EP0543779A1 - Process for optical bleaching of hydrophobic textile material with disperse optical brightness in supercritical CO2 - Google Patents

Process for optical bleaching of hydrophobic textile material with disperse optical brightness in supercritical CO2 Download PDF

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Publication number
EP0543779A1
EP0543779A1 EP92810877A EP92810877A EP0543779A1 EP 0543779 A1 EP0543779 A1 EP 0543779A1 EP 92810877 A EP92810877 A EP 92810877A EP 92810877 A EP92810877 A EP 92810877A EP 0543779 A1 EP0543779 A1 EP 0543779A1
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Prior art keywords
alkyl
formula
phenyl
independently represent
optical brightener
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EP92810877A
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German (de)
French (fr)
Inventor
Wolfgang Dr. Schlenker
Dieter Dr. Werthemann
Claude Dr. Eckhardt
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Novartis AG
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Ciba Geigy AG
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Publication of EP0543779A1 publication Critical patent/EP0543779A1/en
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
    • D06M23/10—Processes in which the treating agent is dissolved or dispersed in organic solvents; Processes for the recovery of organic solvents thereof
    • D06M23/105—Processes in which the solvent is in a supercritical state
    • 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
    • Y—GENERAL 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
    • Y10S8/92—Synthetic fiber dyeing
    • Y10S8/922—Polyester fiber

Definitions

  • the present invention relates to a method for optically brightening hydrophobic textile material with disperse optical brighteners.
  • Hydrophobic textile materials are usually lightened from aqueous liquors. You never achieve complete bath exhaustion, i.e. the brighteners do not pull quantitatively onto the textile material. This in turn leads to the fact that the brightener liquor remaining after the brightening still contains, depending on the respective optical brighteners and substrates, more or less large amounts of optical brighteners. Therefore, relatively large amounts of waste water are produced, which have to be cleaned in a complex manner.
  • the present invention has for its object to provide a method for optically brightening textile material, in which no or no significant amounts of waste water are obtained.
  • the present invention thus relates to a method for optically brightening hydrophobic textile material with optical brighteners, which is characterized in that the textile material is treated in supercritical carbon dioxide with an optical brightener.
  • the process according to the invention provides for the use of brightener liquors in which the water is replaced by supercritical carbon dioxide instead of the aqueous liquors described above.
  • supercritical CO2 means CO2 in which the pressure and the temperature of the CO2 are above the critical pressure and the critical temperature.
  • the supercritical CO2 has approximately the viscosity of the corresponding gas and a density that is approximately comparable with the density of the correspondingly liquefied gas.
  • the method according to the invention has a number of advantages. Due to the fact that the supercritical CO2 used does not get into the wastewater, but is used again after brightening, no wastewater pollution occurs in the process according to the invention. Furthermore, in the method according to the invention, the mass transfer processes required for the lightening of the textile substrate take place much faster in comparison to aqueous systems. This in turn means that the textile substrate can be flowed through particularly well and quickly.
  • the method according to the invention e.g. when lightening winding bodies, there are no irregularities with regard to the flow through the winding body.
  • disperse brighteners there is practically no undesired agglomeration on the fiber material, as is sometimes the case with the conventional aqueous processes, so that stains are avoided by using the process according to the invention.
  • Another advantage of the method according to the invention is that it is possible to use disperse optical brighteners which consist exclusively of the actual brightener and do not contain the usual dispersants and adjusting agents.
  • optical brighteners used in the process according to the invention are water-insoluble compounds which contain two identical or different radicals selected from the group consisting of styryl, stilbenyl, naphthotriazolyl, benzoxazolyl, coumarin, naphthalimide, pyrene and triazinyl, which directly or via a bridge member , selected from the group consisting of vinylene, styrene, stilbenylene, thienylene, phenylene, naphthylene and oxadiazolylene.
  • alkyl radicals are generally understood to mean straight-chain, branched or cyclic alkyl groups. It is e.g. around methyl, ethyl, propyl, i-propyl, butyl, i-butyl, tert-butyl, amyl, tert-amyl (1,1-dimethylpropyl), 1,1,3,3-tetramethylbutyl, hexyl, 1-methylpentyl , Neopentyl, 1-, 2- or 3-methylhexyl, heptyl, n-octyl, tert.-octyl, 2-ethylhexyl, n-nonyl, isononyl, decyl, cyclopentyl, cyclohexyl, methylcyclohexyl and the associated isomers.
  • the non-cyclic alkyl radicals preferably contain 1 to 6 carbon atoms, especially 1 to 4 carbon
  • alkyl radicals can be substituted, e.g. by halogen, hydroxy, alkoxy, cyan or phenyl.
  • substituted alkyl radicals are hydroxyethyl, methoxymethyl, ethoxyethyl, cyanoethyl, propoxypropyl, benzyl, chloroethyl or cyanoethyl.
  • Suitable alkoxy radicals are preferably those with 1 to 4 carbon atoms, e.g. Methoxy, ethoxy, propoxy, iso-propoxy, n-butoxy, iso-butoxy or tert-butoxy.
  • phenyl radicals can also be substituted, e.g. by chlorine, bromine, C1-C4-alkyl, C1-C4-alkoxy, nitro or cyan.
  • Halogen means fluorine, iodine, bromine or especially chlorine.
  • optical brighteners listed in the examples are very particularly preferred.
  • optical brighteners of the formulas (1) to (13) are known or can be produced in a manner known per se.
  • the method according to the invention is suitable for the optical brightening of semi-synthetic and in particular synthetic hydrophobic fiber materials, especially textile materials.
  • Textile materials made from blended fabrics that contain such semi-synthetic or synthetic hydrophobic textile materials can also be optically brightened using the process according to the invention.
  • Cellulose-2 1/2-acetate and cellulose triacetate are particularly suitable as semi-synthetic textile materials.
  • Synthetic hydrophobic textile materials consist primarily of linear, aromatic polyesters, for example those made of terephthalic acid and glycols, especially ethylene glycol or condensation products made of terephthalic acid and 1,4-bis (hydroxymethyl) cyclohexane; from polycarbonates, e.g. from ⁇ , ⁇ -dimethyl-4,4'-dihydroxy-diphenylmethane and phosgene, from fibers based on polyvinylchloride, polypropylene or polyamide, e.g. Polyamide 6.6, polyamide 6.10, polyamide 6, polyamide 11, poly (1,4-phenylene terephthalamide) or poly (1,3-phenylene isophthalamide).
  • the temperature used in the method according to the invention depends essentially on the substrate. Usually it is between about 90 and 200 ° C, preferably between about 100 and 150 ° C.
  • the pressure to be applied must be at least so high that the CO2 is in a supercritical state.
  • the pressure is preferably between about 73 and 400 bar, in particular between about 150 and 250 bar.
  • the pressure is approximately 200 bar.
  • optical brighteners are preferably applied in a concentration of 0.001 to 2% by weight, in particular 0.005 to 0.5% by weight, based on the weight of the textile material. Mixtures of two or more of the above-mentioned optical ones can also be used Brighteners can be used.
  • the "liquor ratio" (mass ratio of textile material: CO2) in the optical brightening according to the inventive method depends on the goods to be treated and their presentation. Usually, it varies between a value of 1: 2 to 1: 100, preferably about 1: 5 to 1:75. If, for example, polyester yarns which are wound on corresponding cross-wound bobbins are to be brightened optically by the process according to the invention, this is preferably done at relative short fleet ratios, ie Fleet ratios between 1: 2 to 1: 5. Such short liquor ratios generally cause difficulties in the conventional process in the aqueous system, since due to the high concentration of optical brightener there is often the risk that the finely dispersed systems agglomerate. However, this does not occur with the method according to the invention.
  • the optical brighteners separate out in liquid or solid form and can be collected and reused accordingly.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
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Abstract

Polyester textile materials can be brightened with disperse optical brighteners in supercritical CO2.

Description

Die vorliegende Erfindung betrifft ein Verfahren zum optischen Aufhellen von hydrophobem Textilmaterial mit dispersen optischen Aufhellern.The present invention relates to a method for optically brightening hydrophobic textile material with disperse optical brighteners.

Hydrophobe Textilmaterialien werden üblicherweise aus wässrigen Flotten aufgehellt. Dabei erreicht man niemals eine vollständige Baderschöpfung d.h. die Aufheller ziehen nicht quantitativ auf das Textilmaterial. Dies wiederum führt dazu, dass die nach dem Aufhellen verbleibende Aufhellerflotte noch, abhängig von den jeweiligen optischen Aufhellern und Substraten, mehr oder weniger grosse Mengen an optischen Aufhellern enthält. Daher fallen relativ grosse Mengen an Abwässern an, die aufwendig gereinigt werden müssen.Hydrophobic textile materials are usually lightened from aqueous liquors. You never achieve complete bath exhaustion, i.e. the brighteners do not pull quantitatively onto the textile material. This in turn leads to the fact that the brightener liquor remaining after the brightening still contains, depending on the respective optical brighteners and substrates, more or less large amounts of optical brighteners. Therefore, relatively large amounts of waste water are produced, which have to be cleaned in a complex manner.

Der vorliegenden Erfindung liegt die Aufgabe zugrunde, ein Verfahren zum optischen Aufhellen von Textilmaterial zur Verfügung zu stellen, bei dem keine oder keine nennenswerten Mengen an Abwässern anfallen.The present invention has for its object to provide a method for optically brightening textile material, in which no or no significant amounts of waste water are obtained.

Diese Aufgabe wird durch das erfindungsgemässe Verfahren gelöst.This object is achieved by the method according to the invention.

Die vorliegende Erfindung betrifft somit ein Verfahren zum optischen Aufhellen von hydrophobem Textilmaterial mit optischen Aufhellern, das dadurch gekennzeichnet ist, dass man das Textilmaterial in überkritischem Kohlendioxid mit einem optischen Aufheller behandelt.The present invention thus relates to a method for optically brightening hydrophobic textile material with optical brighteners, which is characterized in that the textile material is treated in supercritical carbon dioxide with an optical brightener.

Das erfindungsgemässe Verfahren sieht vor, anstelle der vorstehend beschriebenen wässrigen Flotten solche Aufhellerflotten zu verwenden, bei denen das Wasser durch überkritisches Kohlendioxid ersetzt ist. Unter dem Begriff überkritisches CO₂ versteht man CO₂, bei dem der Druck und die Temperatur des CO₂ oberhalb des kritischen Druckes und der kritischen Temperatur liegen. Hierbei weist das überkritische CO₂ annähernd die Viskosität des entsprechenden Gases und eine Dichte auf, die näherungsweise mit der Dichte des entsprechend verflüssigten Gases vergleichbar ist.The process according to the invention provides for the use of brightener liquors in which the water is replaced by supercritical carbon dioxide instead of the aqueous liquors described above. The term supercritical CO₂ means CO₂ in which the pressure and the temperature of the CO₂ are above the critical pressure and the critical temperature. Here, the supercritical CO₂ has approximately the viscosity of the corresponding gas and a density that is approximately comparable with the density of the correspondingly liquefied gas.

Das erfindungsgemässe Verfahren weist eine Reihe von Vorteilen auf. Bedingt dadurch, dass das hierbei eingesetzte überkritische CO₂ nicht ins Abwasser gelangt, sondern nach dem Aufhellen erneut eingesetzt wird, treten bei dem erfindungsgemässen Verfahren keine Abwasserbelastungen auf. Ferner laufen bei dem erfindungsgemässen Verfahren die für das Aufhellen des textilen Substrates erforderlichen Stoffaustauschvorgänge im Vergleich zu wässrigen Systemen wesentlich schneller ab. Dies wiederum führt dazu, dass das textile Substrat besonders gut und schnell durchströmt werden kann. Bei Anwendung des erfindungsgemässen Verfahrens treten z.B. beim Aufhellen von Wickelkörpern keine Ungleichmässigkeiten bezüglich der Durchströmung des Wickelkörpers auf. Bei der Verwendung von dispersen Aufhellern kommt es praktisch nicht zu unerwünschten Agglomerationen auf dem Fasermaterial, wie dies bei den herkömmlichen wässrigen Verfahren bisweilen der Fall ist, so dass somit durch Anwendung des erfindungsgemässen Verfahrens Fleckenbildungen vermieden werden.The method according to the invention has a number of advantages. Due to the fact that the supercritical CO₂ used does not get into the wastewater, but is used again after brightening, no wastewater pollution occurs in the process according to the invention. Furthermore, in the method according to the invention, the mass transfer processes required for the lightening of the textile substrate take place much faster in comparison to aqueous systems. This in turn means that the textile substrate can be flowed through particularly well and quickly. When using the method according to the invention, e.g. when lightening winding bodies, there are no irregularities with regard to the flow through the winding body. When using disperse brighteners, there is practically no undesired agglomeration on the fiber material, as is sometimes the case with the conventional aqueous processes, so that stains are avoided by using the process according to the invention.

Ein weiterer Vorteil des erfindungsgemässen Verfahrens besteht darin, dass man disperse optische Aufheller einsetzen kann, die ausschliesslich aus dem eigentlichen Aufheller bestehen und nicht die üblichen Dispergatoren und Stellmittel enthalten.Another advantage of the method according to the invention is that it is possible to use disperse optical brighteners which consist exclusively of the actual brightener and do not contain the usual dispersants and adjusting agents.

Bei den im erfindungsgemässen Verfahren verwendeten optischen Aufhellern handelt es sich um wasserunlösliche Verbindungen, welche zwei gleiche oder verschiedene Reste, ausgewählt aus der Gruppe Styryl, Stilbenyl, Naphthotriazolyl, Benzoxazolyl, Cumarin, Naphthalimid, Pyren und Triazinyl, enthalten, die direkt oder über ein Brückenglied, ausgewählt aus der Gruppe Vinylen, Styrylen, Stilbenylen, Thienylen,Phenylen, Naphthylen und Oxadiazolylen, miteinander verbunden sind.The optical brighteners used in the process according to the invention are water-insoluble compounds which contain two identical or different radicals selected from the group consisting of styryl, stilbenyl, naphthotriazolyl, benzoxazolyl, coumarin, naphthalimide, pyrene and triazinyl, which directly or via a bridge member , selected from the group consisting of vinylene, styrene, stilbenylene, thienylene, phenylene, naphthylene and oxadiazolylene.

Für das erfindungsgemässe Verfahren besonders geeignete optische Aufheller sind:

  • a) Distyrylbenzole der Formel
    Figure imgb0001
     worin R₁ und R₂ unabhängig voneinander je H, CN oder SO₂-C₁-C₄-Alkyl bedeuten;
  • b) Vinylstilbene der Formel
    Figure imgb0002
     worin R₃ und R₄ unabhängig voneinander je CN oder COO-C₁-C₄-Alkyl bedeuten;
  • c) Stilben-naphthotriazole der Formel
    Figure imgb0003
     worin R₅, R₆ und R₇ unabhängig voneinander je H, C₁-C₄-Alkyl, Halogen oder CN bedeuten;
  • d) Stilben-benzoxazole der Formel
    Figure imgb0004
     worin R₈ und R₉ unabhängig voneinander je H oder C₁-C₆-Alkyl und R₁₀ C₁-C₄-Alkyl, C₁-C₄-Alkenyl, Phenyl oder C₁-C₄-Alkylphenyl bedeuten;
  • e) Bis-benzoxazole der Formel
    Figure imgb0005
     worin R₈ und R₉ unabhängig voneinander je H oder C₁-C₆-Alkyl und X Vinylen, Thienylen, Naphthylen, Styrylen oder Stilbenylen bedeutet;
  • f) Cumarine der Formel
    Figure imgb0006
     worin R₁₁ und R₁₂ unabhängig voneinander je einen Phenyl- oder Pyrazolylrest bedeuten oder einen Rest der Formel
    Figure imgb0007
     worin R₁₃ C₁-C₆-Akyl, Phenyl oder Halogen und R₁₄ und R₁₅ unabhängig voneinander je C₁-C₆-Akyl oder -Alkoxy, Phenyl oder Halogen bedeuten oder worin R₁₄ und R₁₅ zusammen mit den beiden sie verbindenden C-Atomen einen Phenyl- oder Naphthylrest bedeuten;
  • g) Naphthalimide der Formel
    Figure imgb0008
     worin R₁₆, R₁₇ und R₁₈ unabhängig voneinander je H, C₁-C₁₀-Alkyl oder -Alkoxy bedeuten;
  • h) Triazine der Formel
    Figure imgb0009
     worin R₁₉ Pyrenyl, R₂₀, R₂₁, R₂₂ und R₂₃ unabhängig voneinander je C₁ -C₆-Akyl oder -Alkoxy, Phenyl, C₁-C₄-Alkylphenyl oder C₁-C₄-Alkoxyphenyl und X Vinylen, Thienylen, Naphthylen, Styrylen oder Stilbenylen bedeutet;
  • i) Styrol-benzoxazole der Formel
    Figure imgb0010
     worin R₈ und R₉ unabhängig voneinander je H oder C₁-C₄-Alkyl und R₂₄ CN, Phenyl oder COOC₁-C₄-Alkyl bedeuten;
  • j) Distyryl-biphenyle der Formel
    Figure imgb0011
     worin R₂₅ und R₂₆ je H, C₁-C₄-Alkyl oder -Alkoxy bedeuten.
Optical brighteners which are particularly suitable for the process according to the invention are:
  • a) Distyrylbenzenes of the formula
    Figure imgb0001
     wherein R₁ and R₂ each independently represent H, CN or SO₂-C₁-C₄-alkyl;
  • b) vinyl style plane of the formula
    Figure imgb0002
     wherein R₃ and R₄ are each independently CN or COO-C₁-C₄-alkyl;
  • c) stilbene-naphthotriazoles of the formula
    Figure imgb0003
     wherein R₅, R₆ and R₇ each independently represent H, C₁-C₄ alkyl, halogen or CN;
  • d) stilbene-benzoxazoles of the formula
    Figure imgb0004
     wherein R₈ and R₉ each independently represent H or C₁-C₆-alkyl and R₁₀ C₁-C₄-alkyl, C₁-C₄-alkenyl, phenyl or C₁-C₄-alkylphenyl;
  • e) bis-benzoxazoles of the formula
    Figure imgb0005
     wherein R₈ and R₉ are each independently H or C₁-C₆ alkyl and X is vinylene, thienylene, naphthylene, styrenic or stilbenylene;
  • f) Coumarins of the formula
    Figure imgb0006
     wherein R₁₁ and R₁₂ each independently represent a phenyl or pyrazolyl radical or a radical of the formula
    Figure imgb0007
     wherein R₁₃ C₁-C₆-alkyl, phenyl or halogen and R₁₄ and R₁₅ independently of one another each represent C₁-C₆-alkyl or alkoxy, phenyl or halogen or wherein R₁₄ and R₁₅ together with the two carbon atoms connecting them represent a phenyl or naphthyl radical mean;
  • g) naphthalimides of the formula
    Figure imgb0008
     wherein R₁₆, R₁₇ and R₁₈ each independently represent H, C₁-C₁₀ alkyl or alkoxy;
  • h) triazines of the formula
    Figure imgb0009
     wherein R₁₉ pyrenyl, R₂₀, R₂₁, R₂₂ and R₂₃ independently of one another each represent C₁-C₆-alkyl or alkoxy, phenyl, C₁-C₄-alkylphenyl or C₁-C₄-alkoxyphenyl and X is vinylene, thienylene, naphthylene, styrene or stilbenylene;
  • i) styrene-benzoxazoles of the formula
    Figure imgb0010
     wherein R₈ and R₉ each independently represent H or C₁-C₄ alkyl and R₂₄ CN, phenyl or COOC₁-C₄ alkyl;
  • j) Distyryl biphenyls of the formula
    Figure imgb0011
     wherein R₂₅ and R₂₆ each represent H, C₁-C₄ alkyl or alkoxy.

Unter Alkylresten sind erfindungsgemäss generell geradkettige, verzweigte oder cyclischen Alkylgruppen zu verstehen. Es handelt sich z.B. um Methyl, Ethyl, Propyl, i-Propyl, Butyl, i-Butyl, tert.-Butyl, Amyl, tert-Amyl(1,1-Dimethylpropyl), 1,1,3,3-Tetramethylbutyl, Hexyl, 1-Methylpentyl, Neopentyl, 1-, 2- oder 3-Methylhexyl, Heptyl, n-Octyl, tert.-Octyl, 2-Ethylhexyl, n-Nonyl, Isononyl, Decyl, Cyclopentyl, Cyclohexyl, Methylcyclohexyl sowie die dazugehörenden Isomeren. Die nicht cyclischen Alkylreste enthalten vorzugsweise 1 bis 6 C-Atome, vor allem 1 bis 4 C-Atome.According to the invention, alkyl radicals are generally understood to mean straight-chain, branched or cyclic alkyl groups. It is e.g. around methyl, ethyl, propyl, i-propyl, butyl, i-butyl, tert-butyl, amyl, tert-amyl (1,1-dimethylpropyl), 1,1,3,3-tetramethylbutyl, hexyl, 1-methylpentyl , Neopentyl, 1-, 2- or 3-methylhexyl, heptyl, n-octyl, tert.-octyl, 2-ethylhexyl, n-nonyl, isononyl, decyl, cyclopentyl, cyclohexyl, methylcyclohexyl and the associated isomers. The non-cyclic alkyl radicals preferably contain 1 to 6 carbon atoms, especially 1 to 4 carbon atoms.

Diese Alkylreste können substituiert sein, z.B. durch Halogen, Hydroxy, Alkoxy, Cyan oder Phenyl. Beispiele für solche substituierte Alkylreste sind Hydroxyethyl, Methoxymethyl, Ethoxyethyl, Cyanethyl, Propoxypropyl, Benzyl, Chlorethyl oder Cyanoethyl.These alkyl radicals can be substituted, e.g. by halogen, hydroxy, alkoxy, cyan or phenyl. Examples of such substituted alkyl radicals are hydroxyethyl, methoxymethyl, ethoxyethyl, cyanoethyl, propoxypropyl, benzyl, chloroethyl or cyanoethyl.

Geeignete Alkoxyreste sind vorzugsweise solche mit 1 bis 4 C-Atomen z.B. Methoxy, Ethoxy, Propoxy, iso-Propoxy, n-Butoxy, iso-Butoxy oder tert.-Butoxy.Suitable alkoxy radicals are preferably those with 1 to 4 carbon atoms, e.g. Methoxy, ethoxy, propoxy, iso-propoxy, n-butoxy, iso-butoxy or tert-butoxy.

Auch die Phenylreste können substituiert sein, z.B. durch Chlor, Brom, C₁-C₄-Alkyl, C₁-C₄-Alkoxy, Nitro oder Cyan.The phenyl radicals can also be substituted, e.g. by chlorine, bromine, C₁-C₄-alkyl, C₁-C₄-alkoxy, nitro or cyan.

Halogen bedeutet Fluor, Jod, Brom oder vor allem Chlor.Halogen means fluorine, iodine, bromine or especially chlorine.

Wegen ihrer guten Eigenschaften im erfindungsgemässen Verfahren sind die in den Beispielen aufgeführten optischen Aufheller ganz besonders bevorzugt.Because of their good properties in the process according to the invention, the optical brighteners listed in the examples are very particularly preferred.

Die optischen Aufheller der Formeln (1) bis (13) sind bekannt oder lassen sich auf an sich bekannte Art herstellen.The optical brighteners of the formulas (1) to (13) are known or can be produced in a manner known per se.

Das erfindungsgemässe Verfahren eignet sich zum optischen Aufhellen von halbsynthetischen und insbesondere synthetischen hydrophoben Fasermaterialien, vor allem Textilmaterialien. Textilmaterialien aus Mischgeweben, die derartige halbsynthetische bzw. synthetische hydrophobe Textilmaterialien enthalten, können ebenfalls nach dem erfindungsgemässen Verfahren optisch aufgehellt werden.The method according to the invention is suitable for the optical brightening of semi-synthetic and in particular synthetic hydrophobic fiber materials, especially textile materials. Textile materials made from blended fabrics that contain such semi-synthetic or synthetic hydrophobic textile materials can also be optically brightened using the process according to the invention.

Als halbsynthetische Textilmaterialien kommen vor allem Cellulose-2 1/2-Acetat und Cellulosetriacetat in Frage.Cellulose-2 1/2-acetate and cellulose triacetate are particularly suitable as semi-synthetic textile materials.

Synthetische hydrophobe Textilmaterialien bestehen vor allem aus linearen, aromatischen Polyestern, beispielsweise solchen aus Terephthalsäure und Glykolen, besonders Ethylenglykol oder Kondensationsprodukten aus Terephthalsäure und 1,4-Bis-(hydroxymethyl)-cyclohexan; aus Polycarbonaten, z.B. aus α,α-Dimethyl-4,4'-dihydroxy-diphenylmethan und Phosgen, aus Fasern auf Polyvinylchlorid-, Polypropylen- oder Polyamid-Basis, z.B. Polyamid 6.6, Polyamid 6.10, Polyamid 6, Polyamid 11, Poly(1,4-phenylenterephthalamid) oder Poly(1,3-phenylenisophthalamid).Synthetic hydrophobic textile materials consist primarily of linear, aromatic polyesters, for example those made of terephthalic acid and glycols, especially ethylene glycol or condensation products made of terephthalic acid and 1,4-bis (hydroxymethyl) cyclohexane; from polycarbonates, e.g. from α, α-dimethyl-4,4'-dihydroxy-diphenylmethane and phosgene, from fibers based on polyvinylchloride, polypropylene or polyamide, e.g. Polyamide 6.6, polyamide 6.10, polyamide 6, polyamide 11, poly (1,4-phenylene terephthalamide) or poly (1,3-phenylene isophthalamide).

Die bei dem erfindungsgemässen Verfahren angewendete Temperatur richtet sich im wesentlichen nach dem Substrat. Normalerweise liegt sie etwa zwischen 90 und 200°C, vorzugsweise zwischen etwa 100 und 150°C.The temperature used in the method according to the invention depends essentially on the substrate. Usually it is between about 90 and 200 ° C, preferably between about 100 and 150 ° C.

Der anzuwendende Druck muss mindestens so gross sein, dass das CO₂ in überkritischem Zustand vorliegt. Vorzugsweise liegt der Druck zwischen etwa 73 und 400 bar, insbesondere zwischen etwa 150 und 250 bar. Bei der bevorzugten Temperatur von ca. 130°C für das optische Aufhellen von Polyestermaterial beträgt der Druck etwa 200 bar.The pressure to be applied must be at least so high that the CO₂ is in a supercritical state. The pressure is preferably between about 73 and 400 bar, in particular between about 150 and 250 bar. At the preferred temperature of approximately 130 ° C. for the optical brightening of polyester material, the pressure is approximately 200 bar.

Die optischen Aufheller werden vorzugsweise in einer Konzentration von 0,001 bis 2 Gew.%, insbesondere 0,005 bis 0,5 Gew.%, bezogen auf das Gewicht des Textilmaterials, appliziert. Es können auch Gemische aus zwei oder mehreren der genannten optischen Aufheller eingesetzt werden.The optical brighteners are preferably applied in a concentration of 0.001 to 2% by weight, in particular 0.005 to 0.5% by weight, based on the weight of the textile material. Mixtures of two or more of the above-mentioned optical ones can also be used Brighteners can be used.

Das " Flottenverhältnis" (Massenverhältnis Textilmaterial: CO₂) beim optischen Aufhellen nach dem erfindungsgemässen Verfahren richtet sich nach der zu behandelnden Ware und deren Aufmachung. Ueblicherweise variiert es zwischen einem Wert von 1 : 2 bis 1 : 100, vorzugsweise etwa 1 : 5 bis 1 : 75. Sollen beispielsweise Polyestergarne, die auf entsprechende Kreuzspulen aufgewickelt sind, nach dem erfindungsgemässen Verfahren optisch aufgehellt werden, so geschieht dies vorzugsweise bei relativ kurzen Flottenverhältnissen, d.h. Flottenverhältnissen zwischen 1 : 2 bis 1 : 5. Derartige kurze Flottenverhältnisse bereiten in der Regel bei dem herkömmlichen Verfahren im wässrigen System Schwierigkeiten, da hierbei, bedingt durch die hohe Konzentration an optischem Aufheller, häufig die Gefahr besteht, dass die feindispersen Systeme agglomerieren. Dies tritt jedoch bei dem erfingunsgemässen Verfahren nicht auf.The "liquor ratio" (mass ratio of textile material: CO₂) in the optical brightening according to the inventive method depends on the goods to be treated and their presentation. Usually, it varies between a value of 1: 2 to 1: 100, preferably about 1: 5 to 1:75. If, for example, polyester yarns which are wound on corresponding cross-wound bobbins are to be brightened optically by the process according to the invention, this is preferably done at relative short fleet ratios, ie Fleet ratios between 1: 2 to 1: 5. Such short liquor ratios generally cause difficulties in the conventional process in the aqueous system, since due to the high concentration of optical brightener there is often the risk that the finely dispersed systems agglomerate. However, this does not occur with the method according to the invention.

Zur Reinigung des überkritischen CO₂ nach dem Aufhellen bestehen mehrere Möglichkeiten. Man kann z.B. den in dem überkritischen CO₂ verbleibenden Aufhellerrest über entsprechende Filter ad- bzw. absorbieren. Hierfür eignen sich insbesondere die an sich bekannten Kieselgel-, Kieselgur-, Kohle-, Zeolith- und Aluminiumoxidfilter.There are several options for cleaning the supercritical CO₂ after lightening. You can e.g. ad or absorb the brightener residue remaining in the supercritical CO₂ via appropriate filters. The known silica gel, diatomaceous earth, carbon, zeolite and aluminum oxide filters are particularly suitable for this.

Darüberhinaus besteht die Möglichkeit, die nach dem optischen Aufhellen in dem überkritischen CO₂ verbleibenden Aufheller durch eine Temperatur- und/oder Druckerniedrigung und/oder eine Volumenvergrösserung zu entfernen. Hierbei wandelt sich das überkritische CO₂ in das entsprechende Gas um, das dann aufgefangen wird und erneut nach Ueberführung in den überkritischen Zustand zum Aufhellen von weiteren Substraten verwendet wird. Hierbei scheiden sich die optischen Aufheller in flüssiger oder fester Form ab, und können entsprechend gesammelt und erneut verwendet werden.In addition, there is the possibility of removing the brightener remaining after the optical brightening in the supercritical CO₂ by lowering the temperature and / or pressure and / or increasing the volume. Here, the supercritical CO₂ is converted into the corresponding gas, which is then collected and used again after the transition to the supercritical state for brightening further substrates. The optical brighteners separate out in liquid or solid form and can be collected and reused accordingly.

Nach dem erfindungsgemässen Verfahren erhält man auf dem Textilmaterial sehr hohe Weisseffekte, die vergleichbar sind mit denen, die nach den in der Textilindustrie üblichen wässrigen Verfahren erzielt werden. Auch die Lichtechtheiten sind den nach üblichen Applikationsverfahren erhaltenen ebenbürtig.According to the process according to the invention, very high whitening effects are obtained on the textile material, which are comparable to those achieved by the aqueous processes customary in the textile industry. The light fastnesses are also equivalent to those obtained by customary application processes.

Die nachfolgenden Beispiele erläutern die Erfindung, ohne sie darauf zu beschränken.The following examples illustrate the invention without restricting it.

Beispiel 1example 1

7,3 mg des optischen Aufhellers der Formel

Figure imgb0012

werden in einem Autoklaven vorgelegt. Ein Streifen Polyestergewebe von 5,16 g wird auf einem Materialträger im Autoklav befestigt. Nach dem Schliessen des Autoklaven werden 360 g CO₂ aus einer Vorratsflasche in den Autoklaven gegeben. Dann wird auf 130° C aufgeheizt, wobei der Druck im Autoklaven auf 220 bar ansteigt. Nach einer Verweilzeit von 30 Minuten bei dieser Temperatur wird die Apparatur abgekühlt und das Polyestergewebe entnommen. Es entspricht nach dieser Behandlung einem auf übliche Weise aufgehellten Muster.7.3 mg of the optical brightener of the formula
Figure imgb0012
are placed in an autoclave. A 5.16 g strip of polyester fabric is attached to a material carrier in the autoclave. After closing the autoclave, 360 g of CO₂ from a storage bottle are added to the autoclave. The mixture is then heated to 130 ° C., the pressure in the autoclave rising to 220 bar. After a residence time of 30 minutes at this temperature, the apparatus is cooled and the polyester fabric is removed. After this treatment, it corresponds to a pattern brightened in the usual way.

Beispiele 2 bis 9Examples 2 to 9

Arbeitet man wie im Beispiel 1 beschrieben, verwendet jedoch die in der folgenden Tabelle aufgeführten optischen Aufheller, so erhält man ebenfalls Gewebe, die in ihren Eigenschaften den nach üblichen Verfahren aufgehellten entsprechen.

Figure imgb0013
Figure imgb0014
Figure imgb0015
Figure imgb0016
 If you work as described in Example 1, but using the optical brighteners listed in the following table, you also obtain fabrics whose properties correspond to those brightened by conventional methods.
Figure imgb0013
Figure imgb0014
Figure imgb0015
Figure imgb0016

Claims (22)

Verfahren zum optischen Aufhellen von hydrophobem Textilmaterial mit optischen Aufhellem, dadurch gekennzeichnet, dass man das Textilmaterial in überkritischem Kohlendioxid mit einem optischen Aufheller behandelt.Process for the optical brightening of hydrophobic textile material with optical brighteners, characterized in that the textile material is treated in supercritical carbon dioxide with an optical brightener. Verfahren gemäss Anspruch 1, dadurch gekennzeichnet, dass man als optischen Aufheller eine wasserunlösliche Verbindung verwendet, welche zwei gleiche oder verschiedene Reste, ausgewählt aus der Gruppe Styryl, Stilbenyl, Naphthotriazolyl, Benzoxazolyl, Cumarin, Naphthalimid, Pyren und Triazinyl, enthält, die direkt oder über ein Brückenglied, ausgewählt aus der Gruppe Vinylen, Styrylen, Stilbenylen, Thienylen, Phenylen, Naphthylen und Oxadiazolylen, miteinander verbunden sind.A method according to claim 1, characterized in that a water-insoluble compound is used as the optical brightener, which contains two identical or different radicals selected from the group styryl, stilbenyl, naphthotriazolyl, benzoxazolyl, coumarin, naphthalimide, pyrene and triazinyl, which directly or are connected to one another via a bridge member selected from the group consisting of vinylene, styrylene, stilbenylene, thienylene, phenylene, naphthylene and oxadiazolylene. Verfahren gemäss Anspruch 2, dadurch gekennzeichnet, dass man einen optischen Aufheller aus einer der folgenden Klassen verwendet: a) Distyrylbenzole der Formel
Figure imgb0017
 worin R₁ und R₂ unabhängig voneinander je H, CN oder SO₂-C₁-C₄-Alkyl bedeuten; b) Vinylstilbene der Formel
Figure imgb0018
 worin R₃ und R₄ unabhängig voneinander je CN oder COO-C₁-C₄-Alkyl bedeuten; c) Stilben-naphthotriazole der Formel
Figure imgb0019
 worin R₅, R₆ und R₇ unabhängig voneinander je H, C₁-C₄-Alkyl, Halogen oder CN bedeuten; d) Stilben-benzoxazole der Formel
Figure imgb0020
 worin R₈ und R₉ unabhängig voneinander je H oder C₁-C₆-Alkyl und R₁₀ C₁-C₄-Alkyl, C₁-C₄-Alkenyl, Phenyl oder C₁-C₄-Alkylphenyl bedeuten; e) Bis-benzoxazole der Formel
Figure imgb0021
 worin R₈ und R₉ unabhängig voneinander je H oder C₁-C₆-Alkyl und X Vinylen, Thienylen, Naphthylen, Styrylen oder Stilbenylen bedeutet; f) Cumarine der Formel
Figure imgb0022
 worin R₁₁ und R₁₂ unabhängig voneinander je einen Phenyl- oder Pyrazolylrest bedeuten oder einen Rest der Formel
Figure imgb0023
 worin R₁₃ C₁-C₆-Alkyl, Phenyl oder Halogen und R₁₄ und R₁₅ unabhängig voneinander je C₁-C₆-Alkyl oder -Alkoxy, Phenyl oder Halogen bedeuten oder worin R₁₄ und R₁₅ zusammen mit den beiden sie verbindenden C-Atomen einen Phenyl- oder Naphthylrest bedeuten; g) Naphthalimide der Formel
Figure imgb0024
 worin R₁₆, R₁₇ und R₁₈ unabhängig voneinander je H, C₁-C₁₀-Alkyl oder -Alkoxy bedeuten; h) Triazine der Formel
Figure imgb0025
 worin R₁₉ Pyrenyl, R₂₀, R₂₁, R₂₂ und R₂₃ unabhängig voneinander je C₁-C₆-Alkyl oder -Alkoxy, Phenyl, C₁-C₄-Alkylphenyl oder C₁-C₄-Alkoxyphenyl und X Vinylen, Thienylen, Naphthylen, Styrylen oder Stilbenylen bedeutet; i) Styrol-benzoxazole der Formel
Figure imgb0026
 worin R₈ und R₉ unabhängig voneinander je H oder C₁-C₄-Alkyl und R₂₄ CN, Phenyl oder COOC₁-C₄-Alkyl bedeuten; j) Distyryl-biphenyle der Formel
Figure imgb0027
 worin R₂₅ und R₂₆ je H, C₁-C₄-Alkyl oder -Alkoxy bedeuten. A method according to claim 2, characterized in that one uses an optical brightener from one of the following classes: a) Distyrylbenzenes of the formula
Figure imgb0017
 wherein R₁ and R₂ each independently represent H, CN or SO₂-C₁-C₄-alkyl; b) vinyl style plane of the formula
Figure imgb0018
 wherein R₃ and R₄ are each independently CN or COO-C₁-C₄-alkyl; c) stilbene-naphthotriazoles of the formula
Figure imgb0019
 wherein R₅, R₆ and R₇ each independently represent H, C₁-C₄ alkyl, halogen or CN; d) stilbene-benzoxazoles of the formula
Figure imgb0020
 wherein R₈ and R₉ each independently represent H or C₁-C₆-alkyl and R₁₀ C₁-C₄-alkyl, C₁-C₄-alkenyl, phenyl or C₁-C₄-alkylphenyl; e) bis-benzoxazoles of the formula
Figure imgb0021
 wherein R₈ and R₉ are each independently H or C₁-C₆ alkyl and X is vinylene, thienylene, naphthylene, styrenic or stilbenylene; f) Coumarins of the formula
Figure imgb0022
 wherein R₁₁ and R₁₂ each independently represent a phenyl or pyrazolyl radical or a radical of the formula
Figure imgb0023
 wherein R₁₃ C₁-C₆ alkyl, phenyl or halogen and R₁₄ and R₁₅ each independently represent C₁-C₆ alkyl or alkoxy, phenyl or halogen or wherein R₁ Halogen and R₁₅ together with the two carbon atoms connecting them represent a phenyl or naphthyl radical mean; g) naphthalimides of the formula
Figure imgb0024
 wherein R₁₆, R₁₇ and R₁₈ each independently represent H, C₁-C₁₀ alkyl or alkoxy; h) triazines of the formula
Figure imgb0025
 wherein R₁₉ pyrenyl, R₂₀, R₂₁, R₂₂ and R₂₃ are each independently C₁-C₆ alkyl or alkoxy, phenyl, C₁-C₄ alkylphenyl or C₁-C₄ alkoxyphenyl and X is vinylene, thienylene, naphthylene, styrene or stilbenylene; i) styrene-benzoxazoles of the formula
Figure imgb0026
 wherein R₈ and R₉ each independently represent H or C₁-C₄ alkyl and R₂₄ CN, phenyl or COOC₁-C₄ alkyl; j) Distyryl biphenyls of the formula
Figure imgb0027
 wherein R₂₅ and R₂₆ each represent H, C₁-C₄ alkyl or alkoxy. Verfahren gemäss Anspruch 3, dadurch gekennzeichnet, dass man als optischen Aufheller ein Distyrylbenzol der Formel (1) verwendet, worin R₁ und R₂ je CN bedeuten.Process according to Claim 3, characterized in that a distyrylbenzene of the formula (1) is used as the optical brightener, in which R₁ and R₂ each denote CN. Verfahren gemäss Anspruch 3, dadurch gekennzeichnet, dass man als optischen Aufheller ein Vinylstilben der Formel (2) verwendet, worin R₃ und R₄ je COOC₁-C₄-Alkyl bedeuten.A method according to claim 3, characterized in that a vinyl stilbene of the formula (2) is used as the optical brightener, wherein R₃ and R₄ each represent COOC₁-C₄-alkyl. Verfahren gemäss Anspruch 3, dadurch gekennzeichnet, dass man als optischen Aufheller ein Stilben-naphthotriazol der Formel (3) verwendet, worin R₅, R₆ und R₇ unabhängig voneinander je H oder CN bedeuten.Process according to Claim 3, characterized in that a stilbene-naphthotriazole of the formula (3) is used as the optical brightener, in which R₅, R₆ and R₇ each independently represent H or CN. Verfahren gemäss Anspruch 3, dadurch gekennzeichnet, dass man als optischen Aufheller ein Stilben-benzoxazol der Formel (4) verwendet, worin R₈ und R₉ unabhängig voneinander je C₁-C₄-Alkyl und R₁₀ C₁-C₄-Alkyl oder Phenyl bedeuten.Process according to claim 3, characterized in that a stilbene-benzoxazole of the formula (4) is used as the optical brightener, in which R₈ and R₉ each independently represent C₁-C₄-alkyl and R₁₀ C₁-C₄-alkyl or phenyl. Verfahren gemäss Anspruch 3, dadurch gekennzeichnet, dass man als optischen Aufheller ein Bis-benzoxazol der Formel (5) verwendet, worin R₈ und R₉ unabhängig voneinander je H oder C₁-C₄-Alkyl und X Vinylen, Thienylen, Naphthylen, Styrylen oder Stilbenylen bedeuten.Process according to Claim 3, characterized in that a bis-benzoxazole of the formula (5) is used as the optical brightener, in which R₈ and R₉ independently of one another are each H or C₁-C₄-alkyl and X is vinylene, thienylene, naphthylene, styrene or stilbenylene . Verfahren gemäss Anspruch 3, dadurch gekennzeichnet, dass man als optischen Aufheller ein Cumarin der Formel (6) verwendet, worin R₁₁ Naphthotriazolyl, Phenyltriazolyl, Phenyl-methyltriazolyl oder Methylpyrazolyl und R₁₂ Phenyl oder Chlorpyrazolyl bedeuten.Process according to Claim 3, characterized in that a coumarin of the formula (6) is used as the optical brightener, in which R₁₁ is naphthotriazolyl, phenyltriazolyl, phenylmethyltriazolyl or methylpyrazolyl and R₁₂ is phenyl or chloropyrazolyl. Verfahren gemäss Anspruch 3, dadurch gekennzeichnet, dass man als optischen Aufheller ein Naphthalimid der Formel (9) verwendet, worin R₁₆ und R₁₇ unabhängig voneinander je C₁-C₄-Alkoxy und R₁₈ C₁-C₄-Alkyl bedeuten.Process according to Claim 3, characterized in that a naphthalimide of the formula (9) is used as the optical brightener, in which R₁₆ and R₁₇ independently of one another are each C₁-C₄-alkoxy and R₁₈ C₁-C₄-alkyl. Verfahren gemäss Anspruch 3, dadurch gekennzeichnet, dass man als optischen Aufheller ein Triazin der Formel (10) verwendet, worin R₁₉ Pyrenyl und R₂₀ und R₂₁ unabhängig voneinander je C₁-C₄-Alkoxy bedeuten, oder der Formel (11), worin R₂₀, R₂₁, R₂₂ und R₂₃ unabhängig voneinander je Phenyl und X Stilbenylen bedeuten.Process according to Claim 3, characterized in that a triazine of the formula (10) is used as the optical brightener, in which R₁₉ pyrenyl and R₂₀ and R₂₁ each independently represent C₁-C₄ alkoxy, or of the formula (11) in which R₂₀, R₂₁ , R₂₂ and R₂₃ each independently represent phenyl and X stilbenylene. Verfahren gemäss Anspruch 3, dadurch gekennzeichnet, dass man als optischen Aufheller ein Styrol-benzoxazol der Formel (12) verwendet, worin R₈ und R₉ unabhängig voneinander je C₁-C₄-Alkyl und R₂₄ COOC₁-C₄-Alkyl bedeuten.Process according to Claim 3, characterized in that a styrene-benzoxazole of the formula (12) is used as the optical brightener, in which R₈ and R₉ each independently represent C₁-C₄-alkyl and R₂₄ COOC₁-C₄-alkyl. Verfahren gemäss Anspruch 3, dadurch gekennzeichnet, dass man als optischen Aufheller ein Distyryl-biphenyl der Formel (13) verwendet, worin R₂₅ und R₂₆ unabhängig voneinander je C₁-C₄-Alkoxy bedeuten.A method according to claim 3, characterized in that a distyryl-biphenyl of the formula (13) is used as the optical brightener, wherein R₂₅ and R₂₆ each independently represent C₁-C₄ alkoxy. Verfahren nach einem der Ansprüche 1 bis 13, dadurch gekennzeichnet, dass man einen optischen Aufheller einsetzt, der frei von Zusätzen, insbesondere frei von Stellmitteln und Dispergiermitteln, ist.Method according to one of claims 1 to 13, characterized in that an optical brightener is used which is free of additives, in particular free of adjusting agents and dispersing agents. Verfahren nach einem der Ansprüche 1 bis 14, dadurch gekennzeichnet, dass man bei Temperaturen zwischen etwa 90°C und etwa 200°C, vorzugsweise zwischen etwa 100°C und etwa 150°C, optisch aufhellt.Method according to one of claims 1 to 14, characterized in that optically brightened at temperatures between about 90 ° C and about 200 ° C, preferably between about 100 ° C and about 150 ° C. Verfahren nach einem der Ansprüche 1 bis 15, dadurch gekennzeichnet, dass man bei einem Druck zwischen etwa 73 bar und etwa 400 bar, vorzugsweise zwischen etwa 150 bar und etwa 250 bar, optisch aufhellt.Method according to one of claims 1 to 15, characterized in that one optically brightens at a pressure between about 73 bar and about 400 bar, preferably between about 150 bar and about 250 bar. Verfahren nach einem der Ansprüche 1 bis 16, dadurch gekennzeichnet, dass man das Substrat in einem Flottenverhältnis zwischen etwa 1 : 2 bis etwa 1 : 100, vorzugsweise zwischen etwa 1 : 5 und etwa 1 : 75, optisch aufhellt.Method according to one of claims 1 to 16, characterized in that the substrate is optically brightened in a liquor ratio between about 1: 2 to about 1: 100, preferably between about 1: 5 and about 1:75. Verfahren nach einem der Ansprüche 1 bis 17, dadurch gekennzeichnet, dass man nach dem optischen Aufhellen das verwendete überkritische CO₂ reinigt und erneut zum Aufhellen verwendet.Method according to one of claims 1 to 17, characterized in that after the optical brightening, the supercritical CO₂ used is cleaned and used again for the brightening. Verfahren nach Anspruch 18, dadurch gekennzeichnet, dass man das überkritische CO₂ mittels eines Filters reinigt.A method according to claim 18, characterized in that the supercritical CO₂ is cleaned by means of a filter. Verfahren nach Anspruch 18 oder 19, dadurch gekennzeichnet, dass man das überkritische CO₂ durch eine Temperatur- und/oder Druckerniedrigung und/oder Volumenvergrösserung reinigt.A method according to claim 18 or 19, characterized in that the supercritical CO₂ is cleaned by lowering the temperature and / or pressure and / or increasing the volume. Anwendung des Verfahren gemäss einem der Ansprüche 1 bis 20 zum optischen Aufhellen von Textilmaterial aus Polyester.Application of the method according to one of claims 1 to 20 for the optical brightening of textile material made of polyester. Das nach dem Verfahren gemäss einem der Ansprüche 1 bis 21 optisch aufgehellte Textilmaterial.The textile material which has been optically brightened by the process according to one of Claims 1 to 21.
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Families Citing this family (46)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5972045A (en) * 1995-10-06 1999-10-26 Amann & Sohne Gmbh & Co. Process for the dyeing of a textile substrate
DE19631604A1 (en) * 1995-10-17 1997-04-24 Amann & Soehne Dyeing textile substrates suitable for industrial scale operation
US5783082A (en) * 1995-11-03 1998-07-21 University Of North Carolina Cleaning process using carbon dioxide as a solvent and employing molecularly engineered surfactants
US6500605B1 (en) 1997-05-27 2002-12-31 Tokyo Electron Limited Removal of photoresist and residue from substrate using supercritical carbon dioxide process
TW539918B (en) 1997-05-27 2003-07-01 Tokyo Electron Ltd Removal of photoresist and photoresist residue from semiconductors using supercritical carbon dioxide process
US6306564B1 (en) 1997-05-27 2001-10-23 Tokyo Electron Limited Removal of resist or residue from semiconductors using supercritical carbon dioxide
US6165560A (en) 1997-05-30 2000-12-26 Micell Technologies Surface treatment
US6344243B1 (en) 1997-05-30 2002-02-05 Micell Technologies, Inc. Surface treatment
AU742586B2 (en) 1997-05-30 2002-01-10 Micell Technologies Surface treatment
US6287640B1 (en) 1997-05-30 2001-09-11 Micell Technologies, Inc. Surface treatment of substrates with compounds that bind thereto
US6048369A (en) * 1998-06-03 2000-04-11 North Carolina State University Method of dyeing hydrophobic textile fibers with colorant materials in supercritical fluid carbon dioxide
US7064070B2 (en) * 1998-09-28 2006-06-20 Tokyo Electron Limited Removal of CMP and post-CMP residue from semiconductors using supercritical carbon dioxide process
US6277753B1 (en) 1998-09-28 2001-08-21 Supercritical Systems Inc. Removal of CMP residue from semiconductors using supercritical carbon dioxide process
KR100744888B1 (en) 1999-11-02 2007-08-01 동경 엘렉트론 주식회사 Method and apparatus for supercritical processing of a workpiece
US6748960B1 (en) 1999-11-02 2004-06-15 Tokyo Electron Limited Apparatus for supercritical processing of multiple workpieces
JP2001172524A (en) * 1999-12-20 2001-06-26 Toray Ind Inc Dye composition and method for dyeing fiber structure
US6261326B1 (en) 2000-01-13 2001-07-17 North Carolina State University Method for introducing dyes and other chemicals into a textile treatment system
US6890853B2 (en) 2000-04-25 2005-05-10 Tokyo Electron Limited Method of depositing metal film and metal deposition cluster tool including supercritical drying/cleaning module
US6676710B2 (en) 2000-10-18 2004-01-13 North Carolina State University Process for treating textile substrates
DE60109059T2 (en) * 2000-12-20 2006-02-09 Unilever N.V. DRY CLEANING SYSTEM FOR TEXTILES
WO2002050365A1 (en) * 2000-12-20 2002-06-27 Unilever N.V. Fabric cleaning system
JP2005516405A (en) * 2002-01-25 2005-06-02 東京エレクトロン株式会社 Method for reducing the formation of contaminants during a supercritical carbon dioxide process
JP2006508521A (en) * 2002-02-15 2006-03-09 東京エレクトロン株式会社 Drying of resist using solvent bath and supercritical CO2
US6924086B1 (en) 2002-02-15 2005-08-02 Tokyo Electron Limited Developing photoresist with supercritical fluid and developer
WO2003077032A1 (en) * 2002-03-04 2003-09-18 Supercritical Systems Inc. Method of passivating of low dielectric materials in wafer processing
JP4031440B2 (en) * 2002-03-22 2008-01-09 東京エレクトロン株式会社 Contaminant removal using supercritical processing
US7169540B2 (en) * 2002-04-12 2007-01-30 Tokyo Electron Limited Method of treatment of porous dielectric films to reduce damage during cleaning
KR20020096023A (en) * 2002-09-30 2002-12-28 건설화학공업(주) Light-emitting compound and display device adopting light-emitting compound as color-developing substance
US20040177867A1 (en) * 2002-12-16 2004-09-16 Supercritical Systems, Inc. Tetra-organic ammonium fluoride and HF in supercritical fluid for photoresist and residue removal
US20040231707A1 (en) * 2003-05-20 2004-11-25 Paul Schilling Decontamination of supercritical wafer processing equipment
US7307019B2 (en) 2004-09-29 2007-12-11 Tokyo Electron Limited Method for supercritical carbon dioxide processing of fluoro-carbon films
US7491036B2 (en) 2004-11-12 2009-02-17 Tokyo Electron Limited Method and system for cooling a pump
US7291565B2 (en) 2005-02-15 2007-11-06 Tokyo Electron Limited Method and system for treating a substrate with a high pressure fluid using fluorosilicic acid
US20060185694A1 (en) * 2005-02-23 2006-08-24 Richard Brown Rinsing step in supercritical processing
US20060186088A1 (en) * 2005-02-23 2006-08-24 Gunilla Jacobson Etching and cleaning BPSG material using supercritical processing
US20060185693A1 (en) * 2005-02-23 2006-08-24 Richard Brown Cleaning step in supercritical processing
US7550075B2 (en) 2005-03-23 2009-06-23 Tokyo Electron Ltd. Removal of contaminants from a fluid
US7399708B2 (en) * 2005-03-30 2008-07-15 Tokyo Electron Limited Method of treating a composite spin-on glass/anti-reflective material prior to cleaning
US7442636B2 (en) * 2005-03-30 2008-10-28 Tokyo Electron Limited Method of inhibiting copper corrosion during supercritical CO2 cleaning
US20060223899A1 (en) * 2005-03-30 2006-10-05 Hillman Joseph T Removal of porogens and porogen residues using supercritical CO2
US7789971B2 (en) 2005-05-13 2010-09-07 Tokyo Electron Limited Treatment of substrate using functionalizing agent in supercritical carbon dioxide
US20070000519A1 (en) * 2005-06-30 2007-01-04 Gunilla Jacobson Removal of residues for low-k dielectric materials in wafer processing
JP5842844B2 (en) * 2013-03-08 2016-01-13 三菱化学株式会社 High refractive index polymerizable compound
JP6277095B2 (en) * 2014-09-03 2018-02-07 富士フイルム株式会社 Cellulose acylate film, polarizing plate and liquid crystal display device
US10876252B2 (en) 2016-11-16 2020-12-29 Huntsman International Llc Process for dyeing and foaming thermoplastic polyurethane
CN114808320A (en) * 2022-05-20 2022-07-29 石狮市中纺学服装及配饰产业研究院 Supercritical fluid anhydrous oil removal and whitening continuous treatment process for polyester products

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0323399A1 (en) * 1987-11-27 1989-07-05 Ciba-Geigy Ag Optical brightener dispersion
EP0328485A1 (en) * 1988-02-08 1989-08-16 Ciba-Geigy Ag Foamless preparation for finishing synthetic fibres
DE4004111A1 (en) * 1989-02-15 1990-08-23 Deutsches Textilforschzentrum Removing accompanying material from flat textiles - threads or animal hair by treatment with supercritical fluid
DE3905514A1 (en) * 1989-02-23 1990-08-30 Oliver Burt Signal transmitter unit, in particular alarm system for detecting changes in the load on parts of land or buildings
DE3906735A1 (en) * 1989-03-03 1990-09-06 Deutsches Textilforschzentrum Process for bleaching
DE3906724A1 (en) * 1989-03-03 1990-09-13 Deutsches Textilforschzentrum Dyeing process

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3904514C2 (en) * 1989-02-15 1999-03-11 Oeffentliche Pruefstelle Und T Process for cleaning or washing parts of clothing or the like
US5199956A (en) * 1990-09-03 1993-04-06 Ciba-Geigy Corporation Process for dyeing hydrophobic textile material with disperse dyes from super-critical carbon dioxide
ATE120812T1 (en) * 1990-09-03 1995-04-15 Ciba Geigy Ag METHOD FOR DYEING HYDROPHOBIC TEXTILE MATERIAL WITH DISPERSION DYES IN SUPERCRITICAL CO2.
ATE116019T1 (en) * 1990-09-03 1995-01-15 Ciba Geigy Ag METHOD FOR DYEING HYDROPHOBIC TEXTILE MATERIAL WITH DISPERSION DYES IN SUPERCRITICAL CO2.
ATE116018T1 (en) * 1990-09-03 1995-01-15 Ciba Geigy Ag METHOD FOR DYEING HYDROPHOBIC TEXTILE MATERIAL WITH DISPERSION DYES FROM SUPERCRITICAL CO2.
DE59204395D1 (en) * 1991-05-17 1996-01-04 Ciba Geigy Ag Process for dyeing hydrophobic textile material with disperse dyes from supercritical CO2.

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0323399A1 (en) * 1987-11-27 1989-07-05 Ciba-Geigy Ag Optical brightener dispersion
EP0328485A1 (en) * 1988-02-08 1989-08-16 Ciba-Geigy Ag Foamless preparation for finishing synthetic fibres
DE4004111A1 (en) * 1989-02-15 1990-08-23 Deutsches Textilforschzentrum Removing accompanying material from flat textiles - threads or animal hair by treatment with supercritical fluid
DE3905514A1 (en) * 1989-02-23 1990-08-30 Oliver Burt Signal transmitter unit, in particular alarm system for detecting changes in the load on parts of land or buildings
DE3906735A1 (en) * 1989-03-03 1990-09-06 Deutsches Textilforschzentrum Process for bleaching
DE3906724A1 (en) * 1989-03-03 1990-09-13 Deutsches Textilforschzentrum Dyeing process

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JOURNAL OF ORGANIC CHEMISTRY Bd. 49, Nr. 26, 1984, EASTON US Seiten 5097 - 5101W HYATT 'Liquid and Supercritical Carbon Dioxide as Organic Solvents' *

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