WO2010034623A1 - Cationic pyridine and pyridazine dyes - Google Patents
Cationic pyridine and pyridazine dyes Download PDFInfo
- Publication number
- WO2010034623A1 WO2010034623A1 PCT/EP2009/061761 EP2009061761W WO2010034623A1 WO 2010034623 A1 WO2010034623 A1 WO 2010034623A1 EP 2009061761 W EP2009061761 W EP 2009061761W WO 2010034623 A1 WO2010034623 A1 WO 2010034623A1
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- WO
- WIPO (PCT)
- Prior art keywords
- alkyl
- phenyl
- composition according
- detergent composition
- laundry detergent
- Prior art date
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- 0 CN*1c(*=*c2ccc(*)cc2)ccc2c1cccc2 Chemical compound CN*1c(*=*c2ccc(*)cc2)ccc2c1cccc2 0.000 description 2
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/40—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
Definitions
- the present invention relates to the delivery of dyes to fabrics.
- WO 2007/084729 discloses the use of thiazolium dyes in Laundry formulations as a shading agent that does not build up over multiple washes.
- WO 2007/087252 discloses the use of thiazolium dyes in Laundry formulations as a shading agent that does not build up over multiple washes.
- GB1491930 discloses cationic pyridine based mono-azo dyestuffs in composition for hair dyeing. Summary of the Invention
- the present invention provides a laundry treatment composition comprising:
- Ri and R 2 are independently selected from H, alkyl, aryl; alkylaryl; alkylesters; polyethers; and Ri and R2 may be joined to form a five or six member aliphatic ring which may comprise a further hetroatom selected from oxygen and nitrogen;
- R 3 is selected from: H; alkyl; alkylaryl; and, aryl; and,
- Ring A may be further condensed to a benzene ring.
- the present invention provides a domestic method of treating a textile, the method comprising the steps of: (i) treating a textile with an aqueous solution of the cationic pyhdine/pyhdazine dye, the aqueous solution comprising from 1 ppb to 1 ppm of the cationic pyridine/pyhdazine dye, and from 0 ppb to 1 ppm of another dye or pigment selected from: pigments, hydrophobic dyes and direct dyes; and, from 0.0 g/L to 3 g/L of a surfactant; (ii) optionally rinsing the textile; and, (iii) drying the textile.
- the aqueous solution comprises 0.1 to 50 ppm of fluorescer.
- the textile to be laundered is composed of cotton, polyester, nylon or elastane fibres.
- the cationic pyridine/pyhdazine dyes as used in the present invention are blue or violet.
- the cationic pyridine/pyhdazine dyes gives a blue or violet colour to a white cloth with a hue angle of 240 to 345, more preferably 260 to 320, most preferably 270 to 300.
- the white cloth used is bleached non-mercerised woven cotton sheeting.
- the aromatic rings and Ri, R2 and R3 of the dye may be further substituted by suitable uncharged organic groups.
- the suitable uncharged organic groups individually should have a molecular weight of less than 400, preferably less than 150.
- the uncharged organic groups are selected from methyl, ethyl, - A -
- any aromatic ring in the cationic pyridine/pyridazine dye is not substituted directly by OH, i.e., a phenolic moiety should not be present.
- a polyether chain is defined as at least two repeating units that are chemically bound via the ether's oxygen.
- the polyether chain may be branched or linear.
- Preferred polyether chains are selected from ethylene oxides or propylene oxides. Where an alkyl and/or polyether chain is present the chain preferably has a molecular weight of less than 1000, more preferably less than 400, even more preferably less than 200.
- R1 and/or R2 is a polyether chain as defined above.
- Example of polyether groups are (CH 2 CH 2 O) 4 H 1 (CH 2 CH 2 CH 2 O) 3 H, (CH 2 C(CH 3 )HO) 3 H, (CH 2 CH 2 O) 2 (CH 2 C(CH 2 O(CH 2 CH 2 O) 2 H) 2 H and those described in WO2008/087497.
- An- is a counter ion.
- An- is not essential aspect of the invention and may be varied widely.
- An- may be an anion such as RCOO “ , BPh 4 " , CIO 4 “ , BF 4 “ , PF 6 “ , RSO 3 “ , RSO 4 “ , SO 4 2” , NO 3 “ , F “ , Cl “ , Br “ , or I “ , with R being hydrogen, optionally substituted alkyl or optionally substituted aryl.
- R being hydrogen, optionally substituted alkyl or optionally substituted aryl.
- An- is selected from: CH 3 SO 3 “ , CH 3 CO 2 " , BF 4 “ , Cl “ , F “ , Br “ , and I “ .
- the aliphatic ring is a morpholine or pipehdine ring.
- the azo group is preferably ortho to the quanternary nitrogen.
- the A ring When A is further condensed to a benzene ring, the A ring forms an extended aromatic ring system of the form: or
- Ri and R2 are selected from: H; polyethers, C1 -C8-alkyl which may be substituted by -OH, O-C1 -C8-alkyl, -Cl, and -F, -CN; -C1 -C8-alkyl-C(O)2- C1 -C8-alkyl; -C1 -C8-alkyl-OC(O)-C1 -C8-alkyl;-C1 -C8-alkyl-phenyl; -C1 -C8-alkyl- naphthyl; phenyl; and, naphthyl, wherein the benzyl and phenyl may be substituted by a group selected from: -OC1 -C6-alkyl, -C1-C6-alkyl.
- Ri and R 2 are selected from: -H; -CH 3 ; -C 2 H 5 ; -(CH 2 ) 3 H; -(CH 2 ) 4 H; - C 2 H 4 OH; -C 2 H 4 CI; -C 2 H 4 CN; -C 6 H 5 ; -CH 2 C 6 H 5 ; -C 2 H 4 OCOCH 3 ; -C 2 H 4 COOCH 3 ; and, -C 2 H 4 OC 2 H 4 OH.
- Most preferred groups for Ri and R 2 are methyl or ethyl.
- R 3 is selected from: H, C1 -C8-alkyl, -d -C ⁇ -alkyl-phenyl; -C1 -C8-alkyl- naphthyl; phenyl; and, naphthyl. More preferably, R 3 is selected from methyl, ethyl and benzyl. Most preferred groups for R 3 are methyl or ethyl.
- Ring B may carry up to two groups that are selected from: -Br; -Cl; -F; -NO 2 ; -CN; -SO2-benzyl; -C(O)O-CI -C8-alkyl; -OC1 -C8-alkyl; -NHC(O)CI -C4-alkyl, -SO2-C1 - C8-alkyl; and -SO2-phenyl. More preferably -Br; -Cl; -F; -OC1-C4-alkyl and - NHC(O)CI -C4-alkyl.
- the B ring When the B ring is further substituted this is preferably ortho and/or meta to the -NRiR 2 amine group. If substituted by 2 groups, one is preferably ortho and the other meta to the -NRiR 2 amine group and on opposite sides of the ring (i.e. in the 2, 5 positions).
- the most preferred substituents for the B ring are selected from methyl, Cl, NHCOCH 3 , CH 3 O and C 2 H 5 O.
- Deposition of the dye onto polyester may be increased by increasing the number of hydrophobic organic groups on the dye.
- Hydrophobic organic groups are groups which increase the calculate logP of the dye in comparison to a H substituent.
- the dyes are granulated with an acidic binder as described in WO2007/039042 (Unilever). This reduced degradation due to alkaline hydrolysis on storage.
- the composition comprises between 2 to 70 wt% of a surfactant, most preferably 10 to 30 wt %.
- a surfactant most preferably 10 to 30 wt %.
- the nonionic and anionic surfactants of the surfactant system may be chosen from the surfactants described "Surface Active Agents" Vol. 1 , by Schwartz & Perry, lnterscience 1949, Vol. 2 by Schwartz, Perry & Berch, lnterscience 1958, in the current edition of "McCutcheon's Emulsifiers and Detergents” published by Manufacturing Confectioners Company or in "Tenside-Taschenbuch", H. Stache, 2nd Edn., Carl Hauser Verlag, 1981.
- the surfactants used are saturated.
- Suitable nonionic detergent compounds which may be used include, in particular, the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for example, aliphatic alcohols, acids, amides or alkyl phenols with alkylene oxides, especially ethylene oxide either alone or with propylene oxide.
- Specific nonionic detergent compounds are C ⁇ to C22 alkyl phenol- ethylene oxide condensates, generally 5 to 25 EO, i.e. 5 to 25 units of ethylene oxide per molecule, and the condensation products of aliphatic C 8 to Ci 8 primary or secondary linear or branched alcohols with ethylene oxide, generally 5 to 40 EO.
- Suitable anionic detergent compounds which may be used are usually water- soluble alkali metal salts of organic sulphates and sulphonates having alkyl radicals containing from about 8 to about 22 carbon atoms, the term alkyl being used to include the alkyl portion of higher acyl radicals.
- suitable synthetic anionic detergent compounds are sodium and potassium alkyl sulphates, especially those obtained by sulphating higher C 8 to Ci 8 alcohols, produced for example from tallow or coconut oil, sodium and potassium alkyl Cg to C20 benzene sulphonates, particularly sodium linear secondary alkyl C10 to C15 benzene sulphonates; and sodium alkyl glyceryl ether sulphates, especially those ethers of the higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum.
- the preferred anionic detergent compounds are sodium Cu to C15 alkyl benzene sulphonates and sodium C12 to Ci 8 alkyl sulphates.
- surfactants such as those described in EP-A-328 177 (Unilever), which show resistance to salting-out, the alkyl polyglycoside surfactants described in EP-A-070 074, and alkyl monoglycosides.
- Preferred surfactant systems are mixtures of anionic with nonionic detergent active materials, in particular the groups and examples of anionic and nonionic surfactants pointed out in EP-A-346 995 (Unilever).
- surfactant system that is a mixture of an alkali metal salt of a C16 to Ci ⁇ primary alcohol sulphate together with a C12 to C15 primary alcohol 3 to 7 EO ethoxylate.
- the nonionic detergent is preferably present in amounts greater than 10%, e.g. 25 to 90 wt % of the surfactant system.
- Anionic surfactants can be present for example in amounts in the range from about 5% to about 40 wt % of the surfactant system.
- the surfactant may be a cationic such that the formulation is a fabric conditioner.
- the present invention When the present invention is used as a fabric conditioner it needs to contain a cationic compound.
- the quaternary ammonium compound is a quaternary ammonium compound having at least one C12 to C22 alkyl chain.
- the quaternary ammonium compound has the following formula:
- R 1 is a C12 to C22 alkyl or alkenyl chain
- R 2 , R 3 and R 4 are independently selected from Ci to C 4 alkyl chains
- X " is a compatible anion.
- a preferred compound of this type is the quaternary ammonium compound cetyl thmethyl quaternary ammonium bromide.
- a second class of materials for use with the present invention are the quaternary ammonium of the above structure in which R 1 and R 2 are independently selected from Ci2 to C22 alkyl or alkenyl chain; R 3 and R 4 are independently selected from Ci to C 4 alkyl chains and X " is a compatible anion.
- the ratio of cationic to nonionic surfactant is from 1 :100 to 50:50, more preferably 1 :50 to 20:50.
- the cationic compound may be present from 1.5 wt % to 50 wt % of the total weight of the composition.
- the cationic compound may be present from 2 wt % to 25 wt %, a more preferred composition range is from 5 wt % to 20 wt %.
- the softening material is preferably present in an amount of from 2 to 60% by weight of the total composition, more preferably from 2 to 40%, most preferably from 3 to 30% by weight.
- composition optionally comprises a silicone.
- Builders or Complexing agents :
- Builder materials may be selected from 1 ) calcium sequestrant materials, 2) precipitating materials, 3) calcium ion-exchange materials and 4) mixtures thereof.
- calcium sequestrant builder materials examples include alkali metal polyphosphates, such as sodium tripolyphosphate and organic sequestrants, such as ethylene diamine tetra-acetic acid.
- the laundry treatment composition comprises sodium carbonate in the range from 5 to 50 wt%, most preferably 10 to 35 wt%.
- the aqueous wash solution when used with granular laundry treatment composition, preferably comprises 0.1 to 4 g/L of sodium carbonate.
- Examples of calcium ion-exchange builder materials include the various types of water-insoluble crystalline or amorphous aluminosilicates, of which zeolites are the best known representatives, e.g. zeolite A, zeolite B (also known as zeolite P), zeolite C, zeolite X, zeolite Y and also the zeolite P-type as described in EP-A-0,384,070.
- zeolites are the best known representatives, e.g. zeolite A, zeolite B (also known as zeolite P), zeolite C, zeolite X, zeolite Y and also the zeolite P-type as described in EP-A-0,384,070.
- composition may also contain 0-65 % of a builder or complexing agent such as ethylenediaminetetraacetic acid, diethylenetriamine-pentaacetic acid, alkyl- or alkenylsuccinic acid, nithlotriacetic acid or the other builders mentioned below.
- a builder or complexing agent such as ethylenediaminetetraacetic acid, diethylenetriamine-pentaacetic acid, alkyl- or alkenylsuccinic acid, nithlotriacetic acid or the other builders mentioned below.
- Many builders are also bleach-stabilising agents by virtue of their ability to complex metal ions.
- Zeolite and carbonate are preferred builders.
- the composition may contain as builder a crystalline aluminosilicate, preferably an alkali metal aluminosilicate, more preferably a sodium aluminosilicate. This is typically present at a level of less than 15%w.
- Aluminosilicates are materials having the general formula:
- M is a monovalent cation, preferably sodium.
- M a monovalent cation, preferably sodium.
- These materials contain some bound water and are required to have a calcium ion exchange capacity of at least 50 mg CaO/g.
- the preferred sodium aluminosilicates contain 1.5-3.5 SiO 2 units in the formula above. They can be prepared readily by reaction between sodium silicate and sodium aluminate, as amply described in the literature.
- the ratio of surfactants to alumuminosilicate (where present) is preferably greater than 5:2, more preferably greater than 3:1.
- phosphate builders may be used.
- 'phosphate' embraces diphosphate, triphosphate, and phosphonate species.
- Other forms of builder include silicates, such as soluble silicates, metasilicates, layered silicates (e.g. SKS-6 from Hoechst).
- the laundry detergent formulation is a non-phosphate built laundry detergent formulation, i.e., contains less than 1 wt% of phosphate.
- the composition may comprise one or more enzymes, which provide cleaning performance, fabric care and/or sanitation benefits.
- Fluorescent Agent may comprise one or more enzymes, which provide cleaning performance, fabric care and/or sanitation benefits.
- the composition preferably comprises a fluorescent agent (optical bhghtener).
- fluorescent agents are well known and many such fluorescent agents are available commercially. Usually, these fluorescent agents are supplied and used in the form of their alkali metal salts, for example, the sodium salts.
- the total amount of the fluorescent agent or agents used in the composition is generally from 0.005 to 2 wt %, more preferably 0.01 to 0.1 wt %.
- Preferred classes of fluorescer are: Di-styryl biphenyl compounds, e.g. Tinopal (Trade Mark) CBS-X, Di-amine stilbene di-sulphonic acid compounds, e.g.
- Preferred fluorescers are: sodium 2 (4-styryl-3-sulfophenyl)-2H-napthol[1 ,2- d]thazole, disodium 4,4'-bis ⁇ [(4-anilino-6-(N methyl-N-2 hydroxyethyl) amino 1 ,3,5- thazin-2-yl)]amino ⁇ stilbene-2-2' disulfonate, disodium 4,4'-bis ⁇ [(4-anilino-6- morpholino-1 ,3,5-thazin-2-yl)]amino ⁇ stilbene-2-2' disulfonate, and disodium 4,4'- bis(2-sulfostyryl)biphenyl.
- the composition comprises a perfume.
- the perfume is preferably in the range from 0.001 to 3 wt %, most preferably 0.1 to 1 wt %.
- CTFA Cosmetic, Toiletry and Fragrance Association
- top notes are defined by Poucher (Journal of the Society of Cosmetic Chemists 6(2):80 [1955]). Preferred top-notes are selected from citrus oils, linalool, linalyl acetate, lavender, dihydromyrcenol, rose oxide and cis-3-hexanol.
- Perfume and top note may be used to cue the whiteness benefit of the invention.
- the laundry treatment composition does not contain a peroxygen bleach, e.g., sodium percarbonate, sodium perborate, and peracid.
- a peroxygen bleach e.g., sodium percarbonate, sodium perborate, and peracid.
- the composition may comprise one or more polymers.
- polymers include carboxymethylcellulose, poly (ethylene glycol), polyvinyl alcohol), polycarboxylates such as polyacrylates, maleic/acrylic acid copolymers and lauryl methacrylate/acrylic acid copolymers.
- Polymers present to prevent dye deposition for example poly(vinylpyrrolidone), poly(vinylpyridine-N-oxide), and poly(vinylimidazole), are preferably absent from the formulation.
- the yield of reddish brown insoluble material remaining was 2.3g.
- the acetic acid extracts were neutralized by carefully adding sodium hydroxide liquor (40%) to pH 7: this resulted in a colour change, from violet to brown, and the precipitated tarry solid was collected. This was water washed several times, by decantation, and the remaining solid extracted with methylene chloride. The combined methylene chloride extracts were dried, solvent was removed and the residue chromatographed over siligel.
- the desired product was a dark red crystalline solid (0.57g., 12%), mp 152-154 0 C.
- the scale (0.02m) and method employed were similar to that used for the preparation of 5-methyl-2-[(4-dimethylamino)-phenylazo]-pyridine, but replacing the 2-aminopyridine with 2-aminoquinoline (2.88g., 0.02m). Also, the toluene suspension of 2-aminoquonoline and sodamide was allowed to cool before adding the 4-nitroso-N,N-dimethyl aniline (3g., 0.02m). After removal of toluene the residual tar was stirred with methylene chloride and passed through silicagel. The eluate was collected, solvent removed and the residue was treated with ispropanol to yield a brown solid, mp 149 - 151 0 C.
- the dyes listed below were added to a washing powder such that when 4g/L of the powder was dissolved in water the optical density at the lambda max of the dye in the range 400-700nm was 1 at 5cm. In this manner the same amount of colour was added to each powder.
- the washing powder contained 20% LAS surfactant, 30% Na2CO3, 40% NaCI, remainder minors included calcite and fluorescer and moisture.
- the washing powder was used to wash a 1 :1 :1 mixture of white woven cotton cloth, white polyester cloth and white nylon-elastane cloth. This simulates the mixed fabric types found in domestic wash loads. Washes were conducted in 26° French Hard water at 293K with a liquor to cloth ratio of 30:1.
- Basic Violet 35 is a cationic pyrazole monoazo 9.8 10.2 dye.
- Basic Blue 159 is a cationic, 3,4-thiadiazole 5.1 5.6 monoazo dye. Comparative example
- the dyes of the current invention gave more colour to the cloth as indicated by their larger ⁇ E values.
- the powder formulations A, B, C and D were made up with the three pyridine/pyhdazine of example 3 at the level indicated.
- NI(7EO) refers to R-(OCH 2 CH2) n OH, where R is an alkyl chain of C12 to C15, and n is 7.
- NaLAS linear alkyl benzene sulphonate (LAS) and (SLES(3EO)) is Ci 2 -Ci 8 alkyl polyethoxylate (3.0) sulphate.
- Na Alkyl sulphate is PAS.
- a three rinse conditioner formulation for use in the rinse stage of the wash was also created. It contained 13.7wt% N,N-di(tallowoyloxyethyl)-N,N- dimethylammonium chloride, 1.5wt% perfume, 0.001wt% of the three pyridine/pyhdazine of example 3, remainder minors and water.
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
ES09782877.6T ES2450393T3 (en) | 2008-09-23 | 2009-09-10 | Cationic pyridine and pyridazine dyes |
CN200980136871.3A CN102159698B (en) | 2008-09-23 | 2009-09-10 | Cationic pyridine and pyridazine dyes |
EP09782877.6A EP2331669B1 (en) | 2008-09-23 | 2009-09-10 | Cationic pyridine and pyridazine dyes |
ZA2011/01402A ZA201101402B (en) | 2008-09-23 | 2011-02-22 | Cationic pyridine and pyridazine dyes |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP08164876.8 | 2008-09-23 | ||
EP08164876 | 2008-09-23 |
Publications (1)
Publication Number | Publication Date |
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WO2010034623A1 true WO2010034623A1 (en) | 2010-04-01 |
Family
ID=40282504
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2009/061761 WO2010034623A1 (en) | 2008-09-23 | 2009-09-10 | Cationic pyridine and pyridazine dyes |
Country Status (8)
Country | Link |
---|---|
EP (1) | EP2331669B1 (en) |
CN (1) | CN102159698B (en) |
AR (1) | AR073649A1 (en) |
CL (1) | CL2011000620A1 (en) |
ES (1) | ES2450393T3 (en) |
MY (1) | MY153959A (en) |
WO (1) | WO2010034623A1 (en) |
ZA (1) | ZA201101402B (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2014189145A1 (en) * | 2013-05-23 | 2014-11-27 | 学校法人慶應義塾 | Compound for generating second harmonic of light, dye composition for generating second harmonic of light, and cell examination method |
WO2016041679A1 (en) * | 2014-09-18 | 2016-03-24 | Unilever Plc | Whitening composition |
WO2016041680A1 (en) * | 2014-09-18 | 2016-03-24 | Unilever Plc | Whitening composition |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
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US5888252A (en) * | 1993-11-30 | 1999-03-30 | Ciba Specialty Chemicals Corporation | Processes for dyeing keratin-containing fibres with cationicazo dyes |
US20020007521A1 (en) * | 1998-05-25 | 2002-01-24 | Gerard Lang | Dye composition for keratin fibres, with a cationic direct dye and a substantive polymer |
US6530959B1 (en) * | 1998-08-19 | 2003-03-11 | L'oreal S.A. | Dyeing composition for keratinous fibres with a direct cationic coloring agent and a surfactant |
US20060156487A1 (en) * | 1998-08-19 | 2006-07-20 | L'oreal | Composition for dyeing keratinous fibers with a cationic direct dye and a quaternary ammonium salt |
WO2007087252A1 (en) * | 2006-01-23 | 2007-08-02 | Milliken & Company | Laundry care compositions with thiazolium dye |
-
2009
- 2009-09-10 ES ES09782877.6T patent/ES2450393T3/en active Active
- 2009-09-10 MY MYPI2011001265A patent/MY153959A/en unknown
- 2009-09-10 EP EP09782877.6A patent/EP2331669B1/en not_active Not-in-force
- 2009-09-10 CN CN200980136871.3A patent/CN102159698B/en not_active Expired - Fee Related
- 2009-09-10 WO PCT/EP2009/061761 patent/WO2010034623A1/en active Application Filing
- 2009-09-22 AR ARP090103627 patent/AR073649A1/en unknown
-
2011
- 2011-02-22 ZA ZA2011/01402A patent/ZA201101402B/en unknown
- 2011-03-23 CL CL2011000620A patent/CL2011000620A1/en unknown
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5888252A (en) * | 1993-11-30 | 1999-03-30 | Ciba Specialty Chemicals Corporation | Processes for dyeing keratin-containing fibres with cationicazo dyes |
US20020007521A1 (en) * | 1998-05-25 | 2002-01-24 | Gerard Lang | Dye composition for keratin fibres, with a cationic direct dye and a substantive polymer |
US6530959B1 (en) * | 1998-08-19 | 2003-03-11 | L'oreal S.A. | Dyeing composition for keratinous fibres with a direct cationic coloring agent and a surfactant |
US20060156487A1 (en) * | 1998-08-19 | 2006-07-20 | L'oreal | Composition for dyeing keratinous fibers with a cationic direct dye and a quaternary ammonium salt |
WO2007087252A1 (en) * | 2006-01-23 | 2007-08-02 | Milliken & Company | Laundry care compositions with thiazolium dye |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2014189145A1 (en) * | 2013-05-23 | 2014-11-27 | 学校法人慶應義塾 | Compound for generating second harmonic of light, dye composition for generating second harmonic of light, and cell examination method |
JPWO2014189145A1 (en) * | 2013-05-23 | 2017-02-23 | 学校法人慶應義塾 | Optical second harmonic generation compound, optical second harmonic generation dye composition, and cell inspection method |
US9709555B2 (en) | 2013-05-23 | 2017-07-18 | Keio University | Compound for generating second harmonic of light, dye composition for generating second harmonic of light, and cell examination method |
WO2016041679A1 (en) * | 2014-09-18 | 2016-03-24 | Unilever Plc | Whitening composition |
WO2016041680A1 (en) * | 2014-09-18 | 2016-03-24 | Unilever Plc | Whitening composition |
CN106661503A (en) * | 2014-09-18 | 2017-05-10 | 荷兰联合利华有限公司 | Whitening composition |
CN106661504A (en) * | 2014-09-18 | 2017-05-10 | 荷兰联合利华有限公司 | Whitening composition |
CN106661504B (en) * | 2014-09-18 | 2019-07-12 | 荷兰联合利华有限公司 | Lightening compositions |
Also Published As
Publication number | Publication date |
---|---|
EP2331669A1 (en) | 2011-06-15 |
ZA201101402B (en) | 2012-05-30 |
EP2331669B1 (en) | 2013-12-04 |
CL2011000620A1 (en) | 2011-09-23 |
MY153959A (en) | 2015-04-30 |
ES2450393T3 (en) | 2014-03-24 |
CN102159698A (en) | 2011-08-17 |
CN102159698B (en) | 2013-04-24 |
AR073649A1 (en) | 2010-11-24 |
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