CN102575199A - A dye polymer - Google Patents
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- CN102575199A CN102575199A CN2010800464167A CN201080046416A CN102575199A CN 102575199 A CN102575199 A CN 102575199A CN 2010800464167 A CN2010800464167 A CN 2010800464167A CN 201080046416 A CN201080046416 A CN 201080046416A CN 102575199 A CN102575199 A CN 102575199A
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Abstract
The present invention provides polymeric shading dyes to provide a perception of whiteness to white textiles.
Description
Technical field
The present invention relates to polymeric coloured light adjustment dyestuff (shading dye) and their purposes in laundry applications.
Background technology
WO2006/055787 (Procter & Gamble) discloses laundry formulations, contains the cellulose ether polymer with the reactive dyestuffs covalent bonding, is used for fabric brightening.
Summary of the invention
Tone (hue) produces best fabric brightening effect for positive blue dyestuff and pigment to purple.The tone of green-indigo plant that the commercialization reactive blue dye has, it is positive blue to color purple that they can mix acquisition with active red dye.Mixing colouring agent causes the clouding look because of photoabsorption improves.Acquisition can provide correct tone color and not make the dye mixture of the excessive clouding of fabric is ideal.
In one aspect, the present invention provides laundry treatment compositions, and it comprises:
(i) tensio-active agent of 2～70 wt%; With,
(ii) 0.0001～2.0 wt%, preferred 0.05～1wt% with the Reactive blue anthraquinone dye and with the polymer carbohydrate of reactive red azoic dyestuff covalent bonding; It is indigo plant-red polymkeric substance; Its medium blue dyestuff: the weight ratio of red is 10:1～10:4, preferred 10:1～10:2.
On the other hand, the present invention provides the home method of treatment of textiles, and this method comprises the steps:
(i) with the aqueous solution treatment of textiles of the indigo plant-red polymkeric substance of each definition among the claim 1-11, the said aqueous solution comprises: 10 ppb～5000 ppm, preferred 100 ppb～to indigo plant-red polymkeric substance of 100 ppm; Tensio-active agent with 0.0 g/L～3 g/L; With,
(ii) randomly rinsing and dry this textiles.
Preferably, laundry treatment compositions is granular.
Embodiment
Indigo plant-red polymkeric substance
Fasten before polymer carbohydrate at covalency, dyestuffs are can non-conjugated mode together covalently bound.
The total load of dyestuff (Lan Hehong) is preferably 0.00001 wt%～10 wt% on indigo plant-red polymkeric substance, more preferably 0.0001 wt%～1 wt%, most preferably 0.0001 wt%～0.01 wt%.
Preferably, the Reactive blue anthraquinone dye is following form:
Wherein R is the organic group that contains reactive group.Preferably, R is selected from: a chlorotriazine base; The dichlorotriazine base; And vinylsulfonyl.
Preferred reactive blue dye is selected from: Reactive blue 2; Reactive blue 4; Reactive blue 5; Reactive Blue 19 100; Reactive blue 27; Reactive blue 29; Reactive blue 36; Reactive blue 49; Reactive blue 50; With Reactive blue 224.
Preferably, the reactive red azoic dyestuff is the reactive red monoazo-dyes, and preferred reactive red monoazo-dyes has following form:
Wherein A ring is unsubstituted or is replaced by sulfonic group (sulphonate group) or reactive group.Preferably, A ring is naphthyl and is replaced by two sulfonic groups.Preferably, R is the organic group that contains reactive group.Preferred reactive group is a chlorotriazine base; The dichlorotriazine base; And vinylsulfonyl.
Preferred active red dye is 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; With reactive red 253.
Reactive dyestuffs
Reactive dyestuffs are set forth in Industrial Dyes (K. Hunger edits, Wiley VCH 2003).
Many reactive dyestuffs are listed in " color index " (colour index) (Society of Dyers and Colourists and American Association of Textile Chemists and Colorists).
The reactive dyestuffs experience forms covalent linkage with the addition or the substitution reaction of C-OH group.Reactive dyestuffs can combine such as polysaccharide with polymer carbohydrate.
Reactive dyestuffs are colored compounds, have the functional group that one or more can form covalent linkage with suitable substrate, and suitable substrate is generally cotton or other cellulosic fibre.The typical activity group of reactive dyestuffs is a chlorotriazine base, a Cyanuric trifluoride base, two Cyanuric trifluorides, difluoro chloropyrimide, trichloropyrimidine and 2-sulfonyloxy ethylsulfonyl.
Reactive dyestuffs have specific functional group, this functional group can experience with polymkeric substance in existing-OH ,-SH and-addition or the substitution reaction of NH2 group.
Polymer carbohydrate
Polymer carbohydrate has available hydroxyl, this hydroxyl can with reactive dyestuffs reactions so that the dyestuff with the polymer carbohydrate covalent bonding to be provided.
Polymkeric substance is preferably selected from: ether of cellulose is such as WOT Recovery Floc T; CMC 99.5; Comprise that its salt is such as sodium salt; Methylcellulose gum, hydroxy alkyl cellulose such as Natvosol and mixed ether such as methyl hydroxyethylcellulose, methylhydroxypropylcellulose, methyl CMC 99.5; The fatty ester modified-cellulose; Phosphorylated cellulose is such as those disclosed among the WO99/09124; Mierocrystalline cellulose, cationic starch, guar gum, non-charged starch.
When indigo plant-when the red polymkeric substance comprised ether of cellulose such as CMC 99.5, the weight-average molecular weight of this type of ether of cellulose was preferably 1,000,000 dalton at the most; More preferably 25,000 dalton～500,000 dalton; More preferably 30,000 dalton～120,000 dalton again.Ether substitution value for example carboxymethylation degree is preferably 0.2～1.3.
The mensuration of weight-average molecular weight is to carry out according to the general procedure that details in the following document: Journal of Chromatography 1980,192,275-293 page or leaf, or Polymer Degradation and Stability 56 (1997) 331-337; Ether substitution value and measure according to AST method D 1439-03 as the carboxymethylation degree of ether substitution value subclass, dyestuff replaces to be measured by combustion analysis.
Other dyestuff
In a preferred embodiment of the invention, can there be other coloured light adjustment tinting material.They are preferably selected from: indigo plant and purple dye are such as pigment Violet 23; Solvent and dispersed dye such as solvent violet 13,63 ,DIS,PER,SE ,Vio,let, 63 28; The tetrazo substantive dyestuff such as direct purple 9,35,51 and 99 and triphenol dioxazine (triphenodioxazine) substantive dyestuff such as direct purple 54.
More preferably exist again like WO 2008/017570 described acid azines; The content of acid azines should be 0.0001～0.1 wt%.Acid azines is mainly textile clothes provides benefit, and the positively charged ion phenazine dyes is mainly the polyester-cotton blend clothes benefit is provided.Preferred acid azines is acid violet 50, acid blue 59 and acid blue 98.Also can there be blue and Ziyang ion phenazine dyes.
Can exist the photobleaching material such as sulfonation Zn/Al phthalocyanine.
Tensio-active agent
Compsn comprises 2～70 wt%, the tensio-active agent of 10～30 wt% most preferably.Generally speaking, the nonionic of surfactant system and AS are optional plays the tensio-active agent described in the document freely: " Surface Active Agents " Vol. 1, Schwartz Perry; Interscience 1949, and Vol. 2, Schwartz; Perry & Berch, Interscience 1958, latest edition " McCutcheon's Emulsifiers and Detergents "; Manufacturing Confectioners Company publishes, perhaps " Tenside-Taschenbuch ", H. Stache; The 2nd edition, Carl Hauser Verlag, 1981.The tensio-active agent that uses is preferably saturated.
Spendable suitable nonionic detergent compounds is particularly including the reaction product of compound with hydrophobic group and active hydrogen atom and oxirane; Said compound with hydrophobic group and active hydrogen atom for example is fatty alcohol, acid, acid amides or alkylphenol, and oxirane especially is independent or together with the oxyethane of propylene oxide.Concrete nonionic detergent compounds is C
6-C
22Alkylphenol-ethylene oxide condensate is generally 5～25 EO, also is 5～25 unit ethylene oxide per molecules, and aliphatic C
8-C
18The condensation product of straight or branched uncle or secondary alcohol and oxyethane is generally 5～40 EO.
The suitable anionic detergent of available is the water-soluble alkali metal salts of organo-sulfate and sulphonate normally, and said organo-sulfate and sulphonate have the alkyl that contains about 8～about 22 carbon atoms, and term alkyl is used for comprising the moieties of more senior acyl group.Suitable synthetic anionic detergent compound instance is sodium alkyl sulfate and potassium, especially available from the senior C that is generated by for example Tallow, beef or Oleum Cocois
8-C
18Alcohol Sulfated those, alkyl C
9-C
20Supragil GN and potassium, particularly linear secondary alkyl C
10-C
15Supragil GN; With alkyl glycerol base ether sodium sulfate, especially derive from the higher alcohols and those ethers that derive from the synthol of oil of Tallow, beef or Oleum Cocois.The preferred anionic surfactants detergent compound is C
11-C
15Sodium alkyl benzene sulfonate and C
12-C
18Sodium alkyl sulfate.Those tensio-active agents that also can use the demonstration salt tolerant described in EP-A-328 177 (Unilever) to analyse, the alkylpolyglycosides tensio-active agent described in the EP-A-070 074 and alkyl list glycosides.
The preferred surfactants system is the mixture of negatively charged ion and nonionogenic tenside active material, the negatively charged ion of particularly pointing out among the EP-A-346 995 (Unilever) and the cohort and the example of nonionogenic tenside.Especially preferred following surfactant system: C
16-C
18Primary alconol sulfuric acid an alkali metal salt and C
12-C
15The mixture of primary alconol 3～7 EO ethoxylates.
Nonionogenic tenside content preferably account for surfactant system greater than 10%, 25～90 wt% for example.The content of ionic surface active agent can account for about 5%～about 40 wt% of surfactant system.
On the other hand, go back the preferred cationic tensio-active agent, thereby said preparation is a fabric conditioner.
Cation cpd
When the present invention is used as fabric conditioner, need the cation compound.
Quaternary ammonium compound most preferably.
Advantageously, quaternary ammonium compound is to have at least one C
12-C
22The quaternary ammonium compound of alkyl chain.
Preferred quaternary ammonium compound has formula:
R wherein
1Be C
12-C
22The alkyl or alkenyl chain; R
2, R
3And R
4Independently be selected from C
1-C
4Alkyl chain, X
–It is the compatibility negatively charged ion.Preferred this compounds is a hexadecyl QAE bromide.
Second type of material that supplies the present invention to use is the quaternary ammonium with said structure, wherein R
1And R
2Independently be selected from C
12-C
22The alkyl or alkenyl chain; R
3And R
4Independently be selected from C
1-C
4Alkyl chain, X
–It is the compatibility negatively charged ion.
According to the detergent composition of claim 1, wherein (ii) the ratio of cationic materials and (iv) AS is 2:1 at least.
Other suitable quaternary ammonium compounds are disclosed in EP 0 239 910 (Proctor and Gamble).
Positively charged ion is preferably 1:100～50:50, more preferably 1:50～20:50 with the ratio of nonionogenic tenside.
Cation cpd content can be 1.5 wt%～50 wt% of composition total weight.Cation cpd content can be preferably 2 wt%～25 wt%, more preferably 5 wt%～20 wt%.
Softener material content is preferably 2～60 wt% of total composition, more preferably 2～40 wt%, most preferably 3～30 wt%.
The optional siloxanes that comprises of compsn.
Washing assistant or complexing agent
The washing assistant material can be selected from: its mixture deposited material, 3 1) calcium sequestrant material, 2)) calcium ion-exchange material and 4).
The example of calcium sequestrant washing assistant material comprises that alkali metal polyphosphates such as Tri sodium Phosphate and organic sequestering agent are such as YD 30.
The example of deposition washing assistant material comprises sodium orthophosphate and yellow soda ash.
The example of calcium ion-exchanged washing assistant material comprises various water-insoluble crystallizations or amorphous aluminosilicate; Its mesolite is foremost representative; For example zeolite A, zeolite B (having another name called zeolite P), zeolite C, X zeolite, zeolite Y and like EP-A-0,384,070 described zeolite P types.
Compsn also can contain washing assistant or the complexing agent of 0～65 %, such as YD 30, NSC 446-pentaacetic acid, alkyl or alkenyl succsinic acid, nitrilotriacetic acid(NTA) or other following washing assistant.The ability that relies on complexation of metal ions, many washing assistants or bleaching stibilizer.
Zeolite and carbonate (carbonate comprises supercarbonate and sesquicarbonate) are preferred washing assistants.
Compsn can contain crystalline aluminosilicate, preferred as alkali aluminosilicate, more preferably sodium aluminium silicate is as washing assistant.Its content is generally less than 15%w.Aluminosilicate is the material with following general formula:
Wherein M is a monovalent cation, preferred sodium.These materials contain some combination water, must have the calcium ion-exchanged capacity of at least 50 mg CaO/g.Preferred sodium aluminium silicate contains 1.5～3.5 SiO in following formula
2The unit.They can be through easily making as reacting between abundant water glass of describing and sodium aluminate in the document.The ratio of tensio-active agent and aluminosilicate (when existing) is preferably greater than 5:2, more preferably greater than 3:1.
Except that the aluminosilicate washing assistant, alternately or additionally use phosphate builders.In this field, term " phosphoric acid salt " comprises diphosphate, triphosphate and phosphonates.Other forms of washing assistant comprises silicate, such as soluble silicate, metasilicate, layered silicate (for example SKS-6, from Hoechst).
Cloth-washing detergent preparation preferably nonphosphate helps the cloth-washing detergent preparation of washing, and also promptly, contains the phosphoric acid salt that is lower than 1wt%.Cloth-washing detergent preparation preferably carbonate helps and washes.
Fluorescent agent
Compsn preferably comprises fluorescent agent (white dyes).Fluorescent agent is well-known, and many these type of fluorescent agents are commercially available.Usually, these fluorescent agents are with the for example supplied and the use of sodium salt of its an alkali metal salt.The fluorescent agent total amount of using in the compsn is generally 0.005～2 wt%, more preferably 0.01～0.1 wt%.Preferred white dyes classification is: distyryl biphenyl compound, for example Tinopal
TM(trade mark) CBS-X, diamines stilbene disulfonic acid compound, for example pure Xtra of Tinopal DMS and Blankophor
TM(trade mark) HRH, and pyrazoline compounds, for example Blankophor SN.Preferred white dyes is: 2 (4-styryl-3-sulfophenyl)-2H-naphtho-[1,2-d] triazole sodium, 4, and 4'-is two, and { [(4-anilino-6-(N-methyl-N-2-hydroxyethyl) amino 1; 3; 5-triazine-2-yl)] amino } stilbene-2-2' disulfonic acid disodium, 4, two { [(the 4-anilinos-6-morpholino-1,3 of 4'-; 5-triazine-2-yl)] amino } stilbene-2-2' disulfonic acid disodium and 4, two (2-sulfo group styryl) the biphenyl disodiums of 4'-.
Preferably, the aqueous solution of present method use contains white dyes.When white dyes was present in the aqueous solution that present method uses, its amount was preferably 0.0001 g/l～0.1 g/l, more preferably 0.001～0.02 g/l.
Spices
Compsn preferably comprises spices.Amount of flavorants is preferably 0.001～3 wt%, most preferably 0.1～1 wt%.Many suitable spices examples are recorded in CTFA (Cosmetic; Toiletry and Fragrance Association) 1992 International Buyers Guide; CFTA Publications publishes; With OPD 1993 Chemicals Buyers Directory 80 anniversary versions, Schnell Publishing Co publishes.
Often there are a plurality of perfume compositions in the preparation.In the present composition, imagination can exist 4 more many, preferred 5 or more, more preferably 6 or more, perhaps even 7 or more kinds of different perfume composition.
Preferred 15～25 wt% are that head is fragrant in the spice mixt.Head is fragrant by Poucher definition (Journal of the Society of Cosmetic Chemists 6 (2): 80 [1955]).Preferred perfume (or spice) is selected from citrus oil, linalool, Linalyl acetate, true lavender, dihydromyrcenol, rose oxide compound and cis 3-alcohol.
A spices and a perfume (or spice) can be used to point out whiteness gain of the present invention.
Preferably, laundry treatment compositions does not contain peroxygen bleach, for example SPC-D, Sodium peroxoborate and peracid.
Polymkeric substance
Compsn can comprise one or more polymkeric substance.Example is CMC 99.5, gather (terepthaloyl moietie), gather (vinyl alcohol), polycarboxylate such as polyacrylic ester, toxilic acid/PEMULEN TR2 and lauryl methacrylate(LMA)/PEMULEN TR2.
Preferably do not exist in the preparation, for example gather (vinyl pyrrolidone), gather (vinyl pyridine-N-oxide compound) and gather (vinyl imidazole) in order to stop the polymkeric substance of deposition of dye.
Enzyme
In the present composition and when the embodiment of the present invention method, preferably there is one or more enzyme.
The content of every kind of enzyme is preferably 0.0001 wt%～0.1 wt% albumen.
Especially the enzyme of paying close attention to comprises proteolytic enzyme, AMS, cellulase, lipase, px/oxydase, pectate lyase and mannase or its mixture.
Suitable lipase comprises the lipase of bacterium or originated from fungus.The two mutants of chemical modification or protein engineeringization is included.The example of useful lipase comprises: from the lipase of Humicola (Humicola) (have another name called: thermophilic trichosporon spp (Thermomyces)), for example from wool shape humicola lanuginosa (H. lanuginosa) (dredging the thermophilic hyphomycete of continuous shape (T. lanuginosus)) () or from special humicola lanuginosa (H. insolens) () of WO 96/13580 of EP 258 068 and EP 305 216; Rhodopseudomonas (Pseudomonas) lipase; For example from Pseudomonas alcaligenes (P. alcaligenes) or pseudomonas pseudoalcaligenes (P. pseudoalcaligenes) (EP 218 272), pseudomonas cepacia (P. cepacia) (EP 331 376), (GB 1 for Pseudomonas stutzeri (P. stutzeri); 372,034), Pseudomonas fluorescens (P. fluorescens), pseudomonas strain SD 705 (WO 95/06720 and WO 96/27002), Wisconsin pseudomonas (P. wisconsinensis) (WO 96/12012); Bacillus (Bacillus) lipase; For example from subtilis (B. subtilis) (Dartois etc. (1993); Biochemica et Biophysica Acta; 1131,253-360), bacstearothermophilus (B. stearothermophilus) (JP 64/744992) or bacillus pumilus (B. pumilus) (WO 91/16422).
Other example is a Lipase variants, those described in following document: 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 and WO 97/07202, WO 00/60063.
Preferred commercially available lipase comprises Lipolase and Lipolase Ultra, Lipex (Novozymes A/S).
The inventive method can be carried out in the presence of the Phospholipid hydrolase that classifies as EC 3.1.1.4 and/or EC 3.1.1.32.As used herein, the term phospholipids enzyme is that phosphatide is had active enzyme.Phosphatide, such as Yelkin TTS or phosphatidylcholine, by with externally (sn-1) and middle (sn-2) the position esterification and form at the glycerine of the 3rd position esterification of two lipid acid with phosphoric acid; And but the phosphoric acid esterification is an amino alcohol.
Phospholipid hydrolase is the enzyme of participating in the phosphatide hydrolysis.Can distinguish several types of phospholipase activity, comprise: phospholipase A
1And A
2, acyl of its hydrolysis (respectively in sn-1 and sn-2 position) is to form lysophospholipid; And lysophospholipase (or phospholipase B), remaining acyl in its hydrolyzable lysophospholipid.Phospholipase C and Phospholipase D (phosphodiesterase) disengage DG or phosphatidic acid respectively.
Enzyme and coloured light adjustment dyestuff possibly show certain interaction, and it is not negative should causing this interaction to their selection.Can seal and/or be isolated from the product in addition through making enzyme or coloured light adjustment in the dyestuff or another, and avoid some negative interaction.
Suitable proteolytic enzyme comprises animal, plant or microbe-derived proteolytic enzyme.The preferred microorganism source.The two mutants of chemical modification or protein engineeringization is included.Proteolytic enzyme can be Tryase or metalloprotease, preferred alkaline microbial protease or trypsin-like proteolytic enzyme.Preferred commercially available proteolytic enzyme comprises: 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 inventive method can be carried out in the presence of the at that classifies as EC 3.1.1.74.At used according to the invention can be any source.At is preferably microbe-derived, and particularly bacterium, fungi or yeast are originated.
Suitable glycase (α and/or β) comprises the glycase of bacterium or originated from fungus.The two mutants of chemical modification or protein engineeringization is included.Glycase comprises: for example, AMS, it is available from bacillus; For example special Bacillus licheniformis (B. licheniformis) bacterial strain (is set forth in GB 1 more in detail; 296,839), perhaps disclosed Bacillus strain among WO 95/026397 or the WO 00/060060.Commercially available glycase is Duramyl, Termamyl, Termamyl Ultra, Natalase, Stainzyme, Fungamyl and BAN (Novozymes A/S), Rapidase and Purastar (from Genencor International Inc.).
Suitable cellulase comprises the cellulase of bacterium or originated from fungus.The two mutants of chemical modification or protein engineeringization is included.Suitable cellulase comprises: from the cellulase of bacillus, Rhodopseudomonas, Humicola, Fusarium (Fusarium), Thielavia (Thielavia), Acremonium (Acremonium); For example (be disclosed in US 4 by special humicola lanuginosa (Humicola insolens), Tai Ruisisuo spore shell (Thielavia terrestris), the thermophilic fungal cellulase of ruining silk mould (Myceliophthora theromphila) and Fusarium oxysporum (Fusarium oxysporum) generation; 435; 307, US 5,648, and 263, US 5; 691; 178, US 5,776,757, WO 89/09259, WO 96/029397 and WO 98/012307).Commercially available cellulase comprises Celluzyme, Carezyme, Endolase, Renozyme (Novozymes A/S), Clazinase and Puradax HA (Genencor International Inc.) and KAC-500 (B) (Kao Corporation).
Suitable px/oxydase comprises the px/oxydase of plant, bacterium or originated from fungus.The two mutants of chemical modification or protein engineeringization is included.The example of useful px comprises from Coprinus (Coprinus), for example from px and its variant of Coprinus cinereus (C. cinereus), for example those described in WO 93/24618, WO 95/10602 and the WO 98/15257.Commercially available px comprises Guardzyme and Novozym 51004 (Novozymes A/S).
Enzyme stabilizers
Any enzyme that exists in the compsn can use conventional stablizer stable; Conventional stablizer for example is: polyvalent alcohol such as Ucar 35 or glycerine, sugar or sugar alcohol, lactic acid; Boric acid; Or boric acid derivatives, for example aromatic borate or phenyl-boron dihydroxide verivate are such as 4-formyl radical phenyl-boron dihydroxide, and compsn can be like for example WO 92/19709 and WO 92/19708 said the preparation.
As used herein, the corresponding definite article with it of indefinite article " " " said " means at least one, perhaps one or more, except as otherwise noted.
Experiment
Embodiment 1: synthetic
0.5g Natvosol, 0.5g Na
2CO
3Mix in the 100ml demineralized water with the 0.05g reactive dyestuffs, 60 ℃ of heating 5 hours.After reaction, product was to water dialysis (COMW=12000) 72 hours.Remove water through rotary evaporation then.The resulting polymers dried in vacuum.
Used following dye mixture:
Polymkeric substance 1 0.050g reactive blue 4 (RB4)
Polymkeric substance 2 0.050g reactive reds 2 (RR2)
Polymkeric substance 3 0.040g RB4 and 0.010g RR2
Polymkeric substance 4 0.035 RB4 and 0.015 RR2
Polymkeric substance 5 0.030 RB4 and 0.020 RR2
Embodiment 2: scourability
Woven cotton, polyester and nylon-spandex fabric in containing the water-based washing soln (demineralized water) of 1g/L linear alkylbenzene sulfonate, 1g/L yellow soda ash and 1g/L sodium-chlor with the ratio washing of the liquid of 30:1 with cloth.The polymkeric substance that adds embodiment 1 to washing soln is so that washing soln contains the 5ppm polymkeric substance.Stir after 30 minutes, with cloth shift out, rinsing and drying.Repeated washing then is until accomplishing 4 cycles of washing.After second and the 4th washing, on reflectometer, measure the reflection spectrum of cloth, color is with CIE L*a*b* value representation.
Only on cotton fabric, observe deposition of dye.For polymkeric substance 1, polymkeric substance 2, polymkeric substance 3, polymkeric substance 4 and polymkeric substance 5, observed hue-angle on cotton (hue angle) is respectively 234,334,265,287 and 307.Contain the two polymkeric substance of RB4 and RR2 and provide best positive indigo plant to violet tint.
The cotton clouding is represented with sedimentary total color on the cloth, is provided by Δ Ε value:
L wherein
c, a
cAnd b
cIt is the CIE L a b value of the contrast cloth of warp washing under no dyestuff situation;
And L
d, a
dAnd b
dIt is CIE L a b value with the cloth of dyestuff washing.
The increase of cloth whiteness is represented with blue stain:
To each dyestuff, cloth brightens and uses Δ b/ Δ E recently to measure to the clouding effect; Value more greatly then represents whiteness bigger and the clouding degree is more little.
The result provides in following table, represents the MV of second and the 4th washing.
The polymkeric substance calculated value that contains two dyestuffs is that the linear interpolation through single dyestuff polymkeric substance experimental value obtains, therefore,
Calculated value=0.72f
b+ 0.39f
r
F wherein
bBe the weight fraction of RB4, f
rIt is the weight fraction of RR2.
* contrast
RB4 provides the clouding degree more much lower than expected value with the mixture of RR2, as Δ b/ Δ Ε experimental value than calculated value big shown in.
Claims (13)
1. laundry treatment compositions, it comprises:
(i) tensio-active agent of 2～70 wt%; With,
(ii) 0.0001～2.0 wt% with the Reactive blue anthraquinone dye and with the polymer carbohydrate of reactive red azoic dyestuff covalent bonding, i.e. indigo plant-red polymkeric substance, its medium blue dyestuff: the weight ratio of red is 10:1～10:4.
2. according to the laundry treatment compositions of claim 1, wherein the Reactive blue anthraquinone dye has following form:
Wherein R is the organic group that contains reactive group.
3. according to the laundry treatment compositions of claim 2, wherein R is selected from: a chlorotriazine base; The dichlorotriazine base; And vinylsulfonyl.
4. according to the laundry treatment compositions of claim 2, wherein dyestuff is selected from: Reactive blue 2; Reactive blue 4; Reactive blue 5; Reactive Blue 19 100; Reactive blue 27; Reactive blue 29; Reactive blue 36; Reactive blue 49; Reactive blue 50; With Reactive blue 224.
5. according to each laundry treatment compositions in the aforementioned claim, wherein the reactive red azoic dyestuff is the reactive red monoazo-dyes.
6. according to each laundry treatment compositions in the aforementioned claim, wherein the reactive red monoazo-dyes has following form:
Wherein A ring is unsubstituted or is replaced by sulfonic group or reactive group.
7. according to the laundry treatment compositions of claim 6, wherein the A ring is naphthyl and is replaced by two sulfonic groups.
8. according to the laundry treatment compositions of claim 6 or 7, wherein R is the organic group that contains reactive group.
9. according to the laundry treatment compositions of claim 5 or 8, wherein reactive group is selected from: a chlorotriazine base; The dichlorotriazine base; And vinylsulfonyl.
10. according to claim 1,2,3,4 or 5 laundry treatment compositions, wherein dyestuff is 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; With reactive red 253.
11. according to each laundry treatment compositions in the aforementioned claim, wherein polymer carbohydrate is an ether of cellulose.
12. the home method of treatment of textiles, this method comprises the steps:
(i) with the aqueous solution treatment of textiles of the indigo plant-red polymkeric substance of each definition among the claim 1-11, the said aqueous solution comprises: the indigo plant of 10 ppb～5000 ppm-red polymkeric substance; Tensio-active agent with 0.0 g/L～3 g/L; With,
(ii) randomly rinsing and dry this textiles.
13. according to the method for the family expenses treatment of textiles of claim 12, wherein the aqueous solution comprises the white dyes of 0.0001 g/l～0.1 g/l.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010800464167A CN102575199A (en) | 2009-10-13 | 2010-10-04 | A dye polymer |
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| CNPCT/CN2009/001135 | 2009-10-13 | ||
| CN2009001135 | 2009-10-13 | ||
| PCT/EP2010/064744 WO2011045195A1 (en) | 2009-10-13 | 2010-10-04 | Dye polymers |
| CN2010800464167A CN102575199A (en) | 2009-10-13 | 2010-10-04 | A dye polymer |
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| CN102575199A true CN102575199A (en) | 2012-07-11 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106398302A (en) * | 2016-08-30 | 2017-02-15 | 江苏德美科化工有限公司 | Reactive orange dye compound and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006055787A1 (en) * | 2004-11-19 | 2006-05-26 | The Procter & Gamble Company | Whiteness perception compositions |
| EP1852496A1 (en) * | 2006-05-03 | 2007-11-07 | The Procter & Gamble Company | Liquid detergent |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006055787A1 (en) * | 2004-11-19 | 2006-05-26 | The Procter & Gamble Company | Whiteness perception compositions |
| EP1852496A1 (en) * | 2006-05-03 | 2007-11-07 | The Procter & Gamble Company | Liquid detergent |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106398302A (en) * | 2016-08-30 | 2017-02-15 | 江苏德美科化工有限公司 | Reactive orange dye compound and preparation method thereof |
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