EP2142632A1 - Laundry treatment compositions with lamellar visual cues - Google Patents
Laundry treatment compositions with lamellar visual cuesInfo
- Publication number
- EP2142632A1 EP2142632A1 EP08837128A EP08837128A EP2142632A1 EP 2142632 A1 EP2142632 A1 EP 2142632A1 EP 08837128 A EP08837128 A EP 08837128A EP 08837128 A EP08837128 A EP 08837128A EP 2142632 A1 EP2142632 A1 EP 2142632A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- concave
- film particles
- lamellar film
- composition according
- film
- 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.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 76
- 230000000007 visual effect Effects 0.000 title claims abstract description 51
- 239000002245 particle Substances 0.000 claims abstract description 50
- 239000003599 detergent Substances 0.000 claims description 16
- 239000004615 ingredient Substances 0.000 claims description 15
- 230000011514 reflex Effects 0.000 claims description 11
- 238000007373 indentation Methods 0.000 claims description 7
- 238000013461 design Methods 0.000 description 22
- 239000000843 powder Substances 0.000 description 22
- 239000004094 surface-active agent Substances 0.000 description 19
- 239000002699 waste material Substances 0.000 description 15
- 238000004519 manufacturing process Methods 0.000 description 14
- 229920002451 polyvinyl alcohol Polymers 0.000 description 13
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000004372 Polyvinyl alcohol Substances 0.000 description 11
- 238000005520 cutting process Methods 0.000 description 11
- 239000003086 colorant Substances 0.000 description 10
- 239000002304 perfume Substances 0.000 description 10
- 239000000975 dye Substances 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 8
- 238000005204 segregation Methods 0.000 description 8
- 239000011347 resin Substances 0.000 description 7
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- 238000000034 method Methods 0.000 description 6
- -1 alkyl sulphates Chemical class 0.000 description 5
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- 239000007788 liquid Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 241001104043 Syringa Species 0.000 description 3
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- 244000215068 Acacia senegal Species 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- 229920000084 Gum arabic Polymers 0.000 description 2
- 241000533950 Leucojum Species 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 239000000205 acacia gum Substances 0.000 description 2
- 235000010489 acacia gum Nutrition 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000005273 aeration Methods 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 150000003138 primary alcohols Chemical group 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 239000013042 solid detergent Substances 0.000 description 2
- 229910021653 sulphate ion Inorganic materials 0.000 description 2
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical group CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- 241000271566 Aves Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 229920000896 Ethulose Polymers 0.000 description 1
- 239000001859 Ethyl hydroxyethyl cellulose Substances 0.000 description 1
- 241000270290 Gekkota Species 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- 229920002907 Guar gum Polymers 0.000 description 1
- 229920001479 Hydroxyethyl methyl cellulose Polymers 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 101710194948 Protein phosphatase PhpP Proteins 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 239000004141 Sodium laurylsulphate Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- BGRWYDHXPHLNKA-UHFFFAOYSA-N Tetraacetylethylenediamine Chemical compound CC(=O)N(C(C)=O)CCN(C(C)=O)C(C)=O BGRWYDHXPHLNKA-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 229920006322 acrylamide copolymer Polymers 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 150000007942 carboxylates Chemical group 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- MRUAUOIMASANKQ-UHFFFAOYSA-N cocamidopropyl betaine Chemical compound CCCCCCCCCCCC(=O)NCCC[N+](C)(C)CC([O-])=O MRUAUOIMASANKQ-UHFFFAOYSA-N 0.000 description 1
- 229940098691 coco monoethanolamide Drugs 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 230000004069 differentiation Effects 0.000 description 1
- 235000019326 ethyl hydroxyethyl cellulose Nutrition 0.000 description 1
- 239000001761 ethyl methyl cellulose Substances 0.000 description 1
- 235000010944 ethyl methyl cellulose Nutrition 0.000 description 1
- 239000002979 fabric softener Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- DDSRCCOGHFIQDX-UHFFFAOYSA-N furan-2,5-dione;methoxymethane Chemical compound COC.O=C1OC(=O)C=C1 DDSRCCOGHFIQDX-UHFFFAOYSA-N 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000000665 guar gum Substances 0.000 description 1
- 235000010417 guar gum Nutrition 0.000 description 1
- 229960002154 guar gum Drugs 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000000419 plant extract Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000141 poly(maleic anhydride) Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 230000001953 sensory effect Effects 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- RJSZFSOFYVMDIC-UHFFFAOYSA-N tert-butyl n,n-dimethylcarbamate Chemical group CN(C)C(=O)OC(C)(C)C RJSZFSOFYVMDIC-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 239000012463 white pigment Substances 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- 239000002888 zwitterionic surfactant Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
- C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
- C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
- C11D17/044—Solid 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
- C11D3/16—Organic compounds
- C11D3/37—Polymers
-
- 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
- C11D3/40—Dyes ; Pigments
Definitions
- This invention relates to laundry treatment compositions with lamellar visual cues cut from a film.
- Laundry treatment compositions include fabric cleaning and other fabric care compositions, such as fabric softeners, specialist stain removal products etc.
- the compositions may take the form of solid compositions including detergent powders, solid detergent forms like tablets and bars, or liquid compositions.
- GB2358403A suggests the use of shaped lamellae as visual cues in detergent powder compositions.
- the film is a coloured water-soluble plastics material.
- the lamellae are of significantly larger average particle size in at least one dimension than the average particle size of the contrasting powder particles.
- the examples in this patent application use 5 mm diameter circular or star shaped lamellae.
- GB2358403A discloses squares and triangles. Also disclosed are: mixtures of triangles, squares, pentagons and hexagons; mixtures of numerals, mixtures of letters of the alphabet; and mixtures of sun, moon and stars.
- WO2006/079416 discloses an alternative shape for the lamellae serving as visual cues.
- Examples in this application use visual cues made from gum Arabic lamellae.
- the gum Arabic cues are irregularly shaped and are produced by fragmenting a large film to form random shapes with sharp angles, generally having a triangular or "spiky" appearance. Because the shapes are randomly sized, it is necessary to sieve them to get a suitable fraction for use. It is suggested that they could be chosen to pass a 1400 ⁇ m sieve, but not a 500 ⁇ m sieve. Up to 30% of the visual cues produced would need to be recycled, or wasted, if this method of production were used. Furthermore, we have found that consumers do not appreciate randomly shaped visual cues as much as regularly shaped ones.
- WO2007/022229 discloses inclusion of small shapes of film, which may be visible, into a solid cleanser base, such as a soap bar. In addition to provision of visual contrast, the square film inclusions are taught to affect other sensory factors, such as feel of the product.
- EP 1319706 discloses a liquid detergent composition with a solid polymer film immersed in it. The concave lamellae are preferably regular in shape. In addition to the shapes already disclosed in GB2358403A, teddy bear shaped visual cues are also disclosed.
- tiled or tessellated is used in the sense that a surface, especially a plane surface, can be tiled by the shape or shapes.
- tiled means that a shape or shapes are shaped to be fitted together like a jigsaw, to form a continuous tiled planar surface with no gaps or overlaps, except for optional gaps at the edges of the planar surface.
- Tile means that the shapes can be tiled.
- Another, related, problem is the cost effective manufacture of lamellar visual cues that impart additional functionality to laundry treatment compositions.
- Another, related, problem for incorporation of lamellar visual cues in powders is to manufacture visual cues having a shape and size that enables them to be non-segregating and dispersed relatively uniformly throughout the powder.
- a laundry treatment composition comprising a laundry treatment base and from 0.01 to 10 wt% of contrastingly coloured concave lamellar film particles which have a substantially planar surface and a substantially planar periphery wherein: a) the periphery is shaped so that at least one straight line drawn through the substantially planar surface intersects the periphery at more than two places; b) the concave lamellar film particles can be tiled; c) the concave lamellar film particles contrast in colour with the laundry treatment base whereby the concave lamellar film particles function as visual cues.
- Means a consumer perceivable point of differentiation in a detergent composition This could be a feature of the bulk composition: e.g. colour, viscosity, size of granules, or it could be achieved by having visually distinct particles included in the composition, in a minor amount.
- Lamellar Visual Cue (or Lamellae)
- a stereotypical flower having a central generally circular area with a number, preferably six, of rotationally symmetrically dispersed "petals" radiating therefrom.
- concave lamellar film particles function as visual cues. To fulfil this function effectively we have found that they must have at least one visible indentation along their perimeter. This can be expressed mathematically as that for each design of concave lamellae it must be possible to draw a straight line that passes through the periphery of the film particle in more than two places. Convex shaped film particles; like squares, hexagons, and rectangles can never satisfy this requirement. Another way to express the required shape mathematically is that each lamellar film particle must either have at least one internal reflex angle, or it must have an indentation due to a curved part of its periphery.
- a lamellar film particle having two straight parallel sides and two curved sides, one concave and the other convex of the same curvature falls within the broadest scope of the invention, provided it is tileable and of a contrasting colour to the base composition.
- the periphery of each of the lamellae preferably has no internal angles less than 100 degrees and must have at least one internal angle greater than 180 degrees (a reflex angle) . At least two such angles are preferred.
- all internal angles are less than 260 degrees, so that relatively fragile points are avoided.
- the shape of the visual cues is preferably selected from polygons modified to have at least two opposing sides provided with an outwardly extending generally convex distortion and a corresponding inwardly extending concave distortion such that the inward and outward distortions may be fitted together by tiling.
- the shape of the visual cues is most preferably selected from polygons modified to have each side provided with an outwardly extending generally convex distortion and a corresponding inwardly extending concave distortion such that the inward and outward distortions may be fitted together by tiling.
- Preferred polygons are hexagons.
- a preferred shape for the concave lamellae is based on the normal construction of a, so called, Gosper island, as this enables a single and visually effective shape to be used.
- Koch snowflakes may also be employed if two different sized concave lamellae are desired.
- Gosper Islands and Koch snowflakes are well known fractal concepts and have been used previously as a basis for tessellated or tiled designs by mathematicians.
- a first iteration Gosper island is most preferred, as this has 18 straight sides. This shape is described in more detail below, with reference to the drawings .
- the shape of the lamellae to resemble something natural and normally associated with a smell; viz. a petal, a flower, etc.
- the shape of the concave lamellae and the smell of the composition are linked already in nature as this has been found to provoke the best possible response from the user.
- the colour of the concave lamellae adds to the cueing and the colour, shape and smell should all be as close as possible to natural ones and related to the same smell, e.g. a floral smell.
- the size of the concave lamellae does not seem to be as important as its shape or colour.
- This freedom to use smaller than life sized representations of objects as visual cues enables the use of more cues for the same surface area. For instance using a 5 mm diameter visual cue with an approximate cross-sectional area of 13 mm 2 allows incorporation of the concave lamellar visual cues into a laundry treatment composition to deliver from 50 to 100 such cues per wash, preferably about 70 per wash.
- Natural shapes that may also be used for concave lamellae that can be tiled are trees, leaves and animals.
- a particularly advantageous shape for use as a visual cue for perfume is a flower-like shape, especially one based on a hexagon suitably modified to keep its design tilable.
- Each side of the hexagon is preferably modified in an identical fashion.
- each side has both protruding and intruding distortions that are displaced reflections of one another, the previously opposite parallel faces of the hexagon being modified so that the new surfaces are also substantially parallel, but more complex, lines.
- the modified faces may be sinusoidal or they may be formed of three interconnected lines.
- the new perimeter line intersects the original perimeter of the hexagon substantially at the midpoint of a side of the original unmodified hexagon.
- the majority of the sides of the concave lamellae are straight, most preferably they are all straight.
- concave lamellae have substantially the same shape. They may all have substantially the same size to minimise segregation issues.
- the concave lamellae desirably have rotational symmetry.
- the preferred first iteration Gosper islands have this symmetry.
- the concave lamellae may all be the same colour, or they may comprise a mixture of different colours.
- the colour, or colours, of the concave lamellae may be selected to match the pack colour, or colours. Most preferred colours are lilac, pink, yellow, blue, red, purple, green, and orange.
- dark coloured base laundry treatment compositions e.g. blue, green it is possible to use a white contrasting concave lamellar cue. The whiteness may be imported by use of a white pigment.
- the shape of the concave lamellae is directly linked to an aspect of the base laundry treatment composition.
- the shape is the outline shape of a flower and the composition has a perfume, especially a floral perfume.
- the concave lamellae would also be the colour of a flower petal in this instance.
- the concave lamellae are the outline shape of a bolt of lightening and the composition comprises a whitening, or bleaching, ingredient.
- the concave lamellae could be the outline shape of a plant and the composition contain a plant extract, like Aloe Vera.
- the concave lamellae are desirably arranged in rows and columns and they are aligned in columns and offset in rows .
- the concave lamellae (concave lamellar film particles) are manufactured from a film.
- a wide range of film compositions and properties may be used. Soluble film is preferred.
- the thickness of the film is important. Too thick or thin and it cannot be cut efficiently and at the required level of complexity without tears or distortions being created by the shear applied during cutting.
- the maximum thickness of the film is 0.4 mm, preferably 0.25 mm, most preferably 0.2 mm.
- the minimum thickness is 0.05mm, preferably 1 mm.
- the tear strength and brittleness of the film at the thickness used should be tested to ensure that they are suitable. This is a simple matter and the values will vary depending on the exact process being used. Too soft a film will not cut easily whereas too brittle a film may shatter and make it difficult to achieve the desired shape at an economical rate of production. Such fragmentation also increases the amount of undesirable lower sized waste material that may need to be removed before adding the shapes to the laundry composition.
- the properties may be controlled by plasticisers and fillers, as is known in the art.
- the water content of the film may also be adjusted to vary the properties.
- the film may be coloured or opaque or it may be partially clear. In each case, it is possible to print onto the film either before or after it is cut, to provide a single colour, multiple colours or a pattern such as a representation of a natural object, like a leaf or flower.
- Functional ingredients for treatment of laundry may be incorporated into the film before it is cut.
- Useful ingredients include TAED, Gerol, DTI-I, enzymes, fluorescer, shading dye and perfume.
- the most preferred ingredients for use in films are those that only need to be present at very low levels in the powder formulation, especially perfume, shading dye, bleach catalysts, fluorescer. Such materials may be instable in detergents due to interaction with moisture and other ingredients.
- the film also permits a greater range of soluble dyes to be used than was possible for speckles. It also gives the advantage that there is very little if any bleeding of dye into the bulk of the powder. Soluble dyes are generally preferred over pigments.
- the film contains polyvinyl alcohol (PVA) .
- PVA polyvinyl alcohol
- the preferred grades of PVA are selected so that the film picks up water only at an RH well above that of the laundry treatment composition, e.g. detergent powder. Thereby it protects the ingredients from decomposition by water and soluble dyes from bleeding.
- Some film additives such as fluorescer, may increase the effect of the visual cue. It is also possible to include a low level of dye to counter any yellowing.
- the functional ingredient is preferably incorporated into the film at a level to comprise an effective amount for treatment of laundry, based in the total amount of film in an average dose of lamellae to a wash.
- film As an even lighter weight alternative to film it is possible to fabricate meshes or open structures of polymer based material and to cut those into shapes in the same way as films. The same advantages of use of the tilable shapes apply.
- the expression "film” is intended to include such functionally equivalent laminar structures.
- Preferred film compositions comprise soluble polymer and surfactant .
- adjuncts to assist in the manufacture of the film for instance release agents and water.
- water also assists in plasticising the film and regulates its solubility.
- the polymer may be selected from water soluble film forming polymers, especially those used in formulation of detergent powders.
- Preferred polymers include polymers which dissolve and/disperse completely in water within 30 minutes with agitation at a temperature anywhere in the range of from 293 to 333K.
- Preferred water soluble polymers are those capable of being cast into a film or solid mass, for example as described in Davidson and Sittig, Water-Soluble Resins, Van Nostrand Reinhold Company, New York (1968).
- Preferred water-soluble resins include polyvinyl alcohol, cellulose ethers, polyethylene oxide, starch, polyvinylpyrrolidone, polyacrylamide, polyvinyl methyl ether-maleic anhydride, polymaleic anhydride, styrene maleic anhydride, hydroxyethy1cellulose, hydroxypropylmethy1cellulose, polyethylene glycols, carboxymethylcellulose, polyacrylic acid salts, alginates, acrylamide copolymers, guar gum, casein, ethylene-maleic anhydride resin series, polyethyleneimine, ethyl hydroxyethylcellulose, ethyl methylcellulose, hydroxyethyl methylcellulose, sugars.
- Polyvinyl alcohols preferred for use therein have an average molecular weight anywhere between 1,000 and 1,000,000, preferably between 5,000 and 250,000, for example between 15,000 and 150,000.
- Hydrolysis, or alcoholysis is defined as the percent completion of the reaction where acetate groups on the resin are substituted with hydroxyl, -OH, groups,
- a hydrolysis range of from 60-99% of polyvinyl alcohol film-forming resin is preferred, while a more preferred range of hydrolysis is from about 70-90% for water-soluble, polyvinyl alcohol film-forming resins. The most preferred range of hydrolysis is 80-89%.
- polyvinyl alcohol includes polyvinyl acetate compounds with levels of hydroloysis disclosed herein.
- Another suitable polymer is a polyvinyl alcohol film, made of a polyvinyl alcohol copolymer having a comonomer having a carboxylate function.
- the preferred grade of PVA picks up water only at an RH well above that of granular detergent compositions. Thereby, it protects the other film ingredients from decomposition by water and soluble dyes from bleeding.
- the concave lamellae may comprise 10 to 80% polymer or polymer mixture.
- the surfactant is preferably an anionic surfactant, especially if it is added to a granular composition comprising builder.
- Suitable anionic surfactants include are well-known to those skilled in the art.
- Examples of high-foaming sulphonate or sulphate type surfactants include alkylbenzene sulphonates, particularly linear alkylbenzene sulphonates having an alkyl chain length of Cs-Ci 5 ; primary and secondary alkylsulphates, particularly Cs-Ci 5 primary alkyl sulphates; olefin sulphonates; alkyl xylene sulphonates; dialkyl sulphosuccinates; and fatty acid ester sulphonates.
- Sodium salts are generally preferred.
- the preferred anionic surfactants are alkylbenzene sulphonates, more especially linear alkylbenzene sulphonate (LAS), which is preferably present in an amount of from 12 to 24 wt%, more preferably from 12 to 22 wt% and especially from 15 to 22 wt%.
- LAS linear alkylbenzene sulphonate
- PES primary alcohol sulphates
- Cs-Cis particularly C12-C15
- PES primary alcohol sulphates
- a particularly preferred surfactant is primary alcohol sulphate (PAS) with a carbon chain length of 12.
- Visual cue Film particles containing up to 50 % PAS may be used.
- the film may additionally include a second surfactant.
- the second surfactant is preferably chosen from amphoteric surfactants, zwitterionic surfactants, nonionic surfactants and ethoxylated anionic surfactants.
- Preferred amphoteric second surfactants are amine oxides.
- the most preferred amine oxide is coco dimethylamine oxide.
- Preferred zwitterionic second surfactants are betaines, and especially amidobetaines, for example, coco amidopropyl betaine .
- Preferred nonionic second surfactants include the primary and secondary alcohol ethoxylates, especially the C8-C20 aliphatic alcohols ethoxylated with an average of from 1 to 20 moles of ethylene oxide per mole of alcohol, and more especially the C10-C15 primary and secondary aliphatic alcohols ethoxylated with an average of from 1 to 10 moles of ethylene oxide per mole of alcohol.
- Preferred ethoxylated anionic second surfactants include alkyl ether sulphates (ethoxylated alcohol sulphates) .
- Cs-Cis alkyl monoethanolamides for example, coco monoethanolamide .
- the second surfactant system used in the film particle may additionally comprise minor amounts, e.g. less than 5% of the film, of cationic surfactant.
- Surfactant may be included at a level of up to 90 wt%, preferably up to 75 wt%, most preferably up to 60 wt% in the film.
- Non fabric-substantive colorants may be included in the film composition at a level of 0.001 to 0.5 wt%, preferably 0.10 to 0.20 wt%.
- Preferred film colorants selected from the group comprising: orange, yellow, pink, blue, red, green, purple and lilac.
- the tilable shapes used for the concave lamellae may be made by punching or embossed roller cutting processes and some reduction of waste versus the known star or circle shaped visual cues is possible using these processes.
- punching or embossed roller cutting processes some reduction of waste versus the known star or circle shaped visual cues is possible using these processes.
- the preferred tilable shapes can be made at small diameters and with very low waste production via rotary cutting processes.
- small diameter we mean 2 to 10mm across, preferably having a mean diameter of about 5 mm.
- Shapes can be produced with straight sides, which look very similar to an even more complex curved shape. This gives 'real' shapes at an economically acceptable cost.
- a flower- like tilable design shown in Figure 6, with 18 intersecting straight sides is sufficiently similar in shape to a real flower to be almost indistinguishable by the user of the laundry composition.
- Such a shape is therefore preferred over squares and even over hexagons, especially when the composition to which it is added also comprises perfume and most especially when the colour of the flower is selected from the natural flower imitating shades, for example: orange, yellow, pink, blue, red, green, purple and lilac.
- the laundry composition has 0 to 1.5 wt% particles smaller than the target concave lamellar shapes and sizes, preferably as close to zero as economically feasible.
- the visual cues are added towards the end of the manufacturing process to avoid damaging them.
- laundry liquids they may be suspended as described in EP 1319706.
- laundry powder compositions they must not unduly segregate during manufacture including mixing, handling, and transport.
- the laundry treatment composition is advantageously provided in a coloured pack that has a predominant theme colour.
- the colour or colours of the concave lamellae match the pack colours; most preferably, they are a single colour and match the predominant theme colour of the pack.
- the laundry treatment base is preferably a solid detergent composition; most preferably, it is a granular laundry detergent .
- the concave lamellae should have density, thickness, diameter, and shape within defined boundaries. These have been determined experimentally and checked by means of trials .
- Weight and density are the key parameters to keep segregation within acceptable limits. Weight is a function of thickness, diameter and shape.
- the weight of the visual cue should lie in the range 1 to 4 mg, preferably 1.5 to 3.5 mg.
- the density of the film should lie in the range 200 to 800 g/1, preferably 230 to 500 g/1, most preferably 250 to 400 g/1. In principle the higher the weight and the higher the density the less the segregation - up to a limit. However, this is uneconomical as the inclusion level in the powder will have to increase (the number of concave lamellae will stay constant for a given visual effect) .
- the density of the film may be controlled by varying the degree of aeration during film manufacture. Segregation experiment
- Measurements were done with a standard colorimeter on a poured out powder bed. The measurement diameter was around 5 cm.
- the white powder had the following colour (5 measurements) :
- concave lamellae with concavities are beneficial for appearance.
- composition including the concave lamellae
- the potential consumer preference for a flower shape over a hexagon was established by means of a controlled experiment using hand washing.
- the hand wash panellists were asked to describe the attributes of the wash experience and the resulting washing product and they evaluated the flower shaped visual cues above hexagon visual cues in terms of whiteness of the wash and freshness of the wash.
- the overall washing experience was also ranked as superior.
- Fig 1 is a pictorial representation of tiled concave lamellae, which are modified hexagons.
- Fig 2 is a pictorial representation of tiled concave lamellae, which are modified hexagons with a second, more rounded, design.
- Fig 3 is a pictorial representation of tiled concave lamellae of two different sizes and shapes.
- Fig 4 is a pictorial representation of tiled concave lamellae based on three fused hexagons.
- Fig 5 is a drawing showing how the first iteration Gosper Island design is generated.
- Fig 6 is a pictorial representation of the cross-section of the Gosper Island design produced according to Fig 6
- Fig 7 is a pictorial representation of tiled concave lamellae of the design shown in Fig 6.
- Fig 8 is a pictorial representation of a concave lamellae design having an intrusion formed by a single convex curved side and single corresponding concave side.
- Figure 1 shows a complex tilable design of repeating identical shapes, 1, which each have six rotationally symmetrical "petals” that give each shape the impression of looking like a flower.
- Each "flower” can be considered to be a modified hexagon.
- the unmodified side of one of the hexagons 2 has been distorted to have a generally concave intrusion, 3, to the original hexagonal outline and a generally convex protrusion, 4.
- the convex and concave parts join together at the mid point of the original side. In this instance, the each part is rotationally identical to the other.
- the concave part 3 is rotated 180 degrees about the midpoint intersection, it lies over the convex part 4. This means that the area of the shape is not changed from the original hexagon, but the visibility is improved by virtue of the increase in diameter and the overall appearance and functionality as a visual cue is enhanced by virtue of the flower-like appearance.
- Figure 2 shows a modified form of the flower-like tilable shapes of figure 1.
- the concave lamellae have an overall diameter of 5 mm as indicated. They are arranged in columns and the rows are offset relative to one another. Relative to hexagon side 5, the intrusion and protrusion, 6, 7 are more rounded than the corresponding parts of Figure 1.
- the intrusion 6 does not have a sharply defined reflex angle at a junction, as is the case with figure 1.
- the indentation is curved and it forms the necessary indentation and reflex angle by the curvature.
- Figure 3 shows a different type of tilable design where the concave lamellae 8 and 9 are of two different shapes and sizes. For each large particle, 8 there are two small particles, 9.
- the concave lamellae have at least one indentation and a corresponding internal reflex angle.
- Figure 4 is a simple tilable design formed from the fusion of three hexagons.
- Concave lamellae 10 are identical in shape and size. Each concave lamellar particle has an internal reflex angle 11 of 240 degrees and two adjacent internal angles of 120 degrees.
- the concave lamellae may be separated by cutting to leave no waste formed from the area between lamellae and just a small amount of triangular shapes from the edges, depending on the number of rows and columns of concave lamellae that are cut from a single piece of film. This may be sieved and larger pieces used in the composition.
- Figure 5 shows a modified hexagon design that is a first iteration of a shape known as a Gosper island.
- the original hexagon 11 has seven smaller hexagons imposed onto it such that six of the smaller hexagons have a portion 15 that protrudes beyond the original hexagon 11.
- a corresponding intrusion 16 is formed and the protrusion and intrusion have the same areas and are rotationally symmetrical about the midpoint 14 of the original hexagon 11.
- Figure 6 shows in detail the modified shape formed when the concave lamellae 17 are cut out according to the first iteration Gosper island design.
- the concave lamellae has an internal reflex angle 18 and adjacent to each internal reflex angle 18 are two internal obtuse angles 19, the ratio of such obtuse angles 19 to reflex angles 18 is two to one. This gives a simple flower like design using only straight lines for the edges of the shape.
- Figure 7 shows how these concave lamellae shapes are arranged in columns 20, 21, 22 and how two sets of displaced rows are formed by alternate columns .
- Figure 8 shows a simple concave lamellae design 25 that can be tiled. It has a curved indented area formed by side 26 and corners 27 and 28 are obtuse and acute respectively. The necessary reflex angle is provided by the curved side 26.
- a polymer film is manufactured having the following composition :
- the film is made by dissolving the ingredients in water to form a homogeneous solution. This solution passes through an aeration unit, where air is mixed into the solution. The aerated liquid is then cast into a film and dried.
- the film thickness is 0.18 - 0.19 mm and its relative density is about 0.3. It is cut into the flower-like tilable shapes according to figures 6 and 7. The maximum diameter of the shape is 5 mm and the cross-sectional area of one of the flat faces of the flower shape is approximately 16 mm 2 .
- Two processes were used to cut the film into the required shapes: Rotary cutting and punching. The former generated some edge waste that was reduced by sieving. The latter produced a web of waste film that needed to be recycled. The amount of such film was, however, less than would have been generated by punching of non-tilable designs.
- the cut concave lamellae were incorporated into a white carbonate STPP built LAS surfactant based detergent powder with a particle size of granule of less than lmm, in a manner similar to that used for other ingredients that are dosed at the end of the powder making process.
- the shapes were dosed, either manually or by a dosing unit, into mixing equipment where they were incorporated into the product. This mixing was either done mechanically, using a rotary mixing unit, or was done by blowing air into the powder. After mixing, the final powder is transported to the filling machines where the powder is conditioned in coloured bags or boxes of different sizes.
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- 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)
- Detergent Compositions (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
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Abstract
Description
Claims
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP08837128A EP2142632B1 (en) | 2007-10-12 | 2008-09-25 | Laundry treatment compositions with lamellar visual cues |
| PL08837128T PL2142632T3 (en) | 2007-10-12 | 2008-09-25 | Laundry treatment compositions with lamellar visual cues |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IN2033MU2007 | 2007-10-12 | ||
| EP08150096 | 2008-01-08 | ||
| EP08837128A EP2142632B1 (en) | 2007-10-12 | 2008-09-25 | Laundry treatment compositions with lamellar visual cues |
| PCT/EP2008/062872 WO2009047124A1 (en) | 2007-10-12 | 2008-09-25 | Laundry treatment compositions with lamellar visual cues |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP2142632A1 true EP2142632A1 (en) | 2010-01-13 |
| EP2142632B1 EP2142632B1 (en) | 2010-11-10 |
Family
ID=40352072
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP08837128A Revoked EP2142632B1 (en) | 2007-10-12 | 2008-09-25 | Laundry treatment compositions with lamellar visual cues |
Country Status (13)
| Country | Link |
|---|---|
| EP (1) | EP2142632B1 (en) |
| CN (1) | CN101755040B (en) |
| AR (1) | AR068856A1 (en) |
| AT (1) | ATE487787T1 (en) |
| AU (1) | AU2008309814B2 (en) |
| BR (1) | BRPI0811568A2 (en) |
| CA (1) | CA2686494C (en) |
| CL (1) | CL2008003016A1 (en) |
| DE (1) | DE602008003428D1 (en) |
| MX (1) | MX2009012389A (en) |
| MY (1) | MY145126A (en) |
| PL (1) | PL2142632T3 (en) |
| WO (1) | WO2009047124A1 (en) |
Families Citing this family (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BRPI1011346A2 (en) | 2009-04-16 | 2016-10-18 | Unilever Nv | polymer particle, surfactant composition, polymer particle formation processes, and use thereof |
| GB201011515D0 (en) * | 2010-07-08 | 2010-08-25 | Unilever Plc | Surfactant compositions comprising curved lamellar elements as a visual cue |
| RU2635921C2 (en) | 2012-06-08 | 2017-11-17 | Амкол Интернешнел Корпорейшен | Visually contrasting aesthetic particles having improved solubility in water, especially useful for combining with powdered or granular compositions |
| US10633617B2 (en) | 2015-04-23 | 2020-04-28 | The Procter & Gamble Company | Detergent compositions |
| CN109072141A (en) * | 2016-06-21 | 2018-12-21 | 宝洁公司 | Aesthetic Particles |
| EP3472297B1 (en) * | 2016-06-21 | 2023-12-06 | The Procter & Gamble Company | Aesthetic particles |
| MX2019009279A (en) * | 2017-02-06 | 2019-09-19 | Procter & Gamble | Laundry detergent sheet comprising lines of frangibility. |
| KR102360241B1 (en) | 2017-02-06 | 2022-02-10 | 더 프록터 앤드 갬블 캄파니 | Laundry detergent sheet with microcapsules |
| WO2018205240A1 (en) * | 2017-05-12 | 2018-11-15 | The Procter & Gamble Company | A method for making particles |
| US11512267B2 (en) | 2017-09-22 | 2022-11-29 | Symrise Ag | Active substance wafer |
| US20190233781A1 (en) * | 2018-01-26 | 2019-08-01 | The Procter & Gamble Company | Pluralities of water-soluble articles and related processes |
| US11053466B2 (en) | 2018-01-26 | 2021-07-06 | The Procter & Gamble Company | Water-soluble unit dose articles comprising perfume |
| KR20200086739A (en) | 2018-01-26 | 2020-07-17 | 더 프록터 앤드 갬블 캄파니 | Water soluble unit dose article containing enzyme |
| JP7110356B2 (en) | 2018-01-26 | 2022-08-01 | ザ プロクター アンド ギャンブル カンパニー | Water soluble unit dose article containing perfume |
| EP3743503B1 (en) * | 2018-01-26 | 2026-04-29 | The Procter & Gamble Company | Process for making water-soluble articles |
| WO2019168829A1 (en) | 2018-02-27 | 2019-09-06 | The Procter & Gamble Company | A consumer product comprising a flat package containing unit dose articles |
| US10982176B2 (en) | 2018-07-27 | 2021-04-20 | The Procter & Gamble Company | Process of laundering fabrics using a water-soluble unit dose article |
| US12234431B2 (en) | 2018-10-03 | 2025-02-25 | The Procter & Gamble Company | Water-soluble unit dose articles comprising water-soluble fibrous structures and particles |
| CN113748195B (en) | 2019-01-28 | 2024-01-19 | 宝洁公司 | Recyclable, renewable or biodegradable packaging |
| EP3942008A1 (en) | 2019-03-19 | 2022-01-26 | The Procter & Gamble Company | Process of reducing malodors on fabrics |
| EP3712237A1 (en) | 2019-03-19 | 2020-09-23 | The Procter & Gamble Company | Fibrous water-soluble unit dose articles comprising water-soluble fibrous structures |
| JP7605842B2 (en) | 2020-08-19 | 2024-12-24 | ザ プロクター アンド ギャンブル カンパニー | FLEXIBLE POROUS DISSOLVEABLE SOLID SHEET ARTICLE CONTAINING DIRECT-LOAD MICROCAPSULES AND METHODS FOR MAKING SAME - Patent application |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2299066Y (en) * | 1997-08-06 | 1998-12-02 | 王珏 | Soap body |
| GB2358403B (en) * | 2000-01-24 | 2004-09-29 | Unilever Plc | Detergent compositions |
| CN2420281Y (en) * | 2000-04-17 | 2001-02-21 | 马峻峰 | Soap with core |
| GB0129983D0 (en) * | 2001-12-14 | 2002-02-06 | Unilever Plc | Unit dose products |
| GB0228354D0 (en) * | 2002-12-05 | 2003-01-08 | Unilever Plc | Detergent compositions |
-
2008
- 2008-09-25 DE DE602008003428T patent/DE602008003428D1/en active Active
- 2008-09-25 EP EP08837128A patent/EP2142632B1/en not_active Revoked
- 2008-09-25 PL PL08837128T patent/PL2142632T3/en unknown
- 2008-09-25 BR BRPI0811568A patent/BRPI0811568A2/en not_active Application Discontinuation
- 2008-09-25 AU AU2008309814A patent/AU2008309814B2/en not_active Ceased
- 2008-09-25 MY MYPI20094805A patent/MY145126A/en unknown
- 2008-09-25 CA CA2686494A patent/CA2686494C/en not_active Expired - Fee Related
- 2008-09-25 MX MX2009012389A patent/MX2009012389A/en active IP Right Grant
- 2008-09-25 CN CN2008800203511A patent/CN101755040B/en not_active Expired - Fee Related
- 2008-09-25 AT AT08837128T patent/ATE487787T1/en not_active IP Right Cessation
- 2008-09-25 WO PCT/EP2008/062872 patent/WO2009047124A1/en not_active Ceased
- 2008-10-10 CL CL2008003016A patent/CL2008003016A1/en unknown
- 2008-10-14 AR ARP080104466A patent/AR068856A1/en unknown
Non-Patent Citations (1)
| Title |
|---|
| See references of WO2009047124A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| DE602008003428D1 (en) | 2010-12-23 |
| MY145126A (en) | 2011-12-30 |
| AU2008309814B2 (en) | 2010-09-02 |
| MX2009012389A (en) | 2010-01-29 |
| WO2009047124A1 (en) | 2009-04-16 |
| CA2686494A1 (en) | 2009-04-16 |
| CA2686494C (en) | 2012-08-14 |
| CL2008003016A1 (en) | 2009-06-05 |
| AR068856A1 (en) | 2009-12-09 |
| BRPI0811568A2 (en) | 2016-07-19 |
| EP2142632B1 (en) | 2010-11-10 |
| ATE487787T1 (en) | 2010-11-15 |
| CN101755040A (en) | 2010-06-23 |
| PL2142632T3 (en) | 2011-04-29 |
| CN101755040B (en) | 2012-04-18 |
| AU2008309814A1 (en) | 2009-04-16 |
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