EP0321393A1 - Optical brightener dispersion - Google Patents

Optical brightener dispersion Download PDF

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Publication number
EP0321393A1
EP0321393A1 EP88810793A EP88810793A EP0321393A1 EP 0321393 A1 EP0321393 A1 EP 0321393A1 EP 88810793 A EP88810793 A EP 88810793A EP 88810793 A EP88810793 A EP 88810793A EP 0321393 A1 EP0321393 A1 EP 0321393A1
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Prior art keywords
brightener
stable
alkyl
dispersion according
coor
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Granted
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EP88810793A
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German (de)
French (fr)
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EP0321393B1 (en
Inventor
Werner Dr. Fringeli
Martin Dr. Jöllenbeck
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Novartis AG
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Ciba Geigy AG
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    • EFIXED CONSTRUCTIONS
    • E21EARTH OR ROCK DRILLING; MINING
    • E21BEARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B43/00Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
    • E21B43/16Enhanced recovery methods for obtaining hydrocarbons
    • E21B43/24Enhanced recovery methods for obtaining hydrocarbons using heat, e.g. steam injection
    • E21B43/243Combustion in situ
    • E21B43/247Combustion in situ in association with fracturing processes or crevice forming processes
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06LDRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/60Optical bleaching or brightening
    • D06L4/65Optical bleaching or brightening with mixtures of optical brighteners
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06LDRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/60Optical bleaching or brightening
    • D06L4/664Preparations of optical brighteners; Optical brighteners in aerosol form; Physical treatment of optical brighteners
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S8/00Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
    • Y10S8/92Synthetic fiber dyeing
    • Y10S8/922Polyester fiber

Definitions

  • the invention relates to a stable brightener dispersion and its production and its use for the optical brightening of textile fiber materials, in particular polyester materials.
  • Aqueous dispersions of water-insoluble or poorly soluble optical brighteners are known (DE-AS-2745872, DE-OS-2816746). Disadvantages of these brightener dispersions include their low storage stability and their low lightening effect at temperatures of 160-190 ° C in the block thermosol process. It has now been found that the addition of specific synthetic copolymers surprisingly eliminates these disadvantages.
  • the new brightener dispersions are stable for several months at temperatures up to 40 ° C and, after application by means of a block thermosol process, show a higher degree of whiteness on polyester fiber material than known brightener dispersions, despite the use of the same brighteners with the same active ingredient concentrations.
  • the invention thus relates to new stable, aqueous brightener dispersions comprising at least one water-insoluble or poorly soluble optical brightener, at least one anionic, cationic and / or nonionic dispersant and, if appropriate, other auxiliaries, characterized in that the dispersion additionally comprises a copolymer of 2-vinylpyrrolidone with 3- Contains vinyl propionic acid.
  • the dispersion according to the invention preferably contains 4-20% water-insoluble to sparingly water-soluble optical brighteners, 2-20% dispersants, 1-15% copolymer of 2-vinylpyrrolidone with 3-vinylpropionic acid and 0.1-25% other auxiliaries.
  • dispersions which contain 8-15% brightener, 2-10% dispersant, 2-10% copolymer of 2-vinylpyrrolidone with 3-vinylpropionic acid and 0.1-20% other auxiliaries.
  • the percentages here and below relate to percentages by weight.
  • the water-insoluble or poorly soluble optical brighteners are compounds or mixtures of compounds e.g. from the class of the stilbenes, distyryl-benzenes, diphenyl-distyryl, triazinyls, benzoxazoles, bis-benzoxazoles, bis-benzoxazolylthiophenes, bis-benzoxazolylnaphthalenes, pyrenes, coumarins and naphthalene-peri-dicarboximides.
  • Preferred compounds correspond to the formula:
  • M Li, Na, K, ammonium or C 1 -C 4 alkylammonium and the mixtures I to VI of compounds of the formulas:
  • the cationic, anionic and / or nonionic dispersants are the usual dispersants for water-insoluble or poorly soluble brighteners.
  • Anionic dispersants include, for example, condensation products of aromatic sulfonic acids with formaldehyde and lignin sulfonates.
  • Formaldehyde condensation products with naphthalene sulfonic acid and dihexyl sulfosuccinates are particularly suitable.
  • Quaternary fatty amine polyglycol ethers are suitable as cationic dispersants.
  • nonionic dispersants are preferably used.
  • Ethylene oxide adducts from the class of addition products of ethylene oxide with higher fatty acids, saturated or unsaturated fatty alcohols, mercaptans, fatty acid amides, fatty acid alkylolamides or fatty amines or with alkylphenols or alkylthiophenols with at least 7 carbon atoms in the alkyl radical, with 1 mol of the above mentioned Compounds preferably 5 to 100 moles of ethylene oxide come, as well as ethylene oxide-propylene oxide block polymers and ethylene diamine-ethylene oxide-propylene oxide adducts.
  • Some of the ethylene oxide units can be replaced by other epoxides, e.g. Styrene oxide or in particular propylene oxide can be replaced.
  • the dispersion according to the invention can contain other auxiliaries, for example textile auxiliaries, shading dyes, foam-suppressing agents, in particular antifreeze agents such as e.g. Polyols, in particular di- or polyalcohols such as ethylene glycol, propylene glycol, diethylene glycol, glycerin and / or sorbitol, humectants, surfactants such as e.g. Polyethylene glycols with molecular weights between 200 and 6000 and / or antimicrobials such as Contain chloroacetamide or aqueous formalin solutions as well as fungicides.
  • auxiliaries for example textile auxiliaries, shading dyes, foam-suppressing agents, in particular antifreeze agents such as e.g. Polyols, in particular di- or polyalcohols such as ethylene glycol, propylene glycol, diethylene glycol, glycerin and / or sorbitol, humectants,
  • the brightener dispersion contains a copolymer of 2-vinylpyrrolidone with 3-vinylpropionic acid. These copolymers are known and can be prepared by known methods.
  • the brightener dispersion according to the invention is produced, for example, a) by mixing the separately manufactured and formed individual components or b) by jointly forming the individual components e.g. by grinding in a microsol, pearl, sand or dyno mill to a particle size of less than 5 microns.
  • the brightener dispersions according to the invention are used for the optical brightening of textile fiber materials, preferably polyester fiber material.
  • the application takes place according to known application methods, preferably according to a block thermosol method. It is also possible to lighten polyester / cellulose blended fabrics.
  • the application is then carried out either by a one-step process with the addition of a cellulose brightener, in which case the polyester and cellulose components are lightened simultaneously, or by a two-step process, in the first step the polyester component using the brightener dispersion according to the invention and in the second step with the addition of a cellulose brightener Cellulose content can be lightened.
  • Example 1 40 parts of the brightener mixture I
  • Example 1 40 parts of the brightener mixture I or II according to Example 1 or 2, 20 parts of a nonionic dispersant as in Example 1 and 140 parts of water are ground in a microsol mill as in Example 1. After the glass beads have been separated off, a homogeneous, easily pourable and pumpable liquid form with a brightener content of 20% is obtained. 100 parts of this liquid form are mixed with 10 parts of 1,2-propylene glycol, 16 parts of 30% aqueous 2-vinylpyrrolidone / 3-vinylpropionic acid copolymer, 1 part of 37% formaldehyde and 73 parts of water in a beaker while stirring. A low-viscosity dispersion with a brightener content of 10% is obtained, which remains stable in storage at room temperature and 40 ° C. for a long time and has no sedimentation.
  • the dispersions are no longer stable in storage; they sediment after a short time.
  • a polyester fabric (Terylene type 540) is treated at 40 ° C. on a dyeing machine at a liquor ratio of 1:20 with an aqueous bath containing 1 g of brightener preparation according to Example 1, 2 or 3 and 1 g / l of a fatty alcohol polyglycol ether. The temperature is raised to 130 ° C. within 30 minutes and left at this level for a further 30 minutes. Then you cool down to 40 ° C within 15 minutes. For the after-treatment, the textile is rinsed in flowing deionized water for 30 seconds and dried at 180 ° C. The polyester fabric treated in this way has a high lightening effect.
  • a polyester fabric (Terylene type 540) is padded at room temperature with an aqueous liquor containing 1 g of brightener preparation according to Example 1, or 3 and 1 ml / l of alkylphenol polyphenol ether. The squeezing effect is 65%. It is then dried for 30 minutes at a temperature of 80 ° C and then heat set at 200 ° C.
  • the polyester fabric treated in this way has a higher lightening effect than if the same preparation is used, but which instead of 2-vinylpyrrolidone / 3-vinylpropionic acid copolymer contains a polyvinyl alcohol which is preferably used in practice.

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  • Engineering & Computer Science (AREA)
  • Geology (AREA)
  • Textile Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Mining & Mineral Resources (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Fluid Mechanics (AREA)
  • Environmental & Geological Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Luminescent Compositions (AREA)
  • Detergent Compositions (AREA)
  • Cosmetics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Colloid Chemistry (AREA)

Abstract

Beschrieben werden wässrige Aufhellerdispersionen enthaltend wasserunlösliche oder schwerlösliche optische Aufheller, Dispergiermittel gegebenenfalls weitere Hilfsmittel sowie ein Copolymerisat von 2-Vinylpyrrolidon mit 3-Vinylpropionsäure, sowie deren Herstellung und deren Verwendung zum optischen Aufhellen von textilen Fasermaterialien. Diese neuen Aufhellerdispersionen sind lagerstabil.Aqueous brightener dispersions containing water-insoluble or sparingly soluble optical brighteners, dispersants, if appropriate further auxiliaries and a copolymer of 2-vinylpyrrolidone with 3-vinylpropionic acid, and the preparation and use thereof for the optical brightening of textile fiber materials are described. These new brightener dispersions are stable on storage.

Description

Die Erfindung betrifft eine stabile Aufhellerdispersion und deren Herstellung sowie deren Verwendung zum optischen Aufhellen von textilen Fasermaterialien, insbesondere Polyestermaterialien.The invention relates to a stable brightener dispersion and its production and its use for the optical brightening of textile fiber materials, in particular polyester materials.

Wässrige Dispersionen von wasserunlöslichen oder schwerlöslichen optischen Aufhellern sind bekannt (DE-AS-2745872, DE-OS-2816746). Nachteile dieser Aufhellerdispersionen sind u.a. ihre geringe Lagerstabilität sowie ihre geringe Aufhellwirkung bei Temperaturen von 160-190°C im Klotz-Thermosolverfahren. Es wurde nun gefunden, dass der Zusatz spezifischer synthetischer Copolymerisate diese Nachteile überraschenderweise aufhebt. Die neuen Aufhellerdispersionen sind bei Temperaturen bis 40°C mehrere Monate stabil und zeigen, nach der Applikation mittels eines Klotz-Thermosolverfahrens, einen höheren Weissgrad auf Polyesterfasermaterial als bekannte Aufhellerdispersionen und zwar trotz der Verwendung von gleichen Aufhellern mit gleichen Wirkstoffkonzentrationen.Aqueous dispersions of water-insoluble or poorly soluble optical brighteners are known (DE-AS-2745872, DE-OS-2816746). Disadvantages of these brightener dispersions include their low storage stability and their low lightening effect at temperatures of 160-190 ° C in the block thermosol process. It has now been found that the addition of specific synthetic copolymers surprisingly eliminates these disadvantages. The new brightener dispersions are stable for several months at temperatures up to 40 ° C and, after application by means of a block thermosol process, show a higher degree of whiteness on polyester fiber material than known brightener dispersions, despite the use of the same brighteners with the same active ingredient concentrations.

Gegenstand der Erfindung sind somit neue stabile, wässrige Aufhellerdispersionen enthaltend mindestens einen wasserunlöslichen oder schwerlöslichen optischen Aufheller, mindestens ein anionisches, kationisches und/oder nichtionoges Dispergiermittel sowie gegebenenfalls weitere Hilfsmittel, dadurch gekennzeichnet, dass die Dispersion zusätzlich ein Copolymerisat von 2-Vinylpyrrolidon mit 3-Vinylpropionsäure enthält. Vorzugsweise enthält die erfindungsgemässe Dispersion 4-20 % wasserunlöslichen bis in Wasser schwer löslichen optischen Aufheller, 2-20 % Dispergiermittel, 1-15 % Copolymerisat von 2-Vinylpyrrolidon mit 3-Vinylpropionsäure sowie 0,1-25 % weitere Hilfsmittel. Von besonderem Interesse sind Dispersionen die 8-15 % Aufheller, 2-10 % Dispergiermittel, 2-10 % Copolymerisat von 2-Vinylpyrrolidon mit 3-Vinylpropionsäure und 0,1-20 % weitere Hilfsmittel enthalten. Die %-Angaben beziehen sich hier und im folgenden auf Gewichtsprozente.The invention thus relates to new stable, aqueous brightener dispersions comprising at least one water-insoluble or poorly soluble optical brightener, at least one anionic, cationic and / or nonionic dispersant and, if appropriate, other auxiliaries, characterized in that the dispersion additionally comprises a copolymer of 2-vinylpyrrolidone with 3- Contains vinyl propionic acid. The dispersion according to the invention preferably contains 4-20% water-insoluble to sparingly water-soluble optical brighteners, 2-20% dispersants, 1-15% copolymer of 2-vinylpyrrolidone with 3-vinylpropionic acid and 0.1-25% other auxiliaries. Of particular interest are dispersions which contain 8-15% brightener, 2-10% dispersant, 2-10% copolymer of 2-vinylpyrrolidone with 3-vinylpropionic acid and 0.1-20% other auxiliaries. The percentages here and below relate to percentages by weight.

Bei den wasserunlöslichen oder schwerlöslichen optischen Aufhellern handelt es sich um Verbindungen oder Mischungen von Verbindungen z.B. aus der Klasse der Stilbene, Distyryl-benzole, Diphenyl-distyryle, Triazinyle, Benzoxazole, Bis-benzoxazole, Bis-benzoxazolylthiophene, Bis-benzoxazolylnaphthaline, Pyrene, Cumarine und Naphthalin-peri-dicarbonsäureimide. Bevorzugte Verbindungen entsprechen der Formel:The water-insoluble or poorly soluble optical brighteners are compounds or mixtures of compounds e.g. from the class of the stilbenes, distyryl-benzenes, diphenyl-distyryl, triazinyls, benzoxazoles, bis-benzoxazoles, bis-benzoxazolylthiophenes, bis-benzoxazolylnaphthalenes, pyrenes, coumarins and naphthalene-peri-dicarboximides. Preferred compounds correspond to the formula:

Figure imgb0001
Figure imgb0002
Figure imgb0003
Figure imgb0004
Figure imgb0005
Figure imgb0006
Figure imgb0007
worin

  • A = 2-Benzoxazolyl, -CH=CH-CN, -CH=CH-COOR2, -COOR2 oder Halogen,
  • B = Phenyl falls A 2-Benzoxazolyl,
  • B = -CH=CH-CN falls A -CH=CH-CN,
  • B = -CH=CH-COOR2 falls A -CH=CH-COOR2,
  • B = 2-Benzoxazolyl falls A -COOR2,
  • B = Naphthalin-triazolyl falls A Halogen oder -COOR2,
  • B = 1,2,4-Oxadiazol falls A 2-Benzoxazolyl und
  • R = H, C1-C4-Alkyl
  • R1 = H, C1-C4-Alkyl und CN
  • R2 = C1-C4-Alkyl
  • Rs = C1-C4-Alkyl oder Phenyl
  • X=C,N
  • Y = Phenyl oder ein Rest der Formel
    Figure imgb0008
    und
  • n=0-2
  • bedeutet.
Figure imgb0001
Figure imgb0002
Figure imgb0003
Figure imgb0004
Figure imgb0005
Figure imgb0006
Figure imgb0007
wherein
  • A = 2-benzoxazolyl, -CH = CH-CN, -CH = CH-COOR 2 , -COOR 2 or halogen,
  • B = phenyl if A 2-benzoxazolyl,
  • B = -CH = CH-CN if A -CH = CH-CN,
  • B = -CH = CH-COOR 2 if A -CH = CH-COOR 2 ,
  • B = 2-benzoxazolyl if A -COOR 2 ,
  • B = naphthalene-triazolyl if A is halogen or -COOR 2 ,
  • B = 1,2,4-oxadiazole if A is 2-benzoxazolyl and
  • R = H, C 1 -C 4 alkyl
  • R 1 = H, C 1 -C 4 alkyl and CN
  • R 2 = C 1 -C 4 alkyl
  • Rs = C 1 -C 4 alkyl or phenyl
  • X = C, N
  • Y = phenyl or a radical of the formula
    Figure imgb0008
    and
  • n = 0-2
  • means.

Von besonderem Interesse sind die Verbindungen der Formel:

Figure imgb0009
Figure imgb0010
Figure imgb0011
Figure imgb0012
Figure imgb0013
Figure imgb0014
Figure imgb0015
Figure imgb0016
Figure imgb0017
Figure imgb0018
Figure imgb0019
Figure imgb0020
Of particular interest are the compounds of the formula:
Figure imgb0009
Figure imgb0010
Figure imgb0011
Figure imgb0012
Figure imgb0013
Figure imgb0014
Figure imgb0015
Figure imgb0016
Figure imgb0017
Figure imgb0018
Figure imgb0019
Figure imgb0020

und M = Li, Na, K, Ammonium oder C1-C4-Alkylammonium sowie die Mischungen I bis VI von Verbindungen der Formeln:

Figure imgb0021
Figure imgb0022
Figure imgb0023
and M = Li, Na, K, ammonium or C 1 -C 4 alkylammonium and the mixtures I to VI of compounds of the formulas:
Figure imgb0021
Figure imgb0022
Figure imgb0023

Bei den kationischen, anionischen und/oder nichtionogenen Dispergiermitteln handelt es sich um die üblichen Dispergiermittel für wasserunlösliche bzw. schwerlösliche Aufheller.The cationic, anionic and / or nonionic dispersants are the usual dispersants for water-insoluble or poorly soluble brighteners.

Als anionische Dispergiermittel sind beispielsweise genannt Kondensationsprodukte von aromatischen Sulfonsäuren mit Formaldehyd sowie Ligninsulfonate. Besonders geeignet sind Formaldehyd-Kondensationsprodukte mit Naphthalinsulfonsäure sowie Dihexyl-sulfosuccinate.Anionic dispersants include, for example, condensation products of aromatic sulfonic acids with formaldehyde and lignin sulfonates. Formaldehyde condensation products with naphthalene sulfonic acid and dihexyl sulfosuccinates are particularly suitable.

Als kationische Dispergiermittel kommen zum Beispiel quaternäre Fettaminpolyglykolether in Frage.Quaternary fatty amine polyglycol ethers, for example, are suitable as cationic dispersants.

Vorzugsweise werden jedoch nichtionogene Dispergiermittel eingesetzt. In Frage kommen zum Beispiel: Ethylenoxid-Addukte aus der Klasse der Anlagerungsprodukte von Ethylenoxid an höhere Fettsäuren, gesättigte oder ungesättigte Fettalkohole, Mercaptane, Fettsäureamide, Fettsäurealkylolamide oder Fettamine oder an Alkylphenole oder Alkylthiophenole mit mindestens 7 Kohlenstoffatomen im Alkylrest, wobei auf 1 Mol der genannten Verbindungen bevorzugt 5 bis 100 Mol Ethylenoxid kommen, sowie Ethylenoxid-Propylenoxid-Blockpolymere und Ethylendiamin-Ethylenoxid-Propylenoxid-Addukte. Einzelne der Ethylenoxideinheiten können durch andere Epoxide, wie z.B. Styroloxid oder insbesondere Propylenoxid ersetzt sein.However, nonionic dispersants are preferably used. For example: Ethylene oxide adducts from the class of addition products of ethylene oxide with higher fatty acids, saturated or unsaturated fatty alcohols, mercaptans, fatty acid amides, fatty acid alkylolamides or fatty amines or with alkylphenols or alkylthiophenols with at least 7 carbon atoms in the alkyl radical, with 1 mol of the above mentioned Compounds preferably 5 to 100 moles of ethylene oxide come, as well as ethylene oxide-propylene oxide block polymers and ethylene diamine-ethylene oxide-propylene oxide adducts. Some of the ethylene oxide units can be replaced by other epoxides, e.g. Styrene oxide or in particular propylene oxide can be replaced.

Als Ethylenoxid-Addukte sind im einzelnen genannt:

  • a) Umsetzungsprodukte von gesättigten und/oder ungesättigten Fettalkoholen mit 8 bis 20 C-Atomen, mit 20 bis 100 Mol Ethylenoxid (EO) je Mol Alkohol, vorzugsweise gesättigte lineare C16-C18 Alkohole mit 25 bis 80 insbesondere 25 Mol Ethylenoxid je Mol Alkohol;
  • b) Umsetzungsprodukte von gesättigten und/oder ungesättigten Fettsäuren mit 8 bis 20 C-Atomen mit 5 bis 20 Mol Ethylenoxid je Mol Säure, vorzugsweise Rizinusölethoxylat;
  • c) Umsetzungsprodukte von Alkylphenolen mit 7 bis 12 C-Atomen im Alkylrest mit 5 bis 25 Mol Ethylenoxid je Mol phenolische Hydroxylgruppe, vorzugsweise Mono- oder Dialkylphenole mit 10 bis 20 Mol Ethylenoxid je Mol phenolische Hydroxylgruppe;
  • d) Umsetzungsprodukte von gesättigten und/oder ungesättigten Fettsäureamiden mit 8 bis 20 C-Atomen mit 5 bis 20 Mol Ethylenoxid je Mol Säureamid, vorzugsweise Oelsäureamide mit 8 bis 15 Mol Ethylenoxid je Mol Säureamid;
  • e) Umsetzungsprodukte von gesättigten und/oder ungesättigten Fettaminen mit 8 bis 20 C-Atomen mit 5 bis 20 Mol Ethylenoxid je Mol Amin, vorzugsweise Oleylamine mit 8 bis 15 Mol Ethylenoxid je Mol Amin.
  • f) Ethylenoxid-Propylenoxid-Blockpolymere mit 10-80 % Ethylenoxid und Molekulargewichten von 1000-80000;
  • g) Ethylenoxid-Propylenoxid-Addukte an Ethylendiamin.
The following are specifically mentioned as ethylene oxide adducts:
  • a) Reaction products of saturated and / or unsaturated fatty alcohols with 8 to 20 carbon atoms, with 20 to 100 moles of ethylene oxide (EO) per mole of alcohol, preferably saturated linear C 16 -C 18 alcohols with 25 to 80, in particular 25 moles of ethylene oxide per mole Alcohol;
  • b) reaction products of saturated and / or unsaturated fatty acids with 8 to 20 carbon atoms with 5 to 20 moles of ethylene oxide per mole of acid, preferably castor oil ethoxylate;
  • c) reaction products of alkylphenols with 7 to 12 carbon atoms in the alkyl radical with 5 to 25 moles of ethylene oxide per mole of phenolic hydroxyl group, preferably mono- or dialkylphenols with 10 to 20 Moles of ethylene oxide per mole of phenolic hydroxyl group;
  • d) reaction products of saturated and / or unsaturated fatty acid amides with 8 to 20 carbon atoms with 5 to 20 moles of ethylene oxide per mole of acid amide, preferably oleic acid amides with 8 to 15 moles of ethylene oxide per mole of acid amide;
  • e) reaction products of saturated and / or unsaturated fatty amines with 8 to 20 carbon atoms with 5 to 20 moles of ethylene oxide per mole of amine, preferably oleylamines with 8 to 15 moles of ethylene oxide per mole of amine.
  • f) ethylene oxide-propylene oxide block polymers with 10-80% ethylene oxide and molecular weights of 1000-80000;
  • g) ethylene oxide-propylene oxide adducts with ethylenediamine.

Von diesen sind die unter a) genannten bevorzugt. Auch Gemische der Ethylenoxid-Addukte nach a) bis g) untereinander sind verwendbar.Of these, the ones mentioned under a) are preferred. Mixtures of the ethylene oxide adducts according to a) to g) with one another can also be used.

Des weiteren kann die erfindungsgemässe Dispersion weitere Hilfsmittel beispielsweise Textilhilfsmittel, Nuancierfarbstoffe, schaumdämpfende Mittel, insbesondere Gefrierschutzmittel wie z.B. Polyole insbesondere Di- oder Polyalkohole wie Ethylenglykol, Propylenglykol, Diethylenglykol, Glycerin und/oder Sorbit, Feuchthaltemittel, Tenside wie z.B. Polyethylenglykole mit Molgewichten zwischen 200 und 6000 und/oder Antimikrobica wie z.B. Chloracetamid oder wässrige Formalinlösungen sowie Fungizide enthalten.Furthermore, the dispersion according to the invention can contain other auxiliaries, for example textile auxiliaries, shading dyes, foam-suppressing agents, in particular antifreeze agents such as e.g. Polyols, in particular di- or polyalcohols such as ethylene glycol, propylene glycol, diethylene glycol, glycerin and / or sorbitol, humectants, surfactants such as e.g. Polyethylene glycols with molecular weights between 200 and 6000 and / or antimicrobials such as Contain chloroacetamide or aqueous formalin solutions as well as fungicides.

Erfindungswesentlich ist, dass die Aufhellerdispersion ein Copolymerisat von 2-Vinylpyrrolidon mit 3-Vinylpropionsäure enthält. Diese Copolymerisate sind bekannt und können nach bekannten Methoden hergestellt werden.It is essential to the invention that the brightener dispersion contains a copolymer of 2-vinylpyrrolidone with 3-vinylpropionic acid. These copolymers are known and can be prepared by known methods.

Die Herstellung der erfindungsgemässen Aufhellerdispersion erfolgt z.B. a) durch Mischen der separat hergestellten und formierten Einzelkomponenten oder b) durch gemeinsame Formierung der Einzelkomponenten z.B. durch Mahlung in einer Mikrosol-, Perl-, Sand-, oder Dynomühle auf eine Korngrösse der Teilchen von kleiner als 5 µm.The brightener dispersion according to the invention is produced, for example, a) by mixing the separately manufactured and formed individual components or b) by jointly forming the individual components e.g. by grinding in a microsol, pearl, sand or dyno mill to a particle size of less than 5 microns.

Verwendung finden die erfindungsgemässen Aufhellerdispersionen zum optischen Aufhellen von textilen Fasermaterialien vorzugsweise von Polyester-fasermaterial. Die Applikation erfolgt nach bekannten Applikationsverfahren vorzugsweise nach einem Klotz-Thermosolverfahren. Es ist auch möglich Polyester/ Cellulose-Mischgewebe aufzuhellen. Die Applikation erfolgt dann entweder nach einem Einstufenverfahren unter Zusatz eines Cellulose-Aufhellers wobei dann der Polyester- und der Celluloseanteil gleichzeitig aufgehellt werden oder nach einem Zweistufenverfahren wobei im ersten Schritt der Polyesteranteil mittels der erfindungsgemässen Aufhellerdispersion und im zweiten Schritt unter Zusatz eines Cellulose-Aufhellers der Celluloseanteil aufgehellt werden.The brightener dispersions according to the invention are used for the optical brightening of textile fiber materials, preferably polyester fiber material. The application takes place according to known application methods, preferably according to a block thermosol method. It is also possible to lighten polyester / cellulose blended fabrics. The application is then carried out either by a one-step process with the addition of a cellulose brightener, in which case the polyester and cellulose components are lightened simultaneously, or by a two-step process, in the first step the polyester component using the brightener dispersion according to the invention and in the second step with the addition of a cellulose brightener Cellulose content can be lightened.

Die nachfolgenden Beispiele erläutern die Erfindung, ohne sie darauf zu beschränken. Prozente und Teile bedeuten Gewichtsprozente bzw. -teile.The following examples illustrate the invention without restricting it. Percentages and parts mean percentages or parts by weight.

Beispiel 1: 40 Teile der Aufhellermischung IExample 1: 40 parts of the brightener mixture I

Figure imgb0024
20 Teile C16-C18-Fettalkohol mit 25 EO (HLB ca. 16), 20 Teile 1,2-Propylenglykol, 32 Teile 300/oiges wässriges 2-Vinylpyrrolidon/3-Vinylpropionsäure-Copolymerisat, 2 Teile Formaldehyd 37 % und 286 Teile Wasser werden in einer Mikrosolmühle gemahlen, bis die Aufhellerteilchen eine Korngrösse von kleiner als 5 µm aufweisen. Nach dem Abtrennen der Glasperlen erhält man eine homogene, gut giess- und pumpbare Flüssigform mit einem Aufhellergehalt von 10%. Diese Aufhellerzubereitung ist bei Raumtemperatur und 40°C mehrere Monate lang lagerstabil.
Figure imgb0024
20 parts of C 16 -C 18 fatty alcohol with 25 EO (HLB approx. 16), 20 parts of 1,2-propylene glycol, 32 parts of 300% aqueous 2-vinylpyrrolidone / 3-vinylpropionic acid copolymer, 2 parts of formaldehyde 37% and 286 Parts of water are ground in a microsol mill until the brightener particles have a grain size of less than 5 μm. After the glass beads have been separated off, a homogeneous, easily pourable and pumpable liquid form with a brightener content of 10% is obtained. This brightener preparation is stable for several months at room temperature and 40 ° C.

Beispiel 2: 10 Teile der Aufhellermischung IIExample 2: 10 parts of the brightener mixture II

Figure imgb0025
Figure imgb0025

5 Teile C16-C18-Fettalkohol mit 25 EO (HLB ca. 16), 5 Teile 1,2-Propylenglykol, 0,5 Teile Formaldehyd 37%, 8 Teile 30 %iges wässriges 2-Vinylpyrrolidon/3-Vinylpropionsäure-Copolymerisat und 71,5 Teile Wasser werden in einer Rührwerkskugelmühle vermahlen. Nach dem Erreichen der geforderten Feinverteilung siebt man vom Mahlkörper ab. Man erhält eine Dispersion, die 10 % Aufheller enthält und bei Raumtemperatur und 40'C mehrere Monate lang stabil bleibt.5 parts of C 16 -C 18 fatty alcohol with 25 EO (HLB approx. 16), 5 parts of 1,2-propylene glycol, 0.5 part of formaldehyde 37%, 8 parts of 30% aqueous 2-vinylpyrrolidone / 3-vinylpropionic acid copolymer and 71.5 parts of water are ground in an agitator ball mill. After the required fine distribution has been reached, sieve off the grinding media. A dispersion is obtained which contains 10% brightener and remains stable for several months at room temperature and 40'C.

Beispiel 3:Example 3:

40 Teile der Aufhellermischung I bzw. II gemäss Beispiel 1 bzw. 2, 20 Teile eines nichtionogenen Dispergators, wie in Beispiel 1 und 140 Teile Wasser werden wie im Beispiel 1 in einer Mikrosolmühle gemahlen. Nach dem Abtrennen der Glasperlen erhält man eine homogene, gut giess- und pumpbare Flüssigform mit einem Aufhellergehalt von 20 %. 100 Teile dieser Flüssigform werden in einem Becherglas unter Rühren mit 10 Teilen 1,2-Propylenglykol, 16 Teilen 30 %igem wässrigem 2-Vinylpyrrolidon/3-Vinylpropionsäure-Copolymerisat, 1 Teil Formaldehyd 37 % und 73 Teilen Wasser versetzt. Man erhält eine dünnflüssige Dispersion mit einem Aufhellergehalt von 10 %, welche bei Raumtemperatur und 40° C während längerer Zeit lagerstabil bleibt und keine Sedimentation aufweist.40 parts of the brightener mixture I or II according to Example 1 or 2, 20 parts of a nonionic dispersant as in Example 1 and 140 parts of water are ground in a microsol mill as in Example 1. After the glass beads have been separated off, a homogeneous, easily pourable and pumpable liquid form with a brightener content of 20% is obtained. 100 parts of this liquid form are mixed with 10 parts of 1,2-propylene glycol, 16 parts of 30% aqueous 2-vinylpyrrolidone / 3-vinylpropionic acid copolymer, 1 part of 37% formaldehyde and 73 parts of water in a beaker while stirring. A low-viscosity dispersion with a brightener content of 10% is obtained, which remains stable in storage at room temperature and 40 ° C. for a long time and has no sedimentation.

Das gleiche Ergebnis wird erzielt, wenn die Dispersion in einer Perl-, Sand- oder Dynomühle gemahlen wird.The same result is achieved if the dispersion is ground in a pearl, sand or dyno mill.

Wird anstelle von 2-Vinylpyrrolidon/3-Vinylpropionsäure-Copolymerisat mengengleich ein in der Praxis vorzugsweise verwendeter Polyvinylalkohol eingesetzt, so sind die Dispersionen nicht mehr lagerstabil; sie sedimentieren nach kurzer Zeit.If instead of 2-vinylpyrrolidone / 3-vinylpropionic acid copolymer an equal amount of a polyvinyl alcohol used in practice is used, the dispersions are no longer stable in storage; they sediment after a short time.

Beispiel 4:Example 4:

Ein Polyestergewebe (Terylene Typ 540) wird bei 40°C auf einem Färbeapparat bei einem Flottenverhältnis von 1:20 mit einem wässrigen Bad, enthaltend 1 g Aufhellerpräparation gemäss Beispiel 1,2 oder 3 und 1 g/I eines Fettalkoholpolyglykolethers, behandelt. Innerhalb von 30 Minuten steigert man die Temperatur auf 1303 C und belässt sie während weiterer 30 Minuten auf dieser Höhe. Dann kühlt man innerhalb von 15 Minuten wieder auf 40° C ab. Zur Nachbehandlung wird das Textilgut während 30 Sekunden in fliessendem deionisiertem Wasser gespült und bei 180° C getrocknet. Das derart behandelte Polyestergewebe weist einen hohen Aufhelleffekt auf.A polyester fabric (Terylene type 540) is treated at 40 ° C. on a dyeing machine at a liquor ratio of 1:20 with an aqueous bath containing 1 g of brightener preparation according to Example 1, 2 or 3 and 1 g / l of a fatty alcohol polyglycol ether. The temperature is raised to 130 ° C. within 30 minutes and left at this level for a further 30 minutes. Then you cool down to 40 ° C within 15 minutes. For the after-treatment, the textile is rinsed in flowing deionized water for 30 seconds and dried at 180 ° C. The polyester fabric treated in this way has a high lightening effect.

Beispiel 5:Example 5:

Man foulardiert bei Raumtemperatur ein Polyestergewebe (Terylene Typ 540) mit einer wässrigen Flotte enthaltend 1 g Aufhellerpräparation gemäss Beispiel 1, oder 3 und 1 ml/I Alkylphenol polyphenolether. Der Abquetscheffekt beträgt 65 %. Anschliessend wird während 30 Minuten bei einer Temperatur von 80° C getrocknet und daraufhin bei 200° C thermofixiert. Das so behandelte Polyestergewebe weist einen höheren Aufhelleffekt auf, als wenn eine gleiche Präparation verwendet wird, die jedoch anstelle von 2-Vinylpyrrolidon/ 3-Vinylpropionsäure-Copolymerisat einen in der Praxis vorzugsweise verwendeten Polyvinylalkohol enthält.A polyester fabric (Terylene type 540) is padded at room temperature with an aqueous liquor containing 1 g of brightener preparation according to Example 1, or 3 and 1 ml / l of alkylphenol polyphenol ether. The squeezing effect is 65%. It is then dried for 30 minutes at a temperature of 80 ° C and then heat set at 200 ° C. The polyester fabric treated in this way has a higher lightening effect than if the same preparation is used, but which instead of 2-vinylpyrrolidone / 3-vinylpropionic acid copolymer contains a polyvinyl alcohol which is preferably used in practice.

Claims (18)

1. Stabile Aufhellerdispersion enthaltend mindestens einen wasserunlöslichen oder schwerlöslichen optischen Aufheller, mindestens ein anionisches, kationisches und/oder nichtionoges Dispergiermittel sowie gegebenenfalls weitere Hilfsmittel, dadurch gekennzeichnet, dass die Dispersion zusätzlich ein Copolymerisat von 2-Vinylpyrrolidon mit 3-Vinylpropionsäure enthält.1. Stable brightener dispersion containing at least one water-insoluble or sparingly soluble optical brightener, at least one anionic, cationic and / or nonionic dispersant and optionally further auxiliaries, characterized in that the dispersion additionally contains a copolymer of 2-vinylpyrrolidone with 3-vinylpropionic acid. 2. Stabile Aufhellerdispersion gemäss Anspruch 1, dadurch gekennzeichnet, dass sie 4-20 % Aufheller, 2-20 % Dispergiermittel, 1-15 % Copolymerisat von 2-Vinylpyrrolidon mit 3-Vinylpropionsäure sowie 0,1-25 % weitere Hilfsmittel enthält.2. Stable brightener dispersion according to claim 1, characterized in that it contains 4-20% brightener, 2-20% dispersant, 1-15% copolymer of 2-vinylpyrrolidone with 3-vinylpropionic acid and 0.1-25% other auxiliaries. 3. Stabile Aufhellerdispersion gemäss Anspruch 2, dadurch gekennzeichnet, dass sie 8-15 % Aufheller, 2-10 % Dispergiermittel, 2-10 % Copolimerisat von 2-Vinylpyrrolidon mit 3-Vinylpropionsäure und 0,1-20 % weitere Hilfsmittel enthält.3. Stable brightener dispersion according to claim 2, characterized in that it contains 8-15% brightener, 2-10% dispersant, 2-10% copolymer of 2-vinylpyrrolidone with 3-vinylpropionic acid and 0.1-20% other auxiliaries. 4. stabile Aufhellerdispersion gemäss Anspruch 1, dadurch gekennzeichnet, dass sie als Aufheller Verbindungen oder Mischungen von Verbindungen aus der Klasse der Stilbene, Distyryl-benzole, Diphenyl-distyryle, Triazinyle, Benzoxazole, Bis-benzoxazole, Bis-benzoxazolyl-thiophene, Bis-benzoxazolylnaphthaline, Pyrene, Cumarine und Haphthalin-peri-dicarbonsäureimide enthält.4. stable brightener dispersion according to claim 1, characterized in that it is used as brightener compounds or mixtures of compounds from the class of the stilbenes, distyryl-benzenes, diphenyl-distyrylics, triazinyls, benzoxazoles, bis-benzoxazoles, bis-benzoxazolyl-thiophenes, bis- contains benzoxazolylnaphthalenes, pyrenes, coumarins and haphthalene-peri-dicarboximides. 5. Stabile Aufhellerdispersion gemäss Anspruch 4, dadurch gekennzeichnet, dass sie als Aufheller mindestens eine Verbindung der Formel
Figure imgb0026
enthält.
5. Stable brightener dispersion according to claim 4, characterized in that it contains at least one compound of the formula as brightener
Figure imgb0026
contains.
6. Stabile Aufhellerdispersion gemäss Anspruch 4, dadurch gekennzeichnet, dass sie als Aufheller eine Verbindung der Formel
Figure imgb0027
enthält, worin A = 2-Benzoxazolyl, -CH = CH-CN, -CH=CH-COOR2, -COOR2 oder Halogen, B = Phenyl falls A 2-Benzoxazolyl, B = -CH=CH-CN falls A-CH=CH-CN, B = -CH=CH-COOR2 falls A-CH=CH-COOR2, B = 2-Benzoxazolyl falls A -COOR2, B = Naphthalin-triazolyl falls A Halogen oder -COOR2, B = 1,2,4-Oxadiazol falls A 2-Benzoxazolyl und R = H, C1-C4-Alkyl R1 = H, C1-C4-Alkyl und CN R2 =C1-C4-Alkylbedeutet.
6. Stable brightener dispersion according to claim 4, characterized in that it is a brightener a compound of the formula
Figure imgb0027
contains what A = 2-benzoxazolyl, -CH = CH-CN, -CH = CH-COOR 2 , -COOR 2 or halogen, B = phenyl if A 2-benzoxazolyl, B = -CH = CH-CN if A-CH = CH-CN, B = -CH = CH-COOR 2 if A-CH = CH-COOR 2 , B = 2-benzoxazolyl if A -COOR 2 , B = naphthalene-triazolyl if A is halogen or -COOR 2 , B = 1,2,4-oxadiazole if A is 2-benzoxazolyl and R = H, C 1 -C 4 alkyl R 1 = H, C 1 -C 4 alkyl and CN R 2 = C 1 -C 4 alkyl means.
7. Stabile Aufhellerdispersion gemäss Anspruch 4, dadurch gekennzeichnet, dass sie als Aufheller eine Verbindung der Formel
Figure imgb0028
enthält, worin R2 C1-C4-Alkyl bedeutet.
7. Stable brightener dispersion according to claim 4, characterized in that it is a brightener a compound of the formula
Figure imgb0028
contains, wherein R 2 is C 1 -C 4 alkyl.
8. Stabile Aufhellerdispersion gemäss Anspruch 4, dadurch gekennzeichnet, dass sie als Aufheller eine Verbindung der Formel
Figure imgb0029
enthält, worin Y Phenyl oder ein Rest der Formel
Figure imgb0030
X C, N und Rs C1-C4-Alkyl oder Phenyl und R H oder C1-C4-Alkyl bedeutet.
8. Stable brightener dispersion according to claim 4, characterized in that it is a brightener a compound of the formula
Figure imgb0029
contains, wherein Y contains phenyl or a radical of the formula
Figure imgb0030
XC, N and Rs is C 1 -C 4 alkyl or phenyl and RH or C 1 -C 4 alkyl.
9. Stabile Aufhellerdispersion gemäss Anspruch 4, dadurch gekennzeichnet, dass sie als Aufheller eine Verbindung der Formel
Figure imgb0031
enthält, worin n die Zahlen Null bis 2 und R2 Ci-C4-Alkyl bedeutet.
9. Stable brightener dispersion according to claim 4, characterized in that it is a brightener a compound of the formula
Figure imgb0031
contains, where n is the numbers zero to 2 and R 2 Ci-C 4 alkyl.
10. Stabile Aufhellerdispersion gemäss Anspruch 4, dadurch gekennzeichnet, dass sie als Aufheller eine Verbindung der Formel
Figure imgb0032
enthält, worin R2 C1-C4-Alkyl bedeutet.
10. Stable brightener dispersion according to claim 4, characterized in that it is a brightener a compound of the formula
Figure imgb0032
contains, wherein R 2 is C 1 -C 4 alkyl.
11. Stabile Aufhellerdispersion gemäss Anspruch 4, dadurch gekennzeichnet, dass sie als Aufheller eine Verbindung der Formel
Figure imgb0033
enthält.
11. Stable brightener dispersion according to claim 4, characterized in that it is a brightener, a compound of the formula
Figure imgb0033
contains.
12. Stabile Aufhellerdispersion gemäss Anspruch 4, dadurch gekennzeichnet, dass sie als Aufheller eine Verbindung der Formel
Figure imgb0034
enthält, worin M Li, Na, K, Ammonium oder C1-C4-Alkylammonium bedeutet.
12. Stable brightener dispersion according to claim 4, characterized in that it is a brightener, a compound of the formula
Figure imgb0034
contains, wherein M means Li, Na, K, ammonium or C 1 -C 4 alkylammonium.
13. Stabile Aufhellerdispersion gemäss Anspruch 4, dadurch gekennzeichnet, dass sie als Aufheller eine Verbindung der Formel
Figure imgb0035
enthält,
Figure imgb0036
und M Li, Na, K, Ammonium oder C1-C4-Alkylammonium bedeutet.
13. Stable brightener dispersion according to claim 4, characterized in that it is a brightener, a compound of the formula
Figure imgb0035
contains
Figure imgb0036
and M denotes Li, Na, K, ammonium or C 1 -C 4 alkylammonium.
14. Stabile Aufhellerdispersion gemäss Anspruch 4, dadurch gekennzeichnet, dass sie als Aufheller eine Mischung von Verbindungen der Formel14. Stable brightener dispersion according to claim 4, characterized in that it as a brightener is a mixture of compounds of the formula
Figure imgb0037
worin A = 2-Benzoxazolyl, -CH = CH-CN, -CH = CH-COOR2, -COOR2 oder Halogen, B = Phenyl falls A 2-Benzoxazolyl, B = -CH= CH-CN falls A-CH= CH-CN, B = -CH=CH-COOR2 falls A-CH=CH-COOR2, B = 2-Benzoxazolyl falls A -COOR2, B = Naphthalin-triazolyl falls A Halogen oder-COOR2, und R = H, C1-C4-Alkyl R1= H, C1-C4-Alkyl und CN R2 = Ci-C4-Alkylbedeutet mit Verbindungen der Formeln
Figure imgb0038
oder
Figure imgb0039
worin R2 C1-C4-Alkyl bedeutet, enthält.
Figure imgb0037
wherein A = 2-benzoxazolyl, -CH = CH-CN, -CH = CH-COOR2, -COOR 2 or halogen, B = phenyl if A 2-benzoxazolyl, B = -CH = CH-CN if A-CH = CH-CN, B = -CH = CH-COOR 2 if A-CH = CH-COOR 2 , B = 2-benzoxazolyl if A -COOR 2 , B = naphthalene-triazolyl if A is halogen or -COOR 2 , and R = H, C 1 -C 4 alkyl R 1 = H, C 1 -C 4 alkyl and CN R 2 = Ci-C 4 alkyl means with compounds of the formulas
Figure imgb0038
or
Figure imgb0039
wherein R 2 is C 1 -C 4 alkyl contains.
15. Stabile Aufhellerdispersion gemäss Anspruch 4, dadurch gekennzeichnet, dass sie als Aufheller eine Mischung von Verbindungen der Formel
Figure imgb0040
worin R2 C1-C4-Alkyl bedeutet mit einer Verbindung der Formel
Figure imgb0041
enthält.
15. Stable brightener dispersion according to claim 4, characterized in that it as a brightener is a mixture of compounds of the formula
Figure imgb0040
wherein R 2 is C1-C4-alkyl with a compound of the formula
Figure imgb0041
contains.
16. Verwendung der Aufhellerdispersion gemäss Anspruch 1 zum optischen Aufhellen von Polyester-und Polyester/Cellulosefasermaterial.16. Use of the brightener dispersion according to claim 1 for the optical brightening of polyester and polyester / cellulose fiber material. 17. Verfahren zur Herstellung einer stabilen Aufhellerdispersion gemäss Anspruch 1, dadurch gekennzeichnet, dass mindestens ein wasserunlöslicher oder schwerlöslicher optischer Aufheller mit mindestens einem anionischen, kationischen oder nichtionogenen Dispergiermittel, einem Copolymer von 2-Vinylpyrrolidon mit 3-Vinylpropionsäure und Wasser sowie gegebenenfalls weiteren Hilfsmitteln a) durch Mischen der separat hergestellten und formierten Einzelkomponenten oder b) durch gemeinsame Formierung der Einzelkomponenten homogenisiert wird. 17. A process for the preparation of a stable brightener dispersion as claimed in claim 1, characterized in that at least one water-insoluble or sparingly soluble optical brightener with at least one anionic, cationic or nonionic dispersant, a copolymer of 2-vinylpyrrolidone with 3-vinylpropionic acid and water and optionally other auxiliaries a) is homogenized by mixing the separately manufactured and formed individual components or b) by jointly forming the individual components.
EP88810793A 1987-11-27 1988-11-18 Optical brightener dispersion Expired - Lifetime EP0321393B1 (en)

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CN100338296C (en) * 2002-12-10 2007-09-19 西巴特殊化学品控股有限公司 Mixtures of fluorescent whitening agents
US7108913B1 (en) * 2005-05-09 2006-09-19 Mattel, Inc. Light reflecting polymeric articles containing benzoxazolyl-napthalene optical brighteners
MY162539A (en) * 2011-01-20 2017-06-15 Huntsman Advanced Mat (Switzerland) Gmbh Formulations of fluorescent whitening agents in dispersed form
CN113638219A (en) * 2021-08-20 2021-11-12 奥仕集团有限公司 Preparation method of low-temperature-resistant fluorescent whitening slurry

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WO2000011256A1 (en) * 1998-08-25 2000-03-02 Clariant Finance (Bvi) Limited Aqueous compositions of uv-active agents, their production and use
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WO2001031111A1 (en) * 1999-10-25 2001-05-03 Ciba Specialty Chemicals Holding Inc. Mixtures of fluorescent whitening agents
EP2057073B2 (en) 2006-08-30 2019-10-09 Elopak Systems Ag Improvements in or relating to packaging

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