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CN102753672B - Natural shading agents - Google Patents

Natural shading agents Download PDF

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Publication number
CN102753672B
CN102753672B CN201080060945.2A CN201080060945A CN102753672B CN 102753672 B CN102753672 B CN 102753672B CN 201080060945 A CN201080060945 A CN 201080060945A CN 102753672 B CN102753672 B CN 102753672B
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China
Prior art keywords
azulene
dyestuff
dimethyl
detergent
methyl
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Expired - Fee Related
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CN201080060945.2A
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CN102753672A (en
Inventor
S·N·巴切洛
J·M·伯德
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Unilever PLC
Unilever NV
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Unilever NV
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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
    • C11D3/40—Dyes ; Pigments

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

The present invention provides for the use of natural shading agents.

Description

Natural toning agent
Technical field
Dope dye composition (laundry shading dye composition) the present invention relates to do washing.
Background technology
In family expenses clean, can realize the lasting of fabric whiteness and strengthen by the organic fluorescence agent with synthetic and synthetic organic dope dye.
WO2008/090091 (Unilever) discloses synthetic organic fluorescence agent and synthetic organic dope dye of the wide region using in detergent for washing clothes.
WO2001/28973 (Procter & Gamble) discloses a kind of specific azulene (azulene) compound covalently bonded to phenol antioxidant, and it is for removing free radical at cleaning combination.
Bacterium mushroom shape thing indigo newborn mushroom (Lactarius indigo)blueness be because azulene derivative (7-pseudoallyl-4-methyl azulene-1-yl) methyl stearate.
Azulene is the popular name to purple aromatic hydrocarbon for blueness derived from dicyclo [5.3.0] ten pentaenes (decapentaene).Azulene is present in various liverworts, for example, comprise the Calypogeia azurea of Isosorbide-5-Nitrae-dimethyl azulene and methyl-4-methyl azulene-1-carboxylicesters.
Azulene came into question in Rompp natural product encyclopedia (Rompp Encyclopedia of Natural Products) (Georg Thieme Verlag 2000).
Human consumer thirsts for such product, and it comprises natural matter with the whiteness of maintenance and reinforced fabric.
Summary of the invention
We have found that naturally occurring blueness-purple azulene compound can be comprised in detergent for washing clothes, and be deposited on fabric the whiteness with reinforced fabric.
A kind of home method of processing textiles is provided in one aspect of the invention, and the method comprising the steps of:
(i) use the aqueous solution of naturally occurring blueness or purple azulene dyestuff to process textiles, the naturally occurring blueness that this aqueous solution comprises 1ppb to 1ppm or purple azulene dyestuff; And the tensio-active agent of 0.2g/L to 3g/L;
(ii) rinsed textile optionally; And,
(iii) dry textiles.
In another aspect of this invention, provide a kind of detergent for washing clothes preparation, comprise:
(i) 0.0001 to 0.01wt% naturally occurring blueness or purple azulene dyestuff;
(ii) enzyme, comprises 0.0001wt% to 0.1wt% protein; And,
(iii) 2 to 70wt% tensio-active agent.
For azulene of the present invention, be naturally occurring, but also can use synthetic Equivalent.
detailed Description Of The Invention
Naturally occurring azulene comprises Isosorbide-5-Nitrae-dimethyl azulene, methyl-4-methyl azulene-1-carboxylicesters, lindera (linderazulene) and ehuazulene, german chamomile (chamazulene) and guaiene (Guaiazulene).The naturally occurring meaning refers in naturally occurring biology, the natural azulene of for example finding in plant, animal, fungi, mushroom and marine organisms.
Natural azulene is the secondary metabolites of organism.
Preferred azulene is guaiene (Isosorbide-5-Nitrae-dimethyl-7-sec.-propyl azulene).
tensio-active agent
Said composition comprises 2 to 70wt% tensio-active agent, and most preferably 10 to 30wt%.Conventionally, the optional self-described of the nonionic of surfactant system and anion surfactant is the 1st volume from Schwartz & Perry at " tensio-active agent (Surface Active Agents) ", Interscience 1949, from Schwartz, the 2nd volume of Perry & Berch, Interscience 1958, in " emulsifying agent of McCutcheon and washing composition (McCutcheon ' s Emulsifiers and Detergents) " that published by Manufacturing Confectioners Company of current version or at " Tenside-Taschenbuch ", H.Stache, the 2nd edition, Carl Hauser Verlag, tensio-active agent in 1981.The tensio-active agent preferably using is saturated.
Suitable spendable nonionic detergent compounds comprises, particularly, the compound with hydrophobic grouping and reactive hydrogen atom, for example fatty alcohol, acid, acid amides or alkylphenol and epoxy alkane, especially independent oxyethane or the reaction product together with propylene oxide.Concrete nonionic detergent compounds is C 6to C 22alkylphenol-ethylene oxide condensate, is generally 5 to 25EO, namely 5 to 25 ethylene oxide units of per molecule, and aliphatic C 8to C 18the straight or branched alcohol of uncle or the second month in a season and the condensation product of oxyethane, normally 5 to 40EO.
Suitable spendable anionic detergent compound normally has the organo-sulfate of alkyl and the water-soluble alkali metal salts of sulphonate containing 8 to approximately 22 carbon atoms of having an appointment, and the term alkyl of use comprises the moieties of more senior acyl group.The example of suitable synthetic anionic detergent compound is sodium alkyl sulfate and potassium, the senior C especially for example being made by tallow or Oleum Cocois by sulfation 8to C 18those that alcohol obtains, alkyl C 9to C 20benzene sulfonic acid sodium salt and potassium, particularly linear secondary alkyl C 10to C 15benzene sulfonic acid sodium salt; 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 detergent compound is C 11to C 15sodium alkyl benzene sulfonate and C 12to C 18sodium alkyl sulfate.Also spendable be tensio-active agent described in EP-A-328 177 (Unilever) show salting-out resistance those, alkyl poly glucoside surfactant and the alkyl monoglycosides described in EP-A-070 074.
Preferred surfactant system is the mixture of anionic and non-ionic detergent active material, the anionic of particularly pointing out in EP-A-346 995 (Unilever) and set and the example of nonionic surface active agent.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.
Non-ionic detergent is preferably greater than 10% of surfactant system with this, and 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.
On the other hand, tensio-active agent also can be preferably cationic, thereby make preparation, is fabric conditioner.
cation compound
When the present invention is used as fabric conditioner, it need to contain cationic compound.
Quaternary ammonium compound most preferably.
If this quaternary ammonium compound is to have at least one C 12to C 22the quaternary ammonium compound of alkyl chain is favourable.
This quaternary ammonium compound preferably has following formula:
R wherein 1c 12to C 22alkyl or alkenyl chain; R 2, R 3and R 4independently selected from C 1to C 4alkyl chain and X -it is compatible negatively charged ion.Such preferred compound is quaternary ammonium compound cetyl trimethyl quaternary ammonium bromides.
The quaternary ammonium that is said structure for Equations of The Second Kind material of the present invention, wherein R 1and R 2independently selected from C 12to C 22alkyl or alkenyl chain; R 3and R 4independently selected from C 1to C 4alkyl chain and X -it is compatible negatively charged ion.
According to the detergent composition of claim 1, wherein (ii) cationic material is at least 2: 1 with (iv) ratio of aniorfic surfactant.
In EP 0 239 910 (Proctor and Gamble), other suitable quaternary ammonium compound is disclosed.
Cationic and ratio nonionic surface active agent is preferably 1: 100 to 50: 50, more preferably 1: 50 to 20: 50.
Cationic compound can exist with the 1.5wt% to 50wt% of said composition gross weight.This cationic compound preferably can exist with 2wt% to 25wt%, and preferred compositing range is 5wt% to 20wt%.
Submissive material preferably with total composition weight 2 to 60wt%, more preferably 2 to 40wt%, most preferably 3 to 30wt% amount exists.
Said composition optionally includes silicone.
washing assistant or complexing agent:
Washing assistant material can be selected from 1) calcium sequestrant material, 2) precipitation threshold material, 3) calcium ion-exchanged material and 4) their mixture.
The example of calcium sequestrant washing assistant material comprises for example tripoly phosphate sodium STPP and organic sequestering agent ethylenediamine tetraacetic acid (EDTA) for example of alkali metal polyphosphates.
The example of precipitation threshold washing assistant material comprises sodium orthophosphate and sodium carbonate.
The example of calcium ion-exchanged washing assistant material comprises multiple water-insoluble crystallization or amorphous aluminosilicate, its mesolite is the most famous representative, for example Wessalith CS, zeolite B (also referred to as zeolite P), zeolite C, X zeolite, zeolite Y and EP-A-0, disclosed zeolite P type in 384,070.
Described composition also can contain washing assistant or the complexing agent of 0-65%, for example ethylenediamine tetraacetic acid (EDTA), DTPA, alkyl or alkenyl succinic acid, nitrilotriacetic acid(NTA) or following other washing assistants of mentioning.A lot of washing assistants are due to ability or the bleaching stibilizer of their complexation of metal ions.
Zeolite and carbonate (carbonate comprises supercarbonate and sesquicarbonate) are preferred washing assistants.
Described composition can contain crystalline aluminosilicate as washing assistant, preferred as alkali aluminosilicate, more preferably sodium aluminium silicate.It typically exists to be less than the concentration of 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 monovalent cation, preferably sodium.These materials contain some and have at least calcium ion exchange capacity of 50mg CaO/g in conjunction with water and requirement.Preferred sodium aluminium silicate contains 1.5-3.5 SiO in above-mentioned general formula 2unit.They can easily make by the reaction between water glass and sodium aluminate as recorded in detail in document.The ratio of tensio-active agent and aluminosilicate (if present) is preferably higher than 5: 2, more preferably higher than 3: 1.
Phosphate builders can be used for substitution of Al silicate-like builder or uses together with 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 (as the SKS-6 of Hoechst).
Preferably, detergent for washing clothes preparation is that nonphosphate helps the detergent for washing clothes preparation of washing, and contains the phosphoric acid salt that is less than 1wt%.Preferably, detergent for washing clothes preparation is carbonate builders.
fluorescent agent
Preferably, described composition comprises fluorescent agent (white dyes).Fluorescent agent is known, and much this type of fluorescent agent is commercially available.Conventionally, these fluorescent agents are with its an alkali metal salt, as sodium-salt form supply and use.The total amount of one or more fluorescent agents that use in composition is normally 0.005 to 2wt%, and more preferably 0.01 to 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 is as Blankophor SN.Preferred fluorescent agent is: 2-(4-styryl-3-sulfo group phenyl)-2H-naphtho-[1,2-d] 1-Sodium-1,2,4-Triazole, 4,4 '-it is bis-that { [(4-phenylamino 6-(N-methyl-N-2-hydroxyethyl) amino-1,3,5-triazine-2-yl)] amino } stilbene-2,2 '-disulfonic acid disodium, 4,4 '-bis-{ [(4-phenylamino-6-morpholino-1,3,5-triazine-2-yl)] amino } stilbene-2,2 '-disulfonic acid disodium and 4,4 '-bis-(2-sulphophenyl vinyl) biphenyl disodium.
Preferably there is fluorescent agent in the aqueous solution used in the method.While there is fluorescent agent in the aqueous solution used in the method, its preferable range is 0.0001g/l to 0.1g/l, and preferably 0.001 to 0.02g/l.
spices
Said composition preferably comprises spices.Spices preferable range is 0.001 to 3wt%, and most preferably 0.1 to 1wt%.The CTFA publishing in CFTA press (makeup, washes and dresses the Pin He perfume compound (Cosmetic of association, Toiletry and Fragrance Association)) the OPD 1993 chemical purchaser catalogues that 1992 international procurement business guides (International Buyers Guide) and Schnell Publishing Co. publish, provide the many suitable example of spices in the 80th phase annual (OPD1993 Chemicals Buyers Directory 80th Annual Edition).
In preparation, conventionally there is multiple perfume composition.In composition of the present invention, consider there are four kinds or more kinds of, preferably five kinds or more kinds of, more preferably six kinds or more kinds of or even seven kinds or more kinds of different perfume composition.
In spice mixt, preferably 15 to 25wt% is that head is fragrant.Poucher (Society of Cosmetic Chemists's periodical (Journal of the Society of Cosmetic Chemists)) 6 (2): 80[1955]) to have defined head fragrant.Preferred perfume (or spice) is selected from tangerine oil, phantol, phanteine, lavandula angustifolia, dihydromyrcenol, rose oxide and cis-3-hexenol.
Spices and a perfume (or spice) can be used for pointing out the benefit that brightens of the present invention.
Laundry treatment compositions is preferably not for example, containing peroxygen bleach, SPC-D, Sodium peroxoborate and peracid.
polymkeric substance
Said composition can comprise one or more polymkeric substance.Example is that carboxymethyl cellulose, PEG, poly-(vinyl alcohol), polycarboxylate are as polyacrylic ester, toxilic acid/acrylic copolymer and lauryl methacrylate(LMA)/acrylic copolymer.
In preparation, preferably do not exist for preventing the polymkeric substance of deposition of dye, for example PVP, poly-(vinyl pyridine-N-oxide compound) and poly-(vinyl imidazole).
enzyme
In composition of the present invention and when implementing method of the present invention, preferably there are one or more enzymes.
The content of various enzymes is preferably 0.0001wt% to 0.1wt% protein.
Especially the enzyme of considering comprises proteolytic enzyme, α-amylase, cellulase, lipase, peroxidase/oxydase, pectate lyase and mannase or its mixture.
Suitable lipase comprises those of bacterium or originated from fungus.The mutant that comprises chemical modification or protein engineering.The example of available lipase comprises the lipase from Humicola (synonym Thermomyces), for example described in EP 258 068 and EP 305 216 from H.lanuginosa (T.lanuginosus) or described in WO 96/13580 from H.insolens, Pseudomonas Lipases (Pseudoalcaligenes lipase), for example from Alkaligenes (P.alcaligenes) or pseudomonas pseudoalcaligenes, belong to (P.pseudoalcaligenes) (EP 218 272), P.cepacia (EP 331 376), P.stutzeri (GB1, 372, 034), P.fluorescens, pseudomonas strain (Pseudomonas sp.) SD 705 (WO95/06720 and WO 96/27002), P.wisconsinensis (WO 96/12012), bacillus lipase (a Bacillus lipase), such as from Bacillus subtilus (the B.subtilis) (people (1993) such as Dartois, Biochemica et Biophysica Acta, 1131, 253-360), bacstearothermophilus (B.stearothermophilus) (JP64/744992) or bacillus pumilus (B.pumilus) (WO 91/16422).
Other example is lipase Variant, those described in WO 92/05249, WO 94/01541, EP 407 225, EP 260105, WO 95/35381, WO 96/00292, WO 95/30744, WO 94/25578, WO 95/14783, WO 95/22615, WO 97/04079 and WO 97/07202, WO 00/60063.
Preferred commercially available lipase comprises Lipolase tMwith Lipolase Ultra tM, Lipex tM(NovozymesA/S).
Method of the present invention can be carried out under the Phospholipid hydrolase that is categorized as EC 3.1.1.4 and/or EC 3.1.1.32 exists.Term Phospholipid hydrolase used herein is to the activated enzyme of phosphatide tool.
Phosphatide, if Yelkin TTS or phosphatidylcholine are by externally (sn-1) and middle (sn-2) position form with the glycerine of Phosphation with two fatty acid esterifications with in the 3rd position; This phosphoric acid can be esterified on amino alcohol again.Phospholipid hydrolase is the enzyme that participates in phosphatide hydrolysis.Can distinguish the phospholipase activity of several types, comprise that a fatty acyl group of hydrolysis (respectively in sn-1 and sn-2 position) is to form the phospholipase A of lysophospholipid 1and A 2; Lysophospholipase (or phospholipase B) with all the other fatty acyl groups in hydrolyzable lysophospholipid.Phospholipase C and Phospholipase D (phosphodiesterase) discharge respectively DG or phosphatidic acid.
Enzyme and dope dye may show certain interaction, and should select so that this interaction is not negative.Can by one or another kind of in enzyme and dope dye seal and/or product in other isolation avoid some negative interactions.
Suitable proteolytic enzyme comprises animal, plant or microbe-derived those.Microbe-derived is preferred.The mutant that comprises chemical modification or protein engineering.This proteolytic enzyme can be serine protease or metalloprotease, preferred alkaline microbial protease or trypsin like proteases.Preferred commercially available proteolytic enzyme comprises Alcalase tM, Savinase tM, Primase tM, Duralase tM, Dyrazym tM, Esperase tM, Everlase tM, Polarzyme tMand Kannase tM, (Novozymes A/S), Maxatase tM, Maxacal tM, Maxapem tM, Properase tM, Purafect tM, Purafect OxP tM, FN2 tMand FN3 tM(Genencor International Inc.).
Method of the present invention can be carried out under the at existence in being categorized in EC 3.1.1.74.At used according to the invention can be any source.At is preferably microbe-derived, particularly bacterium, fungi or yeast source.
Suitable amylase (α and/or β) comprises those of bacterium or originated from fungus.The mutant that comprises chemical modification or protein engineering.Amylase comprises, for example, available from bacillus, for example GB 1, the α-amylase of disclosed Bacillaceae (Bacillus sp.) bacterial strain in the special bacterial strain of Bacillus licheniformis (B.licheniformis) or WO95/026397 or WO00/060060 in greater detail in 296,839.Commercially available amylase is Duramyl tM, Termamyl tM, Termamyl Ultra tM, Natalase tM, Stainzyme tM, Fungamyl tMand BAN tM(Novozymes A/S), Rapidase tMand Purastar tM(from Genencor International Inc.).
Suitable cellulase comprises those of bacterium or originated from fungus.The mutant that comprises chemical modification or protein engineering.Suitable cellulase comprises from Bacillaceae (the genera Bacillus), Rhodopseudomonas (Pseudomonas), the mould genus of humic (Humicola), Fusarium (Fusarium), Thielavia (Thielavia), the cellulase of the mould Pseudomonas of top spore (Acremonium), for example US 4, 435, 307, US 5, 648, 263, US5, 691, 178, US 5, 776, 757, WO 89/09259, disclosed by Humicola insolens (Humicola insolens) in WO 96/029397 and WO 98/012307, Tai Ruisi bobbin case spore mould (Thielavia terrestris), the thermophilic fungal cellulase of ruining a bacterium (Myceliophthora thermophila) and Fusarium oxysporum (Fusarium oxysporum) generation.Commercially available cellulase comprises Celluzyme tM, Carezyme tM, Endolase tM, Renozyme tM(Novozymes A/S), Clazinase tMwith Puradax HA tM(Genencor International Inc.) and KAC-500 (B) tM(Kao Corporation).
Suitable peroxidase/oxydase comprises those of plant, bacterium or originated from fungus.The mutant that comprises chemical modification or protein engineering.The example of available peroxidase comprises from Coprinus, for example, from the peroxidase of C.cinereus and variant thereof, and those described in WO 93/24618, WO 95/10602 and WO98/15257.Commercially available peroxidase comprises Guardzyme tMand Novozym tM51004 (Novozymes A/S).
enzyme stabilizers
Can use conventional stablizer; for example polyvalent alcohol is as propylene glycol or glycerine, sugar or sugar alcohol, lactic acid, boric acid or boric acid derivatives; for example aromatic borate or phenyl-boron dihydroxide derivative; as 4-formyl radical phenyl-boron dihydroxide carrys out any enzyme existing in stable composition, and can described in WO 92/19709 and WO 92/19708, prepare said composition.
The meaning of " " or " " who here uses unless otherwise indicated, and corresponding " should, described " be at least one or one or more.
experiment
Knitting white polyester (primitive fiber), knitting nylon-spandex fiber (80: 20) and the woven non-mercerized cotton fabric of white are containing 15% linear alkylbenzene sulfonate (LAS) tensio-active agent, 30%Na together 2cO 3, 40%NaCl, all the other minor materials comprise in the washing composition of 4g/L of calcite and fluorescent agent and moisture washs.At room temperature, in softening water, the liquid with 30: 1 cleans 30 minutes with the ratio of fabric.And then repeat this process three times, amounted to 4 cleanings.After cleaning, clothing is rinsing twice in water, dry, measure the reflectance spectrum of nylon-spandex fiber, and color is with CIE L on reflexometer *a *b *value representation (getting rid of UV).
In washing lotion, add the guaiene of 200ppb, repeat this experiment.Guaiene adds with the solution in ethanol.Δ b value representation for the deposition of guaiene on fabric, and due to the deposition of guaiene, the blueness of Δ b=b (contrast)-b (guaiene)+ve value representation fabric/in vain.
Result provides in following table:
Wash number Δb
1 0.3
4 0.6

Claims (6)

1. a home method of processing textiles, the method comprising the steps of:
(i) use the aqueous solution of naturally occurring blueness or purple azulene dyestuff to process textiles, the naturally occurring blueness that this aqueous solution comprises 1ppb to 1ppm or purple azulene dyestuff; And the tensio-active agent of 0.2g/L to 3g/L, wherein azulene dyestuff is selected from: 1,4-dimethyl azulene, methyl-4-methyl azulene-1-carboxylicesters, linderazulene, ehuazulene, chamazulene and Isosorbide-5-Nitrae-dimethyl-7-sec.-propyl azulene;
(ii) rinsed textile optionally; And,
(iii) be dried textiles.
2. according to the home method of the processing textiles of claim 1, wherein azulene dyestuff is Isosorbide-5-Nitrae-dimethyl-7-sec.-propyl azulene:
。
3. according to the home method of the processing textiles of aforementioned claim any one, wherein in this aqueous solution, comprise 0.1 to 50ppm fluorescent agent.
4. a detergent for washing clothes preparation, comprises:
(i) 0.0001 to 0.01wt% naturally occurring blueness or purple azulene dyestuff, wherein azulene dyestuff is selected from: 1,4-dimethyl azulene, methyl-4-methyl azulene-1-carboxylicesters, linderazulene, ehuazulene, chamazulene and Isosorbide-5-Nitrae-dimethyl-7-sec.-propyl azulene;
(ii) enzyme, it is 0.0001wt% to 0.1wt% protein; And,
(iii) 2 to 70wt% tensio-active agent.
5. according to the detergent for washing clothes preparation of claim 4, wherein azulene dyestuff is Isosorbide-5-Nitrae-dimethyl-7-sec.-propyl azulene:
。
6. according to the detergent for washing clothes preparation of any one in claim 4 to 5, wherein this detergent for washing clothes preparation comprises fluorescent agent, be selected from: 2-(4-styryl-3-sulfo group phenyl)-2H-naphtho-[1, 2-d] 1-Sodium-1,2,4-Triazole, 4, 4 '-it is bis-that { [(4-phenylamino 6-(N-methyl-N-2-hydroxyethyl) amino-1, 3, 5-triazine-2-yl)] amino } stilbene-2, 2 '-disulfonic acid disodium, 4, 4 '-bis-{ [(4-anilino-6-morpholino-1, 3, 5-triazine-2-yl)] amino } stilbene-2, 2 '-disulfonic acid disodium and 4, 4 '-bis-(2-sulphophenyl vinyl) biphenyl disodium.
CN201080060945.2A 2010-01-07 2010-11-29 Natural shading agents Expired - Fee Related CN102753672B (en)

Applications Claiming Priority (3)

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EP10150249 2010-01-07
EP10150249.0 2010-01-07
PCT/EP2010/068383 WO2011082889A1 (en) 2010-01-07 2010-11-29 Natural shading agents

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CN102753672B true CN102753672B (en) 2014-11-12

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001028973A1 (en) * 1999-10-19 2001-04-26 The Procter & Gamble Company Radical scavenger
WO2005067875A1 (en) * 2003-12-31 2005-07-28 Kimberly-Clark Worldwide, Inc. Color changing liquid cleansing products
US20050244349A1 (en) * 2004-04-28 2005-11-03 Ratan Chaudhuri Methods for stabilizing ingredients within cosmetics, personal care and household products
JP2007308405A (en) * 2006-05-17 2007-11-29 Eishiyou Kagaku Kogyo Kk Hydrogen peroxide-containing composition for second agent of hair dye

Family Cites Families (43)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1296839A (en) 1969-05-29 1972-11-22
GB1372034A (en) 1970-12-31 1974-10-30 Unilever Ltd Detergent compositions
DK187280A (en) 1980-04-30 1981-10-31 Novo Industri As RUIT REDUCING AGENT FOR A COMPLETE LAUNDRY
EP0070074B2 (en) 1981-07-13 1997-06-25 THE PROCTER & GAMBLE COMPANY Foaming surfactant compositions
WO1987000859A1 (en) 1985-08-09 1987-02-12 Gist-Brocades N.V. Novel lipolytic enzymes and their use in detergent compositions
GB2188653A (en) 1986-04-02 1987-10-07 Procter & Gamble Biodegradable fabric softeners
ATE110768T1 (en) 1986-08-29 1994-09-15 Novo Nordisk As ENZYMATIC DETERGENT ADDITIVE.
NZ221627A (en) 1986-09-09 1993-04-28 Genencor Inc Preparation of enzymes, modifications, catalytic triads to alter ratios or transesterification/hydrolysis ratios
EP0305216B1 (en) 1987-08-28 1995-08-02 Novo Nordisk A/S Recombinant Humicola lipase and process for the production of recombinant humicola lipases
JPS6474992A (en) 1987-09-16 1989-03-20 Fuji Oil Co Ltd Dna sequence, plasmid and production of lipase
GB8803036D0 (en) 1988-02-10 1988-03-09 Unilever Plc Liquid detergents
JP3079276B2 (en) 1988-02-28 2000-08-21 天野製薬株式会社 Recombinant DNA, Pseudomonas sp. Containing the same, and method for producing lipase using the same
US5648263A (en) 1988-03-24 1997-07-15 Novo Nordisk A/S Methods for reducing the harshness of a cotton-containing fabric
EP0406314B1 (en) 1988-03-24 1993-12-01 Novo Nordisk A/S A cellulase preparation
GB8813978D0 (en) 1988-06-13 1988-07-20 Unilever Plc Liquid detergents
CA2001927C (en) 1988-11-03 1999-12-21 Graham Thomas Brown Aluminosilicates and detergent compositions
GB8915658D0 (en) 1989-07-07 1989-08-23 Unilever Plc Enzymes,their production and use
EP0528828B2 (en) 1990-04-14 1997-12-03 Genencor International GmbH Alkaline bacillus lipases, coding dna sequences therefor and bacilli which produce these lipases
KR930702514A (en) 1990-09-13 1993-09-09 안네 제케르 Lipase variant
JP3219765B2 (en) 1991-04-30 2001-10-15 ザ、プロクター、エンド、ギャンブル、カンパニー Builder-containing liquid detergent having boric acid-polyol complex for inhibiting proteolytic enzymes
EP0511456A1 (en) 1991-04-30 1992-11-04 The Procter & Gamble Company Liquid detergents with aromatic borate ester to inhibit proteolytic enzyme
DK72992D0 (en) 1992-06-01 1992-06-01 Novo Nordisk As ENZYME
DK88892D0 (en) 1992-07-06 1992-07-06 Novo Nordisk As CONNECTION
EP0652946B1 (en) 1993-04-27 2005-01-26 Genencor International, Inc. New lipase variants for use in detergent applications
JP2859520B2 (en) 1993-08-30 1999-02-17 ノボ ノルディスク アクティーゼルスカブ Lipase, microorganism producing the same, method for producing lipase, and detergent composition containing lipase
JPH09503664A (en) 1993-10-13 1997-04-15 ノボ ノルディスク アクティーゼルスカブ H-lower 2 O-lower 2 stable peroxidase mutant
JPH07143883A (en) 1993-11-24 1995-06-06 Showa Denko Kk Lipase gene and mutant lipase
MX9603542A (en) 1994-02-22 1997-03-29 Novo Nordisk As A method of preparing a variant of a lipolytic enzyme.
US5824531A (en) 1994-03-29 1998-10-20 Novid Nordisk Alkaline bacilus amylase
JP3851656B2 (en) 1994-05-04 2006-11-29 ジェネンコア インターナショナル インコーポレーテッド Lipase with improved surfactant resistance
AU2884595A (en) 1994-06-20 1996-01-15 Unilever Plc Modified pseudomonas lipases and their use
AU2884695A (en) 1994-06-23 1996-01-19 Unilever Plc Modified pseudomonas lipases and their use
BE1008998A3 (en) 1994-10-14 1996-10-01 Solvay Lipase, microorganism producing the preparation process for the lipase and uses thereof.
US5827719A (en) 1994-10-26 1998-10-27 Novo Nordisk A/S Enzyme with lipolytic activity
JPH08228778A (en) 1995-02-27 1996-09-10 Showa Denko Kk New lipase gene and production of lipase using the same
AU715423B2 (en) 1995-03-17 2000-02-03 Novozymes A/S Novel endoglucanases
JP4307549B2 (en) 1995-07-14 2009-08-05 ノボザイムス アクティーゼルスカブ Modified enzyme with lipolytic activity
ATE267248T1 (en) 1995-08-11 2004-06-15 Novozymes As NOVEL LIPOLYTIC ENZYMES
WO1998012307A1 (en) 1996-09-17 1998-03-26 Novo Nordisk A/S Cellulase variants
CA2265734A1 (en) 1996-10-08 1998-04-16 Novo Nordisk A/S Diaminobenzoic acid derivatives as dye precursors
DK2011864T3 (en) 1999-03-31 2015-04-07 Novozymes As Polypeptides with alkaline alpha-amylase activity and nucleic acids encoding them
WO2000060063A1 (en) 1999-03-31 2000-10-12 Novozymes A/S Lipase variant
MX2009007878A (en) 2007-01-26 2009-08-18 Unilever Nv Shading composition.

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001028973A1 (en) * 1999-10-19 2001-04-26 The Procter & Gamble Company Radical scavenger
WO2005067875A1 (en) * 2003-12-31 2005-07-28 Kimberly-Clark Worldwide, Inc. Color changing liquid cleansing products
US20050244349A1 (en) * 2004-04-28 2005-11-03 Ratan Chaudhuri Methods for stabilizing ingredients within cosmetics, personal care and household products
JP2007308405A (en) * 2006-05-17 2007-11-29 Eishiyou Kagaku Kogyo Kk Hydrogen peroxide-containing composition for second agent of hair dye

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