CN101821373A - Contain the granular detergent compositions that contrasts lamellar visual cues - Google Patents
Contain the granular detergent compositions that contrasts lamellar visual cues Download PDFInfo
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- CN101821373A CN101821373A CN200880110994A CN200880110994A CN101821373A CN 101821373 A CN101821373 A CN 101821373A CN 200880110994 A CN200880110994 A CN 200880110994A CN 200880110994 A CN200880110994 A CN 200880110994A CN 101821373 A CN101821373 A CN 101821373A
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- visual cues
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- 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
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- 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
- C11D1/66—Non-ionic compounds
- C11D1/83—Mixtures of non-ionic with anionic 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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/02—Floating bodies of detergents or of soaps
-
- 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
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- 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
- 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
- C11D3/3753—Polyvinylalcohol; Ethers or esters thereof
-
- 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
Abstract
The granular detergent compositions that comprises anion surfactant and a plurality of lamellar visual cues, each lamellar visual cues comprises at least 30% polymkeric substance and the spices of 0.01 to 50 weight %, it is characterized in that the cross-sectional area of each lamellar visual cues is less than 100mm
2
Description
The present invention relates to comprise the granular detergent compositions of anion surfactant and a plurality of contrast (contrasting) lamellar visual cues (visual cue), particularly comprise the composition of spices.
Technical background
Comprise the visual contrast particulate in the granular detergent compositions, this is known.But described visual contrast particulate delivery functions composition, or may simply be the user visual cues is provided.
In US 4082682, will join in the stain remover powder than the soap particulate that fleshes up with contrasting colour of small proportion.Described particulate comprises non-woven substantive dyestuff (substantive dye) and fluorescent agent.Described powder comprises the decontamination potentiating compounds.Described soap particulate contributes to the detersive power of said composition and reduces foaming.Because described soap particulate can sink on the fabric, therefore definite advantage of described particulate is that they do not cause that fabric is dyeed by the thing that is contacted.
In GB2358403A, in containing the powder detergent compositions of larger proportion white or light particles, dry blending has advanced the lamellar visual comparison with significantly big median size than small proportion, and the significantly big median size of described lamellar visual comparison is than the big at least diameter of median size of white or light particles.This example uses contrast round or the star of being made by the colored polymeric film.Blended green and white circular membrane additive add with 0.4% aggregate level, and red star adds with 0.1% level.Described film additive also can be chosen the unspecified washing function composition that contains the amount of not indicating wantonly.
WO2006/079416 proposes to use high resolution film additive as visual cues.Its suggestion might comprise the amount of not indicating in film functional component is tensio-active agent, spices, antioxidant, antifoam for example.The stain remover powder that embodiment in this application will contain 0.1% visual cues of being made by sheet of polyvinyl alcohol compares with the stain remover powder that contains 0.1% visual cues of being made by the Sudan Gum-arabic thin slice.Can be by 1400 μ m sieve, but can not can be selected by the suitable film additive that 500 μ m sieve, the cross-sectional area maximum of each film additive can be about 2mm
2
The known sensitive composition that can in laundry powder, add the particle form of making separately.This technology can be known as dry blending or after feed intake (post dosing).The particle that becomes known for adding spices carries out by this way.
Proposed film composite itself as cleaning product.FR2120295 has provided the example of described composition.Embodiment 15 comprises glycerine, Sulfuric acid,monododecyl ester, sodium salt, carboxymethyl cellulose, spices and water.Final film composite does not provide.On the solid basis, described spices will be included in the film with the level of 0.18 weight %.
EP 1275368A1 discloses and added flavor compositions in soluble polymeric films.Described polymkeric substance preferably polyethylene alcohol, modified polyvinyl alcohol, polyvinylpyrrolidone, starch, starch derivative and modified-cellulose.Embodiment all use big cross-sectional area interpolation the film of spices: 50cm
2, 25cm
2Do not propose to use the diaphragm that contains granular detergent compositions.
EP1614743 discloses via water-soluble film interpolation fragrance in the laundry stain remover and has been better than directly adding identical fragrance in the laundry stain remover.Described embodiment uses the monolithic polymeric film that contains about 25 weight % spices levels.The cross-sectional area of the film that uses is 113cm
2Described embodiment shows the spices effect of improvement, the perfume intensity from the article that cleaned, and cellulosefilm is better than PVA (PVOH) FILM.
About using the visual cues of polymeric film as fragrance granular detergent compositions (stain remover of particularly doing washing), still existing problems.
A target of the present invention is to comprise a plurality of granular compositions that add functional laminar contrast visual cues in composition.We are surprised to find that if send spices from the lamellar visual cues of specific dimensions, then to have advantage.
Summary of the invention
According to the present invention, a kind of granular detergent compositions that comprises anion surfactant (wherein [the weight % of nonionogenic tenside]/[the weight % of anion surfactant] mark is 0 to 1), comprises a plurality of contrast lamellar visual cues is provided, wherein each visual cues comprises the polymkeric substance of at least 30 weight % and the spices of 0.01 to 50 weight %, and wherein the cross-sectional area of each visual cues is less than 100mm
2For the best visibility of described visual cues, cross-sectional area should be greater than 8mm
2
The stated limit of the cross-sectional area of described lamellar visual cues provides the perfume intensity of improving.
Contain anion surfactant and wherein [the weight % of nonionogenic tenside]/[the weight % of anion surfactant] mark be 0 to 1 cleaning solution, this is optimal.Therefore, nonionic and anionic total surfactant ratio should fall within this scope in the described composition.
In addition, the spices that contains the lamellar visual cues of these diameters also has such advantage, and promptly the spices of wide region is stable to the decomposition that is caused by the SYNTHETIC OPTICAL WHITNER in high pH or the granular composition.
Detailed Description Of The Invention
Granular laundry powder stain remover mainly is made up of tensio-active agent and ionogen.Typical anion surfactant comprises linear alkylbenzene sulfonate, primary alcohol sulfate,, straight chain alcohol ethoxy sulfate, and typical nonionogenic tenside is an alcohol ethoxylate.Typical ionogen is inorganic materials such as sodium sulfate, sodium-chlor, tripoly phosphate sodium STPP, yellow soda ash, silicate and zeolite, organic materials such as polycarboxylate and citric acid.
In order to provide other cleaning benefit, high performance material such as fluorescent agent, aberration dyestuff (shading dyes), enzyme, optical white, antioxidant and catalyzer can be joined in the described composition with low-level.When with the described high performance material of low-level adding is the most cost-efficient, typically adds with the level that is lower than whole composition 0.1 weight %.Described material is made into particle usually, feeds intake in described composition after then.
The another kind of composition that is usually added in the commercial laundry composition is a spices.Laundry product is appreciated according to their smell by the human consumer.Clean in the smell of product, cleaning and the drying process in the packing and the smell of water, and the smell on the clothing of dry back has all become the focus of numerous researchs and many patents.The smell that uses in the cleaning usually and the smell in packing closely related.
Many human consumers impregnated in their clothing in the solution of detergent compositions.Often clothing is put in the water, above described composition is spread on, and with the such placement of clothing 2 to 200 minutes.In the method, in the cleaning operation process, the human consumer all is exposed to from the smell in the water in the starting stage process of dipping and behind dipping.The key factor whether certain laundry products is suitable for their needs is normally estimated in the perception of fragrance.We have found that if fragrance is contained in the soluble polymer film, then fragrance can be enhanced and improve, described polymeric film has been cut into to have less than 100mm
2Discontinuous of low surface area.Can give the dyestuff that they are different from particulate contrast color by adding in described lamellar visual cues, and by they are had greater than 8mm
2Cross-sectional area, thereby make them high-visible in powder and in water.So the lamellar visual cues that forms can be dyed desired color, and can be fashioned into and look the shape of the Xiao Hua or some other the so natural objects that look like to have petal.
Lamellar visual cues is the two-dimentional particulate of being made by flat film basically.They have greater than stain remover particulate first diameter and second diameter, and so they are highly-visible.The thickness of described film is more preferably less than 0.3mm preferably less than 0.5mm, most preferably less than 0.2mm.Described film has relative homogeneous thickness, so that it has foreseeable dissolution characteristics.Thickness is limit poor (tolerance) preferably to be to the maximum and is added deduct 20%, more preferably adds deduct 10%.
Polymkeric substance in the described lamellar visual cues preferably includes polyvinyl alcohol.Described lamellar visual cues further advantageously comprises the tensio-active agent of 5 to 50 weight % to strengthen their solubleness.
Preferably, described tensio-active agent comprises the anion surfactant of at least 5 weight %, most preferably is alkyl-sulphate.
Described polymkeric substance can be selected from the polymkeric substance that water-soluble film forms, and particularly those are used for the polymkeric substance of stain remover power formulations.Preferred polymkeric substance comprises such polymkeric substance, and they, dissolve fully and/or be scattered in the water in 30 minutes along with stirring under any temperature of 293 to 333K scopes.
Preferred water-soluble polymers is those polymkeric substance that can be cast into film or solid mass, for example the polymkeric substance described in the water soluble resin (New York Van NostrandReinhold company publishes (1968)) that Davidson and Sittig showed.Preferred water soluble resin comprises polyvinyl alcohol, ether of cellulose, polyoxyethylene, starch, polyvinylpyrrolidone, polyacrylamide, polyvinyl methyl ether-maleic anhydride, polymaleic anhydride, styrene-maleic anhydride, Natvosol, Vltra tears, polyoxyethylene glycol, carboxymethyl cellulose, polyacrylate, alginate, acrylamide copolymer, guar gum, casein, ethene-maleic anhydride resin series, polymine, Type 3U, ethylmethylcellulose, hydroxyethylmethyl-cellulose, sugar.The resin of the water-soluble polyvinyl alcohol film shaping (film-forming) of preferred lower molecular weight.
At the molecular-weight average of this polyvinyl alcohol that preferably uses for any numerical value between 1000 and 1000000, preferably between 5000 and 250000, for example between 15000 and 150000.Hydrolysis or alcoholysis be defined as on the resin acetate group by hydroxyl ,-percentage that reaction that OH replaces is finished.The hydrolysis scope of the film shaped resin of preferably polyethylene alcohol is 60-99%, yet for the water-soluble polyvinyl alcohol film shaping resin, preferred hydrolysis scope is about 70-90%.Most preferred hydrolysis scope is 80-89%.As used in this application, term " polyvinyl alcohol " comprises the polyvinyl acetate ester cpds with hydrolysis level disclosed herein.
Another kind of suitable polymer blend is a PVA (PVOH) FILM, is made by the polyvinyl alcohol copolymer with the comonomer that contains the carboxylate function.
The PVA of preference ranking only just absorbs moisture under RH is higher than the RH of granular detergent compositions fully.Therefore, it protects other thin film compositions to avoid by water decomposition, and the protection soluble dye avoids oozing out (bleeding).
Described visual cues film particulate can comprise 10 to 80% polymkeric substance or polymeric blends.
Although can use any suitable tensio-active agent or surfactant system.But described tensio-active agent is preferably anion surfactant, if particularly granular composition comprises synergistic agent.
Suitable anion surfactant comprise those skilled in the art well-known those.The example of high foaminess sulfonate or vitriol type tensio-active agent comprises alkylbenzene sulfonate, particularly has C
8-C
15The linear alkylbenzene sulfonate of alkyl chain length; Primary alkyl sulphates and secondary alkyl sulfate, particularly C
8-C
15Primary alkyl sulphates; Alkene sulfonate; Alkylxylene sulfonate; Dialkyl sulfosuccinates; And fatty sulfonate.Common particular certain cancers.
Further information provides in disclosed document, for example rolls up disclosed information among I and the II at " tensio-active agent and stain remover (the Surface-Active Agents andDetergents) " that Schwartz, Perry and Berch showed.
The preferred anionic surfactants tensio-active agent is an alkylbenzene sulfonate, linear alkylbenzene sulfonate (LAS) more particularly, and its preferred amount is 12 to 24 weight %, more preferably 12 to 22 weight %, particularly 15 to 22 weight %.
Even primary alcohol sulfate, (PAS), particularly C more preferably
8-C
18, preferred C
12-C
15, primary alcohol sulfate.Particularly preferred tensio-active agent is that carbon chain lengths is 12 primary alcohol sulfate, (PAS).Can use the visual cues film particulate that contains up to 50%PAS.
Described film can comprise the second surface promoting agent in addition.Described second surface promoting agent is preferably selected from the anion surfactant of amphoterics, zwitterionics, nonionogenic tenside and ethoxylation.
Preferred both sexes second surface promoting agent is an amine oxide.Most preferred amine oxide is a cocoa dimethylin oxide compound.
Preferred zwitter-ion second surface promoting agent is a trimethyl-glycine, particularly amido betaine, for example cocoa aminopropyl trimethyl-glycine.
Preferred nonionic second surface promoting agent comprises primary alcohol ethoxylate and secondary alcohol ethoxyl compound, and particularly average every mol of alcohol contains the C of the ethoxylation of 1 to 20 moles of ethylene oxide
8-C
20Fatty Alcohol(C12-C14 and C12-C18), more particularly average every mol of alcohol contains the C of the ethoxylation of 1 to 10 moles of ethylene oxide
10-C
15Uncle's Fatty Alcohol(C12-C14 and C12-C18) and secondary Fatty Alcohol(C12-C14 and C12-C18).
The negatively charged ion second surface promoting agent of preferred ethoxylation comprises sulfated alkyl ether (alcohol sulfate of ethoxylation).
The second surface promoting agent that is suitable as visual cues of the present invention equally is C
8-C
18Alkyl monoethanol amide, for example, the cocoa single ethanol amide.
The described second surface promoting agent that is used for described film particulate can comprise in a small amount in addition, for example less than film 5%, and cats product.
The tensio-active agent level that is comprised in the film can be up to 90 weight %, preferably up to 75 weight %, most preferably up to 60 weight %.
When thin slice is used as visual cues, they need be in cleaning liquid and under the background of stain remover prescription easily as seen, therefore, preferably that described film is painted.The direct pigment of non-woven can 0.001 to 0.5 weight %, preferred 0.1 to 0.03 weight % level be included in the described film composite.Suitable pigment comprises any pigment that is used for stain remover liquid or powder coloring.Yellow, blueness, purple, red-purple, redness, lavender, orange, green, pink colour are preferred colors.
Described lamellar visual cues can further comprise the optional other beneficiating ingredient that exists with 0.001 to 20% level, and described composition is selected from: aberration dyestuff, optical white, fluorescent agent, antioxidant, enzyme, dye transfer inhibitor, decoupling polymkeric substance, sequestrant and bleaching catalyst.Preferred additional beneficial agent is aberration dyestuff and fluorescent agent.The described composition of a plurality of described lamellar visual cues that comprises has additional advantage promptly, and protection spices and optional other responsive high performance materials are away from the aggressive high pH of granular component.When preferably, described granular composition is in being dissolved in deionized water overbasic (0.1% solution at 25 ℃＞pH 10.5).This has been avoided comprising the needs of any antioxidant or sanitas in described film formulation.In order to reach such alkaline pH, normally, described granular detergent powder comprises a large amount of silicate and/or carbonate.
In addition, in order to reduce the influence of other beneficiating ingredients that described film formulation may can contain spices and it, expect that described lamellar visual cues when they are dissolved in the deionized water when forming 0.1% solution individually, has 3 to 9 pH, preferred 6 to 8 pH.
Expectation is that described lamellar visual cues is a buoyant when being added in the water for the first time especially.This has strengthened described visual cues visibility in use, the prompting clearly that has spices is provided, if there are optional more beneficiating ingredients in the film, then it can help also to reduce that dissolving by the visual cues of the fabric that betides the surface, cleaning away from great majority causes is stained with stain or the infringement of other fabrics.Spices seems it also is useful from the evolution (evolution) of the cleaning solution that the composition of the floating lamellar visual cues that comprises a plurality of claimed types forms.Floating in order to ensure described visual cues, preferably their relative density is more preferably less than 0.5 less than 0.8, most preferably less than 0.4.
Unexpectedly, if our discovery will comprise that the appointment lamellar visual cues of polymkeric substance and spices is used for comprising the composition of cats product, then be useful, wherein [nonionogenic tenside weight %]/[anion surfactant weight %] mark is 0 to 1 in described composition.Preferably [nonionogenic tenside weight %]/[anion surfactant weight %] mark is 0 to 0.1, most preferably is 0.Linear alkylbenzene sulfonate is most preferred anion surfactant.Make that we are surprised to be, preferably fill a prescription at present and in cleaning liquid, provide higher perfume intensity.
The level of anion surfactant is preferably between 4 and 60 weight % in the described granular composition.More preferably between 6 and 20 weight %.
Spices
The amount of spices is 0.01 to 50 weight % in the described lamellar visual cues, is preferably 0.1 to 40 weight % of described visual cues.
We expect that described spices is the spices of sealing (encapsulated), and the amount that spices is sealed in the described lamellar visual cues is 15 to 40 weight % of described visual cues.
The example of spendable spices is referring to WO2004/111174, WO2004/111171, WO2004/111172 and WO2005/059077.Spices generally is not one compound, normally the compounding mixture of transferring (fragrance notes) to be mixed and made into by multiple fragrance.The present invention includes the use of individualized compound (fragrance accent) and compounding mixture.
The present invention is particularly suitable for high pH or the unsettled spices of SYNTHETIC OPTICAL WHITNER.Especially, in the aqueous solution of pH 11, place to decompose in 7 days and surpass 20% spices, or be exposed to the inclined to one side acetate that contains 2mM hydrogen peroxide or pH 11 and decompose spices in the time of 7 days above 20%.The percentage ratio unit of being meant is the loss of the concentration of every liter of mole.Test should adopt 1mM spices to carry out at 293K.For the described spices of solubilising, can use tensio-active agent, the sodium lauryl sulphate (SDS) of preferred 1g/L.
This comprises the compound of the different functional groups with wide in range degree, described functional group for example, alcohol, ketone, ester, lactone, aldehyde, terpene and phenol.
The example of preferred aldehydes spices is: cyclamen aldehyde (cyclamen aldehyde), laurine (hydroxycitronellal), hydrocinnamic aldehyde, Ling Lanquan, LYRAL, nonadienal and phenylacetic aldehyde.
The example that preferably contains the phenol of spices is: raspberry ketone, Vanillin, vanillal, 4-propyl group-2-methoxy phenol, 4-allyl group-2-methoxy phenol, 4-propenyl-2-methoxy phenol, hexyl salicylate, cis-3-hexenyl salicylate and methyl salicylate.
Spices is easy to obtain from following company: International Flavors and Fragrances (IFF), Firmenich SA and Givaudan.
It is the tabulation that can be used for preferred spices of the present invention below: α damascone (demascone), the δ damascone, Iso E super, phenylacrolein, hexyl cinnamic aldehyde, butyl cinnamic aldehyde, phenyl aldehyde, anisiquealdehyde, coriandrol, the tetrahydrochysene coriandrol, methyl decenol (Undecavertol), Geraniol, vernol, geraniol, citral, Oxyde de Rose, acetate Mang geraniol ester, geraniol acetate, tonka bean camphor (Coumarine), phanteine, nitric acid Mang geraniol ester, citronellyl nitrile (Citronellyl nitrile), cinnamyl nitrile (Cinnamonitrile), citrus nitrile (Citronitrile), pinane, all roads ketone (veloutone), the purple ketone of Alpha-Methyl, Tujue's ketenes (damascenone), γ-Song Youxi, grass blue or green aldehyde (trifernal), Ling Lanquan (lilial), geranial, cyclosal, heliopropanal, zestover, C12 aldehyde, tridecylene aldehyde, Cyclosia base, octenal, pulegone;
Coeur, from vertofix coeur and the terpinolene of IFF.
Especially, seal, then can obtain favourable spices releasing effect if be included in the spices of described lamellar visual cues.The spices of sealing is that mixing to form maximum diameter with polymer materials is the spices of 100 microparticles.Preferably, the vapour pressure of described spices is in the particulate of sealing, reduce under 293K and 1 normal atmosphere.
The typical material that is used for encapsulated perfume is treated starch, Mierocrystalline cellulose, amino-plastics-resin (amino-plast-resins) and polyacrylic ester.
The aberration dyestuff
Randomly, to comprise that further the aberration dyestuff of 0.1 to 1 weight % or pigment are used for fabric pure white for described lamellar visual cues.Described composition and spices are compatible, and can the mode identical with spices be incorporated in the film.
Described aberration dyestuff or pigment are selected from:
Pigment
Pigment is coloured particulate of preferred 0.05 to 10 micron size, and it is dissolved in the water medium that contains tensio-active agent hardly.Preferred pigment is blueness or purple.
Can use inorganic pigment such as pigment blue 29 or pigment purple 15, however preferred organic pigment.
Pigment indigo plant 1,1:2,1:3,2,2:1,2:2,3,4,5,7,10,10:1,11,12,13,14,15,15:1,15:2,15:3,15:4,15:6,18,19,20,21,22,23,25,26,27,28,29,30,31,32,34,35,36,57,58,59,60,61,61:1,62,63,64,65,66,67,69,71,72,73,74,75,80,83
And pigment purple 3,3:1,3:3,3:4,5,7:1,8,9,11,12,13,14,15,16,18,19,23,25,27,28,29,31,35,37,39,41,43,44,45,47,48,50,54,55 and 56.
Preferred organic pigment is pigment purple 1,1:1,1:2,2,3,5:1,13,19,23,25,27,31,32,37,39,42,44,50
And pigment indigo plant 1,2,9,10,14,15,15:1,15:2,15:3,15:4,15:6,16,18,19,24:1,25,56,60,61,62,66,75,79 and 80.
Preferred pigment is a pigment purple 3,13,23,27,37,39, pigment indigo plant 14,25,66 and 75.
Most preferably the pigment purple 23.
Pigment purple 23
Also can use white pigment, if described granular detergent compositions is a shade, for example green or blue, then these white pigment are suitable especially.Suitable white pigment is listed in the color index (Society of Dyers and Colourists and American Association of TextileChemists and Colorists 2002), can use the white 1～pigment of pigment white 35 so that petal bleaches.Preferably white 6, pigment white 4 of white 27, the pigment of white 26, the pigment of white 18, the pigment of pigment and Metallic stearates, wherein said metal is selected from Ba, Ca, Mg or Zn.
White pigment is " industrial inorganic pigment (Industrial Inorganic Pigments) " (the 3rd edition, 2005 G.Buxbaum, G.Pfaff eds, Wiley VCH) has a detailed description in, and comprise TiO2, zinc white (ZnO), zinc sulphide and zinc sulfide white (lithopone).
Substantive dyestuff
Preferred directly purple and sun blue dyestuff.Preferably, described dyestuff is two azos or trisazo dye.Be not preferably based on the dyestuff of carcinogenic p-diaminodiphenyl (benzidene).
Most preferably, described substantive dyestuff is the direct purple with following structure.
Or
Wherein
R
1Be hydrogen or alkyl,
R
2Be hydrogen, alkyl or replacement or unsubstituted aryl, preferred phenyl,
R
3And R
4Be hydrogen or alkyl independently,
X and Y are hydrogen, alkyl or alkoxyl group independently,
Preferably, described dyestuff has X=methyl and Y=methoxyl group,
N is 0,1 or 2, preferred 1 or 2.
Preferred dyestuff is directly purple 7, directly purple 9, directly purple 11, directly purple 26, directly purple 31, directly purple 35, directly purple 40, directly purple 41, directly purple 51 and directly purple 99.
In another embodiment, described substantive dyestuff can be covalently attached to optical white, for example described in WO2006/024612.
Matching stain
Cotton directly matching stain is of value to and contains cotton clothes.The mixture of preferred dyestuff and dyestuff is blueness or purple.Preferred matching stain is: (i) azines, and wherein said dyestuff has following core texture:
R wherein
a, R
b, R
cAnd R
dBe selected from: C H, side chain or straight chain
1To C
7-alkyl chain, benzyl, phenyl and naphthyl;
Described dyestuff is by at least one SO
3 -Or-COO
-Group replaces; The B ring does not carry negative charge group or its salt;
And the A ring can further be replaced to form naphthyl; Described dyestuff is chosen wantonly by following groups and is replaced: amine, methyl, ethyl, hydroxyl, methoxyl group, oxyethyl group, phenoxy group, Cl, Br, I, F and NO
2
Preferred azines is: acid blue 98, acid violet 50 and acid blue 59, more preferably acid violet 50 and acid blue 98.
(ii) acid violet 17, acid violet 50, Acid Black 1, Xylene Red 51, azogeramine 7 and acid blue 29.
Hydrophobic dye
Described composition can comprise one or more hydrophobic dyes, and described hydrophobic dye is selected from: benzo two furans, methyne (methine), tritane, naphthalimide (napthalimides), pyrazoles, naphthoquinones (napthoquinone), anthraquinone and monoazo or two azo dye chromophores.Hydrophobic dye is not conform to the dyestuff that any charged water solubilization radical is arranged.Optional self-dispersing dye of hydrophobic dye and solvent dye.Preferred blue and purple anthraquinone and monoazo-dyes.
Preferred dyestuff comprises solvent violet 13,63 ,DIS,PER,SE ,Vio,let, 63 27,63 ,DIS,PER,SE ,Vio,let, 63 26,63 ,DIS,PER,SE ,Vio,let, 63 28,63 ,DIS,PER,SE ,Vio,let, 63 63 and 63 ,DIS,PER,SE ,Vio,let, 63 77.
Basic dyestuff
Basic dyestuff is the organic dye that has clean positive charge.They are deposited on the cotton.They have particular utility in the composition that mainly comprises cats product.Dyestuff can be selected from alkaline purple and alkali blue listed in the color index.Preferred examples comprises triarylmethane basic dyestuff, methane basic dyestuff, anthraquinone basic dyestuff, alkali blue 16, alkali blue 65, alkali blue 66, alkali blue 67, Blue 71, alkali blue 159, alkaline purple 19, alkaline purple 35, alkaline purple 38, alkalescence purple 48, Basic Blue 3, Blue 75, alkali blue 95, alkali blue 122, alkali blue 124, alkali blue 141.
Also can use blue and purple thiazole (thiazolium) monoazo-dyes, as described at WO2007/084729.
Reactive dyestuffs
Reactive dyestuffs are to comprise the dyestuff that can react and described dyestuff is covalently attached to cellulosic organic group with Mierocrystalline cellulose.They are deposited on the cotton.
Preferably, described active group is hydrolysis, or the active group of described dyestuff with organism class (species) thus such as polymkeric substance taken place the reaction described dyestuff is connected in this thing class.Dyestuff can be selected from reactive violet listed in the color index and reactive blue dye.Example is
Preferred examples comprises Reactive Blue 19 100, Reactive blue 163, Reactive blue 182 and Reactive blue, Reactive blue 96.
The dyestuff conjugate
The dyestuff conjugate by via physical force with acidity or basic dyestuff is directly connected in polymkeric substance or particulate forms.Depend on the selection of polymkeric substance or particulate, they are deposited on cotton or synthetics.In WO2006/055787, provided description.They are not preferred.
Optical white
Randomly, except that spices, the optical white that described lamellar visual cues comprises 0.01 to 1 weight % is used for the pure white and cleaning of fabric.The combination of preferred especially aberration dyestuff and optical white.Described optical white can mix simultaneously with other additives, spices and optional aberration dyestuff.
Preferred singlet oxygen (singlet oxygen) optical white.
The function of singlet oxygen optical white (PB) is as follows:
PB+ light → PB
*
PB
＊+
3O
2→PB+
1O
2
Described optical white molecular absorption light also arrives excited electronic state PB
*This excited electronic state is by the triplet oxygen in the environment (triplet oxygen)
3O
2Thereby cancellation forms singlet
1O
2Singlet oxygen is the high activity SYNTHETIC OPTICAL WHITNER.
Suitable singlet oxygen optical white can be selected from the water soluble metal phthalocyanine compound, and particularly metallized phthalocyanine compound, wherein said metal are Zn or Al-Zl, and wherein Zl is halogenide, vitriol, nitrate, carboxylate, alkanolate or hydroxyl ion.Preferably, described phthalocyanine has the 1-4 covalently bound with it SO
3The X group, wherein X is basic metal or ammonium ion.Described compound has description in WO2005/014769 (Ciba).
The dyestuff of preferred xanthene type, particularly based on following structure:
Wherein, described dyestuff can be replaced by halogen and other elements/group.Particularly preferred example is Food Red 14 and rose-red (Rose Bengal), phloxin (Phloxin) B, eosin W or W S.
The quantum yield that is suitable for the photosensitive formation of singlet oxygen can be referring to J.Phys.Chem.Ref.Data1993, volume 22, nol 113-262 page or leaf.If at organic solvent or D
2The quantum yield that is suitable for singlet oxygen formation measured among the O then is preferred, more preferably greater than 0.1 greater than 0.05.
Other compounds that produce singlet oxygen comprise chlorophyll, tonka bean camphor, porphyrin, myohaemoglobin, riboflavin, bilirubin and methylenum coeruleum.
Fluorescent agent
Randomly, can to comprise further that the fluorescent agent of 0.01 to l weight % is used for fabric pure white for described lamellar visual cues.
Fluorescent agent is well-known, and many such fluorescent agents are commercially available.Usually, these fluorescent agents be with they an alkali metal salt for example sodium-salt form provide and use.
Being used for a kind of fluorescent agent of laundry treatment compositions or the total amount of multiple fluorescent agent is 0.005 to 2 weight %, more preferably 0.01 to 0.1 weight %.Preferred fluorescent agent is: 2 (4-styryl-3-sulfophenyl)-2H-naphthols (napthol) [1,2-d] triazole sodium, 4,4 '-it is two that { [(4-anilino-6-(N methyl-N-2 hydroxyethyl) amino 1,3,5-triazine-2-yl)] amino } stibene (stilbeno)-2-2 ' disulfonic acid disodium, 4,4 '-two [(4-anilinos-6-morpholino-1,3,5-triazine-2-yl) amino] stibene-2-2 ' disulfonic acid disodium and 4,4 '-two (2-sulfo group styryl) biphenyl disodium.
With reference to following non-limiting example will the present invention is described further.
Embodiment 1
The polymeric film that the spices that comprises 33 weight % is sealed (Denali, ex IFF) is prepared as follows:
30% solution of polymkeric substance (polyvinyl alcohol) and tensio-active agent (sodium lauryl ether sulphates) is dissolved in the water at 60 ℃.After dissolving fully, little (microencapsulated) spices (ex IFF) of sealing is scattered in this solution.Then final dispersion liquid is coated with into skim on the sheet glass of 24 * 34cm, and dry.
Behind complete drying, the gained film is taken away and cut from sheet glass.
Embodiment 2
The particulate laundry detergent compositions that has prepared two part of 10 gram sample.It comprises 18% LAS sodium, 73% salt (silicate, tripoly phosphate sodium STPP, sodium sulfate, yellow soda ash), and remaining is impurity, water and submember (enzyme and fluorescent agent).This powder does not contain spices.Described sample is marked as A and B.
In A, add 0.13g spices and seal (Denali, ex IFF).The described cutting spices film that in B, adds 0.4g embodiment 1.Therefore, initial, A and B comprise the spices of same amount.Described spices film is cut into the rectangle that 5-6mm takes advantage of 1-2mm.With described two kinds of powder thorough mixing, and be tested and appraised device and measure perfume intensity in the described powder.
Then with in the open tank of described sample retention in humidity cabinet (310K and 70% relative humidity).By identical identifier monitoring fragrance scent as time passes.Before estimating each time, with the violent jolting of this powder to discharge volatile matter.
The result is displayed in Table 1.
Measure perfume intensity based on grade 0 (nothing) to 5 (height).
Table 1
| Storage time | ??A | ??B |
| ??0 | 4 fruity, peach flavor, muskmelon flavor | 2 sharp flavors |
| 2 hours | 2 fruity | 3 fruity+sharp flavor |
| 20 hours | 2 peaches flavor | 3 fruity+sharp flavor+abundant aromatising flavour |
From this result, shown by higher scoring and more descriptor (italic), A compares with B, and A has initial very high and more complicated smell.Yet when storing, very rapidly, B obtains higher scoring and has more complicated smell.
Comprising spices in the film provides the granular composition of the spices effect with improvement.
Embodiment 3
The described spices film of embodiment 1 is cut into the sample of following different size:
C 2 * 3cm sheet
D 2 * 2mm sheet
Each sample size is weighed up 0.15g, and they are joined 40ml contain in the solution of 0.5g/L total surfactant under 293K, do not stir.The tensio-active agent that is used for this research is linear alkylbenzene sulfonate (LAS), nonionogenic tenside R-(OCH
2CH
2)
nOH, wherein R is C
12To C
15Alkyl chain, n are 7 (NI), and 1: 1 mixture of LAS: NI.
Estimate the smell of described liquor immediately, and leave standstill postevaluation in 4 minutes at 293K.Measure perfume intensity based on grade 0 (nothing) to 5 (height).
The result provides in table 2.
Table 2
Less the maximum cross-section area film D compares with bigger cross-sectional area film C, provides more spices in cleaning liquid.From the prescription that contains LAS, detect more spices, and never contain in the prescription of nonionogenic tenside and detect maximum spices.
Embodiment 4
The described spices film of 0.15 gram embodiment 1 is joined in the cleaning powder of 5 gram embodiment 2.Adopt the spices film of the identical total area to cut into the rectangle of each different cross-sectional areas and make four duplicate samples.Go mineral water to join in the described powder 120ml, and with this solution jolting 1 minute.Smell at three cleaning liquids of 5 minutes inner evaluations.Measure perfume intensity based on grade 0 (nothing) to 5 (height).The result is displayed in Table 3.
Table 3
| Spices film diameter | Perfume intensity |
| ??2×3cm(600mm 2) | ??0.2 |
| ??1×1.5cm(150mm 2) | ??0.5 |
| ??1×0.75cm(75mm 2) | ??1.3 |
| ??2×2mm(4mm 2) | ??1.3 |
Sample with small cross sectional is compared with the sample with comparatively large cross-sectional area, provides higher spices scoring.
Embodiment 5
The described spices film of embodiment 1 is cut into the sample of different size:
C 5 * 20mm sheet
D 2 * 2mm sheet
Weigh up a kind of in each sample size, and it is joined 100ml at 293K contain in the solution of total surfactant of 0.5g/L, do not stir.The tensio-active agent that is used for this research is linear alkylbenzene sulfonate (LAS), nonionogenic tenside R-(OCH
2CH
2)
nOH, wherein R is C
12To C
15Alkyl chain, n are 7 (NI), and 1: 1 mixture of LAS: NI.
The gross weight that joins the film in the LAS solution is 0.048g.Join LAS: the gross weight of the film in the NI solution is 0.042g.The gross weight that joins the film in the NI solution is 0.046g.Therefore, the weight maximum that the spices that adds via film is sealed is 0.016g.
Estimate the smell of described liquor immediately, and leave standstill postevaluation in 4 minutes at 293K.At first, the smell of described cleaning liquid be LAS＞LAS＞: NI＞NI.Can detect considerably less spices from described NI surfactant soln, but can be from described LAS: detect considerable spices the NI, its smell is almost the same strong with the smell of pure LAS solution.After 4 minutes, the order of perfume intensity remains unchanged.
After 4 minutes, described diaphragm is still visible and be obviously complete in all liquid.With less sheet shift out, dry and weigh once more.The weight % that is kept is 62% for LAS, is 57% for LAS: NI, is 75% for NI.To such an extent as to the too little difference that can not explain viewed spices of these differences of solubleness.Spices is to discharge by the complicated diffusion mechanism of not understanding fully as yet.
Repeat this experiment, join in the cleaning liquid but 0.03g Denali spices sealed directly.At first, from any cleaning liquid, all do not detect spices, be different from the situation of spices film.In order to discharge spices, with described solution jolting and left standstill 20 minutes.Spices in all samples still very a little less than, the order of odor intensity is NI＞LAS～LAS: NI.Difference between the described solution is little a lot of than the difference among the film embodiment.
Can not explain viewed difference for the manufacturing temperature that shows film, 0.09gDenali spices is encapsulated in 293K for we and 333K joins in the 100g water.Then will be than cold the going of sample of heat to 293K, and estimate the perfume intensity of two duplicate samples.There is not recognizable difference.
Exemplary granular detergent compositions A, B, C, D
| Composition | ??A | ??B | ??C | ??D |
| ??NaLAS | ??15 | ??20 | ??10 | ??12 |
| ??NI(7EO) | ??- | ??- | ??- | ??8 |
| Tripoly phosphate sodium STPP | ??7 | ??15 | ??- | ??- |
| Soap | ??- | ??- | ??- | ??1 |
| Zeolite A24 | ??- | ??- | ??- | ??17 |
| Water glass | ??5 | ??4 | ??5 | ??1 |
| Yellow soda ash | ??23 | ??20 | ??30 | ??20 |
| Sodium sulfate | ??40 | ??30 | ??40 | ??20 |
| Carboxymethyl cellulose | ??0.2 | ??0.3 | ??- | ??0.5 |
| Percarbonate | ??- | ??3 | ??- | ??10 |
| ??TAED | ??- | ??0.8 | ??- | ??4 |
| Proteolytic enzyme | ??0.005 | ??0.01 | ??- | ??0.005 |
| Spices | ??0.1 | ??0.1 | ??0.1 | ??0.1 |
| Composition | ??A | ??B | ??C | ??D |
| Spices (visual cues) | ??0.2 | ??0.1 | ??0.03 | ??0.3 |
| Lamellar visual cues ** | ??1 | ??0.5 | ??0.1 | ??2 |
| Cellulase | ??- | ??0.003 | ??- | ??- |
| Fluorescent agent | ??0.1 | ??0.15 | ??0.05 | ??0.3 |
| Directly purple 9 (visual cues) | ??0.00016 | ??0.0004 | ??0.0002 | |
| Direct purple 99 | ??- | ??- | ??0.0002 | ??- |
| Solvent violet 13 | ??- | ??0.02 | ??- | ??- |
| Solvent violet 13 (visual cues) | ??- | ??- | ??- | ??0.01 |
| Sulfonated Zn phthalocyanine optical white | ??0.002 | ??0.004 | ??- | ??- |
| Water/impurity/submember | Residuum | Residuum | Residuum | Residuum |
*Described lamellar visual cues has 10 to 20mm
2Cross-sectional area, and contain the film composite of forming by primary alkyl sulfonate and polyvinyl alcohol polymer.The amount that provides in the figure comprises beneficiating ingredient in a small amount, and described beneficiating ingredient is included in the described film particulate and can be differentiated respectively by " (visual cues) ".
Directly the level of purple 9, direct purple 99, solvent violet 13 and Sulfonated Zn phthalocyanine (Pthalocyanine) optical white is to provide as pure dyestuff.NI (7EO) is meant R-(OCH
2CH
2)
nOH, wherein R is C
12To C
15Alkyl chain, and n is 7.
Claims (14)
1. granular detergent compositions that comprises anion surfactant and optional nonionogenic tenside, wherein [the weight % of nonionogenic tenside]/[the weight % of anion surfactant] mark is 0 to 1, and further it comprises a plurality of lamellar visual cues, wherein each lamellar visual cues comprises at least 30% polymkeric substance and the spices of 0.01 to 50 weight %, and the cross-sectional area that it is characterized in that each lamellar visual cues is less than 100mm
2
2. according to the granular detergent compositions of claim 1, the amount of the spices in the wherein said lamellar visual cues is 0.1 to 40 weight % of additive.
3. according to the granular detergent compositions of claim 1, wherein spices is that spices of sealing and the amount that is encapsulated in the spices in the lamellar visual cues are 15 to 40 weight % of additive.
4. according to the granular detergent compositions of any aforementioned claim, wherein said lamellar visual cues is given dyestuff or the pigment that they are different from the correlated color of particulate and is become visual by comprising.
5. according to the granular detergent compositions of any aforementioned claim, wherein when described composition dissolves is in deionized water overbasic (1% solution under 25 ℃＞pH 10.5), and described lamellar visual cues is had 3 to 9 pH when forming 1% solution, preferred 6 to 8 pH when it is dissolved in separately in the deionized water.
6. according to the granular detergent compositions of claim 5, wherein said granular detergent powder comprises silicate and/or carbonate.
7. according to the granular detergent compositions of any aforementioned claim, the polymkeric substance in the wherein said lamellar visual cues comprises polyvinyl alcohol.
8. according to the granular detergent compositions of any aforementioned claim, wherein said lamellar visual cues further comprises the tensio-active agent of 5 to 50 weight %.
9. according to the granular detergent compositions of any aforementioned claim, wherein [the weight % of nonionogenic tenside]/[the weight % of anion surfactant] mark is 0 to 0.1, is preferably 0.
10. according to the granular detergent compositions of any aforementioned claim, the anion surfactant in the wherein said particle is a linear alkylbenzene sulfonate.
11. granular detergent compositions according to any aforementioned claim, wherein said lamellar visual cues further comprises the beneficiating ingredient of 0.001 to 20% other level, and described beneficiating ingredient is selected from aberration dyestuff, optical white, fluorescent agent, dye transfer inhibitor, sequestrant, decoupling polymkeric substance, antioxidant, enzyme, bleaching catalyst and their mixture.
12. according to the granular detergent compositions of claim 11, wherein said lamellar visual cues comprises the aberration dyestuff.
13. according to the granular detergent compositions of claim 11 or 12, wherein said lamellar visual cues comprises fluorescent agent.
14. according to the granular detergent compositions of any aforementioned claim, wherein said lamellar visual cues is from the soluble film material preparation, described thin-film material floats on the cleaning liquid that is formed by the dissolving of granular detergent compositions.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IN2036MU2007 | 2007-10-12 | ||
| IN2036/MUM/2007 | 2007-10-12 | ||
| EP08150102.5 | 2008-01-08 | ||
| EP08150102 | 2008-01-08 | ||
| PCT/EP2008/062875 WO2009047127A1 (en) | 2007-10-12 | 2008-09-25 | Granular detergent compositions with contrasting lamellar visual cues |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101821373A true CN101821373A (en) | 2010-09-01 |
Family
ID=40303420
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200880110994A Pending CN101821373A (en) | 2007-10-12 | 2008-09-25 | Contain the granular detergent compositions that contrasts lamellar visual cues |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP2201092A1 (en) |
| CN (1) | CN101821373A (en) |
| AR (1) | AR068859A1 (en) |
| CL (1) | CL2008003019A1 (en) |
| WO (1) | WO2009047127A1 (en) |
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|---|---|---|---|---|
| US4209417A (en) * | 1976-08-13 | 1980-06-24 | The Procter & Gamble Company | Perfumed particles and detergent composition containing same |
| DE60309052T2 (en) * | 2002-08-27 | 2007-02-08 | Unilever N.V. | PERFUME COMPOSITION |
-
2008
- 2008-09-25 CN CN200880110994A patent/CN101821373A/en active Pending
- 2008-09-25 WO PCT/EP2008/062875 patent/WO2009047127A1/en active Application Filing
- 2008-09-25 EP EP08804760A patent/EP2201092A1/en not_active Withdrawn
- 2008-10-10 CL CL2008003019A patent/CL2008003019A1/en unknown
- 2008-10-14 AR ARP080104469A patent/AR068859A1/en unknown
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI486438B (en) * | 2013-05-09 | 2015-06-01 | Inst Nuclear Energy Res Atomic Energy Council | Foam decontaminant and method of fabricating the same |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2009047127A1 (en) | 2009-04-16 |
| CL2008003019A1 (en) | 2009-06-26 |
| EP2201092A1 (en) | 2010-06-30 |
| AR068859A1 (en) | 2009-12-09 |
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