CN102782111A - Detergent formulation containing spray dried granule - Google Patents

Detergent formulation containing spray dried granule Download PDF

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Publication number
CN102782111A
CN102782111A CN2010800609522A CN201080060952A CN102782111A CN 102782111 A CN102782111 A CN 102782111A CN 2010800609522 A CN2010800609522 A CN 2010800609522A CN 201080060952 A CN201080060952 A CN 201080060952A CN 102782111 A CN102782111 A CN 102782111A
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CN
China
Prior art keywords
dyestuff
acid
laundry detergent
group
particulate laundry
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CN2010800609522A
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Chinese (zh)
Inventor
R·B·巴奇尼
S·N·巴切洛
R·M·赫尔曼特
J·A·韦林加
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Unilever PLC
Unilever NV
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Unilever NV
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents ; Methods for using cleaning compositions
    • C11D11/02—Preparation in the form of powder by spray drying
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/046—Salts
    • 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/225—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin etherified, e.g. CMC
    • 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
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in 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
    • C11D3/40—Dyes ; Pigments
    • 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
    • C11D3/42—Brightening agents ; Blueing agents

Abstract

The present invention concerns laundry shading dye compositions and in particular the strength of dye containing granules.

Description

The detergent formulations that contains spray-dried granules
Technical field
Dope dye compsn (laundry shading dye composition) the present invention relates to do washing.
Background technology
WO2005/014769 (Ciba) discloses the particle of the azo (azo), tritane and the phthalocyanine pigment that comprise 2-70wt%, is used for being included in granular detergent composition.This particle preferably prepares through fluidized-bed process or spraying drying.
WO2008/017570 (Unilever) discloses the acid azines that is included in the detergent for washing clothes preparation.
WO/2009/141173 (Unilever) discloses the positively charged ion azophenlyene or the acid azines powder of preferably spray drying, and it comprises 20 to 100wt% dyestuff.Preferably, dye powder has 0.1 to 300 micron, preferred 10 to 100 microns average particle size particle size, APS.Spray-dired dye powder and Na 2SO 4Or particle matrix or whole detergent formulations of NaCl or preparation in advance mix so that 0.1 to 5 dyestuff wt% mixture to be provided mutually.Then, this dry mixture is mixed in the granular preparation.
WO2007/039042 (Unilever) discloses in particle, but with the stability of the carboxylic acid blended dyestuff that comprises polymkeric substance and sodium sulfate.
Be included in the detergent granules preparation, spray-dired dye granule lacks intensity to prevent particle and powder or Na 2SO 4Or NaCl is broken when mixing.The particulate fragmentation can cause the variable color (discoloration) of powder.
Summary of the invention
The present invention provides a kind of particle, and it has the soundness of wanting that is used for laundry detergent composition and is provided at the dyestuff dust that processing reduces.
One side of the present invention provides a kind of particulate laundry detergent compsn, comprises:
(a) 0.00005 to 0.2wt% spray-dired dye granule, wherein dye granule comprises:
(i) 20 to 90wt% blueness or purple dope dye;
(ii) 1 to 20wt% the polymer poly compound that comprises carboxylic acid, preferably carboxymethyl cellulose sodium;
(iii) 0 to 60wt% an alkali metal salt is selected from sodium sulfate and sodium-chlor;
(b) 2 to 70wt% tensio-active agent;
(c) 5 to 50wt% washing assistant is selected from: calcium sequestrant material, precipitation threshold material (precipitating material) and calcium ion-exchanged material; With
(d) 0.05 to 50wt% water-soluble carrier salt; And,
(e) other composition of 0 to 20wt%.
Preferably, spray-dired particle has 0.1 to 300 micron average particle size particle size, APS.APS is through the laser diffraction granularity analyser, and the Malvern HP that preferably has the 100mm camera lens records.
Detailed Description Of The Invention
Dyestuff in spray-dired dye granule is preferably selected from cationic dyestuff, anionic dyestuff and uncharged alkoxylate dyestuff.When being delivered to cleaning from particle, these dyestuffs are effective especially in toning (shading).
Dyestuff preferably from:
(1) acid azines wherein should have following core texture by the acidity azines:
Figure BPA00001595202900021
R wherein a, R b, R cAnd R dBe selected from: H, side chain or straight chain C 1-C7 alkyl chain, benzyl, phenyl and naphthyl;
This dyestuff is by at least one SO 3 -Or-COO -Group replaces;
The B ring does not have negative charge group or its salt;
And the A ring can further be substituted the formation naphthyl;
This dyestuff randomly is selected from following group and is replaced: amine, methyl, ethyl, hydroxyl, methoxyl group, oxyethyl group, phenoxy, Cl, Br, I, F and NO 2
(2) positively charged ion azines;
(3) cation mono azoic dyestuff is preferably selected from thiazole
Figure BPA00001595202900022
dyestuff, isothiazole
Figure BPA00001595202900023
dyestuff, pyridine/pyridazine dyestuff;
(4) positively charged ion lactin (naptholactam) dyestuff how;
(5) directly purple and sun blue dyestuff, for example directly purple 9, directly purple 99, directly purple 51, directly purple 35;
(6) uncharged alkoxylate dyestuff, preferred monoazo, it preferably has structure:
Figure BPA00001595202900031
Wherein D representes aromatics or heteroaromatic group and R 1And R 2Be independently selected from and have 2 or more multiple multiple unitary polyoxyalkylene chain (polyoxyalkylene chain).
Preferably, polyoxyalkylene chain has 4 to 20 repeating units.The example of polyoxyalkylene chain comprises oxyethane, propylene oxide, Racemic glycidol oxide compound (glycidol oxide), butylene oxide ring and composition thereof.
Preferred polyoxyalkylene chain is [(CH 2CR 3HO) X(CH 2CR 4HO) YR 5], X+Y≤5 wherein, wherein Y>=1 and Z=0 to 5, R 3Be selected from: H, CH 3, CH 2O (CH 2CH 2O) ZH and composition thereof; R 4Be selected from: H, CH 2O (CH 2CH 2O) ZH and composition thereof; And R 5Be selected from: H and CH 3
Most preferred, dyestuff is selected from: acid blue 59, acid blue 98 and acid violet 50.
The polymkeric substance that contains carboxylic acid
This polymkeric substance should have greater than 2000 daltonian weight-average molecular weight, and this polymkeric substance must comprise hydroxy-acid group.Preferred polymkeric substance is selected from Xylo-Mucine and comprises the polymerizing acrylic acid thing.Preferred, be selected from vinylformic acid/maleic acid and Xylo-Mucine.Most preferred, polymkeric substance is an Xylo-Mucine.
Xylo-Mucine (SCMC) preferably has: up to 1,000, and 000 dalton, more preferably 25,000 to 500,000 dalton, even more preferably 30,000 dalton to 120,000 daltonian weight-average molecular weight.
Tensio-active agent
Said composition comprises 2 to 70wt%, most preferably 10 to 30wt% tensio-active agent.Usually, the optional self-described of the nonionic of surfactant system and AS is at " tensio-active agent (Surface Active Agents) ", from the 1st volume of Schwartz & Perry; Interscience 1949; From Schwartz, the 2nd volume of Perry & Berch, Interscience 1958; In " McCutcheon ' s Emulsifiers and Detergents " that publish by Manufacturing Confectioners Company of present version or at H.Stache; The 2nd edition, Carl Hauser Verlag, the tensio-active agent in 1981 " Tenside-Taschenbuch ".The preferred tensio-active agent that uses is saturated.
Suitable spendable nonionic detergent compounds comprises; Particularly; Reaction product with compound of hydrophobic grouping and reactive hydrogen atom, for example Fatty Alcohol(C12-C14 and C12-C18), acid, acid amides or alkylphenol and alkylene oxide (alkylene oxide), especially independent oxyethane or with propylene oxide.Concrete nonionic detergent compounds is C 6To C 22Alkylphenol-ethylene oxide condensate is generally 5 to 25EO, 5 to 25 ethylene oxide units of per molecule just, and aliphatic C 8To C 18Uncle or secondary straight or branched alcohol and oxyethane, normally 5 to 40EO, condensation product.
Suitable spendable anionic detergent compound normally has to contain has an appointment 8 to the organo-sulfate of the alkyl of about 22 carbon atoms and the water-soluble alkali metal salts of sulphonate, and used term alkyl comprises the moieties of more senior acyl group.The instance of suitable synthetic anionic detergent compound is sodium alkyl sulfate and alkylsurfuric acid potassium, especially through the senior C of sulfation 8To C 18Those that alcohol obtains are for example processed C by tallow or Oleum Cocois 9To C 20Sodium alkyl benzene sulfonate and C 9To C 20Alkyl benzene sulphonate(ABS) potassium, particularly linear secondary alkyl C 10To C 15Supragil GN; With alkyl glycerol base ether sodium sulfate, especially derived from the higher alcohols of tallow or Oleum Cocois with derived from those ethers of the synthol of oil.Preferred anionic surfactants type detergent compound is C 11To C 15Sodium alkyl benzene sulfonate and C 12To C 18Sodium alkyl sulfate.Described in also spendable tensio-active agent such as the EP-A-328 177 (Unilever) those, it shows alkyl polyglucoside surfactant and the alkyl monoglycosides described in anti-saltouing property, the EP-A-070 074.
The preferred surfactants system is the mixture of anionic and non-ionic detergent active material, the anionic of particularly pointing out among the EP-A-346 995 (Unilever) and the group and the instance of non-ionics.Especially preferred is C 16To C 18An alkali metal salt of primary alconol sulfuric ester and C 12To C 15The surfactant system of the form of mixtures of primary alconol 3 to 7EO ethoxylates.
This non-ionic detergent preferably with this surfactant system greater than 10%, for example 25 to 90wt% amount exists.Aniorfic surfactant can be for example exists with about amount of 5% to about 40wt% of this surfactant system.
Washing assistant
The washing assistant material can be selected from 1) calcium sequestrant material, 2) precipitation threshold material, 3) calcium ion-exchanged material and 4) their mixture.
Calcium sequestrant washing assistant examples of material comprises for example tripoly phosphate sodium STPP and organic sequestering agent YD 30 for example of Tripyrophosphoric acid an alkali metal salt.
Precipitation threshold washing assistant examples of material comprises sodium orthophosphate and yellow soda ash.Preferably, laundry treatment compositions comprises 5 to 50wt%, most preferably 10 to 35wt% yellow soda ash.In said method, when being used for the granular laundry treatment compositions, aqueous cleaning solution preferably contains 0.1 to 4g/L yellow soda ash.
Calcium ion-exchanged washing assistant examples of material comprises polytype water-insoluble crystallization or amorphous aluminosilicate; Its mesolite is the most famous representative; For example zeolite A, zeolite B (being also referred to as zeolite P), zeolite C, X zeolite, zeolite Y and EP-A-0, disclosed zeolite P type in 384,070.
Said compsn also can contain washing assistant or the complexing agent of 0-65%, for example YD 30, NSC 446-pentaacetic acid, alkyl or alkenyl Succinic Acid, NTA or following other washing assistants of mentioning.A lot of washing assistants are because the ability or the bleaching stibilizer of their complexation of metal ions.
Zeolite and carbonate (carbonate (comprising supercarbonate and sesquicarbonate)) are preferred washing assistants.
Said composition can contain crystalline aluminosilicate as washing assistant, preferred manosil AS an alkali metal salt, more preferably sodium aluminium silicate.It typically exists with the level that is less than 15%w.Aluminosilicate is the material with following general formula:
0.8-1.5M 2O·Al 2O 3·0.8-6SiO 2
Wherein M is a monovalent cation, preferred sodium.These materials contain some combination water and requirement has the calcium ion exchange capacity of 50mg CaO/g at least.Preferred sodium aluminium silicate contains 1.5-3.5 SiO in above-mentioned general formula 2The unit.They can easily make through the reaction between water glass and the sodium aluminate as write up in the document.The ratio of tensio-active agent and aluminosilicate (if existence) preferably is higher than 5: 2, more preferably is higher than 3: 1.
The alternative aluminosilicate washing assistant of phosphate builders uses or uses with the aluminosilicate washing assistant.Term " phosphoric acid salt " comprises diphosphate, triphosphate and phosphonate thing class in the art.Other forms of washing assistant comprises silicate, for example soluble silicate, metasilicate, layered silicate (like the SKS-6 of Hoechst).
Preferably, the detergent for washing clothes preparation is that nonphosphate helps the detergent for washing clothes preparation of washing, and promptly contains the phosphoric acid salt that is less than 1wt%.
Enzyme
Said composition can contain one or more enzymes, and it provides clean-up performance, fabric nursing and/or hygienic benefit.
Especially the enzyme of paying close attention to comprises proteolytic enzyme, AMS, cellulase, lypase, px/oxydase, polygalacturonase, lyase and mannase, perhaps their mixture.
WO2007/087257 discloses the most suitable lypase.
Fluorescent agent
Preferably, said compsn comprises fluorescent agent (white dyes).Fluorescent agent is known, and much this type of fluorescent agent is commercially available getting.Usually, these fluorescent agents are with its an alkali metal salt (like sodium salt) supplied and use.The total amount of one or more fluorescent agents that use in the compsn is normally from 0.005 to 2wt%, more preferably 0.01-0.1wt%.Preferred fluorescent agent kind has: distyryl biphenyl compound, for example Tinopal (trade mark) CBS-X; Diamines stilbene two-sulfoacid compound, Tinopal DMS pure Xtra and Blankophor (trade mark) HRH for example, and pyrazoline compounds such as Blankophor SN.Preferred fluorescent agent is: 2-(4-styryl-3-sulfo group phenyl)-2H-naphtho-(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 stilbene-2,2 '-disulfonic acid disodium, 4; 4 '-two { [(4-anilino-6-morpholino-1,3,5-triazines-2-yl)] amino } stilbene-2; 2 '-disulfonic acid disodium and 4,4 '-two (2-sulfo group styryl) biphenyl disodium.
Spices
Said composition preferably comprises spices.Spices is preferably 0.001 to 3wt%, and most preferably 0.1 to 1wt%.The CTFA that publishes in CFTA press (makeup, washes and dresses article and the (Cosmetic of perfume compound association; Toiletry and Fragrance Association)) 1992 international procurement merchant guides (International Buyers Guide) and the Schnell Publishing Co. OPD 1993 chemical purchaser catalogues of publishing provide the many suitable instance of spices in the 80th phase annual (OPD 1993 Chemicals Buyers Directory 80th Annual Edition).It is very common that multiple fragrance component is present in the preparation.In compsn of the present invention, consider there are four kinds or more kinds of, preferred five kinds or more kinds of, more preferably six kinds or more kinds of, or seven kinds or more kinds of different fragrance component even.
Preferably, 15-25wt% is head fragrant (top notes) in the spice mixt.Poucher (Society of Cosmetic Chemists periodical (Journal of the Society of Cosmetic Chemists) 6 (2): 80 [1955]) defined head perfume.Preferred perfume (or spice) is selected from PH 6968, phantol, phanteine, lavandula angustifolia, dihydromyrcenol, rose oxide and cis-3-hexenol.
A spices and a perfume (or spice) can be used for pointing out whiteness benefit of the present invention.
Experiment
Embodiment 1
The water-soluble serous particle for preparing that comprises batching through spraying drying with 100 microns average particle size particle size.Particle has following composition:
Particle 1
57% acid violet 50
43% Na 2SO 4
Particle 2
57% acid violet 50
33% Na 2SO 4
10% Sokalan from BASF TM, the sodium salt of vinylformic acid/maleic acid.
Particle 3
62% acid violet 50
28% Na 2SO 4
10% Xylo-Mucine (SCMC)
Embodiment 2
The particle of the embodiment 1 of 0.3wt% mixed with sodium sulfate 5 minutes.Sodium sulfate is sieved into the fragment of 250 to 500 micron-scales.After mixing, use reflectometry blended color, and use with respect to the Δ E value of the sodium sulfate that does not contain dyestuff and represent.In following table, provide the result.
ΔE
Particle 1 37
Particle 2 28
Particle 3 15
Particle 2 comprises the acid violet 50 with particle 1 same concentrations.Particle 3 comprises the acid violet 50 more more a little than particle 1.
The particulate fragmentation causes fading of sodium sulfate in mixing process.The particle that comprises polymkeric substance provides lower Δ E value, is stronger to show it.
Particle 2 has the Δ E value lower than particle 1, shows that it is stronger.
Particle 3 has the Δ E value lower than particle 1, shows that it is stronger.
Embodiment 3
The spray-dired particle of embodiment 1 adds to by 20% tensio-active agent, 30% Na 2CO 3, residuum is Na 2SO 4And in the white granular detergent powder of other less material composition, to such an extent as to powder comprises the acid violet 50 of 0.0018wt%.Violent mixed powder also is placed in the hard box of plastics of opening, and be stored under room temperature and the humidity.Sample for reference after storing one day, the powder color that is checked through is following
Particle 1: lavender powder
Particle 2: white powder
Particle 3: white powder

Claims (7)

1. particulate laundry detergent compsn comprises:
(a) 0.00005 to 0.2wt% spray-dired dye granule, wherein dye granule comprises:
(i) 20 to 90wt% blueness or purple dope dye;
(ii) 1 to 20wt% the polymer poly compound that comprises carboxylic acid;
(iii) 0 to 60wt% an alkali metal salt is selected from sodium sulfate and sodium-chlor;
(b) 2 to 70wt% tensio-active agent;
(c) 5 to 50wt% washing assistant is selected from: calcium sequestrant material, precipitation threshold material and calcium ion-exchanged material; With
(d) 0.05 to 50wt% water-soluble carrier salt; And,
(e) other composition of 0 to 20wt%.
2. according to the particulate laundry detergent compsn of claim 1, the polymkeric substance that wherein comprises carboxylic acid is an Xylo-Mucine.
3. according to the particulate laundry detergent compsn of claim 1 or 2, wherein spray-dired dye granule has 0.1 to 300 micron average particle size particle size, APS.
4. according to each particulate laundry detergent compsn of aforementioned claim, wherein this dyestuff is selected from cationic dyestuff, anionic dyestuff and uncharged alkoxylate dyestuff.
5. according to the particulate laundry detergent compsn of claim 4, wherein dyestuff is selected from:
(1) acid azines wherein should have following core texture by the acidity azines:
Figure FPA00001595202800011
R wherein a, R b, R cAnd R dBe selected from: H, side chain or straight chain C 1-C7 alkyl chain, benzyl, phenyl and naphthyl;
This dyestuff is by at least one SO 3 -Or-COO -Group replaces;
The B ring does not have negative charge group or its salt;
And the A ring can further be substituted the formation naphthyl;
This dyestuff randomly is selected from following group and is replaced: amine, methyl, ethyl, hydroxyl, methoxyl group, oxyethyl group, phenoxy, Cl, Br, I, F and NO 2
(2) positively charged ion azines;
(3) cation mono azoic dyestuff is preferably selected from thiazole
Figure FPA00001595202800021
dyestuff, isothiazole
Figure FPA00001595202800022
dyestuff, pyridine/pyridazine dyestuff;
(4) positively charged ion lactin dyestuff how;
(5) directly purple and sun blue dyestuff;
(6) uncharged alkoxylate dyestuff, preferred monoazo, it preferably has structure:
Figure FPA00001595202800023
Wherein D representes aromatics or heteroaromatic group and R 1And R 2Be independently selected from and have 2 or more multiple multiple unitary polyoxyalkylene chain.
6. according to the particulate laundry detergent compsn of claim 5, wherein dyestuff is selected from: acid blue 59, acid blue 98 and acid violet 50.
7. according to each particulate laundry detergent compsn of aforementioned claim, wherein said composition comprises fluorescent agent, is selected from: 2-(4-styryl-3-sulfo group phenyl)-2H-naphtho-[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 } stilbene-2,2 '-disulfonic acid disodium, 4,4 '-two { [(4-anilinos-6-morpholino-1; 3; 5-triazine-2-yl)] amino } stilbene-2,2 '-disulfonic acid disodium and 4,4 '-two (2-sulfo group styryl) biphenyl disodium.
CN2010800609522A 2010-01-07 2010-09-27 Detergent formulation containing spray dried granule Pending CN102782111A (en)

Applications Claiming Priority (3)

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EP10150207.8 2010-01-07
EP10150207A EP2343359A1 (en) 2010-01-07 2010-01-07 Detergent formulation containing spray dried granule
PCT/EP2010/064246 WO2011082842A1 (en) 2010-01-07 2010-09-27 Detergent formulation containing spray dried granule

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EP2521764A1 (en) 2012-11-14
BR112012016789A2 (en) 2018-03-27
WO2011082842A1 (en) 2011-07-14
AR078826A1 (en) 2011-12-07

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Application publication date: 20121114