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    • 专利摘要:
    Method for Obtaining a Dye Polymer, Dye Polymer, Washing Composition, and Dye Wash Method, Composition A Textile Product The present invention provides dye polymers for use in clothing applications.
    公开号:BR112012018985B1
    申请号:R112012018985-9
    申请日:2011-01-26
    公开日:2019-11-12
    发明作者:Michelle Bird Jayne；Wang Jinfang；Tao Qingsheng；Meng Sheng；Norman Batchelor Stephen；Chen Wei
    申请人:Unilever Nv；
    IPC主号:
    专利说明:

    The present invention relates to the provision and use of coloring polymers for shading clothing.
    Background of the Invention
    W02006 / 055787 (Procter & Gamble) describes laundry washing formulations containing a cellulose ether polymer covalently bonded to a reactive dye to lighten the cellulosic tissue.
    Summary of the Invention
    Reactive dyes bound to water-soluble polyester polymers (RDPET) were found to deposit well on cotton fabrics in a first wash, without unacceptably large deposition on polyester, cotton, nylon and elastane after multiple washes.
    Anti-dirt benefits are found with RDPETs at surprisingly low levels, which are not seen with PET alone.
    In one aspect, the present invention provides a method for obtaining a dye polymer, the method comprising the step of reacting a polymer with a reactive dye to form a dye polymer, wherein the polymer is comprised of comonomers of a phenyl dicarboxylate, an oxyalkylenoxy and a polyoxyalkylenoxy and the polymer comprises at least one free OH group.
    The present invention also extends to dye polymers obtainable from the method.
    In another aspect, the present invention provides a laundry treatment composition comprising:
    I
    2/19 (i) from 2 to 70% by weight of a surfactant; and, (ii) from 0.0001 to 20.0% by weight of the dye polymer, preferably 0.01 to 5% by weight.
    In another aspect, the present invention provides a method of treating a textile clothing product, the method comprising the steps of:
    (i) treating a textile product with an aqueous solution of the dye polymer, the aqueous solution comprising from 10 ppb to 500 ppm of the dye polymer (preferably 0.1 to 50 ppm, more preferably 0.5 to 20 ppm); and, from 0.0 g / L to 3 g / L, preferably 0.3 to 2 g / L, of a surfactant;
    (ii) optionally rinse; and, (iii) drying the textile product.
    Preferably, the laundry treatment composition is granular and, preferably, the granular composition contains sodium carbonate, with predominantly anionic surfactants, more preferably LAS.
    Detailed Description of the Invention
    Polymer
    Polyesters of terephthalic acids and other aromatic dicarboxylic acids having dirt release properties are widely described in the state of the art, in particular, the so-called PET / POET (polyethylene terephthalate / polyoxyethylene terephthalate) and PET / PEG (polyether terephthalate) polyesters polyethylene / polyethylene glycol), which are described, for example, in US3557039 (ICI), GB1467098 and EP1305A (Procter & Gamble). Other patent publications describing dirt-release polymers, which are products for compensating aromatic dicarboxylic acids and dihydric alcohols, include EP185427A, EP241984A, EP241985A and EP272033A and W092 / 17523 (Procter & Gamble) and WO2009 / 138177 (Clariant ).
    The polymer must have at least one mole of the free OH group per mole of polymer, to allow covalent bonding to the reactive dye (s). More preferably, the polymer comprises at least two free OH groups.
    Preferably, the OH groups are the terminal groups of the polymer.
    3/19
    Preferably, the oxyalkylenoxy [-O (CH 2 ) to -] θ selected from: oxy-1,2-propyleneoxy [-OCH2CH (Me) O-]; oxy-1,3-propyleneoxy [O-CH2CH2CH2O-]; and, oxy-1,2-ethylenoxy [-OCH 2 CH 2 O-] (t is an integer). As is evident, one or more CH 2 groups of the oxyalkylenoxy can be replaced by C 1 to C 4 alkyl group (s).
    Polyoxyalkylenoxy facilitates the polymer's water solubility. Preferably, the polyoxyalkylenoxy [-0 (CH 2 ) w -] S O- is selected from: polyoxy-1,2-propyleneoxy [-O (CH 2 CH (Me) -] s O-; polyoxy-1,3- propylenoxy [OCH 2 CH 2 CH 2 -] S O-; θ, polyoxy-1,2-ethylenoxy [O-CH 2 CH 2 -] S O-; The polyoxyalkylenoxy may be a different mixture of oxyalkylenoxy Different types of polyoxyalkyleneoxy can appear in the polymer, (sew are whole numbers).
    Preferably, the phenyl dicarboxylate is a phenyl 1,4-dicarboxylate. Preferably, the phenyl dicarboxylate is of the form: -OC (O) CeH 4 C (O) O-.
    Examples of preferred polymers that are reacted with the reactive dye are a polymer of PET / POET (polyethylene terephthalate / polyoxyethylene terephthalate), PEG / POET (Polyethylene glycol / polyoxyethylene terephthalate) or PET / PEG (polyethylene terephthalate / polyethylene glycol) ). Most preferably, a PET / POET.
    The structure of a preferred polymer is found below.
    on what
    R 2 is selected from H or CH 3 , preferably H;
    b is 2 or 3, preferably 2;
    y is 2 to 100, preferably 5 to 50;
    nor are they independently 1 to 100, preferably 2 to 30; and, the terminal (final) groups of the polymer are (CH 2 ) bOH.
    4/19
    Polymers can be synthesized by a variety of routes, for example, an esterification reaction of dimethyl terephthalate with ethylene glycol and polyethylene glycol, this reaction is discussed in Polymer Bulletin 28, 451 to 458 (1992). Another example would be the direct esterification of terephthalic acid with ethylene glycol and / or propylene glycol and polypropylene glycol.
    Other examples would be the transesterification of a polyethylene terephthalate with a polyethylene glycol or polypropylene glycol.
    It is preferred that the numerical average molecular weight of the polymer is in the range of 1000 to 50,000, preferably, the average molecular weight of the polymer is in the range of 1000 to 15000, more preferably from 2000 to 10,000.
    Reactive Dyes
    A reactive dye can be considered to be made from a chromophore, which is attached to a reactive group. Reactive dyes undergo addition or substitution reactions with -OH, -SH and -NH 2 groups to form covalent bonds. The chromophore can be linked directly to a reactive group or through a group and bridge. The chromophore serves to provide a color and the reactive group is covalently attached to a substrate.
    Reactive dyes are described in Industrial Dyes (K. Hunger ed, Wiley VCH 2003). Many reactive dyes are listed in the coloring index (Society of Dyes and Colorists and American Association of Textile Chemicals and Colorists).
    Preferred reactive groups for reactive dyes are dichlorotriazinyl, difluorochloropyrimidine, monofluorotrazinyl, dichloroquinoxaline, vinylsulfone, difluorotriazine, monochlorotriazinyl, bromoacrylamide and trichloropyrimidine.
    The most preferred reactive groups are monochlorotriazinyl, dichlorotriazinyl and vinylsulfonyl.
    Chromophores are preferably selected from azo, anthraquinone, phthalocyanine, formazan and trifendioaxazine. More
    5/19 preferably, azo, anthraquinone, phthalocyanine and trifendioaxazine. Most preferably, azo and anthraquinone.
    Reactive dyes are preferably selected from reactive blue, reactive black, reactive red, reactive violet dyes.
    Preferably, reactive dye mixtures are used to provide optimal shading effects. Preferred mixtures are selected from reactive black and reactive red; reactive blue and reactive red; reactive black and reactive violet; reactive blue and reactive violet. Preferably, the number of portions of blue or black dye is in excess of the portions of red or violet dye. Most preferably, a combination of reactive blue and reactive red dyes is used.
    Examples of reactive red dyes are reactive red 21, reactive red 23, reactive red 180, reactive red 198, reactive red 239, reactive red 65, reactive red 66, reactive red 84, 15 reactive red 116, reactive red 136, reactive red 218 , reactive red 228, reactive red 238, reactive red 245, reactive red 264, reactive red 267, reactive red 269, reactive red 270, reactive red 271, reactive red 272, reactive red 274, reactive red 275, red reactive 277, reactive red 278, reactive red 20 280, reactive red 281, reactive red 282.
    Examples of reactive black azo dye are reactive black 5, reactive black 31, reactive black 47, reactive black 49.
    Examples of azo reactive azo blue dyes are reactive blue 59, reactive blue 238, reactive blue 260, reactive blue 265, reactive blue 25 270, reactive blue 27 270, reactive blue 275. Azo reactive blue dyes are preferably bis- azo.
    Examples of reactive blue triphenodioxazine dyes are reactive blue 266, reactive blue 268, reactive blue 269.
    Examples of reactive blue formazan dyes are reactive blue 220 and reactive blue 235.
    6/19 'Examples of preferred phthalocyanine dyes reactive blue are reactive blue 7, reactive blue 11, reactive blue 14, reactive blue 17, reactive blue 18, reactive blue 21, reactive blue 23, reactive blue 25, reactive blue 30, reactive blue 35, reactive blue 38, reactive blue 41, reactive blue 71, reactive blue 72.
    Preferably, the reactive blue anthraquinone dye is in the following form:
    where R is an organic group that contains a reactive group. Preferably, R is selected from: monochlorotriazinyl; dichlorotriazinyl and vinylsulfonyl.
    Preferred reactive blue dyes are selected from: Reactive blue 2; Reactive blue 4; Reactive blue 5; Reactive blue 19; Reactive blue 27; Reactive blue 29; Reactive blue 36; Reactive blue 49; Reactive Blue 50 and Reactive Blue 224.
    Preferably, the reactive azo red dye is a reactive red monoazo dye and the preferred reactive red monoazo dye is as follows:
    wherein ring A is unsubstituted or substituted by a sulfonate group or a reactive group. Preferably, ring A is naphthyl and is replaced by two sulfonate groups.
    7/19
    Preferably, D is an organic group that contains a reactive group. Preferred reactive groups are monochlorotriazinyl; dichlorotriazinyl and vinylsulfonyl.
    The preferred reactive red dyes are selected from: Reactive red 1; Reactive red 2; Reactive red 3; Reactive red 12; Reactive red 17; Reactive red 24; Reactive red 29; Reactive red 83; Reactive red 88; Reactive red 120; Reactive red 125; Reactive red 194; Reactive red 189; Reactive red 198; Reactive red 219; Reactive red 220; Reactive red 227; Reactive red 241; Reactive red 261 and Reactive red 253.
    The dye polymer has a solubility in water at 20 ° C of at least 0.1 mg / L.
    Other Dyes
    In a preferred embodiment of the invention, other shade colors may be present. They are preferably selected from blue and violet pigment such as violet pigment 23, solvent and dispersed dyes such as violet solvent 13, dispersed violet 28, bis-azo direct dyes such as direct violet 9, 35, 51 and 99, and direct triphenodioxazine dyes such as direct violet 54.
    Even more preferred is the presence of acid azine dyes as described in WO 2008/017570; the level of acid azine dyes should be in the range of 0.0001 to 0.1% by weight. Acid azine dyes provide benefit predominantly for pure cotton garments and phenazine cationic dyes for polyalcotton garments. Preferred azine acid dyes are violet acid 50, blue acid 59 and blue acid 98. The cationic phenazine blue and violet dyes may also be present.
    Photo-bleaches such as sulfonated Zn / AI phthalocyanines may be present.
    Surfactant
    8/19 —— ^ A ^ COMPOstTION - pãfãToupa comprises between 2 to 70 weight percent of a surfactant, more preferably 10 to 30 weight percent. In general, the nonionic and anionic surfactants in the surfactant system can be chosen from the surfactants described in “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 Ed., Carl Hauser Verlag, 1981. Preferably the surfactants used are saturated.
    Suitable non-ionic detergent compounds, which can be used, include, in particular, the reaction products of the compounds having a hydrophobic group and a reactive hydrogen atom, for example, aliphatic alcohols, acids, amides or alkyl phenols with oxides of alkylene, especially ethylene oxide either alone or with propylene oxide. The specific non-ionic detergent compounds are condensed from C 8 to C 22 alkyl phenol-ethylene oxide, generally 5 to 25 EO, that is, 5 to 25 ethylene oxide units per molecule, and the condensation products from Cs to Ci 8 primary or secondary aliphatic alcohols, linear or branched 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 sulfates and sulfonates 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 sulfates, especially those obtained by sulfating C 8 to C 8 higher alcohols, produced, for example, from tallow or coconut oil, Cg to C20 alkyl benzene sulfonates of sodium or potassium, particularly Cw to C15 linear secondary sodium benzene sulfonate and sodium alkyl glyceryl ether sulfates, especially those higher alcohol ethers derived from tallow or coconut oil and synthetic petroleum derivatives. The
    9/19 preferred anionic detergent compounds are Cn to C15 alkyl benzene sulfonates and sodium C 2 to C 8 alkyl sodium sulfates. Also applicable are 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.
    The preferred surfactant systems are mixtures of anionic with nonionic detergent active materials, in particular the groups and examples of anionic and nonionic surfactants mentioned in EP-A-346 995 (Unilever). Especially preferred is the surfactant system which is a mixture of an alkali metal salt of a Ci 6 to Ci 8 primary alcohol sulfate with “a C 12 to C 15 primary alcohol 3 to 7 EO ethoxylate.
    The non-ionic detergent is preferably present in amounts less than 50% by weight, more preferably less than 20% by weight of the surfactant system. Anionic surfactants can be present, for example, in amounts in the range of about 50% to 100% by weight of the surfactant system.
    In another aspect that is also preferred, the surfactant can be a cationic, so that the formulation is a fabric softener.
    Cationic Compound
    When the present invention is used as a fabric softener, it is necessary to contain a cationic compound.
    Most preferred are quaternary ammonium compounds.
    It is advantageous if the quaternary ammonium compound is a quaternary ammonium compound having at least one C 2 to C 22 alkyl chain.
    It is preferred if the quaternary ammonium compound has the following formula:
    R2
    I +
    R1-N-R3 X
    I
    R4 ή where R is a C 2 to C 2 2 alkyl or alkenyl chain; R 2 , R 3 and R 4 are independently selected from C 1 to C 4 alkyl chains and X is a compatible anion. A preferred compound of this type is
    10/19 quaternary ammonium compound, quaternary ammonium cetyl trimethyl bromide.
    A second class of materials for use with the present invention is the quaternary ammonium of the above structure in which R 1 and R 2 are independently selected from a chain of C12 θ C22 alkyl or alkenyl; R 3 and R 4 are independently selected from chains of C1 to C4 alkyl and X 'is a compatible anion.
    A detergent composition according to claim 1, wherein the ratio of (ii) cationic material to (iv) anionic surfactant is at least 2: 1.
    Other suitable quaternary ammonium compounds are described in EP0239910 (Procter and Gamble).
    It is preferred if the ratio of cationic to nonionic surfactant is 1: 100 to 50:50, more preferably 1:50 to 20:50.
    The cationic compound can be present from 1.5% by weight to 50% by weight of the total weight of the composition. Preferably, the cationic compound can be present from 2% by weight to 25% by weight, a more preferred composition range is 5% by weight to 20% by weight.
    The softening material is preferably present in an amount of 2 to 60% by weight of the total composition, more preferably from 2 to 40%, 0 more preferably from 3 to 30% by weight.
    The composition optionally comprises a silicone.
    Builders or Complexing Agents
    The building materials can be selected from 1) calcium scavenging materials, 2) precipitation materials, 3) calcium ion exchange materials and 4) their mixtures.
    Examples of calcium-scavenging building materials include alkali metal polyphosphates, such as sodium tripolyphosphate and organic scavengers, such as ethylene diamine tetraacetic acid.
    11/19
    Examples of precipitation-building materials include sodium orthophosphate and sodium carbonate.
    Examples of calcium ion exchange building materials include the various types of water-insoluble amorphous or crystalline aluminosilicates, of which zeolites are the most well-known representatives, for example, zeolite A, zeolite B (also known as zeolite P), zeolite C, zeolite X, zeolite Y and also zeolite type P as described in EP-A-0.384.070.
    The composition can also contain from 0 to 65% of a builder or complexing agent, such as an ethylene diaminetetraacetic acid, diethylenetriamineapentaacetic acid, alkyl or alkenyl succinic acid, nitrilotriacetic acid or the other builders mentioned below. Many builders are also bleach-stabilizing agents because of their ability to complex metal ions.
    Zeolite and carbonate (carbonate (including bicarbonate and sesquicarbonate)) are preferred builders.
    The composition may contain as a builder a crystalline aluminum silicate, preferably an alkali metal aluminum silicate, more preferably a sodium aluminum silicate. This is typically present at a level of less than 15% by weight. Aluminosilicates are materials having the general formula:
    0.8-1.5 M 2 O. Ahos. 0.8-6 SiO 2 where M is a monovalent cation, preferably sodium. These materials contain little limited water and are required to have a calcium ion exchange capacity of at least 50 mg of CaO / g. Preferred sodium aluminosilicates contain 1.5-3.5 SiO 2 units in the above formula. They can be prepared quickly by the reaction between sodium silicate and sodium aluminate, as widely described in the literature. The ratio of surfactants to aluminosilicate (where present) is preferably greater than 5: 2, more preferably greater than 3: 1.
    Alternatively or in addition to aluminosilicate builders, phosphate builders can be used. In this technique, the term phosphate ”
    12/19 includes a variety of diphosphate, triphosphate and phosphonate. Other forms of builder include silicates, such as soluble silicates, metasilicates, layered silicates (eg Hoechst SKS-6).
    Preferably, the laundry detergent formulation is a laundry detergent formulation constructed of non-phosphate, that is, it contains less than 1% by weight of phosphate. Preferably, the laundry detergent formulation is constructed of carbonate.
    Fluorescent Agent
    The composition preferably comprises a fluorescent agent (optical brightener). Fluorescent agents are well known and many of these fluorescent agents are commercially available. Usually, these fluorescent agents are supplied and used in the form of their alkali metal salts, for example, sodium salts. The total amount of the fluorescent agent (s) used in the composition is generally from 0.005 to 2% by weight, more preferably 0.01 to 0.1% by weight. The preferred classes of fluorescents are: biphenyl di-styryl compounds, for example, Tinopal (Trademark) CBS-X, disulfonic stilbene diamine compounds, for example, Pure Tinopal DMS Xtra and Blankophor (Trademark) HRH, and pyrazoline compounds , for example, Blankophor SN. Preferred fluorescents are: 2 (4-styryl-3-sulfophenyl) -2H-naptol [1,2-d] sodium triazole, 4,4'bis {[(4-aniline-6- (N methyl-N- 2 hydroxyethyl) amino1,3,5-triazin-2-yl)] amino} disodium stybene-2-2'disulfonate, 4,4'-bis {[(4-anilino-6-morpholino-1,3,5triazin -2-yl)] amino} stilbene-2-2 'disodium disulfonate and disodium 4,4'-bis (2sulfostyryl) biphenyl.
    It is preferred that the aqueous solution used in the method has a fluorescent present. When a fluorescent is present in the aqueous solution used in the method, it will preferably be in the range of 0.0001 g / l to 0.1 g / l, preferably 0.001 to 0.02 g / l.
    perfume
    13/19
    Preferably, the composition comprises a perfume. The perfume is preferably in the range of 0.001 to 3% by weight, most preferably from 0.1 to 1% by weight. Many suitable examples of perfumes are provided in the 1992 CTFA (Cosmetics, Personal Care and Fragrance Association) International Buyers Guide, published by CFTA Publications and the 1993 Annual Edition of the 80th OPD Chemical Buyers Directory, published by Schnell Publishing Co.
    It is common for a plurality of perfume components to be present in a formulation. 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% by weight are higher grades. The top marks are defined by Poucher (Journal of the Society of Cosmetic Chemicals 6 (2): 80 [1955]). Preferred top notes are selected from citrus oils, linalool, linalyl acetate, lavender, dihydromyrcenol, rose oxide and cis-3-hexanol.
    The perfume and the top note can be used to benefit from the whiteness of the invention.
    It is preferred that the laundry treatment composition does not contain a peroxygen bleach, for example, sodium percarbonate, sodium perborate and peracid.
    Other Polymers
    The composition can comprise one or more other polymers. Examples are carboxymethylcellulose, poly (ethylene glycol), poly (vinyl alcohol), polycarboxylates such as polyacrylates, maleic acid / acrylic 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.
    14/19
    Enzymes
    One or more enzymes are preferably 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% by weight to 0.1% by weight of protein.
    Especially contemplated enzymes include proteases, alphaamtlases, cellulases, lipases, peroxidases / oxidases, pectate lyases and mannanases or mixtures thereof.
    Suitable lipases include those of bactericidal or fungal origin. Protein engineered or chemically modified mutants are included. Examples of useful lipases include Humicola lipases (synonym Thermomyces), for example, H. lanuginosa (T. lanuginosus), as described in EP258068 and EP305216 or H. insolens as described in WO 96/13580, a Pseudomonas lipase, for example example, from P. alcaligenes or P. pseudoalcaligenes (EP218272), P. cepacia (EP331376), P. stutzeri (GB 1,372,034), P. fluorescens, strain SD 705 from Pseudomonas sp. (WO 95/06720 and WO 96/27002), P. wisconsinensis (WO 96/12012), a Bacillus lipase, for example, from B. subtilis (Dartois et al. (1993), Biochemica et Biophysica Acta, 1131, 253 -360), B. stearothermophilus (JP 64/744992) or B. pumilus (WO 91/16422).
    Other examples are lipase variants such as those described in WO92 / 05249, WO94 / 01541, EP407225, EP260105, WO95 / 35381, W096 / 00292, WO95 / 30744, WO94 / 25578, WO95 / 14783, WO95 / 22615, W097 / 04079 and W097 / 07202, WO00 / 60063.
    Preferred commercially available lipase enzymes include Lipolase® and Lipolase Ultra®, Lipex® (Novozymes A / S).
    The method of the invention can be carried out in the presence of phospholipase classified as EC 3.1.1.4 and / or EC 3.1.1.32. As used here, the term phospholipase is an enzyme that has activity with respect to phospholipids. Phospholipids, such as lecithin or phosphatidylcholine, consist of glycerol esterified with two fatty acids in an exit (sn-1) and middle position
    15/19 (sn-2), and esterified with phosphoric acid in the third position; phosphoric acid, in turn, can be esterified to an amino alcohol. Phospholipases are enzymes that participate in the hydrolysis of phospholipids. Several types of phospholipase activity can be distinguished, including phospholipases Ai and A 2 that hydrolyze a group of acyl grease (in the sn-1 and sn-2 positions, respectively) to form a lysophospholipid; and lysophospholipase (or phospholipase B) which can hydrolyze the remaining acyl grease group in the lysophospholipid. Phospholipase C and phospholipase D (phosphodiesterases) release diacyl glycerol or phosphatidic acid, respectively.
    The enzyme and shading dye may show some interaction and should be chosen so that this interaction is not negative. Some negative interactions can be avoided by encapsulating one or another enzyme or shading dye and / or other segregation within the product.
    Suitable proteases include those of animal, vegetable or microbial origin. The microbial origin is preferred. Protein engineered or chemically modified mutants are included. The protease can be a serine protease or a metal protease, preferably an alkaline microbial protease or a trypsin-like protease. 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 can be carried out in the presence of cutinase, classified in EC 3.1.1.74. The cutinase used according to the invention can be of any origin. Preferably, the cutinases are of microbial origin, in particular of bactericidal, fungal or yeast origin.
    Suitable amylases (alpha and / or beta) include those of bacterial or fungal origin. Protein engineering or chemically modified mutants are included. Amylases include, for example, alpha-amylases obtained from Bacillus, for example, a special strain of B.
    16/19
    Víefrentfbrmís ^ escTite ^ in GB 1296839, or the strains Bacillus sp. described in WO95 / 026397 or WO00 / 060060. The commercially available amylases are Duramyl®, Termamyl®, Termamyl Ultra®, Natalase®, Stainzyme®, Fungamyl® and BAN® (Novozymes A / S), Rapidase® and Purastar® (from Genencor International Inc.).
    Suitable cellulases include those of bactericidal or fungal origin. Protein engineered or chemically modified mutants are included. Suitable cellulase include cellulases of the genera Bacillus, Pseudomonas, Humicola, Fusarium, Thielavia, Acremonium, for example, fungal cellulase produced from Humicola insolens, Thielavia terrestris, Myceliophthora thermophila, and Fusarium oxisporum described in US4435307, US56482675, US56482675, US5648263, US5648263, US56482675, US5648263 / 09259,
    WO96 / 029397, and W098 / 012307. Commercially available cellulases include Celluzyme®, Carezyme®, Endolase®, Renozyme® (Novozymes A / S), Clazinase® and Puradax HA® (Genencor International Inc.), and KAC-500 (B) ® (Kao Corporation).
    Suitable peroxidases / oxidases include those of plant, bactericidal or fungal origin. Protein engineered or chemically modified mutants are included. Examples of useful peroxidases include Coprinus peroxidases, for example, C. cinereus, and variants thereof such as those described in WO93 / 24618, WO95 / 10602, and WO98 / 15257. Commercially available peroxidases include Guardzyme® and Novozym® 51004 (Novozymes A / S).
    Enzyme Stabilizers
    Any enzyme present in the composition can be stabilized using conventional stabilizing agents, for example, a polyol such as propylene glycol or glycerol, a sugar or sugar alcohol, lactic acid, boric acid or a boric acid derivative, for example, an ester of aromatic borate, or a derivative of phenyl boronic acid such as 4-formylphenyl acid
    17/19 boromic, and the composition can be formulated as described in, for example, WO92 / 19709 and WO92 / 19708.
    Where the alkyl groups are long enough to form cyclic or branched chains, the alkyl groups encompass cyclic, linear and branched alkyl chains. The alkyl groups are preferably linear or branched, most preferably linear. The indefinite article "one" or "one" and its corresponding definite article "o", as used here, means at least one, or one or more, unless otherwise specified.
    Experimental
    Example 1: Synthesis of Polymer Dye
    A PET / POET polymer was synthesized with a numerical average molecular weight of 4,900 and a PET to POET ratio of 1: 2.
    0.5 g of PET POET polymer, 0.5 g of Na2CO3 and 0.1 g of reactive dye were mixed together in 35 ml of demineralized water and heated at 80 ° C for 5 hours.
    Following the reaction, the product was dialyzed against water (COMW = 3500) for 72 hours. The water was then removed by rotary evaporation. The resulting polymer was dried in vacuo.
    Example 2: Washing performance
    The woven cotton, polyester and nylon-elastane fabrics were washed in an aqueous washing solution (demineralized water) containing 1 g / L of linear alkyl benzene sulfonate, 1 g / L of sodium carbonate and 1 g / L of chloride sodium in a liquor for cloth ratio of 30: 1. For the shading of the washing solution, the polymers of example 1 were added so that the washing solution contained 5 ppm of polymer. After 30 minutes of shaking, the clothes were rinsed and dried. The washes were then repeated until 4 wash cycles were performed. After 2 to 4 and the washing of clothes reflectance spectra were measured on reflectometer and the color expressed as CIE L * a * b *.
    The increase in whiteness of clothing was expressed as the change in blue:
    18/19
    Ab b — b C ontrol b po | dye ion
    The results are given in the table below
    Polymer Ab washing 4 Polyester Cotton Nylon-spandex PET POET-RB4 0.3 0.5 0.0
    The PET POET dye polymer shows good deposition on cotton and also on polyester.
    Example 3: Polymer Dye with Reactive Blue and Red Dye
    Reactive
    0.07 g of reactive blue 4 and 0.03 g of reactive red 3 were mixed with 1 g of a PET POET polymer, TexCare SRN-300 (ex Clariant) in a manner analogous to example 1, except for the reaction that was conducted at 65 ° C for 6 hours.
    The washes were carried out with the dye polymer following the protocol of example 2 and the results are given in the table below:
    Polymer Washing Ab 2 Polyester Cotton Nylon-spandex SRN 0.1 0.9 0.0 300 / RB4 / RR2
    The dye polymer shows good deposition on cotton fabrics.
    Example 4: Dirt Anti-Replenishment Benefits
    Squares of white cotton fabrics 4 fabrics and 4 knitted fabrics (15x15cm) were washed in a liquor: clothes 25: 1 in a thermometer in water at 26 ° F with 4 g / L of a laundry detergent powder that contained 15% of a linear alkyl benzene sulfonate (LAS) surfactant, 30% Na2CO3, 40% NaCI, remaining minor ones included calcite and flourescenders and moisture. For the washing liquor, 1 ppm of the required polymer was added.
    The clothes were dried, then the washes repeated four times, with the addition of new dirt test strips for each wash. The subject strips used were 4 x SBL 2004 Soil Ballast Fabrics (ex wfk Testgewebe
    19/19
    -GrnbFTGermany) and ~ 2 ”5c multimix soil ballast fabric (ex CFT Holland). All strips of subject were pieces of 7.5x15cm in cotton.
    After washing, the reflectance at 740 nm of the initially white cotton fabrics was measured on a reflectometer.
    The values are shown in the table below:
    Woven cotton Knitted cotton Non-polymer control 84.5 85.9 SRN300 84.0 85.3 SRN 300 / RB4 / RR2 87.7 88.0
    The white cotton fabric washed in the dye polymer has significantly higher reflectance than the control or those washed in the dye-free polymer. This is because the dirt released from the dirt strips deposits less on the white cotton fabric due to the dye polymer.
    The dye polymer is effective in preventing dirt repositioning at low levels in the wash.
    权利要求:
    Claims (10)
    [1]
    1. Method for obtaining a dye polymer, the method characterized by the step of reacting a polymer with a reactive dye to form the dye polymer, in which the polymer is comprised of comonomers of a phenyl dicarboxylate, an oxyalkylenoxy and a polyoxyalkylenoxy and the polymer comprises at least one free OH group.
    [2]
    2/3

    where R 2 is selected from H or CH 3 ;
    b is 2 or 3;
    y is 2 to 100;
    Method for obtaining a dye polymer according to claim 1, characterized in that the polymer comprises at least two free OH groups.
    [3]
    3/3 (ii) from 0.0001% to 20.0% by weight of the dye polymer as defined in claim 12.
    Composition according to Claim 13, characterized in that the treatment of clothing is granular.
    3. Method for obtaining a dye polymer according to claim 1 or 2, characterized in that the oxyalkylenoxy is selected from: oxy-1,2-propyleneoxy; oxy-1,3-propyleneoxy; and, oxy-1,2-ethylenoxy.
    [4]
    Method for obtaining a dye polymer according to any one of claims 1 to 3, characterized in that the polyoxyalkylenoxy is selected from: polyoxy-1,2-propyleneoxy; polyoxy-1,3-propyleneoxy; and, polyoxy-1,2-ethylenoxy.
    [5]
    5 15. Method of washing a textile product, the method characterized by comprising the steps of:
    (i) treating a textile product with an aqueous solution of the dye polymer as defined in claim 12, the aqueous solution comprising from 10 ppb to 500 ppm of the dye polymer and from 0.0 g / L to 3 g / L of a surfactant ;
    5 nor are they independently selected from 1 to 100; and, terminal groups of the polymer are (CH 2 ) b OH.
    Method for obtaining a dye polymer according to any one of claims 1 to 4, characterized in that the phenyl dicarboxylate is a phenyl 1,4-dicarboxylate.
    [6]
    Method for obtaining a dye polymer according to claim 5, characterized in that the polymer is polyoxyethylene terephthalate polyoxyethylene.
    [7]
    7. Method for obtaining a dye polymer, according to claim 1, characterized in that the polymer is selected from:
    [8]
    8. Method for obtaining a dye polymer according to claim 1, characterized in that the reactive group of the reactive dye is selected from: dichlorotriazinyl; difluorochloropyrimidine; monofluorotrazinyl;
    10 dichloroquinoxaline; vinylsulfone; difluorotriazine; monochlorotriazinyl; bromoacrylamide, and trichloropyrimidine.
    [9]
    9. Method for obtaining a dye polymer, according to claim 1, characterized in that the chromophore of the reactive dye is selected from: azo; anthraquinone; phthalocyanine; formazan; and,
    15 trifendioxazine.
    10. Method for obtaining a dye polymer, according to claim 1, characterized by the chromophores of the reactive dye being selected from: azo; and, anthraquinone.
    11. Method for obtaining a dye polymer, according to
    Any one of claims 2 to 10, characterized in that the polymer is reacted with reactive red dye and a reactive blue dye, wherein when the weight ratio of the blue dye: red dye is 10: 1 to 10: 4.
    Dye polymer obtainable from the method as defined in any one of claims 1 to 11.
    13. Washing composition, characterized by comprising:
    (i) from 2% to 70% by weight of a surfactant; and,
    [10]
    (Ii) optionally rinse; and, (iii) drying the textile product.
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    同族专利:
    公开号 | 公开日
    CN102741357B|2014-05-28|
    AR080147A1|2012-03-14|
    CL2012002194A1|2013-01-25|
    EP2534206A1|2012-12-19|
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    BR112012018985A2|2017-10-10|
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    CN102741357A|2012-10-17|
    ZA201205562B|2013-09-25|
    WO2011098355A1|2011-08-18|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    DE1155203B|1958-12-19|1963-10-03|Du Pont|Process for the preparation of polymeric dyes with a chain-like molecular structure|
    GB1088984A|1963-06-05|1967-10-25|Ici Ltd|Modifying treatment of shaped articles derived from polyesters|
    GB1296839A|1969-05-29|1972-11-22|
    GB1372034A|1970-12-31|1974-10-30|Unilever Ltd|Detergent compositions|
    US3959230A|1974-06-25|1976-05-25|The Procter & Gamble Company|Polyethylene oxide terephthalate polymers|
    US3962152A|1974-06-25|1976-06-08|The Procter & Gamble Company|Detergent compositions having improved soil release properties|
    US4116885A|1977-09-23|1978-09-26|The Procter & Gamble Company|Anionic surfactant-containing detergent compositions having soil-release properties|
    DK187280A|1980-04-30|1981-10-31|Novo Industri As|RUIT REDUCING AGENT FOR A COMPLETE LAUNDRY|
    GR76189B|1981-07-13|1984-08-03|Procter & Gamble|
    DE3147153A1|1981-11-27|1983-06-01|Bayer Ag, 5090 Leverkusen|COLORING PROCEDURE|
    DE3585505D1|1984-12-21|1992-04-09|Procter & Gamble|BLOCK POLYESTER AND SIMILAR COMPOUNDS, USED AS A DETOIL REMOVER IN DETERGENT COMPOSITIONS.|
    US4933287A|1985-08-09|1990-06-12|Gist-Brocades N.V.|Novel lipolytic enzymes and their use in detergent compositions|
    GB2188653A|1986-04-02|1987-10-07|Procter & Gamble|Biodegradable fabric softeners|
    US4713194A|1986-04-15|1987-12-15|The Procter & Gamble Company|Block polyester and like compounds having branched hydrophilic capping groups useful as soil release agents in detergent compositions|
    US4711730A|1986-04-15|1987-12-08|The Procter & Gamble Company|Capped 1,2-propylene terephthalate-polyoxyethylene terephthalate polyesters useful as soil release agents|
    DE3750450T2|1986-08-29|1995-01-05|Novo Industri As|Enzyme-based detergent additive.|
    NZ221627A|1986-09-09|1993-04-28|Genencor Inc|Preparation of enzymes, modifications, catalytic triads to alter ratios or transesterification/hydrolysis ratios|
    GB8629936D0|1986-12-15|1987-01-28|Procter & Gamble|Laundry compositions|
    ES2076939T3|1987-08-28|1995-11-16|Novo Nordisk As|RECOMBINANT LUMPY OF HUMICOLA AND PROCEDURE FOR THE PRODUCTION OF RECOMBINANT LIPAS OF HUMICOLA.|
    JPS6474992A|1987-09-16|1989-03-20|Fuji Oil Co Ltd|Dna sequence, plasmid and production of lipase|
    GB8803036D0|1988-02-10|1988-03-09|Unilever Plc|Liquid detergents|
    JP3079276B2|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|
    JP2728531B2|1988-03-24|1998-03-18|ノボノルディスクアクティーゼルスカブ|Cellulase preparation|
    US5776757A|1988-03-24|1998-07-07|Novo Nordisk A/S|Fungal cellulase composition containing alkaline CMC-endoglucanase and essentially no cellobiohydrolase and method of making thereof|
    GB8813978D0|1988-06-13|1988-07-20|Unilever Plc|Liquid detergents|
    CA2001927C|1988-11-03|1999-12-21|Graham Thomas Brown|Aluminosilicates and detergent compositions|
    GB8915658D0|1989-07-07|1989-08-23|Unilever Plc|Enzymes,their production and use|
    GB8916941D0|1989-07-25|1989-09-13|Berol Limited|Improvements in or relating to water-soluble dyestuffs suitable as inks|
    EP0528828B2|1990-04-14|1997-12-03|Genencor International GmbH|Alkaline bacillus lipases, coding dna sequences therefor and bacilli which produce these lipases|
    WO1992005249A1|1990-09-13|1992-04-02|Novo Nordisk A/S|Lipase variants|
    CA2106217A1|1991-03-28|1992-09-29|Robert Y. L. Pan|Nonionic soil release agents|
    DE69209500T2|1991-04-30|1996-10-31|Procter & Gamble|SCAFFOLDED LIQUID DETERGENTS WITH BORIC ACID-POLYOL COMPLEX FOR PTOTEOLYTIC ENZYMIN INHIBITION|
    EP0511456A1|1991-04-30|1992-11-04|The Procter & Gamble Company|Liquid detergents with aromatic borate ester to inhibit proteolytic enzyme|
    DK72992D0|1992-06-01|1992-06-01|Novo Nordisk As|ENZYME|
    DK88892D0|1992-07-06|1992-07-06|Novo Nordisk As|CONNECTION|
    AT287946T|1993-04-27|2005-02-15|Genencor Int|NOVEL LIPASE VARIATIONS FOR USE IN DETERGENTS|
    JP2859520B2|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|
    EP0724631A1|1993-10-13|1996-08-07|Novo Nordisk A/S|H 2?o 2?-stable peroxidase variants|
    JPH07143883A|1993-11-24|1995-06-06|Showa Denko Kk|Lipase gene and mutant lipase|
    WO1995022615A1|1994-02-22|1995-08-24|Novo Nordisk A/S|A method of preparing a variant of a lipolytic enzyme|
    MX196038B|1994-03-29|2000-04-14|Novo Nordisk As|Alkaline bacillus amylase.|
    EP0755442B1|1994-05-04|2002-10-09|Genencor International, Inc.|Lipases with improved surfactant resistance|
    WO1995035381A1|1994-06-20|1995-12-28|Unilever N.V.|Modified pseudomonas lipases and their use|
    AU2884695A|1994-06-23|1996-01-19|Unilever Plc|Modified pseudomonas lipases and their use|
    BE1008998A3|1994-10-14|1996-10-01|Solvay|Lipase, microorganism producing the preparation process for the lipase and uses thereof.|
    KR970707275A|1994-10-26|1997-12-01|안네 제케르|An enzyme having lipolytic activity |
    JPH08228778A|1995-02-27|1996-09-10|Showa Denko Kk|New lipase gene and production of lipase using the same|
    CN102080070B|1995-03-17|2016-01-20|诺沃奇梅兹有限公司|new endoglucanase|
    DE69633825T2|1995-07-14|2005-11-10|Novozymes A/S|Modified enzyme with lipolytic activity|
    ES2221934T3|1995-08-11|2005-01-16|Novozymes A/S|NEW LIPOLITIC ENZYMES.|
    CN100362100C|1996-09-17|2008-01-16|诺沃奇梅兹有限公司|Cellulase variants|
    WO1998015257A1|1996-10-08|1998-04-16|Novo Nordisk A/S|Diaminobenzoic acid derivatives as dye precursors|
    US5766268A|1997-03-13|1998-06-16|Milliken Research Corporation|Poly-substituted colorant|
    BR0009392B1|1999-03-31|2012-06-12|mutant of a polypeptide with alpha-amylase activity, and use of the polypeptide or variant.|
    US6939702B1|1999-03-31|2005-09-06|Novozymes A/S|Lipase variant|
    WO2001038467A2|1999-11-29|2001-05-31|Rhodia, Inc.|Composition for cleaning carpets, curtains and covering fabrics and/or for facilitating the removal of stains|
    US7686892B2|2004-11-19|2010-03-30|The Procter & Gamble Company|Whiteness perception compositions|
    MY146614A|2006-08-10|2012-09-14|Unilever Plc|Shading composition|
    DE102008023803A1|2008-05-15|2009-11-26|Clariant International Ltd.|Additives for detergents and cleaners|EP2540824A1|2011-06-30|2013-01-02|The Procter & Gamble Company|Cleaning compositions comprising amylase variants reference to a sequence listing|
    EP2551335A1|2011-07-25|2013-01-30|The Procter & Gamble Company|Enzyme stabilized liquid detergent composition|
    WO2013025742A1|2011-08-15|2013-02-21|The Procter & Gamble Company|Detergent compositions containing pyridinol-n-oxide compounds|
    WO2013043855A2|2011-09-20|2013-03-28|The Procter & Gamble Company|High suds detergent compositions comprising isoprenoid-based surfactants|
    MX2014003280A|2011-09-20|2014-05-13|Procter & Gamble|Detergent compositions comprising sustainable surfactant systems comprising isoprenoid-derived surfactants.|
    US20130072415A1|2011-09-20|2013-03-21|The Procter & Gamble Company|DETERGENT COMPOSITIONS COMPRISING SPECIFIC BLEND RATIOS of ISOPRENOID-BASED SURFACTANTS|
    CA2849478A1|2011-09-20|2013-03-28|The Procter & Gamble Company|Detergent compositions comprising primary surfactant systems comprising highly branched surfactants especially isoprenoid - based surfactants|
    AR088758A1|2011-09-20|2014-07-02|Procter & Gamble|EASY DETERGENT COMPOSITIONS RINSE THAT UNDERSTAND ISOPRENOID BASED SURFACTANTS|
    KR20140091045A|2011-11-10|2014-07-18|캐논 가부시끼가이샤|Novel compound having bisazo dye skeleton, pigment composition containing the same, pigment dispersion, ink, and color filter resist composition|
    US9176407B2|2011-11-10|2015-11-03|Canon Kabushiki Kaisha|Toner and method for manufacturing toner particles|
    JP2015530424A|2012-07-26|2015-10-15|ザ プロクター アンド ギャンブルカンパニー|Low pH liquid cleaning composition with enzyme|
    EP2712915A1|2012-10-01|2014-04-02|The Procter and Gamble Company|Methods of treating a surface and compositions for use therein|
    EP2911761A1|2012-10-24|2015-09-02|The Procter and Gamble Company|Anti foam compositions comprising partly phenyl bearing polyorganosilicons|
    WO2014066308A1|2012-10-24|2014-05-01|The Procter & Gamble Company|Anti foam compositions comprising aryl bearing polyorganosilicons|
    EP2929005A1|2012-12-06|2015-10-14|The Procter and Gamble Company|Soluble pouch comprising hueing dye|
    EP2740785A1|2012-12-06|2014-06-11|The Procter and Gamble Company|Use of composition to reduce weeping and migration through a water soluble film|
    EP2767581B1|2013-02-19|2020-10-21|The Procter & Gamble Company|Method of laundering a fabric|
    EP2767582A1|2013-02-19|2014-08-20|The Procter and Gamble Company|Method of laundering a fabric|
    EP2767579B1|2013-02-19|2018-07-18|The Procter and Gamble Company|Method of laundering a fabric|
    EP2978831B1|2013-03-28|2020-12-02|The Procter and Gamble Company|Cleaning compositions containing a polyetheramine, a soil release polymer, and a carboxymethylcellulose|
    CA2909458C|2013-04-12|2018-07-31|The Procter & Gamble Company|Fibrous structures comprising polysaccharide filaments|
    MX2015014318A|2013-04-12|2015-12-08|Procter & Gamble|Fibrous structures exhibiting improved whiteness index values.|
    EP2984214A1|2013-04-12|2016-02-17|The Procter and Gamble Company|Hydroxyl polymer fiber structures comprising ammonium alkylsulfonate salts and methods for making same|
    CA2911332A1|2013-05-28|2014-12-04|The Procter & Gamble Company|Surface treatment compositions comprising photochromic dyes|
    ES2713084T3|2013-07-30|2019-05-17|Procter & Gamble|Method for preparing granular detergent compositions comprising surfactants|
    EP2832843B1|2013-07-30|2019-08-21|The Procter & Gamble Company|Method of making granular detergent compositions comprising polymers|
    WO2015112341A1|2014-01-22|2015-07-30|The Procter & Gamble Company|Fabric treatment composition|
    EP3097173B1|2014-01-22|2020-12-23|The Procter and Gamble Company|Fabric treatment composition|
    WO2015112338A1|2014-01-22|2015-07-30|The Procter & Gamble Company|Method of treating textile fabrics|
    EP3097174A1|2014-01-22|2016-11-30|The Procter and Gamble Company|Method of treating textile fabrics|
    WO2015123199A1|2014-02-11|2015-08-20|The Procter & Gamble Company|Polymeric structures comprising a dual purpose material and/or component thereof and methods for making same|
    US9556406B2|2014-02-19|2017-01-31|Milliken & Company|Compositions comprising benefit agent and aprotic solvent|
    EP3107989A1|2014-02-19|2016-12-28|The Procter and Gamble Company|Composition comprising benefit agent and aprotic solvent|
    WO2015130653A1|2014-02-25|2015-09-03|The Procter & Gamble Company|A process for making renewable surfactant intermediates and surfactants from fats and oils and products thereof|
    EP3110778A1|2014-02-25|2017-01-04|The Procter and Gamble Company|A process for making renewable surfactant intermediates and surfactants from fats and oils and products thereof|
    EP3122850A1|2014-03-27|2017-02-01|The Procter and Gamble Company|Cleaning compositions containing a polyetheramine|
    EP3122849B1|2014-03-27|2021-07-21|The Procter & Gamble Company|Cleaning compositions containing a polyetheramine|
    EP3152288A1|2014-06-06|2017-04-12|The Procter and Gamble Company|Detergent composition comprising polyalkyleneimine polymers|
    EP3307129A1|2015-06-11|2018-04-18|The Procter and Gamble Company|Device and methods for applying compositions to surfaces|
    EP2987849A1|2014-08-19|2016-02-24|The Procter and Gamble Company|Method of Laundering a Fabric|
    EP2987848A1|2014-08-19|2016-02-24|The Procter & Gamble Company|Method of laundering a fabric|
    CA2956095C|2014-08-27|2019-10-08|The Procter & Gamble Company|Detergent composition comprising a cationic polymer|
    US9617501B2|2014-08-27|2017-04-11|The Procter & Gamble Company|Method of treating a fabric by washing with a detergent comprising an acrylamide/DADMAC cationic polymer|
    CA2956081C|2014-08-27|2021-03-16|The Procter & Gamble Company|Detergent composition comprising a cationic polymer|
    CA2956088C|2014-08-27|2019-07-30|The Procter & Gamble Company|Detergent composition comprising a cationic polymer|
    US9617502B2|2014-09-15|2017-04-11|The Procter & Gamble Company|Detergent compositions containing salts of polyetheramines and polymeric acid|
    US20160090552A1|2014-09-25|2016-03-31|The Procter & Gamble Company|Detergent compositions containing a polyetheramine and an anionic soil release polymer|
    CA2958655C|2014-09-25|2018-09-18|The Procter & Gamble Company|Cleaning compositions containing a polyetheramine|
    JP6430632B2|2014-09-25|2018-11-28|ザ プロクター アンド ギャンブル カンパニー|Fabric care composition containing polyetheramine|
    US9388368B2|2014-09-26|2016-07-12|The Procter & Gamble Company|Cleaning compositions containing a polyetheramine|
    MX2017006377A|2014-11-17|2017-08-21|Procter & Gamble|Benefit agent delivery compositions.|
    CN107532116B|2015-04-29|2021-05-07|宝洁公司|Method for treating fabric|
    CN107624127A|2015-04-29|2018-01-23|宝洁公司|The method for handling fabric|
    EP3674387A1|2015-04-29|2020-07-01|The Procter & Gamble Company|Method of treating a fabric|
    HUE039245T2|2015-04-29|2018-12-28|Procter & Gamble|Detergent composition|
    CN107667166B|2015-04-29|2021-01-15|宝洁公司|Method for treating fabric|
    WO2017011234A1|2015-07-10|2017-01-19|The Procter & Gamble Company|Layered fibrous structures and methods for making same|
    CN108291180A|2015-11-26|2018-07-17|宝洁公司|Include the liquid detergent composition of protease and encapsulated lipase|
    US20170284025A1|2016-04-04|2017-10-05|The Procter & Gamble Company|Fibrous Structures Different Fibrous Elements|
    WO2017176661A1|2016-04-04|2017-10-12|The Procter & Gamble Company|Fibrous structures different fibrous elements|
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    WO2017176660A1|2016-04-04|2017-10-12|The Procter & Gamble Company|Fibrous structures with improved surface properties|
    WO2017176665A1|2016-04-04|2017-10-12|The Procter & Gamble Company|Layered fibrous structures with different common intensive properties|
    EP3535372B1|2016-11-01|2020-09-09|The Procter & Gamble Company|Leuco polymers as bluing agents in laundry care compositions|
    JP2019534356A|2016-11-01|2019-11-28|ミリケン・アンド・カンパニーＭｉｌｌｉｋｅｎ ＆ Ｃｏｍｐａｎｙ|Roy copolymer as a bluing agent in laundry care compositions|
    WO2018132626A1|2017-01-13|2018-07-19|The Procter & Gamble Company|Compositions comprising branched sulfonated surfactants|
    BR112019015689A2|2017-02-01|2020-04-14|Procter & Gamble|cleaning compositions comprising amylase variants|
    US11248194B2|2019-03-14|2022-02-15|The Procter & Gamble Company|Cleaning compositions comprising enzymes|
    WO2020186052A1|2019-03-14|2020-09-17|The Procter & Gamble Company|Method for treating cotton|
    US20200291332A1|2019-03-14|2020-09-17|The Procter & Gamble Company|Cleaning compositions comprising enzymes|
    WO2020264552A1|2019-06-24|2020-12-30|The Procter & Gamble Company|Cleaning compositions comprising amylase variants|
    WO2021133701A1|2019-12-23|2021-07-01|The Procter & Gamble Company|Compositions comprising enzymes|
    CN110964195A|2019-12-24|2020-04-07|宝美施化工有限公司|Polymer dye colorant and preparation method thereof|
    法律状态:
    2018-04-10| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2019-02-19| B06T| Formal requirements before examination|
    2019-10-08| B09A| Decision: intention to grant|
    2019-11-12| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 26/01/2011, OBSERVADAS AS CONDICOES LEGAIS. (CO) 20 (VINTE) ANOS CONTADOS A PARTIR DE 26/01/2011, OBSERVADAS AS CONDICOES LEGAIS |
    2021-02-09| B25A| Requested transfer of rights approved|Owner name: UNILEVER IP HOLDINGS B.V. (PB) |
    优先权:
    申请号 | 申请日 | 专利标题
    CN2010000181|2010-02-09|
    PCT/EP2011/051070|WO2011098355A1|2010-02-09|2011-01-26|Dye polymers|
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