 50 nanometers to about 100 microns, more preferably from about 2 to about 40 microns, even more preferably from about 4 to 15 microns. A particularly preferred range is from about 5 to 10 microns, for example 6 to 7 microns.
  • the capsule distribution can be narrow, broad or multimodal. Multimodal distributions may be composed of different types of capsule chemistries.
  • benefit agents are hydrophobic materials that can provide a beneficial effect to the substrate fabric.
  • the preferred benefit agents according to the present invention have a ClogP greater than 0.5.
  • Preferred benefit agents include perfumes, lubricants any other oily materials. Particularly preferred benefit agents include, but not limited to, the following:
  • perfume components include both odiferous materials and pro-fragrance materials.
  • the perfume is typically present in an amount of from 10-85% by total weight of the particle, preferably from 20 to 75% by total weight of the particle.
  • the perfume suitably has a molecular weight of from 50 to 500.
  • 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 Nostr and; or Perfume and Flavor Chemicals by S. Arctander 1969, Montclair, N.J. (USA ).
  • perfume in this context is not only meant a fully formulated product fragrance, but also selected components of that fragrance, particularly those which are prone to loss, such as the so-called 'top notes'.
  • 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 within the encapsulate.
  • 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.
  • perfume components which have a low LogP (i.e. those which will be partitioned into water), preferably with a LogP of less than 3.0.
  • materials, of relatively low boiling point and relatively low LogP have been called the "delayed blooming" perfume ingredients and include the following materials:
  • perfume components 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 from the list given of delayed blooming perfumes given above present in the encapsulated perfume.
  • 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. By means of the present invention these materials can be transferred to textile articles that will be worn or otherwise come into contact with the human body (such as handkerchiefs and bed linen).
  • the capsules for use in the invention can also comprise a carrier oil in the core.
  • the oil must be compatible with the benefit agent, which is preferably a perfume.
  • the carrier oils are hydrophobic materials that are miscible in the perfume materials used in the present invention. Suitable oils are those having reasonable affinity for the fragrance chemicals. Suitable materials include, but are not limited to triglyceride oil, mono and diglycerides, mineral oil, silicone oil, diethyl phthalate, polyalpha olefins, castor oil and isopropyl myristate.
  • the oil is a triglyceride oil, most preferably a capric/caprylic triglyceride oil.
  • the capsules can also comprise a filler.
  • Suitable fillers can be inorganic, organic or a mixture of both including but not restricted to, for example, micro-crystalline celluloses, long-chain fatty acids, silicas both precipitated and fumed, clays natural and synthetic, nano-metaols, carbon-black, pigments, zinc sulphide, zince pyrythirone, barium sulphate, aluminium oxides, ligin, lignin sulphates, calcium carbonate and talcs.
  • the coating comprises a modified polyvinyl alcohol.
  • the modified polyvinyl alcohol (m-PVOH) is derived from a parent polyvinyl alcohol (also referred to herein as the starting polyvinyl alcohol, and designated PVOH).
  • PVOH Mowiol range (Trade Mark), ex Kuraray Specialities Europe GmBh.
  • the parent polyvinyl alcohol preferably has a molecular weight of from 1,000 to 300,000, preferably from 2,000 to 100,000, most preferably from 2,000 to 75,000.
  • the modified PVOH comprises:
  • alkyl is intended to cover saturated and unsaturated functional groups, preferably saturated.
  • the mole ratio of hydrophobic groups to hydrophilic groups is from 1:0.5 to 1:10, more preferably from 1:1.5 to 1:7 and most preferably from 1:2 to 1:7, based on the extent of modification of the OH groups on the starting polyvinyl alcohol.
  • the hydrophobic group is attached to the starting polyvinyl alcohol by reaction of the starting PVOH with a suitable parent material (said parent material is also referred to herein as a Type HB parent material).
  • the hydrophobic group is preferably present in the polyvinyl alcohol at a level of from 2.0 mol % to 15 mol %, preferably from 2.0 mol % to 14 mol %, most preferably from 2.0 to 13 mol %.
  • the mole % is based on the number of OH groups present in the starting (unmodified) polyvinyl alcohol.
  • the Type HB parent material is selected from aldehydes, acetals, ketals, esters, fluorinated organic compounds, ethers, alkanes, alkenes and aromatic compounds, which also contain the desired hydrophobic group in accordance with the invention, most preferably aldehydes and acteals.
  • the hydrophilic group is attached to the starting polyvinyl alcohol by reaction of the starting PVOH with a suitable parent material (said parent material is also referred to herein as a Type HL parent material).
  • the Type HL parent material is selected from a material having a ClogP of from 0.5 to 6, more preferably from 1 to 6 and most preferably from 2 to 6, e.g. from 3 to 5.
  • ClogP is calculated using the methods given in: Ghose, Viswanadhan and Wendoloski, Prediction of Hydrophobic (Lipophilic) Properties of Small Organic Molecules Using Fragment Methods: An Analysis of AlogP and CLogP Methods. J. Phys. Chem. A, 1998, 102, 3762-3772 . This method is implemented within the software: "Pipeline Pilot", available from SciTegic, a wholly owned subsidiary of Accelrys, Inc.
  • the hydrophilic group is preferably present in the polyvinyl alcohol at a level of from at least 0.1 mol % to 20 mol %, preferably from 5 mol % to 18 mol %, most preferably from 8 mol % to 15 mol %.
  • the mole % is based on the number of OH groups present in the starting (unmodified) polyvinyl alcohol.
  • Preferred hydrophilic groups can be derived from Type HL parent materials selected from aldehydes, acetals, ketals, esters, fluorinated organic compounds, ethers, alkanes, alkenes, aromatic compounds, which also contain the desired hydrophilic group in accordance with the invention.
  • Type HL parent groups are aldehydes such as: amino-butyraldehyde, amino-octyl aldehyde, amino-dodecyl aldehyde, amino-2-ethyl hexanal, amino-cyclohexane carboxy-aldehyde, amino-citral, amino-propionaldehyde, amino(2-methoxyethoxy) acetaldehyde, amino-dimethylacetal and amino-benzaldehyde, although it will be readily apparent to the person skilled in the art that other suitable parent groups having the requisite ClogP are also suitable for use in the invention.
  • aldehydes such as: amino-butyraldehyde, amino-octyl aldehyde, amino-dodecyl aldehyde, amino-2-ethyl hexanal, amino-cyclohexane carboxy-aldehyde, amino-citral, amino-propionaldeh
  • a particularly preferred mPVOH for use in the present invention can be represented by the following formula: Wherein R is the hydrophobic group and R' is the hydrophilic (amine) group.
  • the hydrophilic group (R') is preferably derived from one or more of:
  • acetate groups present in the modified PVOH which arise from the starting PVOH material. These are typically present in an amount of from 1 to 12 mol %, preferably from 1 to 2 mol %, based on the total amount of OH groups present in the starting PVOH material.
  • the hydrophobic group (R) is preferably derived one or more of: butyraldehyde, octyl aldehyde, dodecyl aldehyde, 2-ethyl hexanal, cyclohexane carboxy-aldehyde, citral, propionaldehyde, (2-methoxyethoxy) acetaldehyde dimethylacetal, and benzaldehyde.
  • the particle has a weight ratio of the capsule to the coating in the range of from 1:1 to 4:1, preferably from 1:1 to 3:1. In another preferred embodiment, the weight ratio of capsule to coating is in the range of from 2:1 to 4:1.
  • the modified polyvinyl alcohol has a level of hydrophobic modification of from 2.0 to 15.0 mol % with the proviso that at a weight ratio of capsule to coating from 1:1 to 1.25:1 the level of hydrophobic modification is from 2 to 10 mol %.
  • modified PVOH prefferably provided as a cross-linked polymeric structure.
  • the level of cross-linking should be kept low so as to avoid the formation of an insoluble material.
  • cross-linking agents include formaldehyde; polyesters; epoxides; amidoamines; anhydrides; phenols; isocyanates; vinyl esters; urethanes; polyimides; arylics; bis(methacrylkoxypropyl) tetramethylsiloxane (styrenes, methylmethacrylates); n-diazopyruvates; phenyboronic acids; cis-platin; divinylbenzene; polyamides; dialdehydes; triallyl cyanurates; N-(-2-ethanesulfonylethyl)pyridinium halides; tetraalkyltitanates; mixtures of titanates and borates or zirconates; polyvalent ions of Cr, Zr, Ti; dialdehydes, diketones; alcohol complexes of organotitanates, zircoates and borates and copper (II) complexes.
  • the preferred cross-linking agent is a metalloid oxide such as borate, tellurate, arsenate, and precursors thereof.
  • Other known cross-linkers include the vanadyl ion, titanium ion in the plus three valence state, or a permanganate ion (disclosed in patent US 3,518,242 ).
  • Alternative cross-linkers are given in the book: Polyvinylalcohol - Properties and applications, Chapter 9 by C.A. Finch (John Wiley & Sons, New York, 1973 ).
  • the modification of the polymer can be accomplished by a range of known processes.
  • an acidic solution of PVOH preferably formed at a temperature of above 80 degrees Celsius
  • an aldehyde/acetal preferably added dropwise. After the addition of the components the reaction is allowed to proceed for several hours at STP.
  • modified PVOH produced as outlined above of the present invention can be added to the encapsulate slurry prior to addition to the final product, or it can be added to the formulation containing the encapsulates.
  • the former process is preferred.
  • Co-softeners may be used. When employed, they are typically present at from 0.1 to 20% and particularly at from 0.5 to 10%, based on the total weight of the composition.
  • Preferred co-softeners include fatty esters, and fatty N-oxides.
  • Fatty esters that may be employed include fatty monoesters, such as glycerol monostearate, fatty sugar esters, such as those disclosed WO 01/46361 (Unilever ).
  • compositions for use in the present invention may comprise a fatty complexing agent.
  • Suitable fatty complexing agents include fatty alcohols and fatty acids. Of these, fatty alcohols are most preferred.
  • Fatty complexing material may be used to improve the viscosity profile of the composition.
  • 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).
  • the fatty complexing agent is preferably present in an amount greater than 0.3 to 5% by weight based on the total weight of the composition. More preferably, the fatty component is present in an amount of from 0.4 to 4%.
  • the weight ratio of the mono-ester component of the quaternary ammonium fabric softening material to the fatty complexing agent is preferably from 5:1 to 1:5, more preferably 4:1 to 1:4, most preferably 3:1 to 1:3, e.g. 2:1 to 1:2.
  • compositions may further comprise a nonionic surfactant. Typically these can be included for the purpose of stabilising the compositions. These are particularly suitable for compositions comprising hardened quaternary ammonium compounds.
  • Suitable nonionic surfactants include addition products of ethylene oxide and/or propylene oxide with fatty alcohols, fatty acids and fatty amines. Any of the alkoxylated materials of the particular type described hereinafter can be used as the nonionic surfactant.
  • Y is typically: -O-, -C(O)O- , -C(O)N(R)- or -C(O)N(R)R- in which R has the meaning given above or can be hydrogen; and Z is at least about 8, preferably at least about 10 or 11.
  • the nonionic surfactant has an HLB of from about 7 to about 20, more preferably from 10 to 18, e.g. 12 to 16.
  • GenapolTM C200 (Clariant) based on coco chain and 20 EO groups is an example of a suitable nonionic surfactant.
  • the nonionic surfactant is present in an amount from 0.01 to 10%, more preferably 0.1 to 5 by weight, based on the total weight of the composition.
  • Optional shading dyes can be used. Preferred dyes are violet or blue. Suitable and preferred classes of dyes are discussed below. Moreover 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 presence of a shading dye also reduces the risk of yellowing from this source.
  • the level of shading dye present in the compositions of the present invention depend, 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 are the class of water soluble dyes which have an 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: or wherein:
  • Preferred dyes are direct violet 7, direct violet 9, direct violet 11, 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 .
  • 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: wherein R a , R b , R c and R d are selected from: H, a branched or linear C1 to C7-alkyl chain, benzyl a phenyl, and a naphthyl; the dye is substituted with at least one SO 3 - or -COO - group; the B ring does not carry a negatively charged group or salt thereof; and the 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, Cl, Br, I, F, and NO 2 .
  • Preferred azine dyes are: acid blue 98, acid violet 50, and acid blue 59, more preferably acid violet 50 and acid blue 98.
  • non-azine acid dyes are acid violet 17, acid black 1 and acid blue 29.
  • the acid dye is present at 0.0005 wt% to 0.01 wt% of the formulation.
  • 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 chromophores.
  • 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.
  • 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 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 11, 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.
  • compositions of the present invention may comprise one or more perfumes if desired.
  • the perfume is preferably present in an amount from 0.01 to 10 % by weight, more preferably from 0.05 to 5 % by weight, even more preferably from 0.1 to 4.0 %, most preferably from 0.15 to 4.0 % by weight, based on the total weight of the composition.
  • 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 Nostr and; or Perfume and Flavor Chemicals by S. Arctander 1969, Montclair, N.J. (USA ).
  • perfume in this context is not only meant a fully formulated product fragrance, but also selected components of that fragrance, particularly those which are prone to loss, such as the so-called 'top notes'.
  • 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 within the encapsulate.
  • perfume or pro-fragrance may be encapsulated, 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.
  • 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.
  • Clog P i.e. those which will be partitioned into water
  • 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 perfume raw material (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 hydrophobicity of a material--the higher the ClogP value, the more hydrophobic the material.
  • 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, 4-I
  • compositions of the present invention 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 from the list given of delayed blooming perfumes given above and/or the list of perfume components with a ClogP above 3 present in the perfume.
  • 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.
  • compositions of the invention may contain one or more other ingredients.
  • ingredients include further preservatives (e.g. bactericides), pH buffering agents, perfume carriers, hydrotropes, polyelectrolytes, anti-shrinking agents, anti-wrinkle agents, anti-oxidants, sunscreens, anti-corrosion agents, drape imparting agents, anti-static agents, ironing aids, silicones, antifoams, colourants, pearlisers and/or opacifiers, natural oils/extracts, processing aids, e.g. electrolytes, hygiene agents, e.g. anti-bacterials and antifungals, thickeners and skin benefit agents.
  • compositions are liquids.
  • the liquid compositions have a pH ranging from 2.0 to 5.0, preferably from 2.5 to 4.5, most preferably from 2.5 to 4.0.
  • the compositions of the invention may also contain pH modifiers such as hydrochloric acid or lactic acid.
  • the composition may be a concentrate to be diluted in a solvent, including water, before use.
  • the composition may also be a ready-to-use (in-use) composition.
  • the composition is provided as a ready to use liquid comprising an aqueous phase.
  • the aqueous phase may comprise water-soluble species, such as mineral salts or short chain (C 1-4 ) alcohols.
  • compositions of the present invention are preferably rinse-added softening compositions suitable for use in a laundry process.
  • the composition is preferably for use in the rinse cycle of a home textile laundering operation, where, it may be added directly in an undiluted state to a washing machine, e.g. through a dispenser drawer or, for a top-loading washing machine, directly into the drum. Alternatively, it can be diluted prior to use.
  • the compositions may also be used in a domestic hand-washing laundry operation. It is also possible for the compositions of the present invention to be used in industrial laundry operations, e.g. as a finishing agent for softening new clothes prior to sale to consumers.
  • compositions of the invention may typically be made by combining a melt comprising the fabric softening active and optional co-softener with an aqueous phase. Further components may be combined with the water phase, or may be post dosed into the composition after combination of the melt and water phase.
  • PVOH Movable Polymer-98; 2 g
  • deionised water 20 mL
  • the mixture was then warmed to 90°C with stirring until the polymer dissolved completely. Thereafter, the solution was cooled to 70°C and HCl catalyst (0.2 mL of a 37% solution in water) was added to the stirred solution.
  • a dilute solution of aldehyde/acetal in deionised water (about 7 %, neutral pH) was prepared and the required amount of the solution was added dropwise slowly to the reactor over about 0.5 hour.
  • the reaction mixture was stirred at 70°C for 5 hours and then at room temperature for additional 20 hours. NaOH solution (1 M) (2 mL) was then added to the reaction mixture to neutralize the pH of the product solution.
  • the resulting product was the modified PVOH.
  • Modified PVOH (1.0 mL) was taken out from the reactor after the completion of the reaction and freeze-dried.
  • Samples for 1 H NMR spectroscopy characterization were prepared by dissolving polymer powder in d 6 -DMSO. The spectrum was recorded by Bruker 400 MHz spectrometer.
  • Example 3 Preparation of fabric conditioner formulations comprising modified PVOH coated capsules (designated E1 to E6 at a weight ratio of capsule to coating of 1:1 and E1' to E6' at a ratio of 2:1); and preparation of comparative examples (designated A at a ratio of 1:1: A' at a ratio of 2:1 and E1" to E6" and A" at a ratio of 5:1: and B)
  • Capsule slurry (0.72 g), a 10 % aqueous solution of modified PVOH (0.13 g) (chosen from S1-S6 as prepared above) and free water (1.15 g) were mixed together and stirred at 250 rpm for 10 min to make an encapsulation slurry solution.
  • the final weight ratio of modified PVOH to capsule was 1:1.
  • the encapsulation slurry solution was added slowly into the fabric conditioner base referred to in Table 1 (38 g) under mechanical stirring at 250 rpm and stirred for another 10 min after addition completed.
  • the formulation sample was then incubated at 40°C for 2 days before measurement.
  • E1 to E6 at a ratio of 1:1; E1' to E6' at a ratio of 2:1, and comparative examples E1" to E6" at a ratio of 5:1, which contained the modified PVOH materials S1-S6 prepared above.
  • E1-E6 and E1'-E6' E1, E6 and E6' were comparative examples and E2-E5 and E1'-E5' were in accordance with the invention.
  • Comparative examples (designated A at a ratio of 1:1; A' at a ratio of 2:1 and A" at a ratio of 5:1) were also prepared, where A, A' and A" contained capsules coated only with the non-modified starting PVOH material and B contained capsules with no coating. Finally, a control C consisted of the fabric conditioner base alone.
  • Table 3 The formulations are summarised in Table 3.
  • Table 3 Sample information for modified PVOH coated capsules Ratio of particle:coating (wt/wt) Particle 1:1 2:1 5:1 A A' A" Capsule coated with Mowiol 10-98 (starting PVOH) B B B Capsule, no coating C C C No capsule E1 E1' E1" Capsule coated with S1 E2 E2' E2" Capsule coated with S2 E3 E3' E3" Capsule coated with S3 E4 E4' E4" Capsule coated with S4 E5 E5' E5" Capsule coated with S5 E6 E6' E6" Capsule coated with S6
  • E2-E5 and E1'-E5' are in accordance with the invention.
  • Example 4 Viscosity properties of fabric conditioners E1-E6 & E1'-E6', E1; where E1, E6 and E6' were comparative examples and comparative examples E1"-E6", A, A', A" and B; and control C
  • the viscosities of fabric conditioner formulations were evaluated using a rheometer (Physica MCR501, Anton Paar). The main parameters were as follows: Waiting time before measurement was 180s, shear rate was from 0.1 ⁇ 200 s -1 and viscosity data was acquired at 2, 20 and 106 s -1 .
  • Viscosity change of fabric conditioners E1-E6 & E1'-E6' wherein E1, E6, E6' were comparative examples; comparative examples E1 "-E6", A, A', A" and B; and control C after 2 days storage 40°C.
  • Fabric Conditioner particle coat (wt ratio) Viscosity at different shear rate (x10 -2 ) 2s -1 20s -1 106s -1 A 1:1 185.0 41.6 17.9 B n/a 257.0 53.3 21.8 C n/a 162.0 38.5 16.5 E1 1:1 260.0 56.8 23.0 E2 1:1 128.0 32.2 15.8 E3 1:1 122.0 32.2 15.5 E4 1:1 140.0 34.9 16.1 E5 1:1 86.4 24.4 12.3 E6 1:1 194.0 45.1 19.7 A' 2:1 206.0 44.8 19.2 B n/a 257.0 53.3 21.8 C n/a 162.0 38.5 16.5 E1' 2:1 187.0 42.8 18.9 E2' 2:1 142.0 34.4 16.2 E3' 2:1 166.0 41.1 18.4 E4' 2:1 174.0 41.1 18.2 E5' 2:1 194.0 43.9 19.0 E6' 2:1 204.0 44.8 19.5 A" 5:1 200.0 43.4 18.7 B n/a 257.0 53.3 21.8 C n/a 162.0 38.5 16.5 E1" 5:

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Claims (17)

  1. Flüssige Weichspüler-Zusammensetzung umfassend:
    (a) eine Weichspülerbasis, umfassend einen Weichspülwirkstoff, welcher eine quaternäre Ammoniumverbindung ist und einen pH-Wert von 2,0 bis 5,0 hat; und
    (b) ein Teilchen umfassend:-
    (b1) eine Kapsel, welche umfasst:-
    (x) einen Kern, der ein nützliches Mittel umfasst; und
    (y) eine Schale; und
    (b2) eine einen modifizierten Vinylalkohol umfassende Beschichtung; wobei der modifizierte Polyvinylalkohol umfasst:
    (i) eine hydrophobe Gruppe, ausgewählt aus einer Alkylkette und einer Arylkette mit 4 bis 16 Kohlenstoffatomen; und
    (ii) eine hydrophile Gruppe, die aus einer Alkylkette und einer Arylkette ausgewählt ist, wobei die hydrophile Gruppe 4 bis 16 Kohlenstoffatome hat und eine aus einem primären, sekundären und tertiären Amin ausgewählte Amingruppe umfasst; und
    (iii) wobei das Molverhältnis von hydrophoben Gruppen zu
    hydrophilen Gruppen 1:0,5 bis 1:10 beträgt; und
    wobei das Teilchen ein Gewichtsverhältnis von der Kapsel zu der Beschichtung von 1:1 bis 4:1 hat; und
    der modifizierte Polyvinylalkohol ein Ausmaß der hydrophoben Modifizierung von 2,0 bis 15,0 Mol-% hat, mit der Maßgabe, dass bei einem Gewichtsverhältnis von Kapsel zu Beschichtung von 1:1 bis 1,25:1 das Ausmaß der hydrophoben Modifizierung von 2 bis 10 Mol-% beträgt.
  2. Weichspüler-Zusammensetzung gemäß Anspruch 1, wobei die Schale der Kapsel Melamin-Formaldehyd umfasst.
  3. Weichspüler-Zusammensetzung gemäß Anspruch 1 oder 2, wobei das nützliche Mittel ein Riechstoff ist.
  4. Weichspüler-Zusammensetzung gemäß irgendeinem der vorhergehenden Ansprüche, wobei die quaternäre Ammoniumverbindung eine Ester-verknüpfte Verbindung ist, die eine Verteilung von Monoester-, Diester- und Triesterverbindungen umfasst.
  5. Weichspüler-Zusammensetzung gemäß Anspruch 4, wobei die quaternäre Ammoniumverbindung eine Ester-verknüpfe Triethanolamin-quaternäre Ammoniumverbindung ist.
  6. Weichspüler-Zusammensetzung gemäß irgendeinem der vorhergehenden Ansprüche, wobei der Weichspülwirkstoff in einer Menge von 2 bis 50 Gew.-% der gesamten Zusammensetzung vorhanden ist.
  7. Weichspüler-Zusammensetzung gemäß irgendeinem der vorhergehenden Ansprüche, wobei das Gewichtsverhältnis der Kapsel zur Beschichtung 1:1 bis 3:1 nach Gewicht des Teilchens beträgt.
  8. Weichspüler-Zusammensetzung gemäß irgendeinem der Ansprüche 1 bis 6, wobei das Gewichtsverhältnis der Kapsel zur Beschichtung 2:1 bis 4:1 beträgt.
  9. Weichspüler-Zusammensetzung gemäß irgendeinem der vorhergehenden Ansprüche, wobei das Teilchen eine Teilchengröße von 0,2 bis 50 Mikrometer hat, vorzugsweise 2 bis 50 Mikrometer.
  10. Weichspüler-Zusammensetzung gemäß irgendeinem der vorhergehenden Ansprüche, wobei das Ausmaß der hydrophoben Modifizierung 2,0 bis 13 Mol-% ist mit der Maßgabe, dass bei einem Gewichtsverhältnis von Kapsel zu Beschichtung von 1:1 bis 1,25:1 das Ausmaß der hydrophoben Modifizierung von 2 bis 10 Mol-% beträgt.
  11. Weichspüler-Zusammensetzung gemäß irgendeinem der vorhergehenden Ansprüche, wobei die hydrophobe Gruppe von einem Grundmaterial abgeleitet ist, welches aus der Gruppe bestehend aus Aldehyden, Acetalen, Ketalen, Estern, fluorierten organischen Verbindungen, Ethern, Alkanen, Alkenen und aromatischen Verbindungen ausgewählt ist.
  12. Weichspüler-Zusammensetzung gemäß Anspruch 11, wobei die hydrophobe Gruppe von einem oder mehreren aus der Gruppe bestehend aus Butyraldehyd, Octylaldehyd, Dodecylaldehyd, 2-Ethylhexanal, Cyclohexancarboxyaldehyd, Citral, Propionaldehyd, (2-Methoxyethoxy)-Acetaldehyddimethylacetal und Benzaldehyd abgeleitet ist.
  13. Weichspüler-Zusammensetzung gemäß irgendeinem der vorhergehenden Ansprüche, wobei der modifizierte Polyvinylalkohol von Polyvinylalkohol mit einem Molekulargewicht von 1.000 bis 300.000 abgeleitet ist.
  14. Weichspüler-Zusammensetzung gemäß irgendeinem der vorhergehenden Ansprüche, wobei die hydrophile Gruppe von einem Grundmaterial mit einem ClogP von 0,5 bis 6,0 abgeleitet ist.
  15. Verfahren zur Verbesserung der Viskositäts-Stabilität eines flüssigen Weichspülers, wobei der Weichspüler ein Teilchen umfassend einen Kern umfasst, der ein nützliches Mittel und eine Schale umfasst; umfassend den Schritt das Teilchen mit einer Beschichtung zu versehen, die einen modifizierten Polyvinylalkohol umfasst; wobei der modifizierte Polyvinylalkohol umfasst:
    (i) eine hydrophobe Gruppe, ausgewählt aus einer Alkylkette und einer Arylkette mit 4 bis 16 Kohlenstoffatomen; und
    (ii) eine hydrophile Gruppe, die aus einer Alkylkette und einer Arylkette ausgewählt ist, wobei die hydrophile Gruppe 4 bis 16 Kohlenstoffatome hat und eine aus einem primären, sekundären und tertiären Amin ausgewählte Amingruppe umfasst; und
    (iii) wobei das Molverhältnis von hydrophoben Gruppe zu hydrophilen Gruppen 1:0,5 bis 1:10 beträgt; und
    wobei das Teilchen ein Gewichtsverhältnis von der Kapsel zur Beschichtung von 1:1 bis 4:1 hat; und der modifizierte Polyvinylalkohol ein Ausmaß der hydrophoben Modifizierung von 2,0 bis 15,0 Mol-% hat, mit der Maßgabe, dass bei einem Gewichtsverhältnis von Kapsel zu Beschichtung von 1:1 bis 1,25:1 das Ausmaß der hydrophoben Modifizierung 2 bis 10 Mol-% beträgt und wobei der flüssige Weichspüler eine quaternäre Ammoniumverbindung umfasst.
  16. Verfahren zum Weichspülen von Stoffen, umfassend den Schritt des Kontaktierens einer Zusammensetzung gemäß irgendeinem der Ansprüche 1 bis 14 mit Stoff.
  17. Verfahren gemäß Anspruch 16, umfassend die Schritte des Kontaktierens einer Zusammensetzung gemäß irgendeinem der Ansprüche 1 bis 14 mit Stoff in einer Spüllauge, und nachfolgendem Spülen der Stoffe.
EP12734951.2A 2011-08-25 2012-07-12 Verkapselter pflegestoff Not-in-force EP2748295B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN2011001419 2011-08-25
PCT/EP2012/063728 WO2013026620A1 (en) 2011-08-25 2012-07-12 Encapsulated benefit agent

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EP2748295A1 EP2748295A1 (de) 2014-07-02
EP2748295B1 true EP2748295B1 (de) 2015-10-14

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BR (1) BR112014004266A2 (de)
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ZA (1) ZA201400527B (de)

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CN105408016B (zh) * 2013-07-30 2017-10-13 荷兰联合利华有限公司 与包封的有益剂相关的改善

Family Cites Families (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2800457A (en) 1953-06-30 1957-07-23 Ncr Co Oil-containing microscopic capsules and method of making them
US3518242A (en) 1966-03-30 1970-06-30 Du Pont Polyvinyl alcohol and derivatives crosslinked with titanium,permanganate,or vanadyl ions
US3516941A (en) 1966-07-25 1970-06-23 Minnesota Mining & Mfg Microcapsules and process of making
US4145184A (en) 1975-11-28 1979-03-20 The Procter & Gamble Company Detergent composition containing encapsulated perfume
GB1567947A (en) 1976-07-02 1980-05-21 Unilever Ltd Esters of quaternised amino-alcohols for treating fabrics
JPS602100B2 (ja) 1977-09-28 1985-01-19 三菱製紙株式会社 微小カプセルの製造方法
JPS5651238A (en) 1979-10-02 1981-05-08 Fuji Photo Film Co Ltd Production of microminiature capsule
DE2940786A1 (de) 1979-10-08 1981-04-16 Basf Ag, 6700 Ludwigshafen Verfahren zur herstellung von mikrokapseln
DE3027611A1 (de) 1980-07-21 1982-02-18 Bayer Ag, 5090 Leverkusen Di- und oligo-1,2,4-triazolidin-3,5-dione und verfahren zu ihrer herstellung
EP0311154B1 (de) 1987-04-10 1994-01-19 The Procter & Gamble Company Feste unverdauliche fettähnliche Verbindungen
CA2009047C (en) 1989-02-27 1999-06-08 Daniel Wayne Michael Microcapsules containing hydrophobic liquid core
US5578563A (en) 1994-08-12 1996-11-26 The Procter & Gamble Company Composition for reducing malodor impression on inanimate surfaces
GB9930435D0 (en) 1999-12-22 2000-02-16 Unilever Plc Fabric softening compositions
BRPI0305777B1 (pt) * 2002-08-14 2018-04-03 Givaudan Sa Composição compreendendo um tensoativo e um material encapsulado em uma cápsula, e, cápsulas
GB0222964D0 (en) 2002-10-03 2002-11-13 Unilever Plc Polymeric film for water soluble package
US7304026B2 (en) * 2004-04-15 2007-12-04 Colgate-Palmolive Company Fabric care composition comprising polymer encapsulated fabric or skin beneficiating ingredient
US7799098B2 (en) 2004-08-30 2010-09-21 Ciba Specialty Chemicals Corp. Shading process
US7686892B2 (en) 2004-11-19 2010-03-30 The Procter & Gamble Company Whiteness perception compositions
GB0518451D0 (en) * 2005-09-09 2005-10-19 Unilever Plc Fabric conditioning composition
GB0803124D0 (en) 2008-02-21 2008-03-26 Unilever Plc Improvements relating to benefit particles
GB0803165D0 (en) 2008-02-21 2008-04-02 Unilever Plc Encapsulated benefit agent

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ZA201400527B (en) 2015-09-30
WO2013026620A1 (en) 2013-02-28
EP2748295A1 (de) 2014-07-02
ES2555456T3 (es) 2016-01-04
BR112014004266A2 (pt) 2017-03-21

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