CN1650064A - Method for brightening textile materials - Google Patents

Method for brightening textile materials Download PDF

Info

Publication number
CN1650064A
CN1650064A CNA038100355A CN03810035A CN1650064A CN 1650064 A CN1650064 A CN 1650064A CN A038100355 A CNA038100355 A CN A038100355A CN 03810035 A CN03810035 A CN 03810035A CN 1650064 A CN1650064 A CN 1650064A
Authority
CN
China
Prior art keywords
compound
weight
alkyl
general formula
formula iii
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.)
Granted
Application number
CNA038100355A
Other languages
Chinese (zh)
Other versions
CN1333129C (en
Inventor
D·韦伯
H·赖歇尔特
G·瓦根布拉斯特
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of CN1650064A publication Critical patent/CN1650064A/en
Application granted granted Critical
Publication of CN1333129C publication Critical patent/CN1333129C/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/02—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using azo dyes
    • D06P1/04—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using azo dyes not containing metal
    • D06P1/08—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using azo dyes not containing metal cationic azo dyes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/60—Optical bleaching or brightening
    • 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
    • C11D1/38—Cationic compounds
    • C11D1/62—Quaternary ammonium 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
    • C11D3/39—Organic or inorganic per-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
    • C11D3/40—Dyes ; Pigments
    • C11D3/42—Brightening agents ; Blueing agents
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/60—Optical bleaching or brightening
    • D06L4/614—Optical bleaching or brightening in aqueous solvents
    • D06L4/636—Optical bleaching or brightening in aqueous solvents with disperse brighteners
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/60—Optical bleaching or brightening
    • D06L4/657—Optical bleaching or brightening combined with other treatments, e.g. finishing, bleaching, softening, dyeing or pigment printing
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/13—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using azomethine dyes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/16—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using dispersed, e.g. acetate, dyestuffs
    • D06P1/18—Azo dyes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/16—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using dispersed, e.g. acetate, dyestuffs
    • D06P1/20—Anthraquinone dyes

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Coloring (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Diaphragms For Electromechanical Transducers (AREA)
  • Detergent Compositions (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Compounds Of Unknown Constitution (AREA)

Abstract

Disclosed is a method for brightening textile materials by treating said materials with optical brighteners in an aqueous bath. The inventive method is characterized by the fact that 20 to 80 percent by weight of compound (I) are used as optical brighteners, the percentage by weight being in relation to the total of all brightening compounds and up to 40 molar percent of (I) being in the form of cis isomer, 80 to 20 percent by weight of at least one compound (II), selected among (II m, p'), (II p, o'), (II o, o'), (II p, p'), and 0 to 30 percent by weight of a compound of general formula (III), in which R is selected among C4-C10 alkyl. The treatment is done in the presence of one or several shading blue or purple dyes from the class of anthrachinones, azo dyes, or methine dyes.

Description

The method of whitening of textile material
The present invention relates to a kind of by handle the method that textile material is brightened with the aqueous solution of fluorescent whitening agent, this method is included in can select to exist one or more blueness or following Compound I of using (each percentage is benchmark with the total amount that all brighten compound) 20～80 weight % of purple dope dye (shading dyes) from anthraquinone, azo dyes or methine dyes
Wherein 40mol% can exist with cis-isomer at the most; At least a Compound I I that is selected from following material with 80～20 weight %;
Figure A0381003500052
And at least a compound with general formula III of 0～30 weight %,
Figure A0381003500061
Wherein R is selected from C 4-C 10-alkyl.
As the auxiliary agent of textile industry and plastics industry, fluorescent whitening agent has huge Economic Importance.Known chemical compound lot can make textiles or plastics have white.Yet also there is disadvantage in these compound known of great majority.For example, known compound from EP 0 023 026 with general formula 1,
Figure A0381003500062
R wherein 1And R 2Can be respectively for example hydrogen, fluorine, chlorine, phenyl, trifluoromethyl, alkyl or multiple other group, V be selected from
-CH＝CH-
And it can be used at low temperatures, but owing to need make many goods reach required white effect, so their efficient is limited.
Be known that in addition wherein said compound can be from for example learning CH-A 366 512, CH-A 382 709, CH-A 388294, CH-A 389 585, CH-A 411 329, CH-A 416 078 and the CH-A 465 548 by handling the method that textiles is brightened with the diphenylethyllene benzene compound.The list of references of quoting among EP-A 0 023 027 and EP-B2 0 030 917 and the EP-B2 0 030 917 has illustrated and has used two or more dicyano styrene base benzene compounds that polyester is carried out fluorescent brightening.
EP 0 023 026 discloses the mixture of fluorescent whitening agent, its contain 0.05～0.95 weight portion one or more have the compound of formula 2p
Wherein A is by adjacent-or phenyl of replacing of right-cyano group; Be selected from the other compound of numerous other compounds with one or more of 0.95～0.05 weight portion.2p preferably, o '
Mixture with compound with general formula 1
Figure A0381003500073
, the R of its Chinese style 1 1And R 2Can be respectively: hydrogen, fluorine, chlorine, phenyl, trifluoromethyl, C 1-C 9-alkyl, alkoxyl, alkyl amino and multiple other group of lifting at the 2nd page of 14-21 ranks, V defines as mentioned,
Perhaps with the mixture of compound with formula 3b-4b
Wherein B is a functional group, R 1And R 2Definition as mentioned respectively, n is an integer, R 3Be selected from hydrogen and C 1-C 4-alkoxyl, R 4Be selected from C 1-C 4-alkoxyl, R 5Be selected from for example C 1-C 6-alkyl, B is preferably functional group, perhaps in addition with the mixture with compound of formula 5b-6b
Figure A0381003500081
R wherein 6To R 10Be selected from multiple group respectively, V defines as mentioned.
From this species diversity of embodiment, table 2 understands that for example these mixtures mainly are meant 2p, o ' or other isomers and 3c
Figure A0381003500082
With with the mixture of the derivative of following 4b.1 and 4b.2.
Figure A0381003500083
Can use the brightening agent with this definition by several different methods, this brightening agent can provide good CIE whiteness.
EP-A 0 023 028 is claimed contain 0.05～0.95 weight portion by 20～100 weight %2p, o '
Respectively be the 2p of 0～80 weight %, p ' and 2o, the mixture that o ' compound is formed
Figure A0381003500092
With the mixture of the derivative of one or more formulas 1a of 0.05～0.95 weight portion and 3a-6a, this mixture can be used as fluorescent whitening agent, and wherein basic the and EP-A's 0 023 026 of the definition of 1a and 3a-6a is similar.
DE-A 197 32 109 has illustrated the derivative by 1a type compound
Figure A0381003500093
(R wherein 1And R 2Be H or C independently 1-C 6-alkyl, A are selected from N and CH, and X is selected from
-CH＝CH-
With Stilbene base, styryl or imidazole radicals) with isomers or a kind of formula 4 of one or more formulas 2
Figure A0381003500101
Derivative or the mixture of multiple other derivative (for example with 5b (the seeing above)) method of polyamide or polyurethane being carried out fluorescent brightening.As demonstration, specified the mixture of (embodiment 19-21) 1a.1 and 4b.1.
Figure A0381003500102
These mixtures are demonstrating synergy aspect CIE whiteness and the good light fastness.
EP-A 0 321 393 has illustrated 1b type compound
(wherein D is C 1-C 4-alkyl) and the purposes of formula 2 compounds in the brightening agent dispersion.1b or 2 type compounds itself are disclosed or are disclosed with the form of specific mixture, have mentioned 1b or 2 type compounds with mixture 1-6 in the list of references of being quoted (6-8 page or leaf).The 9th page of 18 row in EP-A 0 321 393 illustrated that the crucial part of this invention is the copolymer that described mixture contains 2-vinyl pyrrolidone and 3-vinyl propionic acid.
In EP-A 0 682 145, by handling the light resistance that improves textiles with the preparation that contains the fluorescence UV absorbent that absorbs at 280nm～400nm wavelength place, wherein said fluorescence UV absorbent is selected from 4,4 '-two Triazinylaminostilbedisulphonics-2,2 '-disulfonic acid, 4,4 '-xenyl Stilbene, 4,4 '-distyryl biphenyl, 4-phenyl-4 '-benzoxazolyl Stilbene, Stilbene base aphthotriazoles, 4-styryl Stilbene, cumarin, pyrazoline, the benzene-naphthalene diimide class, the triazine radical pyrene, 2-styryl benzoxazole or 2-styryl Nai Bing oxazole derivative, the benzimidazole benzofuran, oxanilide derivative and Er benzoxazole-2-base and bisbenzimidazole-2-radical derivative, the derivative of formula 1c or 1d (claim 8) for example
Figure A0381003500111
Wherein
Each R 14Be hydrogen or C independently 1-C 4-the alkyl or the tert-butyl group or-C (CH 3) 2-phenyl or COO-C 1-C 4-alkyl, R 15And R 16Identical or different and be selected from H, C 1-C 4-alkyl and CH 2-CH 2-OH, each R 17Identical or different and be selected from H and SO 3-,
X is selected from
Figure A0381003500112
Figure A0381003500113
-CH＝CH-
And X 1Be selected from
Figure A0381003500121
-CH＝CH-。
Yet sunproof raising is subjected to usually except that the control to the other factors the fluorescent brightening effect of textiles.
Bright white (for example in plastic products of textiles and moulding) in numerous goods has huge Economic Importance.Above the white that shows of the mixture that particularly illustrates in the embodiment of EP-A 0 023 026 and EP-A 0 023 028 and EP-A 0 682 145 of Shuo Ming multiple mixture is not enough to satisfy the bright effect that the consumer requires usually.In addition, other performance characteristic also has much room for improvement.At last, wish that for the factor of economic aspect brightening agent is more effective, because need realize identical or better effect with less brightening agent.
The purpose of this invention is to provide
-a kind of method that textile material is brightened, it can provide effect and improved efficient and other same improved performance characteristic of special brilliant white;
-be used to make the method that textile material brightens preparation and
The purposes of-this new formulation.
We have found that this purpose can start the method realization of definition by this paper.
The textile material that is used for the object of the invention comprises fiber, shred, yarn, filament, textiles, knitting, nonwoven product and the clothes of being made up of for example polyester or polyester mixture.Textile material is preferably by synthesizing polyester or contain the mixture of 45～90 weight % polyester.
Brighten compound or the fluorescent brightening compound that are used for the object of the invention also can be at upper wavelength place emitted fluorescence compounds for being received in enough suction the in 280～400nm place.Example comprises the compound from following type: Stilbene, diphenylethyllene benzene, xenyl talan, triazines, benzoxazole, Er benzoxazole, dibenzo oxazolyl thiophene, dibenzo oxazolyl naphthalene, pyrene, cumarin and naphthalene peri-position dicarboximide (naphthaleneperidicarboximide).Brighten or the fluorescent brightening compound is meant brightening of formula I, II and III or fluorescent brightening compound especially.Unless explain especially in addition, hereinafter percetage by weight should be to brighten the total amount of compound.
Terminology used here " aqueous solution " also comprises except the water as main component and also contains the solution of one or more other solvents of 40 volume % (for example alcohols such as ethanol) at the most.The pH of solution used according to the invention is preferably 3～12, and more preferably 3～8.
The method that this paper starts definition is specially by with following mass treatment textile material: 20～80 weight %, preferred 20～70 weight %, the more preferably formula I compound of 30～50 weight %
Figure A0381003500131
Wherein 40mol% can be corresponding cis-isomer form at the most; At least a formula II compound with 80～20 weight %;
Figure A0381003500132
And the compound of 0～30 weight % general formula III,
Figure A0381003500141
Wherein R is selected from C 4-C 10-alkyl, for example normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, n-pentyl, isopentyl, sec-amyl, neopentyl, 1,2-dimethyl propyl, isopentyl, n-hexyl, isohesyl, Sec-Hexyl, n-heptyl, different heptyl, n-octyl, 2-ethylhexyl, n-nonyl and positive decyl; Preferred normal-butyl and 2-ethylhexyl.
Except the formula I compound of 20～80 weight %, also preferred the use: the Compound I I p of the compound of 0～30 weight % general formula III and each 20～70 weight %, o ' or m, at least a among the p '.
Especially preferably use the Compound I I p of 20～70 weight %, the Compound I I m of o ' and 10～50 weight %, the compound of the Compound I of p ' and 20～70 weight % and the general formula III of 0～30 weight %.
Another particularly preferred embodiment is except the compound of the general formula III of 30～50 weight % Compound I and 0～30 weight %, also use the Compound I I p of 30～60 weight %, the Compound I I o of o ', 10～30 weight %, o ' and the Compound I I m of 10～50 weight % selectively, p '.
For example according to US 2,842,545, US 2,875,089 or US 3,147, the mode synthetic compound I described in 253.For the present invention, the definition of I also comprises the isomer mixture that contains 0.2～40mol%, preferred 0.7～20mol% cis-isomer.The percentage of cis-isomer is definite by spectrum well known to those skilled in the art or chromatography, referring to for example J.Chromat.1967, and 27 (2), 413-22.
Use dicyano styrene based compound II p, o ', II m, p ', II p, p ' and II o, o ' with the form of its transisomer.They contain the isomers with at least one cis-double bonds of 0.01～10mol%, preferred 0.1～5mol% usually, and the percentage of cis-isomer is determined by spectrographic technique well known by persons skilled in the art.They can easily react by benzene dicarboxyl aldehyde and corresponding cyano group benzyl phosphamide (cyanobenzyl phosphorylide) are obtained by double Wittg.
In implementing the method according to this invention, advantageously add one or more bluenesss or purple dope dye.Available dope dye generally belongs to DISPERSE DYES and reducing dye class.These are custom names.Colour Index has listed these dyestuffs for example Disperse Blue (disperse blue) or DisperseViolet (disperse violet) or Vat Blue (vat blue) or Vat Violet (reduction is purple).
Blue dyes from anthraquinone, azo dyes or methine dyes is especially suitable.
Dyestuff from anthraquinone meets for example formula A1-A4,
Figure A0381003500151
Wherein
Z 1For by 1 in the ether official energy 2 oxygen atoms interrupt or not by its interruption and by C 1-C 4-alkoxy carbonyl group or cyano group replace or not by the C of its replacement 1-C 10-alkyl perhaps is by C 1-C 4-alkoxyl, phenyl replace or not by the phenyl of its replacement,
Z 2By 1 in the ether official energy 2 oxygen atoms interrupt or not by its interruption and by hydroxyl, phenyl or C 1-C 8-alkoxy carbonyl group replaces or not by the C of its replacement 1-C 10-alkyl,
Z 3Be oxygen or N-H,
Z 4Be hydrogen, perhaps be by 1 in the ether official energy 2 oxygen atoms interrupt or not by its interruption and by C 1-C 4-alkoxy carbonyl group or cyano group replace or not by the C of its replacement 1-C 10-alkyl is not perhaps for replacing or by C 1-C 4The phenyl that-alkoxyl replaces,
Z 5Be hydrogen or halogen or CN,
Z 6Be hydrogen or nitro,
Z 7Be C 2-C 6-alkylidene or phenylene.
Dyestuff mentioned above is usually known dyestuff.For example at US-A 2,628,963, US-A3,835,154, described the dyestuff of formula A2 among DE-A 12 66 425 or the DE-A 20 16 794.The dyestuff that meets formula A1, A3 and A4 for example can be from K.Venkataraman, and " The Chemistryof Synthetic Dyes ", the 3rd volume, the 391-423 page or leaf is learnt in 1970.
Suitable azo dyes is in particular the monoazo dyes of the coupling component of diazo component with aniline or heterocyclic and aniline or heterocyclic.
The suitable heterocyclic compound that diazo component is derived from is from for example aminothiophene class, aminothiazole class, aminoisothiazoles class, amino thiadiazole or amino benzo isothiazole.
The suitable heterocyclic compound that coupling component is derived from is from for example thiazoles or diamino-pyridine class.
More particularly, this azo dyes meets a kind of among the formula B1-B7
Figure A0381003500181
Wherein
Z 8Be formoxyl, cyano group, C 1-C 4-alkoxy carbonyl group or benzenesulfonyl,
Z 9Be hydrogen, halogen, C 1-C 8-alkoxyl, phenoxy group, C 1-C 6-alkylthio group, thiophenyl, C-C 4-alkyl sulphonyl, benzenesulfonyl, methyl or do not replace or by chlorine, methoxyl group, ethyoxyl or methyl substituted phenyl,
Z 10For cyano group, by one or two oxygen atom interruption in the ether official energy of alkyl chain or not by the C of its interruption 1-C 6-alkoxy carbonyl group, carbamoyl or list-or two-C 1-C 4-alkyl-carbamoyl,
Z 11And Z 12Be independently interrupted by 1-3 oxygen atom in the ether official energy or not by its interruption and by hydroxyl, cyano group, chlorine, phenyl, C 1-C 6-alkoxyl, C 1-C 6-alkoxy carbonyl group, C 1-C 6-alkoxyl carbonyl oxygen base or list-or two-C 1-C 6-alkyl amino carbonyl oxy replaces or not by the C of its replacement 1-C 8-alkyl perhaps is C 3-C 4-alkenyl, perhaps Z 11Be hydrogen Z 2Be not hydrogen,
Y 1Be hydrogen, C 1-C 4-alkyl, C 1-C 4-alkoxyl, chlorine, bromine perhaps have formula-NH-CO-R 11Group, R wherein 11For by C 1-C 4-alkoxyl, cyano group, hydroxyl, chlorine or C 1-C 4-alkanoyl oxygen base replaces or not by the C of its replacement 1-C 4-alkyl perhaps is C 2-C 3-alkenyl,
Y 2Be hydrogen, C 1-C 4-alkyl or C 1-C 4-alkoxyl,
Z 13For not replacing or by C 1-C 4The C that-alkoxyl replaces 1-C 4-alkyl does not replace or by C 1-C 4The benzyl that-alkoxyl replaces, the phenyl, 2-pyridine radicals or the 3-pyridine radicals that do not replace or replaced by chlorine, methyl, methoxy or ethoxy,
Z 14Be cyano group, chlorine or bromine,
Z 15For not replacing or by C 1-C 4Thienyl that-alkoxyl or acetylamino replace or pyridine radicals and
Z 16Be cyano group, chlorine or bromine.
Azo dyes mentioned above is known in essence.For example at US 5,283, the dyestuff of formula B1 and B2 has been described in 326 or US5,145,952.EP-A 0 087 616, EP-A 0 087 677, EP-A 0 121 875, EP-A 0 151 287 and US 4,960,873 disclose the dyestuff of formula B3.US5,216,139 disclose the dyestuff of formula B4.US 5,132, and 412 disclose the dyestuff of formula B5 class.For example at US 3,981,883, DE-A 31 12 427, EP-A 0 064 221 or at Venkataraman " TheChemistry of Synthetic Dyes ", the 3rd volume, described the dyestuff of formula B6 and B7 in the 444-447 page or leaf, perhaps can obtain by the method for wherein mentioning.
Suitable methine dyes meets for example formula C
Wherein
Y 3Be nitrogen or CH,
Z 18For being substituted or unsubstituted and interrupted by one or more oxygen atoms in the ether official energy or not by the C of its interruption 1-C 20-alkyl, phenyl replacement or unsubstituted or hydroxyl,
Z 19Be the pentahydric aromatic heterocycle base,
Z 20Be hydrogen, cyano group, carbamoyl, carboxyl or C 1-C 4-alkoxy carbonyl group,
Z 21For oxygen or have formula C (CN) 2, C (CN) COOZ 23Or C (COOZ 23) 2Group, Z wherein 23Be respectively and interrupted by 1 or 2 oxygen atom in the ether official energy or not by the C of its interruption 1-C 8-alkyl,
Z 22Be hydrogen or C 1-C 4-alkyl.
Unless otherwise mentioned, substituted alkyl can have following substituting group among the formula C: for example phenyl, C 1-C 4-alkyl phenyl, C 1-C 4-alkoxyl phenyl, halogenophenyl, C 1-C 8-alkanoyloxy, C 1-C 8-alkyl amino carbonyl oxy, C 1-C 20-alkoxy carbonyl group, C 1-C 20-alkoxyl carbonyl oxygen base (alkyl chain of described back two kinds of groups is selectively interrupted by 1-4 oxygen atom in the ether official energy and/or replaced by phenyl or phenoxy group), halogen, hydroxyl or cyano group.Substituent number is generally 1 or 2 in substituted alkyl.
Unless otherwise mentioned, the alkyl that is interrupted by the oxygen atom in the ether official energy that occurs in formula C is preferably by 1-4 alkyl that oxygen atom, particularly 1-2 oxygen atom interrupts in the ether official energy.
The substituted phenyl or the pyridine radicals that occur among the formula C can have following substituting group: C for example 1-C 8-alkyl, C 1-C 8-alkoxyl, halogen (particularly chlorine or bromine) or carboxyl.Substituent number is generally 1-3 in substituted phenyl or pyridine radicals.
Z 19Group can be derived from for example pyrroles, thiazole, thiophene or indoles.
Important Z 19Group comprises those groups that for example have formula C1-C4,
Wherein
M is 0 or 1,
Z 24And Z 25Identical or different and be hydrogen independently of one another, replace or unsubstituted and interrupted by one or more oxygen atoms in the ether official energy or not by the C of its interruption 1-C 20-alkyl replaces or unsubstituted phenyl, or it unites to form with middle nitrogen-atoms and have or do not have other heteroatomic 5-or the first saturated heterocyclic group of 6-,
Z 26Be hydrogen, halogen, C 1-C 8-alkyl, do not replace or by C 1-C 4-alkyl-or C 1-C 4The phenyl that-alkoxyl replaces, do not replace or by C 1-C 4-alkyl-or C 1-C 4Benzyl, cyclohexyl, thienyl, hydroxyl or C that-alkoxyl replaces 1-C 8-alkyl monosubstituted amino,
Each Z 27Identical or different and represent hydrogen, hydroxyl independently, do not replace or by phenyl or C 1-C 4The C that-alkyl phenyl replaces 1-C 8-alkyl, do not replace or by phenyl or C 1-C 4The C that-alkyl phenyl replaces 1-C 8-alkoxyl, C 1-C 8-alkanoylamino, C 1-C 8-alkyl sulfonyl-amino or list-or two-C 1-C 8-alkyl sulfonyl amino amino,
Z 28Be cyano group, carbamoyl, list-or two-C 1-C 8-alkyl-carbamoyl, C 1-C 8-alkoxy carbonyl or replacement or unsubstituted phenyl and
Z 29Be halogen, hydrogen, C 1-C 4-alkyl, C 1-C 4-alkoxyl, C 1-C 4-alkylthio group, do not replace or by C 1-C 4-alkyl or C 1-C 4Phenyl or thienyl that-alkoxyl replaces.
For example in existing German patent application DE-A 44 03 083, these methine dyeses have been described.
Particularly importantly wherein handle the method for polyester or polyester mixture in the presence of from one or more bluenesss of anthraquinone class (particularly have formula A those) or purple dope dye.
When implementing described method in the presence of the dyestuff (being known as C.I.Disperse Violet 28 (61102) again) at formula A 3.1, the technique effect of this method is good especially.
Weight in textile material to be brightened, the amount that brightens compound used according to the invention is 0.005～0.07 weight %, preferred 0.02～0.05 weight %, and its white effect that provides is identical or better with the white effect that the fluorescent brightening material of prior art provides.
In the weight of textile material to be brightened, the blueness of use or purple dope dye are generally 0.00005～0.02 weight %, preferred 0.0005～0.002 weight %.But the use of dope dye not necessarily.
Usually by dip method (exhaust process) or by the thermosol method textile material is brightened.
Under 90 to 135 ℃, common about 130 ℃, in the aqueous solution, carry out dip method greatly.For the application that is higher than 100 ℃, must use autoclave, high-tension apparatus or high-pressure installation.The thermosol method is under atmospheric pressure carried out.
Usually the textile material by will be to be brightened infeeds and implements dip method in the aqueous solution, the wherein said aqueous solution contains fluorescent brightening compound, selectable blueness or purple dope dye or its mixture and selectable additive (for example dispersant, carboxylic acid or alkali donor), its pH is generally 3～12, preferred 3～8, temperature is 10～35 ℃.Flowing fluid ratio (weight ratio of liquid and textile material) is 3: 1～40: 1, preferred 5: 1～20: 1.In 15-30 minute, described solution is heated to 90～130 ℃ then, preferred 95～100 ℃, and remained under this temperature 15-60 minute.After this, flushing and the dry textile material that brightens.
In the thermosol method, usually treating the textile material that brightens with the aqueous solution carries out pad dyeing (pad-mangling), and the wherein said aqueous solution contains fluorescent brightening material, selectable blueness or purple dope dye or its mixture and selectable additive (seeing above).Wet adhesion amount is generally 50%～100%.Then, dry textile material and it was kept 5～60 seconds down at 150～200 ℃.
The dispersant that uses is preferably colourless and at the stable dispersant of following jaundice effect up to 210 ℃ at least.
The example of Shi Yi dispersant is anion or non-ionic dispersing agent especially, particularly from the ethylene oxide adduct of fatty alcohol, higher fatty acids or alkyl phenol or the anion or the non-ionic dispersing agent of ethylenediamine-epoxy ethane-epoxy propane adduct.
Particularly preferred dispersant is an alkoxylated polymerization product, and it can trade mark Synperonic based on aliphatic series or alkyl aromatic hydroxyl, amino or hydroxy amino compound And Ukanil , Dehypon , Neopol Ethoxylate, Emulan , Lutensol , Plurafac And Pluronic Or Elfapur Commercially available obtaining.Particularly preferably be alkoxylate phenol.Dispersant very particularly preferably is alkoxylate phenol or its mixture with general formula I V and V,
Figure A0381003500231
Wherein
A and b are integer, like this
A is in 0～180, preferably is in 0～125,
B is in 20～180, is in 35～125 especially, and condition is b 〉=a;
M is an alkali metal, preferred Na or K, more preferably Na;
D is 0 or 1.
The preparation method of compound IV and V is known, and can advantageously pass through phenol VI and VII
Respectively with propylene oxide reaction with subsequently with this adduct and reacting ethylene oxide or by VI and VII are prepared compound IV and V with reacting ethylene oxide respectively.Can this adduct be changed into acid sulfate wholly or in part with chlorosulfonic acid or sulfur trioxide then, and the acid ester of gained can be neutralized with alkali.
Can by in the presence of as the acid of catalyst with bisphenol-A (2,2-(p, p '-dihydroxybiphenyl base) propane) or phenol respectively with 4 or 2mol styrene react and obtain the phenol of formula VI or VII.By known method at acidity or base catalyst (NaOCH for example 3Or SbCl 5) exist down at first with expoxy propane with then with oxirane or only with oxirane phenol VI and VII are changed into accordingly wherein alkoxylated polymerization product IV and the V of d=0 respectively.Alkoxylation can for example pass through US2, and the method for describing in 979,528 realizes.
By alkoxylated polymerization product and chlorosulfonic acid or sulfur trioxide reaction prepares acid sulfate, select sulfovinic acid salinization that the amount of chlorosulfonic acid or sulfur trioxide makes that all dissociate or its that certain percentage sulfation is only arranged.The latter can produce contains free and the formula IV of hydroxyl sulfation or the mixture of V compound.For the purposes as surfactant, He Cheng acid sulfate is converted to water soluble salt like this.Favourable water soluble salt comprises alkali metal, for example sodium or sylvite.Chlorosulfonic acid needs 2 equivalent alkali compoundss, and sulfur trioxide needs 1 equivalent alkali compounds.Used alkali compounds advantageously is an aqueous alkali metal hydroxide.Temperature should be above 70 ℃ in the N-process.The salt of gained can use or use with its separation and with solid form with the form of the aqueous solution.
Preferably wherein a be 0～average 2.5, b average out to 25～250, d are 0～average 0.5 dispersant IV and V.Particularly preferably be wherein a and be 0～average 2.5, b average out to 50～100, the dispersant IV and the V of d average out to 0.5.
The compound of formula IV and V is known, and is for example describing multiple representative instance among the US 4,218,218.
The additive that can select to add also comprises antimicrobial and the water retention aid that for example is usually used in industrial textile.The additive that can select to add also comprises the N-vinyl pyrrolidone of description among the EP-A 0 321 393 and the copolymer of 3-vinyl propionic acid.
The preferred embodiment of this method has been used the preparation with following feature: except water, also contain the brightening agent that (each percentage is benchmark with the weight of preparation) 1～40 weight %, preferred 3～10 weight % above enumerate and the mixture of dope dye; The copolymer of 3～12 weight % anion or non-ionic dispersing agent, 1～15 weight %N-vinyl pyrrolidone and vinyl acetate or propionate or its mixture; With 1～25 other additive of weight % (for example water retention aid or antimicrobial).
Method of the present invention not only can but also can provide outstanding white effect for textile material in dip method in the thermosol method.The material that is brightened has excellent special-purpose fastness.
Can infeed dope dye that separately pre-dispersed fluorescent brightening material and every kind can select to use, dispersant and/and other additive prepares the above-mentioned aqueous solution by metering respectively.
Yet method of the present invention is preferably by using fluorescent brightening compound and selectable one or more above-mentioned dope dyes, dispersant and other additive to carry out as preparation.Therefore the present invention also provides the preparation that contains following material (each percentage is benchmark with the total amount that all brighten compound):
20～80 weight % Compound I;
At least a Compound I I of 20～80 weight %;
At least a formula III compound of 0～30 weight %;
In each case selectively
One or more from the blueness of anthraquinone, azo dyes, methine dyes, violanthrone or indanthrone class or purple dope dye,
One or more dispersants,
Water and other additive.
Usually the mixture that contains the compound that quilt that water and (each percentage is benchmark with the weight of preparation) 1～40 weight %, preferred 3～25 weight % above enumerate brightens according to preparation of the present invention, selectively 0.001～0.1 weight % dope dye, the selectively additive of 0.5～40 weight % dispersant and 5～60 weight %, preferred 5～52 weight %.
The present invention also provides preparation according to the present invention to be used to make the particularly purposes that brightens of polyester or polyester mixture of textile material.
The following examples have illustrated the present invention.
General description
Isomeric distribution is as follows: I cis-trans, 95: 5mol%; II p, o ', II mp ', II o, o ' is higher than the trans of 95mol% in every kind, passes through respectively 1H NMR spectroscopic methodology is determined.
I. high temperature dip method
In autoclave, containing adding 10kg polyester textile in the 100 liters of dye baths of brightening compound (it disperses (" finishing ") also to add then separately) total concentration in water shown in the table 1 under 25 ℃.In 30 minutes, dye bath is heated to 130 ℃ and kept 30 minutes down then at 130 ℃.Shift out this fabric then from bathe, flushing is also dry.Determine that optics CIE whiteness is used for analyzing in situation separately.
Contrast experiment (V) uses 50 weight %II o respectively, and 4 in EP 0 023 026 tables 2 of p ' and 50 weight % b.1.
Figure A0381003500261
Table 1 brightens polyester textile by dip method with the multiple mixture of fluorescent brightening compound
Sequence number Brighten compound [weight %] Total concentration in the solution The CIE whiteness
????I ?II?p，o’ II?m，p’ ?4?b.I
????1.1 ????45 ????55 ????- ??- ????0.02 ????147
????1.2 ????45 ????55 ????- ??- ????0.03 ????155
????1.3 ????45 ????55 ????- ??- ????0.057 ????166
????1.4 ????45 ????55 ????- ??- ????0.077 ????167
????1.5 ????45 ????55 ????- ??- ????0.095 ????167
????1.6 ????40 ????40 ????20 ??- ????0.02 ????150
????1.7 ????40 ????40 ????20 ??- ????0.03 ????158
????1.8 ????40 ????40 ????20 ??- ????0.057 ????164
????1.9 ????40 ????40 ????20 ??- ????0.077 ????169
????1.10 ????40 ????40 ????20 ??- ????0.095 ????169
????V?1.11 ????- ????50 ????- ??50 ????0.02 ????145
????V?1.12 ????- ????50 ????- ??50 ????0.03 ????153
????V?1.13 ????- ????50 ????- ??50 ????0.057 ????163
????V?1.14 ????- ????50 ????- ??50 ????0.077 ????163
????V?1.15 ????- ????50 ????- ??50 ????0.095 ????163
More a spot of when brightening compound when using under situation separately, method of the present invention can provide the effect stronger than the prior art method.Similarly, method of the present invention has realized being issued to maximum whitening effect at the fluorescent brightening material of low concentration.
2. thermosol method
By at room temperature polyester textile being carried out the pad dyeing embodiment 2.1-2.8 that carries out an invention with the aqueous solution that contains the fluorescent brightening compound in the 0.8g/l composition hereinafter described altogether.With acetate with pH regulator to 5.5.Wet adhesion amount is 60%.Then at 110 ℃ of following dry fabric 20s, fixation 30 seconds under the temperature shown in the table 2 afterwards.
Compare EXAMPLE V 2.9-V2.12 with similar approach, the different 50 weight %IIo that are to use, p ' and 50 weight % are from the 0.8g/l solution of the mixture of the following formula: compound of EP 0 023 026 tables 2.
With comparing EXAMPLE V 2.13-V2.16 with the similar method of inventive embodiments, the different 70 weight %II o that are to use 1.5g/l, p ' and 30 weight %II o, the mixture of o '.
Table 2 brightens polyester textile by the thermosol method with the multiple mixture of fluorescent brightening compound;
Fixation under different temperatures.
Sequence number Brighten compound [weight %] Color fixing temperature [℃] The CIE whiteness
????I ?II?p，o’ II?m，p’ II?o，o’ ??4?b.1
????2.1 ????45 ????55 ????- ????- ????- ????140 ????133
????2.2 ????45 ????55 ????- ????- ????- ????150 ????139
????2.3 ????45 ????55 ????- ????- ????- ????160 ????142
????2.4 ????45 ????55 ????- ????- ????- ????170 ????144
????2.5 ????40 ????40 ????20 ????- ????- ????140 ????135
????2.6 ????40 ????40 ????20 ????- ????- ????150 ????139
????2.7 ????40 ????40 ????20 ????- ????- ????160 ????142
????2.8 ????40 ????40 ????20 ????- ????- ????170 ????143
????V?2.9 ????- ????50 ????- ????- ????50 ????140 ????128
????V?2.10 ????- ????50 ????- ????- ????50 ????150 ????132
????V?2.11 ????- ????50 ????- ????- ????50 ????160 ????136
????V?2.12 ????- ????50 ????- ????- ????50 ????170 ????137
????V?2.13 ????- ????70 ????- ????30 ????- ????140 ????130
????V?2.14 ????- ????70 ????- ????30 ????- ????150 ????135
????V?2.15 ????- ????70 ????- ????30 ????- ????160 ????136
????V?2.16 ????- ????70 ????- ????30 ????- ????170 ????140
The inventive method uses the fluorescent brightening compound of less or same amount just can provide stronger effect under identical color fixing temperature.

Claims (12)

1. method by handling textile material is brightened with the aqueous solution of fluorescent whitening agent, this method is included in can select to exist one or more from the blueness of anthraquinone, azo dyes or methine dyes or the Compound I of following 20～80 weight % of use of purple dope dye
Figure A038100350002C1
Wherein 40mol% can exist with cis-isomer at the most; At least a Compound I I that is selected from following material with 80～20 weight %;
Figure A038100350002C2
And at least a compound with general formula III of 0～30 weight %,
Figure A038100350003C1
Wherein R is selected from C 4-C 10-alkyl, each percentage is benchmark with the total amount that all brighten compound.
2. according to the process of claim 1 wherein the Compound I Ip that uses 20～70 weight %, the compound of the Compound I of o ' and 20～80 weight % and the general formula III of 0～30 weight %.
3. according to the method for claim 1 or 2, wherein use 20～70 weight % Compound I Im, the compound of the Compound I of p ' and 20～80 weight % and the general formula III of 0～30 weight %.
4. use 20～70 weight % Compound I Ip, the Compound I Im of o ' and 10～50 weight %, the compound of the Compound I of p ' and 20～70 weight % and the general formula III of 0～30 weight % according to the process of claim 1 wherein.
5. according to the process of claim 1 wherein the Compound I Ip that uses 30～60 weight %, the Compound I Io of o ' and 10～30 weight %, the compound of the Compound I of o ' and 30～60 weight % and the general formula III of 0～30 weight %.
6. according to the method for claim 1, wherein use the Compound I Ip of 20～60 weight %, the Compound I Im of o ', 10～50 weight %, the Compound I Io of p ' and 10～30 weight %, the compound of the Compound I of o ' and 20～50 weight % and the general formula III of 0～30 weight %.
7. according to the method for aforementioned each claim, wherein R is the 2-ethylhexyl in compound III.
8. according to the method for aforementioned each claim, wherein brighten one or more dispersants of other use 0.5～200 weight % of total amount of compound in all.
9. according to the method for aforementioned each claim, wherein textile material is a polyester.
10. according to the method for aforementioned each claim, wherein textile material is the mixture that contains 45～90 weight % polyester.
11. a preparation, it contains each percentage and brightens the Compound I of total amount 20～80 weight % of compound in all; At least a Compound I I of 20～70 weight %; At least a formula III compound of 0～30 weight %; And in each case can be randomly from one or more bluenesss or the purple dope dye of anthraquinone, azo dyes or methine dyes, violanthrone or indanthrone; One or more dispersants; Water and other additive.
12. be used to purposes that textile material is brightened according to the preparation of claim 11.
CNB038100355A 2002-05-03 2003-04-30 Method for brightening textile materials Expired - Fee Related CN1333129C (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10219993A DE10219993A1 (en) 2002-05-03 2002-05-03 Process for lightening textile materials
DE10219993.0 2002-05-03

Publications (2)

Publication Number Publication Date
CN1650064A true CN1650064A (en) 2005-08-03
CN1333129C CN1333129C (en) 2007-08-22

Family

ID=29265083

Family Applications (1)

Application Number Title Priority Date Filing Date
CNB038100355A Expired - Fee Related CN1333129C (en) 2002-05-03 2003-04-30 Method for brightening textile materials

Country Status (15)

Country Link
US (1) US20050235429A1 (en)
EP (1) EP1504149B1 (en)
JP (1) JP2005529245A (en)
KR (1) KR100973535B1 (en)
CN (1) CN1333129C (en)
AT (1) ATE302871T1 (en)
AU (1) AU2003222312A1 (en)
BR (1) BR0309642B1 (en)
DE (2) DE10219993A1 (en)
ES (1) ES2246470T3 (en)
HR (1) HRPK20041141B3 (en)
MX (1) MXPA04010130A (en)
TW (1) TWI279468B (en)
WO (1) WO2003093565A2 (en)
ZA (1) ZA200409769B (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101910395B (en) * 2008-01-11 2012-04-18 荷兰联合利华有限公司 Shading composition
CN103314154A (en) * 2011-01-20 2013-09-18 亨斯迈先进材料（瑞士）有限公司 Formulations of fluorescent whitening agents in dispersed form
CN112048075A (en) * 2020-08-26 2020-12-08 盐城工学院 Photochromic naphthalimide Cd-MOF, preparation method thereof, photochromic printing paste and application

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2316862T3 (en) * 2002-12-10 2009-04-16 Ciba Holding Inc. FLUORESCENT WHITENING AGENTS MIXTURES.
AR049538A1 (en) * 2004-06-29 2006-08-09 Procter & Gamble DETERGENT COMPOSITIONS FOR LAUNDRY WITH EFFICIENT DYING COLOR
PL1794276T3 (en) * 2004-09-23 2009-10-30 Unilever Nv Laundry treatment compositions
EP2009088B1 (en) * 2004-09-23 2010-02-24 Unilever PLC Laundry treatment compositions
DE102005039971A1 (en) * 2005-08-23 2007-03-08 Basf Ag Liquid detergent formulation
US20070174972A1 (en) * 2005-11-14 2007-08-02 Invista North America S.A R.I. Spandex having enhanced whiteness, and fabrics and garments comprising the same
EP1974006A1 (en) * 2006-01-18 2008-10-01 Ciba Specialty Chemicals Holding Inc. Process for the treatment of fiber materials
BRPI0706732B1 (en) * 2006-01-23 2017-06-06 Milliken & Co bleaching agent for laundry care compositions which is a thiazole dye
US20080177089A1 (en) 2007-01-19 2008-07-24 Eugene Steven Sadlowski Novel whitening agents for cellulosic substrates
US7642282B2 (en) 2007-01-19 2010-01-05 Milliken & Company Whitening agents for cellulosic substrates
WO2009074488A1 (en) * 2007-12-10 2009-06-18 Basf Se Dye formulation and process for the treatment of fiber materials
BR112012027594A2 (en) * 2010-04-29 2016-08-09 Unilever Nv laundry treatment composition and method of treating a textile for clothing
US8715368B2 (en) 2010-11-12 2014-05-06 The Procter & Gamble Company Thiophene azo dyes and laundry care compositions containing the same
US9163146B2 (en) 2011-06-03 2015-10-20 Milliken & Company Thiophene azo carboxylate dyes and laundry care compositions containing the same
US9796952B2 (en) 2012-09-25 2017-10-24 The Procter & Gamble Company Laundry care compositions with thiazolium dye

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2060762A1 (en) * 1970-12-10 1972-06-22 Henkel & Cie Gmbh Preparations for the production of cold bleach liquors, in particular washing liquors with a cold bleaching effect
DE2929687A1 (en) * 1979-07-21 1981-02-12 Hoechst Ag MIXTURES OF OPTICAL BRIGHTENERS
DE2929591A1 (en) * 1979-07-21 1981-02-05 Hoechst Ag MIXTURES OF OPTICAL BRIGHTENERS
DE3104992A1 (en) * 1981-02-12 1982-08-26 Hoechst Ag, 6000 Frankfurt "MIXTURES OF OPTICAL BRIGHTENERS"
EP0240461B1 (en) * 1986-04-02 1991-04-17 Ciba-Geigy Ag Mixtures of optical brighteners
DE3878550D1 (en) * 1987-11-27 1993-03-25 Ciba Geigy Ag LIGHTER DISPERSION.
DE3878540D1 (en) * 1987-11-27 1993-03-25 Ciba Geigy Ag LIGHTER DISPERSION.
PT682145E (en) * 1994-05-12 2005-01-31 Ciba Sc Holding Ag TEXTILE TREATMENT
EP0724012A1 (en) * 1995-01-27 1996-07-31 The Procter & Gamble Company Detergent compositions comprising bleaching agent and brightener
DE19732109A1 (en) * 1997-07-25 1999-01-28 Clariant Gmbh Mixtures of optical brighteners

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101910395B (en) * 2008-01-11 2012-04-18 荷兰联合利华有限公司 Shading composition
CN103314154A (en) * 2011-01-20 2013-09-18 亨斯迈先进材料（瑞士）有限公司 Formulations of fluorescent whitening agents in dispersed form
CN103314154B (en) * 2011-01-20 2016-09-14 亨斯迈先进材料（瑞士）有限公司 The fluorescent whitening agent formulation of discrete form
TWI558875B (en) * 2011-01-20 2016-11-21 杭斯曼高級材料公司 An aqueous dispersion containing fluorescent whitening agents, a process for brightening textile materials by treatment with an aqueous dispersion and the use of an aqueous dispersion
CN112048075A (en) * 2020-08-26 2020-12-08 盐城工学院 Photochromic naphthalimide Cd-MOF, preparation method thereof, photochromic printing paste and application

Also Published As

Publication number Publication date
US20050235429A1 (en) 2005-10-27
DE10219993A1 (en) 2003-11-20
WO2003093565A3 (en) 2004-03-04
HRPK20041141B3 (en) 2006-12-31
KR20040106453A (en) 2004-12-17
ES2246470T3 (en) 2006-02-16
JP2005529245A (en) 2005-09-29
AU2003222312A8 (en) 2003-11-17
EP1504149A2 (en) 2005-02-09
DE50301054D1 (en) 2005-09-29
BR0309642A (en) 2005-03-01
BR0309642B1 (en) 2013-11-05
EP1504149B1 (en) 2005-08-24
CN1333129C (en) 2007-08-22
WO2003093565A2 (en) 2003-11-13
HRP20041141A2 (en) 2005-06-30
MXPA04010130A (en) 2005-03-31
KR100973535B1 (en) 2010-08-03
ZA200409769B (en) 2006-06-28
ATE302871T1 (en) 2005-09-15
TWI279468B (en) 2007-04-21
TW200407483A (en) 2004-05-16
AU2003222312A1 (en) 2003-11-17

Similar Documents

Publication Publication Date Title
CN1650064A (en) Method for brightening textile materials
CN1066178C (en) Azo-dye mixer, azo-dye preparation and application thereof
CN1243794C (en) Trichromatic dyeing process
CN1245457C (en) Azoic disperse dye mixture
CN1039860A (en) Use dyeing and printing of cellulosic fibre materials with vat dyes
CN1088597A (en) Comprise the dye mixture that has from the azoic dyestuff of the coupling component of diamino-pyridine series
CN1111444A (en) Process for dyeing keratin-containing fibres
CN1865555A (en) Method for preparing wool comprising milk protein fiber and wool thereby
CN1204203C (en) Asymmetricazo-based metal complex dye, preparation thereof and acidic black dye composition containing the same
CN1861699A (en) Base tri element colour sublimed fastness balancing type dispersion gray dye mixture
CN1781996A (en) Dye component and its use
CN1102842A (en) Dye mixture which can react with fibres and dyeing fibres with same
CN1090305A (en) The purposes of pyridine dye
CN1847324A (en) Reactive fiber dye
CN1505666A (en) Reactive dye mixtures
CN1871306A (en) Disperse azo dyestuffs
CN1810892A (en) Novel reactive yellow dye compounds and mixture thereof
CN1045405A (en) Dispersed dyestuff composition used for dyeing polyester materials
CN1249173C (en) Fibre reactive dye
CN1173903A (en) Process for increasing the sun protection factor of cellulosic fibre materials
CN1923906A (en) Reactivity dye composition and application thereof
CN1286922C (en) Trichromatic dyeing process and dye mixtures used therein
TW201303112A (en) Method of dyeing polyester
CN1052494A (en) Phthalocyanine fibre-reactive dyes
CN1633473A (en) Azo dyestuffs

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
REG Reference to a national code

Ref country code: HK

Ref legal event code: DE

Ref document number: 1075683

Country of ref document: HK

C14 Grant of patent or utility model
GR01 Patent grant
REG Reference to a national code

Ref country code: HK

Ref legal event code: WD

Ref document number: 1075683

Country of ref document: HK

CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20070822

Termination date: 20200430

CF01 Termination of patent right due to non-payment of annual fee