EP2734610B1 - Liquid laundry composition - Google Patents
Liquid laundry composition Download PDFInfo
- Publication number
- EP2734610B1 EP2734610B1 EP12735572.5A EP12735572A EP2734610B1 EP 2734610 B1 EP2734610 B1 EP 2734610B1 EP 12735572 A EP12735572 A EP 12735572A EP 2734610 B1 EP2734610 B1 EP 2734610B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- liquid laundry
- dyes
- composition according
- laundry composition
- sulphonated aromatic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Not-in-force
Links
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
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- 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
- 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
- C11D3/378—(Co)polymerised monomers containing sulfur, e.g. sulfonate
-
- 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
- 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.
- Suitable lipases include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Examples of useful lipases include lipases from Humicola (synonym Thermomyces), e.g. from H. lanuginosa (T. lanuginosus) as described in EP 258 068 and EP 305 216 or from H. insolens as described in WO 96/13580 , a Pseudomonas lipase, e.g. from P. alcaligenes or P. pseudoalcaligenes ( EP 218 272 ), P. cepacia ( EP 331 376 ), P. stutzeri ( GB 1,372,034 ), P.
- the enzyme and the shading dye may show some interaction and should be chosen such that this interaction is not negative. Some negative interactions may be avoided by encapsulation of one or other of enzyme or shading dye and/or other segregation within the product.
- Any enzyme present in the composition may be stabilized using conventional stabilizing agents, e.g., a polyol such as propylene glycol or glycerol, a sugar or sugar alcohol, lactic acid, boric acid, or a boric acid derivative, e.g., an aromatic borate ester, or a phenyl boronic acid derivative such as 4-formylphenyl boronic acid, and the composition may be formulated as described in e.g. WO 92/19709 and WO 92/19708 .
- a polyol such as propylene glycol or glycerol
- a sugar or sugar alcohol lactic acid, boric acid, or a boric acid derivative, e.g., an aromatic borate ester, or a phenyl boronic acid derivative such as 4-formylphenyl boronic acid
Landscapes
- 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)
- Coloring (AREA)
Description
- The present invention concerns liquid laundry compositions incorporating a sulphonated aromatic formaldehyde polycondensate.
-
WO2010/084039 (Unilever ) disclosed shading dyes in spray dried granules containing alkali metal salts of the condensation products of naphthalenesulphonic acids and formaldehyde for use in powder detergents; the condensation product serves to reduce dye migration in the powder thus retaining the aesthetic appeal of the powder. -
DE 21 65 803 A1 discloses a laundry detergent comprising surfactants, such as a mixture of anionic and nonionic surfactants, and sulphonated aromatic formaldehyde condensates. The sulphonated aromatic formaldehyde condensate has an anti-greying effect on different kinds of synthetic fibers. - Elastane is a widely used material in underwear and support wear and upon washing with surfactant becomes grey.
- There is a need to ameliorate the greying of nylon-elastane when liquid detergents are used to treat textiles.
- We have found that a liquid composition containing a surfactant and a sulphonated aromatic formaldehyde polycondensate has improved properties when textiles containing elastane are treated with the composition; there is reduced greying of the elastane. We have also found that the performance of a shading dye is improved by addition to such a composition.
- In one aspect the present invention provides a laundry liquid laundry detergent composition comprising:
- (a) from 0.0001 to 0.01 wt %, preferably from 0.001 to 0.005 w%, of a blue or violet shading dye;
- (b) from 1 to 70 wt% of a surfactant, wherein the surfactant is a mixture of anionic with nonionic detergent active materials;
- (c) from 0,1 to 30 wt% of a sulphonated aromatic formaldehyde polycondensate, and,
- (d) the remainder of the composition being diluents and adjuncts to100 wt %.
- In another aspect the present invention provides a method of treating a textile, the textile comprising elastane, the method comprising the steps of:
- (i) applying the liquid laundry composition to a textile;
- (ii) rinsing the textile with water; and,
- (iii) optionally drying the textile.
- The presence of sulphonated aromatic formaldehyde polycondensate reduces the greying of elastane.
- A sulphonated aromatic formaldehyde polycondensate is the condensation product of sulphonated aromatic compounds with formaldehyde.
- The sulphonated aromatic formaldehyde polycondensate may be produced by the condensation reaction of:
- 1. aromatic sulfonic acids and benzoyl chloride or benzoin.
- 2. alkylarylsulfonic acids with a halogen arylsulfonic acid
- 3. sulphonated phenols or napthols with formaldehyde.
- The products may be ethoxylated. The sulfonic acid groups may be sulfomethyl groups.
- The steps of polycondensation, ethoxylation, sulfonation or sulfomethylation may occur in any sequential order, but the ethoxylation, sulfonation or sulfomethylation are preferred to take place before the polycondensation.
- Preferred alkali metal salts of the present invention are alkali metal salts of the condensation products of naphthalenesulphonic acids and formaldehyde; naphthalenesulphonic acids, cresol and formaldehyde; diphenylethersulphonic acids and formaldehyde; toluenesulphonic acids and formaldehyde; isopropylbenzenesulphonic acids and formaldehyde; cresolsulphonic acids and formaldehyde. Most preferably alkali metal salts of the condensation products of naphthalenesulphonic acids and formaldehyde.
- A commercial example available is TAMOL™, a trade name from BASF. Other suitable commercial examples are produced by Lanxess, Rohm and Haas Co, BASF and Dow Chemical Company.
- Examples of the synthesis of sulphonated aromatic formaldehyde polycondensate are given in
GB1101671 (Ciba-Geigy US3957680 (Mitsui ),DE1163284 (Hoechst ),US3781169 (Hoechst ) andUS3874891 (Hoechst ). - Preferred structures are:
Where j is from 4 to 40, preferably 5 to 20. - Preferably, the minimum level of residual formaldehyde from the polycondensation is 200 PPM, more preferably 50 PPM and even more preferably-10 PPM.
- Shading dyes deposit to fabric during the wash or rinse step of the washing process providing a visible hue to the fabric.
- Shading dyes are discussed in
WO2005/003274 ,WO2006/032327(Unilever ),WO2006/032397(Unilever ),WO2006/045275(Unilever ),WO 2006/027086(Unilever ),WoO2008/017570(Unilever WO 2008/141880(Unilever ),WO2009/132870(Unilever ),WO 2009/141173 (Unilever ),WO 2010/099997(Unilever ),WO 2010/102861 (Unilever ),WO 2010/148624(Unilever ),WO2008/087497 (P&G) andWO2011/011799 (P&G). - Shading of white garments may be done with any colour depending on consumer preference. Blue and Violet are particularly preferred shades and consequently preferred dyes or mixtures of dyes are ones that give a blue or violet shade on white fabrics. The shading dyes used in the present invention are preferably blue or violet. A mixture of shading dyes may be used and indeed are preferred for treating mixed fibre textiles. In this regard the dye 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 in this test is bleached non-mercerised woven cotton sheeting.
- The shading dye chromophore is preferably selected from the group comprising: mono-azo, bis-azo, triphenylmethane, triphenodioxazine, phthalocyanin, naptholactam, azine and anthraquinone. Most preferably mono-azo, bis-azo, azine and anthraquinone.
- Most preferably the dye bears at least one sulfonate group.
- Many examples of shading dyes are found in the classes of basic, solvent, acid, direct and disperse dyes.
- Preferred shading dyes are selected from direct dyes, acid dyes, hydrophobic dyes, cationic dyes and reactive dyes.
- The shading dye is present is present in the liquid composition in range from 0.0001 to 0.01 wt %. Depending upon the nature of the shading dye there are preferred ranges depending upon the efficacy of the shading dye which is dependent on class and particular efficacy within any particular class. As stated above the shading dye is most preferably a blue or violet shading dye.
- Direct violet and direct blue dyes are preferred.
- Preferably the dye is a bis-azo dye.
-
- the ring bearing R3 and R4 may be independently naphthyl or phenyl as shown;
- R1 is selected from: hydrogen and C1-C4-alkyl, preferably hydrogen;
- R2 is selected from: hydrogen, C1-C4-alkyl, substituted or unsubstituted phenyl and substituted or unsubstituted naphthyl, preferably phenyl;
- R3 and R4 are independently selected from: hydrogen and C1-C4-alkyl, preferably hydrogen or methyl;
- X and Y are independently selected from: hydrogen, C1-C4-alkyl and C1-C4-alkoxy; preferably the dye has X= methyl; and, Y = methoxy and n is 0, 1 or 2, preferably 1 or 2.
- Preferred dyes are direct violet 7, direct violet 9, direct violet 11, direct violet 26, direct violet 31, direct violet 35, direct violet 40, direct violet 41, direct violet 51, and direct violet 99. Bis-azo copper containing dyes such as direct violet 66 may be used.
- Benzidene based dyes are not preferred.
- Preferably the direct dye is present at 0.00001 wt% to 0.0010 wt% of the composition.
- In another embodiment the direct dye may be covalently linked to the photo-bleach, for example as described in
WO2006/024612 andWO2010/099997 . - Cotton substantive acid dyes give benefits to cotton containing garments. Preferred dyes and mixes of dyes are blue or violet. Preferred acid dyes are:
- (i) azine dyes, wherein the dye is of the following core structure:
the dye is substituted with at least one SO3 - or -COO- group;
the B ring does not carry a negatively charged group or salt thereof;
and the A ring may further substituted to form a naphthyl;
the dye is optionally substituted by groups selected from: amine, methyl, ethyl, hydroxyl, methoxy, ethoxy, phenoxy, Cl, Br, I, F, and NO2. - Preferred azine dyes are: acid blue 98, acid violet 50, and acid blue 59, more preferably acid violet 50.
- Other preferred non-azine acid dyes are acid violet 17, acid black 1 and acid blue 29.
- Preferably the acid dye is present at 0.0005 wt% to 0.01 wt% of the composition.
- The composition may comprise one or more hydrophobic dyes selected from benzodifuranes, methine, triphenylmethanes, napthalimides, pyrazole, napthoquinone, anthraquinone and mono-azo or di-azo dye chromophores. Hydrophobic dyes are dyes which do not contain any charged water solubilising group. Hydrophobic dyes may be selected from the groups of disperse and solvent dyes. Blue and violet anthraquinone and mono-azo dye are preferred.
- Preferred dyes include solvent violet 13, disperse violet 27 disperse violet 26, disperse violet 28, disperse violet 63 and disperse violet 77.
- The hydrophobic dye may be an alkoxylated dye, preferably an alkoxylated mono-azo thiophene dye.
- Preferably the hydrophobic dye is present at 0.0001 wt% to 0.01 wt% of the composition.
- Cationic dyes bear a cationic charge. Cationic mono-azo, phenazines, triphenyl methane and anthraquinone dyes are preferred. Cationic Mono-azo dye and phenazine dyes are most preferred. To avoid hydrolysis for mono-azo and anthraquinone dyes preferably the cationic charge is present as a quaternary amine on a pendant chain. The dyes may be alkoxylated and mono-azo dyes may additionally bear anionic charged groups, preferably also on pendant chains. Mono-azo dyes containing a hetrocyclic ring are particularly preferred, such as thiophenes.
-
- X3 is selected from: -H; -F; -CH3; -C2H5; -OCH3; and, -OC2H5;
- X4 is selected from: -H; -CH3; -C2H5; -OCH3; and, -OC2H5;
and, - Y2 is selected from: -OH; -OCH2CH2OH; -CH(OH)CH2OH; -OC(O)CH3; and, C(O)OCH3.
- Reactive dyes are dyes which contain an organic group capable of reacting with an aliphatic C-OH, C-NH2 or C-NH-C group to form a covalent bond. They deposit onto cotton.
- Preferably the reactive group is hydrolysed or reactive group of the dyes has been reacted with an organic species such as a polymer, so as to the link the dye to this species. Dyes may be selected from the reactive violet and reactive blue dyes listed in the Colour Index International. Preferably the reactive dye is reacted with a polymer containing NH2 or NH groups.
- The composition comprises between 1 to 70 wt % of a surfactant, most preferably 10 to 30 wt %. The surfactant acts as a detergent. In general, the nonionic and anionic surfactants of the surfactant system may be chosen from the surfactants described "Surface Active Agents" Vol. 1, by Schwartz & Perry, Interscience 1949, Vol. 2 by Schwartz, Perry & Berch, Interscience 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. Preferably 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 C6 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 C8 to C18 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 watersoluble 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. Examples of suitable synthetic anionic detergent compounds are sodium and potassium alkyl sulphates, especially those obtained by sulphating higher C8 to C18 alcohols, produced for example from tallow or coconut oil, sodium and potassium alkyl C9 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 C11 to C15 alkyl benzene sulphonates and sodium C12 to C18 alkyl sulphates. Also applicable are surfactants such as those described in
EP-A-328 177 (Unilever EP-A-070 074 - The surfactant systems is a mixture 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 - The nonionic detergent Is preferably present in amounts greater than 10%, e.g. 25 to 90 wt % of the surfactant system. Anlonic surfactants can be present for example in amounts in the range from about 5% to about 40 wt % of the surfactant system,
- To facilitate ease of use the composition is preferably packed in pack sizes of 0.5 to 5kg. To reduce moisture ingress, the composition is preferably packs in laminated cardboard packs or sealed plastic bags,
- The diluents and adjuncts facilitate the composition are generally other than the shading dye, surfactant; and the modified lignin polymer. The diluents and adjuncts may facilitate fluidization of the composition and/or provide bulking or functionality to the composition. These include water, alcohol etc. Below are found suitable diluents and adjuncts but the composition is not limited to such.
- One or more detergency builders may be suitably present in the liquid detergent composition of the invention.
- Examples of suitable organic detergency builders, when present, include the alkaline metal, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates, polyacetyl carboxylates, carboxymethyloxysuccinates, carboxymethyloxymalonates, ethylene diamine-N,N-disuccinic acid salts, polyepoxysuccinates, oxydiacetates, triethylene tetramine hexa-acetic acid salts, N-alkyl imino diacetates or dipropionates, alpha sulpho-fatty acid salts, dipicolinic acid salts, oxidised polysaccharides, polyhydroxysulphonates and mixtures thereof.
- Specific examples include sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediamino-tetraacetic acid, nitrilo-triacetic acid, oxydisuccinic acid, melitic acid, benzene polycarboxylic acids and citric acid, tartrate mono succinate and tartrate di succinate.
- The composition preferably comprises a fluorescent agent (optical brightener). 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. Tinopal DMS pure Xtra and Blankophor (Trade Mark) HRH, and Pyrazoline compounds, e.g. Blankophor SN. Preferred fluorescers are: sodium 2 (4-styryl-3-sulfophenyl)-2H-napthol[1,2-d]triazole, disodium 4,4'-bis{[(4-anilino-6-(N methyl-N-2 hydroxyethyl) amino 1,3,5-triazin-2-yl)]amino}stilbene-2-2' disulfonate, disodium 4,4'-bis{[(4-anilino-6-morpholino-1,3,5-triazin-2-yl)]amino} stilbene-2-2' disulfonate, and disodium 4,4'-bis(2-sulfostyryl)biphenyl.
- It is preferred that the aqueous solution used in the method has a fluorescer present. When a fluorescer is present in the aqueous solution used in the method it is preferably in the range from 0.0001 g/l to 0.1 g/l, preferably 0.001 to 0.02 g/l.
- Preferably 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 %. Many suitable examples of perfumes are provided in the CTFA (Cosmetic, Toiletry and Fragrance Association) 1992 International Buyers Guide, published by CFTA Publications and OPD 1993 Chemicals Buyers Directory 80th Annual Edition, published by Schnell Publishing Co.
- It is commonplace for a plurality of perfume components to be present in a composition. In the compositions of the present invention it is envisaged that there will be four or more, preferably five or more, more preferably six or more or even seven or more different perfume components.
- In perfume mixtures preferably 15 to 25 wt% are top notes. 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.
- It is preferred that the laundry treatment composition does not contain a peroxygen bleach, e.g., sodium percarbonate, sodium perborate, and peracid.
- The composition may comprise one or more other polymers. Examples are carboxymethylcellulose, poly (ethylene glycol), poly(vinyl 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 composition.
- One or more enzymes are preferred present in a composition of the invention and when practicing a method of the invention.
- Preferably the level of each enzyme is from 0.0001 wt% to 0.1 wt% protein.
- Especially contemplated enzymes include proteases, alpha-amylases, cellulases, lipases, peroxidases/oxidases, pectate lyases, and mannanases, or mixtures thereof.
- Suitable lipases include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Examples of useful lipases include lipases from Humicola (synonym Thermomyces), e.g. from H. lanuginosa (T. lanuginosus) as described in
EP 258 068 EP 305 216 WO 96/13580 EP 218 272 EP 331 376 GB 1,372,034 WO 95/06720 WO 96/27002 WO 96/12012 JP 64/744992 WO 91/16422 - Other examples are lipase variants such as those described in
WO 92/05249 WO 94/01541 EP 407 225 EP 260 105 WO 95/35381 WO 96/00292 WO 95/30744 WO 94/25578 WO 95/14783 WO 95/22615 WO 97/04079 WO 97/07202 WO 00/60063 - Preferred commercially available lipase enzymes include Lipolase™ and Lipolase Ultra™, Lipex™, Lipoclean™ (Novozymes A/S).
- The method of the invention may be carried out in the presence of phospholipase classified as EC 3.1.1.4 and/or EC 3.1.1.32. As used herein, the term phospholipase is an enzyme which has activity towards phospholipids.
- Phospholipids, such as lecithin or phosphatidylcholine, consist of glycerol esterified with two fatty acids in an outer (sn-1) and the middle (sn-2) positions and esterified with phosphoric acid in the third position; the phosphoric acid, in turn, may be esterified to an amino-alcohol. Phospholipases are enzymes which participate in the hydrolysis of phospholipids. Several types of phospholipase activity can be distinguished, including phospholipases A1 and A2 which hydrolyze one fatty acyl group (in the sn-1 and sn-2 position, respectively) to form lysophospholipid; and lysophospholipase (or phospholipase B) which can hydrolyze the remaining fatty acyl group in lysophospholipid. Phospholipase C and phospholipase D (phosphodiesterases) release diacyl glycerol or phosphatidic acid respectively.
- The enzyme and the shading dye may show some interaction and should be chosen such that this interaction is not negative. Some negative interactions may be avoided by encapsulation of one or other of enzyme or shading dye and/or other segregation within the product.
- Suitable proteases include those of animal, vegetable or microbial origin. Microbial origin is preferred. Chemically modified or protein engineered mutants are included. The protease may be a serine protease or a metallo protease, preferably an alkaline microbial protease or a trypsin-like protease. Preferred commercially available protease enzymes include Alcalase™, Savinase™, Primase™, Duralase™, Dyrazym™, Esperase™, Everlase™, Polarzyme™, and Kannase™, (Novozymes A/S), Maxatase™, Maxacal™, Maxapem™, Properase™, Purafect™, Purafect OxP™, FN2™, and FN3™ (Genencor International Inc.).
- The method of the invention may be carried out in the presence of cutinase. classified in EC 3.1.1.74. The cutinase used according to the invention may be of any origin. Preferably cutinases are of microbial origin, in particular of bacterial, of fungal or of yeast origin.
- Suitable amylases (alpha and/or beta) include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Amylases include, for example, alpha-amylases obtained from Bacillus, e.g. a special strain of B. licheniformis, described in more detail in
GB 1,296,839 WO 95/026397 WO 00/060060 - Suitable cellulases include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Suitable cellulases include cellulases from the genera Bacillus, Pseudomonas, Humicola, Fusarium, Thielavia, Acremonium, e.g. the fungal cellulases produced from Humicola insolens, Thielavia terrestris, Myceliophthora thermophila, and Fusarium oxysporum disclosed in
US 4,435,307 ,US 5,648,263 ,US 5,691,178 ,US 5,776,757 ,WO 89/09259 WO 96/029397 WO 98/012307 - Suitable peroxidases/oxidases include those of plant, bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Examples of useful peroxidases include peroxidases from Coprinus; e.g. from C. cinereus, and variants thereof as those described in
WO 93/24618 WO 95/10602 WO 98/15257 - Any enzyme present in the composition may be stabilized using conventional stabilizing agents, e.g., a polyol such as propylene glycol or glycerol, a sugar or sugar alcohol, lactic acid, boric acid, or a boric acid derivative, e.g., an aromatic borate ester, or a phenyl boronic acid derivative such as 4-formylphenyl boronic acid, and the composition may be formulated as described in e.g.
WO 92/19709 WO 92/19708 - The indefinite article "a" or "an" and its corresponding definite article "the" as used herein means at least one, or one or more, unless specified otherwise.
- Average molecular weights refer to weight average molecular weights.
- The following liquid compositions were made:
Reference example A Example 1 LAS 4.9 4.9 NI(7EO) 7.3 7.3 SLES(3EO) 2.4 2.4 Carbobetaine 0.9 0.9 Alkyl Betaine 0.9 0.9 1,2-propanediol 15 15 Triethanolamine 2 2 Perfume 1.4 1.4 sulphonated aromatic formaldehyde polycondensate 0 8.7 Water remainder remainder LAS is sodium C11 to C15 alkyl benzene sulphonate.
NI(7EO) is R-(OCH2CH2)nOH, where R is an alkyl chain of C12 to C15, and n is 7. SLES(3EO) is sodium lauryl ether sulfate with 3 ethoxy groups.
The Alkyl Betaine used was Empigen BB (ex Huntsman).
The sulphonated aromatic formaldehyde polycondensate used was TAMOLT™ NN7718 (ex BASF) and is a napthalenesulfonic acid polycondensate sodium salt All values are wt%. - The compositions were used to wash a mixture of white fabrics: woven cotton, knitted cotton, micro-fibre polyester, woven polycotton and knitted nylon-elastane at a Liquor to cloth ratio of 10:1 in a linitester. The fabrics were of equal area. 26° French hard water was used and each wash lasted 30 minutes and was followed by a running rinse. The compositions were used at 2.3g/L. To simulate soiling, soil strips were added to each wash cycle, the weight ratio of soil strips to the white fabrics was 7:1. The soil strips used were SBL 2004 Soil Ballast Fabrics (ex wfk Testgewebe GmbH) and multimix soil ballast fabric (ex CFT Holland) in the weight ratio of 1:2.
- After 5 washes the white clothes were removed, dried and the colour measured using a reflectometer and expressed as the CIE L*a*b* values. The L* values represent the greying of the fabric.
- The results are given for nylon-elastane below:
New Reference example A Example 1 L* 91.1 82.3 89.8 - The liquid containing the napthalenesulfonic acid polycondensate sodium salt maintains the whiteness as shown by the large L* value.
Claims (13)
- A laundry liquid laundry detergent composition comprising:(a) from 0.0001 to 0.01 wt% of a blue or violet shading dye;(b) from 1 to 70 wt% of a surfactant, wherein the surfactant; is a mixture of anionic with nonlonic detergent active materials;(c) from 0.1 to 30 wit% of a sulphonated aromatic formaldehyde polycondensate; and,(d) the remainder of the composition being diluents and adjuncts to 100 wt %.
- A liquid laundry composition according to claim 1. wherein the sulphonated aromatic formaldehyde polycondensate is a haphthalenesulphonic acid formaldehyde polycondensate.
- A liquid laundry composition according to claim 1 or 2, Wherein the sulphonated aromatic formaldehyde polycondensate is an ethoxylated sulphonated aromatic formaldehyde polycondensate.
- A liquid laundry composition according to claim any one of the preceding claims, wherein the sulphonated aromatic formaldehyde polycondensate is substituted by one or more sulfonic acid groups.
- A liquid laundry composition according to claim any one of the preceding claims, wherein the sulphonated aromatic formaldehyde polycondensate is substituted by one or more sulfomethyl groups.
- A liquid laundry composition according to any one of the preceding claims 1, 3, 4 and 5, wherein the sulphonated aromatic formaldehyde polycondensate is obtainable by condensation of a diphenylethersulphonic acid and formaldehyde.
- A liquid laundry composition according to any one of claims 1 to 5, wherein the sulphonated aromatic formaldehyde polycondensate is obtainable by the condensation of toluenesulphonic acids and formaldehyde.
- A liquid laundry composition according to claim 4, wherein the sulphonated aromatic formaldehyde polycondensate is obtainable by condensation product of isopropylbenzenesulphonic acids and formaldehyde.
- A liquid laundry composition according to claim 4, wherein the sulphonated aromatic formaldehyde polycondensate is the condensation product of cresolsulphonic acids and formaldehyde.,
- A liquid laundry composition according to any one of claims 6 to 9, wherein the minimum level of residual formaldehyde from the polycondensation is 200 PPM.
- A liquid laundry composition according to any one of the preceding claims, wherein the shading dyes are selected from: direct dyes, acid dyes, hydrophobic dyes, cationic dyes and reactive dyes.
- A liquid laundry composition according to claim, 11, wherein the Shading dye chromophore is selected from the group comprising; mono-azo, bis-azo, triphenylmethane, triphenodioxazine, phthalocyanin, naptholactam, azine and anthraquinone.
- A method of treating a textile for ameliorating the greying .of nylon-elastane, the textile comprising elastane, the method comprising the steps of:(I) applying the liquid laundry composition to a textile, the liquid laundry composition as defined in any one of claims 1 to 12;(II) rinsing the textile with water; and,(III) optionally drying the textile
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP12735572.5A EP2734610B1 (en) | 2011-07-21 | 2012-07-18 | Liquid laundry composition |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP11174801 | 2011-07-21 | ||
EP12735572.5A EP2734610B1 (en) | 2011-07-21 | 2012-07-18 | Liquid laundry composition |
PCT/EP2012/064120 WO2013011071A1 (en) | 2011-07-21 | 2012-07-18 | Liquid laundry composition |
Publications (2)
Publication Number | Publication Date |
---|---|
EP2734610A1 EP2734610A1 (en) | 2014-05-28 |
EP2734610B1 true EP2734610B1 (en) | 2015-09-09 |
Family
ID=46514401
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP12735572.5A Not-in-force EP2734610B1 (en) | 2011-07-21 | 2012-07-18 | Liquid laundry composition |
Country Status (8)
Country | Link |
---|---|
EP (1) | EP2734610B1 (en) |
CN (1) | CN103857781A (en) |
AR (1) | AR087267A1 (en) |
BR (1) | BR112014001378A2 (en) |
ES (1) | ES2550051T3 (en) |
MX (1) | MX337154B (en) |
WO (1) | WO2013011071A1 (en) |
ZA (1) | ZA201400467B (en) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102013226152A1 (en) * | 2013-12-17 | 2015-06-18 | Henkel Ag & Co. Kgaa | Graying-inhibiting detergents |
DE102013226151A1 (en) * | 2013-12-17 | 2015-06-18 | Henkel Ag & Co. Kgaa | Graying-inhibiting detergents |
DE102013021276A1 (en) * | 2013-12-17 | 2015-06-18 | Clariant International Ltd. | Color protecting detergents |
EP3194541B1 (en) * | 2014-09-18 | 2019-04-24 | Unilever Plc. | Liquid whitening composition |
CN106661504B (en) * | 2014-09-18 | 2019-07-12 | 荷兰联合利华有限公司 | Lightening compositions |
WO2016041670A1 (en) * | 2014-09-18 | 2016-03-24 | Unilever Plc | Whitening composition |
EP3194543B1 (en) * | 2014-09-18 | 2018-04-04 | Unilever Plc. | Whitening composition |
CN107075416A (en) * | 2014-09-18 | 2017-08-18 | 荷兰联合利华有限公司 | Lightening compositions |
Family Cites Families (68)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1163284B (en) | 1960-10-15 | 1964-02-20 | Hoechst Ag | Use of methylenediaryl compounds as dispersants for dyes that are insoluble or difficult to dissolve in water |
DE1469664B2 (en) | 1964-06-01 | 1974-10-24 | Ciba-Geigy Ag, Basel (Schweiz) | Use of condensation products containing sulfonic acid groups as dispersants for dyes that are poorly insoluble in water |
GB1296839A (en) | 1969-05-29 | 1972-11-22 | ||
DE2032926C3 (en) | 1970-07-03 | 1975-11-27 | Hoechst Ag, 6000 Frankfurt | Dispersing agent for the fine distribution and stabilization of dyes and dye preparations |
GB1372034A (en) | 1970-12-31 | 1974-10-30 | Unilever Ltd | Detergent compositions |
DE2165803A1 (en) * | 1971-12-31 | 1973-07-05 | Henkel & Cie Gmbh | Detergents contg sulphonated phenol-formaldehyde resins - as greying inhibitors |
BE795961A (en) | 1972-02-25 | 1973-08-27 | Hoechst Ag | APPLICATION OF SULPHURIC HEMI-ESTERS TO DISPERSION OF COLORANTS |
US3957680A (en) | 1974-08-19 | 1976-05-18 | Mitsui Toatsu Chemicals, Incorporated | Process for the preparation of surface active agents |
DK187280A (en) | 1980-04-30 | 1981-10-31 | Novo Industri As | RUIT REDUCING AGENT FOR A COMPLETE LAUNDRY |
AU556758B2 (en) | 1981-07-13 | 1986-11-20 | Procter & Gamble Company, The | Foaming compositions based on alkylpolysaccharide |
JPH0697997B2 (en) | 1985-08-09 | 1994-12-07 | ギスト ブロカデス ナ−ムロ−ゼ フエンノ−トチヤツプ | New enzymatic detergent additive |
DE3750450T2 (en) | 1986-08-29 | 1995-01-05 | Novo Industri As | Enzyme-based 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 |
ATE125865T1 (en) | 1987-08-28 | 1995-08-15 | Novo Nordisk As | RECOMBINANT HUMICOLA LIPASE AND METHOD FOR PRODUCING 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 |
EP0406314B1 (en) | 1988-03-24 | 1993-12-01 | Novo Nordisk A/S | A cellulase preparation |
US5648263A (en) | 1988-03-24 | 1997-07-15 | Novo Nordisk A/S | Methods for reducing the harshness of a cotton-containing fabric |
US4908149A (en) * | 1988-06-10 | 1990-03-13 | Milliken Research Corporation | Cleaning composition for textiles containing sulfonated colorless dye site blocker |
GB8813978D0 (en) | 1988-06-13 | 1988-07-20 | Unilever Plc | Liquid detergents |
US4874537A (en) * | 1988-09-28 | 1989-10-17 | The Clorox Company | Stable liquid nonaqueous detergent compositions |
GB8824110D0 (en) * | 1988-10-14 | 1988-11-23 | Unilever Plc | Liquid cleaning products |
GB8915658D0 (en) | 1989-07-07 | 1989-08-23 | Unilever Plc | Enzymes,their production and use |
US5427936A (en) | 1990-04-14 | 1995-06-27 | Kali-Chemie Aktiengesellschaft | Alkaline bacillus lipases, coding DNA sequences therefor and bacilli, which produce these lipases |
AU657278B2 (en) | 1990-09-13 | 1995-03-09 | Novo Nordisk A/S | Lipase variants |
EP0511456A1 (en) | 1991-04-30 | 1992-11-04 | The Procter & Gamble Company | Liquid detergents with aromatic borate ester to inhibit proteolytic enzyme |
WO1992019709A1 (en) | 1991-04-30 | 1992-11-12 | The Procter & Gamble Company | Built liquid detergents with boric-polyol complex 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 |
ATE287946T1 (en) | 1993-04-27 | 2005-02-15 | Genencor Int | NEW LIPASE VARIANTS FOR USE IN CLEANING PRODUCTS |
US5380447A (en) * | 1993-07-12 | 1995-01-10 | Rohm And Haas Company | Process and fabric finishing compositions for preventing the deposition of dye in fabric finishing processes |
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 |
WO1995010602A1 (en) | 1993-10-13 | 1995-04-20 | Novo Nordisk A/S | H2o2-stable peroxidase variants |
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. |
BR9507229A (en) | 1994-03-29 | 1997-09-16 | Novo Nordisk As | Amylase detergent additive detergent composition use of a detergent and an amylase construction of a recombinant cell expression vector dna and process to produce amylase |
US6017866A (en) | 1994-05-04 | 2000-01-25 | Genencor International, Inc. | Lipases with improved surfactant resistance |
AU2884595A (en) | 1994-06-20 | 1996-01-15 | Unilever Plc | Modified pseudomonas lipases and their use |
WO1996000292A1 (en) | 1994-06-23 | 1996-01-04 | Unilever N.V. | 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. |
CA2203398A1 (en) | 1994-10-26 | 1996-05-09 | Thomas Sandal | An 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 |
ATE315083T1 (en) | 1995-03-17 | 2006-02-15 | Novozymes As | NEW ENDOGLUCANASE |
WO1997007202A1 (en) | 1995-08-11 | 1997-02-27 | Novo Nordisk A/S | Novel lipolytic enzymes |
AU6414196A (en) | 1995-07-14 | 1997-02-18 | Novo Nordisk A/S | A modified enzyme with lipolytic activity |
CN101085985B (en) | 1996-09-17 | 2012-05-16 | 诺沃奇梅兹有限公司 | Cellulase variants |
WO1998015257A1 (en) | 1996-10-08 | 1998-04-16 | Novo Nordisk A/S | Diaminobenzoic acid derivatives as dye precursors |
US6939702B1 (en) | 1999-03-31 | 2005-09-06 | Novozymes A/S | Lipase variant |
BR0009392B1 (en) | 1999-03-31 | 2012-06-12 | mutant of a polypeptide with alpha-amylase activity, and use of the polypeptide or variant. | |
EP1417025A1 (en) * | 2001-08-13 | 2004-05-12 | The Procter & Gamble Company | Novel oligomeric hydrophobic dispersants and laundry detergent compositions comprising oligomeric dispersants |
GB0314210D0 (en) | 2003-06-18 | 2003-07-23 | Unilever Plc | Laundry treatment compositions |
WO2006024612A1 (en) | 2004-08-30 | 2006-03-09 | Ciba Specialty Chemicals Holding Inc. | Shading process |
GB0420203D0 (en) | 2004-09-11 | 2004-10-13 | Unilever Plc | Laundry treatment compositions |
GB0421145D0 (en) | 2004-09-23 | 2004-10-27 | Unilever Plc | Laundry treatment compositions |
WO2006032397A1 (en) | 2004-09-23 | 2006-03-30 | Unilever Plc | Laundry treatment compositions |
DE102004052007B4 (en) | 2004-10-25 | 2007-12-06 | Müller Weingarten AG | Drive system of a forming press |
MY146614A (en) | 2006-08-10 | 2012-09-14 | Unilever Plc | Shading composition |
PL2192169T3 (en) | 2007-01-19 | 2012-10-31 | Procter & Gamble | Laundry care composition comprising a whitening agents for cellulosic substrates |
WO2008141880A1 (en) | 2007-05-18 | 2008-11-27 | Unilever Plc | Triphenodioxazine dyes |
BRPI0910682B1 (en) | 2008-05-02 | 2020-09-24 | Unilever N.V. | TONING COLORING GRANULES THAT PRODUCE LESS STAINS, AND GRANULAR DETERGENT COMPOSITION FOR WASHING CLOTHES |
EP2300589B1 (en) | 2008-05-20 | 2013-10-23 | Unilever PLC | Shading composition |
ES2422555T3 (en) * | 2008-09-12 | 2013-09-12 | Unilever Plc No 41424 | Substantive elastane dyes |
WO2010084039A1 (en) | 2009-01-26 | 2010-07-29 | Unilever Plc | Incorporation of dye into granular laundry composition |
WO2010099997A1 (en) | 2009-03-05 | 2010-09-10 | Unilever Plc | Dye radical initiators |
BRPI1013881B1 (en) | 2009-03-12 | 2023-10-17 | Unilever Ip Holdings B.V. | DETERGENT COMPOSITION, AND, HOUSEHOLD FABRIC TREATMENT METHOD |
WO2010148624A1 (en) | 2009-06-26 | 2010-12-29 | Unilever Plc | Dye polymers |
CN103210073B (en) | 2010-11-12 | 2016-06-08 | 宝洁公司 | Thiophene azo dye and the laundry care composition comprising them |
-
2012
- 2012-07-18 ES ES12735572.5T patent/ES2550051T3/en active Active
- 2012-07-18 BR BR112014001378A patent/BR112014001378A2/en active Search and Examination
- 2012-07-18 MX MX2014000846A patent/MX337154B/en active IP Right Grant
- 2012-07-18 CN CN201280034599.XA patent/CN103857781A/en active Pending
- 2012-07-18 EP EP12735572.5A patent/EP2734610B1/en not_active Not-in-force
- 2012-07-18 WO PCT/EP2012/064120 patent/WO2013011071A1/en active Application Filing
- 2012-07-20 AR ARP120102647A patent/AR087267A1/en active IP Right Grant
-
2014
- 2014-01-20 ZA ZA2014/00467A patent/ZA201400467B/en unknown
Also Published As
Publication number | Publication date |
---|---|
AR087267A1 (en) | 2014-03-12 |
CN103857781A (en) | 2014-06-11 |
EP2734610A1 (en) | 2014-05-28 |
WO2013011071A1 (en) | 2013-01-24 |
BR112014001378A2 (en) | 2017-03-01 |
MX2014000846A (en) | 2014-10-24 |
MX337154B (en) | 2016-02-15 |
ES2550051T3 (en) | 2015-11-04 |
ZA201400467B (en) | 2015-09-30 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP2734610B1 (en) | Liquid laundry composition | |
EP2714878B1 (en) | Liquid laundry composition | |
EP2534237B1 (en) | Laundry treatment composition comprising bis-azo shading dyes | |
EP3097152B1 (en) | Dye polymer | |
EP2992054B1 (en) | Alkoxylated bis azo dyes | |
US20160215239A1 (en) | Dye polymer | |
EP2714985B1 (en) | Liquid detergent composition containing dye polymer | |
EP2563893B1 (en) | Bis-heterocyclic azo dyes | |
US10501709B2 (en) | Laundry liquid composition | |
US8439980B2 (en) | Shading composition | |
EP2519624B1 (en) | Shading composition | |
EP3256558B1 (en) | Laundry liquid composition | |
EP3256559B1 (en) | Laundry liquid composition | |
EP3402868B1 (en) | Laundry treatment composition |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 20140117 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
DAX | Request for extension of the european patent (deleted) | ||
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R079 Ref document number: 602012010403 Country of ref document: DE Free format text: PREVIOUS MAIN CLASS: C11D0003370000 Ipc: C11D0001830000 |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
RIC1 | Information provided on ipc code assigned before grant |
Ipc: C11D 1/83 20060101AFI20150219BHEP |
|
INTG | Intention to grant announced |
Effective date: 20150313 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: REF Ref document number: 748139 Country of ref document: AT Kind code of ref document: T Effective date: 20150915 Ref country code: CH Ref legal event code: EP |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 602012010403 Country of ref document: DE |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2550051 Country of ref document: ES Kind code of ref document: T3 Effective date: 20151104 |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: MP Effective date: 20150909 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150909 Ref country code: NO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20151209 Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20151210 Ref country code: LV Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150909 Ref country code: LT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150909 |
|
REG | Reference to a national code |
Ref country code: LT Ref legal event code: MG4D |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: MK05 Ref document number: 748139 Country of ref document: AT Kind code of ref document: T Effective date: 20150909 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: RS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150909 Ref country code: SE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150909 Ref country code: HR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150909 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150909 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20160109 Ref country code: CZ Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150909 Ref country code: IT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150909 Ref country code: EE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150909 Ref country code: SK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150909 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: PT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20160111 Ref country code: RO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150909 Ref country code: PL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150909 Ref country code: AT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150909 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 602012010403 Country of ref document: DE |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 5 |
|
26N | No opposition filed |
Effective date: 20160610 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150909 Ref country code: SI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150909 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: TR Payment date: 20160627 Year of fee payment: 5 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20160722 Year of fee payment: 5 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150909 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: ES Payment date: 20160715 Year of fee payment: 5 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MC Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150909 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20160731 Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20160731 |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: MM4A |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 6 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20160718 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20160718 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R119 Ref document number: 602012010403 Country of ref document: DE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20180201 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CY Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150909 Ref country code: HU Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO Effective date: 20120718 Ref country code: SM Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150909 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150909 Ref country code: MT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20160731 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 7 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BG Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150909 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 20181024 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: AL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150909 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20170719 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20190719 Year of fee payment: 8 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20190719 Year of fee payment: 8 |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20200718 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20200731 Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20200718 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: TR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20170718 |