EP0060439B1 - Spinning mass containing an optical bleaching agent for the preparation of regenerated cellulose fibres - Google Patents

Spinning mass containing an optical bleaching agent for the preparation of regenerated cellulose fibres Download PDF

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Publication number
EP0060439B1
EP0060439B1 EP82101612A EP82101612A EP0060439B1 EP 0060439 B1 EP0060439 B1 EP 0060439B1 EP 82101612 A EP82101612 A EP 82101612A EP 82101612 A EP82101612 A EP 82101612A EP 0060439 B1 EP0060439 B1 EP 0060439B1
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Prior art keywords
formula
denotes
brightener
water
contain
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German (de)
French (fr)
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EP0060439A2 (en
EP0060439A3 (en
Inventor
Udo Dr. Eckstein
Reinhold Dr. Hörnle
Jochen Koll
Hans-Heinz Dr. Mölls
Günter Schäfer
Hans Dr. Theidel
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Bayer AG
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Bayer AG
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • D01F2/06—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from viscose
    • D01F2/08—Composition of the spinning solution or the bath
    • D01F2/16—Addition of dyes to the spinning solution
    • 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

Definitions

  • the dyes used are subject to a wide variety of chemical stresses, which are not found in any other dyeing process in this unusual combination.
  • the dyes have to be both acid and alkali resistant to survive the treatment in the various spinning baths undamaged.
  • Suitable heterocycles which can be formed by 2 of the radicals R 2 -R 3 are saturated 5- or 6-membered types, such as morpholine, piperidine, pyrrolidine and others
  • Suitable heterocycles which can be formed by 3 of these radicals are saturated types, in particular pyridine.
  • Suitable alkyl radicals are in particular those with 1-20 C atoms which can be substituted by CN, OH, halogen, C 1 -C 4 alkoxy or C 1 -C 2 alkylcarbonylamino.
  • Suitable alkenyl radicals are in particular those with 2 to 10 carbon atoms.
  • Suitable aralkyl radicals are phenyl-C i -C 3 alkyl radicals.
  • Suitable aryl radicals are phenyl radicals which can be substituted by halogen, C 1 -C 4 alkyl or C 1 -C 4 alkoxy.
  • Suitable cycloalkyl radicals are especially cyclohexyl radicals.
  • Halogen is preferably understood to mean CI and Br.
  • Suitable cellulose whitening agents from which the radical A is derived, are bistriazolylstilbene, bistilbene and especially bistriazinylaminostilbene disulfonic acids.
  • optical brighteners according to the formulas II ⁇ IV as sulfonic acids or their water-soluble salts, in particular their alkali metal salts, with low molecular weight basic nitrogen compounds of the formula V where Y is a colorless, non-fluorescent anion or OH (-) .
  • the reaction takes place in water and / or organic solvents, such as methanol, ethanol, propanol, isopropanol, butanol, glycol, glycol methyl ether, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, sulfolane, hexamethylphosphoric triamide at temperatures from 20 ° C. to the reflux temperature of the corresponding solvent.
  • organic solvents such as methanol, ethanol, propanol, isopropanol, butanol, glycol, glycol methyl ether, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, sulfolane, hexamethylphosphoric triamide
  • the poorly soluble brightener salts obtained in this way can be used as brightening agents directly or after prior fine grinding or liquid formation.
  • the suspension obtained is then comminuted and wet-ground.
  • Pre-shredding can be carried out using stone or tooth colloid mills.
  • the subsequent wet comminution can be carried out in colloidal vibratory, cone and vibromills as well as in dissolvers or in sub-micron dispersers.
  • continuous agitator mills with grinding media preferably those made of SiO 2 with a diameter of 0.2-5 mm, are preferably used.
  • surface-active substances or hydrotropic substances such as e.g. As ethylene glycol or glycerin, preservatives, wetting agents, defoamers and / or water are added, unless this has already been done at an earlier point in time, for. B. before grinding.
  • the complete reaction of the brightener salts II ⁇ IV with the basic nitrogen compounds V takes place in the grinder, preferably in a continuous agitator mill with Si0 2 grinding media.
  • Suitable surface-active substances are all customary, cationic and nonionic surface-active substances, as are described, for example, in DE-A 2 334 769, pages 8-10 (corresponds to GB-A 1 417071).
  • Nonionic surfactants are preferably used.
  • the compounds of formula (I) show a more or less pronounced fluorescence in the dissolved or finely divided state. They are suitable for whitening cellulose regenerated fibers such as rayon and rayon, which can be processed into woven and non-woven materials (nonwovens).
  • the amount of the compounds I used depends on the desired lightening effect. In general, 0.01-0.5% by weight of pure active substance (based on the fiber material to be lightened) is sufficient.
  • the brightener of the formula (1) is reacted with 7.5 g of benzyldimethylphenylammonium chloride. 12.2 g of light yellow crystals with a melting point of 259260 ° C. are obtained, which can be recrystallized from ethylene glycol.
  • the substance is practically insoluble in water and shows excellent white effects when incorporated into viscose.
  • Brightener of the formula are refluxed with 10 g of benzyl-dodecyl-dimethylammonium chloride in 120 ml of dimethylformamide for 2 hours and, after cooling to 10 ° C., are filtered off. 8.7 g of light yellow crystals of mp: 182-184 ° C. are obtained, which can be recrystallized from ethylene glycol.
  • 16 g of the optical brightener of formula 1 from Example 1 are homogenized with 16 g of benzyl-dodecyl-dimethylammonium chloride, 16 g of emulsifier W and 52 g of water with stirring and pre-comminuted with a toothed colloid mill.
  • the suspension is wet-crushed at room temperature with 4 passes in a bead mill.
  • Example 9 the brightener salts of Examples 4, 5 and 6, which are sparingly or insoluble in water, and the compounds (8) - (20) described in Example 8 can be formed into stable dispersions.
  • Example 8 In the same way as described in Examples 10 and 11, the starting products (8) - (20) described in Example 8 can also be converted and formed into stable dispersions.
  • a comparison of the brightening with equivalent amounts of the starting compound (1) shows that the whiteness obtained with the quaternary ammonium salt precipitated.
  • Example 1 The corresponding amount of the pure active ingredient from Example 1 can also be used and spun in the same way.

Abstract

1. Whitener-containing spinning dopes for the production of regenerated cellulose fibres, characterised in that they contain virtually water-insoluble lowmolecular brightener salts of the formula see diagramm : EP0060439,P8,F4 wherein A denotes the anion of a high-affinity anionic whitener for cellulose, R1 denotes optionally substituted alkyl, alkenyl, aralkyl, aryl or cycloalkyl, R2 , R3 or R4 independently of one another denote hydrogen or R1 , or either 2 or 3 of these radicals jointly form, with the inclusion of the N atom, a heterocyclic structure, and n denotes an integer > 0.

Description

Bei der Spinnfärbung von künstlichen Cellulosefasern unterliegen die verwendeten Farbstoffe den vielfältigsten chemischen Beanspruchungen, die in dieser ungewöhnlichen Kombination bei keinem anderen Färbeverfahren gegeben sind. Beispielsweise müssen die Farbstoffe im hohen Maße sowohl säure- als auch alkalibeständig sein, um die Behandlung in den diversen Spinnbädern unbeschadet zu überstehen.In the dyeing of artificial cellulose fibers, the dyes used are subject to a wide variety of chemical stresses, which are not found in any other dyeing process in this unusual combination. For example, the dyes have to be both acid and alkali resistant to survive the treatment in the various spinning baths undamaged.

Aus diesem Grunde werden bislang für diese Spinnfärberei fast ausschließlich Pigmente als Farbkörper eingesetzt. Weißtöner zur Spinnfärbung von Celluloseregeneratfasern haben sich hingegen bisher nicht am Markt durchsetzen können. Die üblichen Baumwollweißtöner versagen hier völlig, da sie den oben erwähnten drastischen Beanspruchungen nicht gewachsen sind.For this reason, pigments have been used almost exclusively as color bodies for this spin dyeing. However, whiteners for spin dyeing regenerated cellulose fibers have so far not been able to establish themselves on the market. The usual cotton whites fail completely because they are not up to the drastic demands mentioned above.

Daher ist bereits vorgeschlagen worden (vgl. DE-C 1 096 321 = GB-A 815 742), wasserlösliche Celluloseaufheller durch Umsetzung mit polymeren Aminen zu verlacken und die dabei gewonnenen wasserunlöslichen Aufhellungsmittel in Spinnmassen zur Herstellung von weißgetönten Cellulosekunstfasern einzuarbeiten.It has therefore already been proposed (cf. DE-C 1 096 321 = GB-A 815 742) to lacquer water-soluble cellulose brighteners by reaction with polymeric amines and to incorporate the water-insoluble brightening agents obtained in this way into spinning masses for the production of white-tinted cellulose synthetic fibers.

Es zeigte sich indessen, daß diese Aufhellerlacke zwar säure- und alkalistabil sind, jedoch nur unbefriedigende Aufhelleffekte liefern.It was found, however, that these brightener varnishes are acid and alkali stable, but only provide unsatisfactory brightening effects.

Überraschenderweise wurde nun gefunden, daß man Celluloseregeneratfasern nach der Spinnfärbemethode ohne die genannten Nachteile weißtönen kann, wenn man Spinnmassen einsetzt, die in Wasser praktisch unlösliche niedermolekulare (d. h. keine polymeren Gruppen enthaltende) Aufhellersalze der Formel

Figure imgb0001
enthalten,
worin

  • A das Anion eines hochaffinen anionischen Celluloseweißtöners,
  • R1. gegebenenfalls substituiertes Alkyl, Alkenyl, Aralkyl, Aryl oder Cycloalkyl,
  • R2, R3 und R4 unabhängig voneinander Wasserstoff oder R1, oder je 2 bzw. 3 dieser Reste gemeinsam unter Einschluß des N-Atoms einen Heterocyclus bilden, und
  • n eine ganze Zahl>0 bedeuten.
Surprisingly, it has now been found that cellulose regenerated fibers can be whitened by the spin dyeing method without the disadvantages mentioned, if spinning compositions are used which have low molecular weight (ie no polymer groups) brightening salts of the formula which are practically insoluble in water
Figure imgb0001
 contain,
wherein
  • A is the anion of a high-affinity anionic cellulose whitener,
  • R 1 . optionally substituted alkyl, alkenyl, aralkyl, aryl or cycloalkyl,
  • R 2 , R 3 and R 4 independently of one another are hydrogen or R 1 , or in each case 2 or 3 of these radicals together form a heterocycle, including the N atom, and
  • n is an integer> 0.

Geeignete Heterocyclen, die durch 2 der Reste R2-R3 gebildet werden können, sind gesättigte 5- oder 6-gliedrige Typen, wie Morpholin, Piperidin, Pyrrolidin u. a.Suitable heterocycles which can be formed by 2 of the radicals R 2 -R 3 are saturated 5- or 6-membered types, such as morpholine, piperidine, pyrrolidine and others

Geeignete Heterocyclen, die durch 3 dieser Reste gebildet werden können, sind gesättigte Typen, insbesondere Pyridin.Suitable heterocycles which can be formed by 3 of these radicals are saturated types, in particular pyridine.

Geeignete Alkylreste sind insbesondere solche mit 1-20 C-Atomen die durch CN, OH, Halogen, Cl-C4-Alkoxy oder C1-C2-Alkylcarbonylamino substituiert sein können.Suitable alkyl radicals are in particular those with 1-20 C atoms which can be substituted by CN, OH, halogen, C 1 -C 4 alkoxy or C 1 -C 2 alkylcarbonylamino.

Geeignete Alkenylreste sind insbesondere solche mit 2 bis 10 C-Atomen.Suitable alkenyl radicals are in particular those with 2 to 10 carbon atoms.

Geeignete Aralkylreste sind Phenyl-Ci-C3-alkylreste.Suitable aralkyl radicals are phenyl-C i -C 3 alkyl radicals.

Geeignete Arylreste sind Phenylreste, die durch Halogen, C1-C4-Alkyl oder Cl-C4-Alkoxy substituiert sein können.Suitable aryl radicals are phenyl radicals which can be substituted by halogen, C 1 -C 4 alkyl or C 1 -C 4 alkoxy.

Geeignete Cycloalkylreste sind vor allem Cyclohexylreste.Suitable cycloalkyl radicals are especially cyclohexyl radicals.

Unter »Halogen« wird vorzugsweise CI und Br verstanden.“Halogen” is preferably understood to mean CI and Br.

Geeignete Celluloseweißtöner, von denen sich der Rest A ableitet, sind Bistriazolylstilben-, Bistilben-und vor allem Bistriazinylaminostilben-disulfonsäuren.Suitable cellulose whitening agents, from which the radical A is derived, are bistriazolylstilbene, bistilbene and especially bistriazinylaminostilbene disulfonic acids.

Beispiele für geeignete Reste A sind solche der Formel

Figure imgb0002
worin

  • X1 Amino, Methylamino, Ethylamino, Dimethylamino, Diethylamino, 2-Hydroxy-ethylamino, 3-Hydroxypropylamino, Di-(2-hydroxy-ethyl)amino, Di-(2-Hydroxy-propyl)amino, 2-Sulfo-ethylamino, Morpholino, Anilino, Chloranilino, Sulfoanilino, Methylanilino oder Disulfoanilino und
  • X2 Hydroxy, Methoxy, Ethoxy, Methoxyethoxy, Chlor oder X1 bedeuten,

sowie solche der Formel
Figure imgb0003
worin
  • X3 und X4 Wasserstoff, Methyl, Ethyl, Phenyl oder Sulfophenyl bedeuten,

sowie der Formel
Figure imgb0004
worin
  • X5 Wasserstoff, Methyl, Ethyl, Methoxy, Ethoxy, Chlor oder Sulfo bedeuten.
Examples of suitable radicals A are those of the formula
Figure imgb0002
 wherein
  • X 1 amino, methylamino, ethylamino, dimethylamino, diethylamino, 2-hydroxyethylamino, 3-hydroxypropylamino, di- (2-hydroxy-ethyl) amino, di- (2-hydroxypropyl) amino, 2-sulfo-ethylamino, Morpholino, anilino, chloranilino, sulfoanilino, methylanilino or disulfoanilino and
  • X 2 is hydroxy, methoxy, ethoxy, methoxyethoxy, chlorine or X 1 ,

as well as those of the formula
Figure imgb0003
 wherein
  • X 3 and X 4 denote hydrogen, methyl, ethyl, phenyl or sulfophenyl,

as well as the formula
Figure imgb0004
 wherein
  • X 5 is hydrogen, methyl, ethyl, methoxy, ethoxy, chlorine or sulfo.

Bei der Herstellung der Verbindungen der Formel I geht man zweckmäßigerweise so vor, daß man optische Aufheller gemäß den Formeln II―IV als Sulfonsäuren bzw. deren wasserlösliche Salze, insbesondere deren Alkalisalzen, mit niedermolekularen basischen Stickstoffverbindungen der Formel V

Figure imgb0005
worin Y ein farbloses, nichtfluoreszierendes Anion oder OH(-) bedeutet, umsetzt.In the preparation of the compounds of the formula I, the procedure is expediently such that optical brighteners according to the formulas II ― IV as sulfonic acids or their water-soluble salts, in particular their alkali metal salts, with low molecular weight basic nitrogen compounds of the formula V
Figure imgb0005
 where Y is a colorless, non-fluorescent anion or OH (-) .

Die Umsetzung erfolgt in Wasser und/oder organischen Lösungsmitteln, wie Methanol, Ethanol, Propanol, Isopropanol, Butanol, Glykol, Glykolmethylether, Dimethylformamid, Dimethylacetamid, Dimethylsulfoxid, Sulfolan, Hexamethylphosphorsäuretriamid bei Temperaturen von 20°C bis zur Rückflußtemperatur des entsprechenden Lösungsmittel.The reaction takes place in water and / or organic solvents, such as methanol, ethanol, propanol, isopropanol, butanol, glycol, glycol methyl ether, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, sulfolane, hexamethylphosphoric triamide at temperatures from 20 ° C. to the reflux temperature of the corresponding solvent.

Die so erhaltenen schwerlöslichen Aufhellersalze können direkt oder nach vorheriger Feinmahlung oder Flüssigformierung als Aufhellungsmittel eingesetzt werden.The poorly soluble brightener salts obtained in this way can be used as brightening agents directly or after prior fine grinding or liquid formation.

Die erfindungsgemäßen Dispersionen können wie folgt hergestellt werden:

  • Die Preßkuchen und/oder Pulver werden nach Zugabe eines oberflächenaktiven Stoffes und gegebenenfalls Wasser unter starken Rühren homogenisiert. Danach kann eine Erhöhung der Menge des oberflächenaktiven Stoffes, gegebenenfalls auf die gesamte, für die Stabilität der Dispersion benötigte Menge erfolgen.
The dispersions according to the invention can be prepared as follows:
  • The press cakes and / or powders are homogenized with vigorous stirring after the addition of a surface-active substance and optionally water. The amount of the surface-active substance can then be increased, if necessary to the total amount required for the stability of the dispersion.

Die erhaltene Suspension wird dann vorzerkleinert und naßgemahlen.The suspension obtained is then comminuted and wet-ground.

Die Vorzerkleinerung kann über Stein- oder Zahnkolloidmühlen erfolgen.Pre-shredding can be carried out using stone or tooth colloid mills.

Die anschließende Naßzerkleinerung kann in Kolloid-Schwing-, Kegel- und Vibromühlen sowie in Dissolvern oder in Sub-Mikron-Disperser erfolgen. Vorzugsweise werden jedoch kontinuierliche Rührwerksmühlen mit Mahlkörpern, vorzugsweise solche aus Si02 von 0,2-5 mm Durchmesser verwendet.The subsequent wet comminution can be carried out in colloidal vibratory, cone and vibromills as well as in dissolvers or in sub-micron dispersers. However, continuous agitator mills with grinding media, preferably those made of SiO 2 with a diameter of 0.2-5 mm, are preferably used.

Nach der Mahlbehandlung können gegebenenfalls noch weitere Mengen oberflächenaktiven Stoffe oder auch hydrotrope Substanzen wie z. B. Ethylenglykol oder Glycerin, Konservierungsmittel, Netzmittel, Entschäumer und/oder Wasser zugegeben werden, soweit dies nicht schon zu einem früheren Zeitpunkt z. B. vor der Mahlung erfolgte.After the grinding treatment, further amounts of surface-active substances or hydrotropic substances such as e.g. As ethylene glycol or glycerin, preservatives, wetting agents, defoamers and / or water are added, unless this has already been done at an earlier point in time, for. B. before grinding.

Eine weitere Möglichkeit die erfindungsgemäßen in Wasser schwer- bzw. unlöslichen Aufhellungsmittel und ihre Dispersionen herzustellen stellt die Kombination des Reaktions- und Mahlvorganges dar:

  • Dazu werden die Alkalisalze der Aufheller gemäß Formel li-IV zusammen mit den basischen Stickstoffverbindungen der Formel V sowie Wasser und oberflächenaktive Stoffe nach Homogenisierung und Vorzerkleinerung naßzerkleinert.
A further possibility of producing the brightening agents according to the invention which are sparingly or insoluble in water and their dispersions is the combination of the reaction and grinding process:
  • For this purpose, the alkali salts of the brighteners according to formula li-IV are wet-comminuted together with the basic nitrogen compounds of formula V and water and surface-active substances after homogenization and pre-comminution.

Die vollständige Reaktion der Aufhellersalze II―IV mit den basischen Stickstoffverbindungen V findet dabei im Mahlapparat, vorzugsweise in einer kontinuierlichen Rührwerksmühle mit Si02-Mahlkörpern statt.The complete reaction of the brightener salts II ― IV with the basic nitrogen compounds V takes place in the grinder, preferably in a continuous agitator mill with Si0 2 grinding media.

Die nach den beiden Verfahren hergestellten, erfindungsgemäßen Dispersionen enthalten 1-25 %, vorzugsweise 5-20% der erfindungsgemäßen in Wasser schwer- bzw. unlöslichen Aufhellersalze, 1-50%, vorzugsweise 5-20% oberflächenaktive Stoffe, 0-15% Konservierungsmittel und Wasser, wobei ein Teil des Wassers durch hydrotrope Substanzen ersetzt werden kann (% = Gewichtsprozent).The dispersions according to the invention produced by the two processes contain 1-25%, preferably 5-20% of the brightener salts according to the invention which are sparingly or insoluble in water, 1-50%, preferably 5-20% of surface-active substances, 0-15% of preservatives and Water, whereby part of the water can be replaced by hydrotropic substances (% = weight percent).

Als oberflächenaktive Stoffe kommen alle üblichen, kationischen und nichtionogenen oberflächenaktiven Stoffe in Betracht, wie sie beispielsweise in der DE-A 2 334 769, Seiten 8-10 (entspricht GB-A 1 417071) beschrieben sind.Suitable surface-active substances are all customary, cationic and nonionic surface-active substances, as are described, for example, in DE-A 2 334 769, pages 8-10 (corresponds to GB-A 1 417071).

Bevorzugt werden nichtionogene Tenside eingesetzt.Nonionic surfactants are preferably used.

Die Verbindungen der Formel (I) zeigen in gelösten oder feinverteilten Zustand eine mehr oder weniger ausgeprägte Fluoreszenz. Sie eignen sich zum Weißtönen von Celluloseregeneratfasern wie Reyon und Zellwolle, die zu gewebten und ungewebten Materialien (Vliese) verarbeitet werden können.The compounds of formula (I) show a more or less pronounced fluorescence in the dissolved or finely divided state. They are suitable for whitening cellulose regenerated fibers such as rayon and rayon, which can be processed into woven and non-woven materials (nonwovens).

Die Einsatzmenge der Verbindungen I richtet sich nach dem angestrebten Aufhelleffekt. Im allgemeinen genügen 0,01-0,5 Gew.-Prozent reiner Wirksubstanz (bezogen auf das aufzuhellende Fasermaterial).The amount of the compounds I used depends on the desired lightening effect. In general, 0.01-0.5% by weight of pure active substance (based on the fiber material to be lightened) is sufficient.

Beispiel 1example 1

10 g des optischen Aufhellers der Formel

Figure imgb0006
und 10 g Benzyl-n-dodecyldimethylammoniumchlorid werden in 100 ml Wasser 30 Min. am Rückfluß erhitzt. Danach wird bei ca. 60°C abfiltriert und mit 60°C warmen Wasser gewaschen. Nach Trocknen i. Vak. erhält man 14,5 g des quartären Ammoniumsalzes des opt. Aufhellers der obigen Formel vom Schmelzpunkt: 258-259°C, das in n-Butanol umkristallisiert werden kann. Die Substanz ist in Wasser unlöslich und zeigt eingearbeitet in Viskosespinnmassen auf der Faser hervorragende Weißeffekte.10 g of the optical brightener of the formula
Figure imgb0006
 and 10 g of benzyl-n-dodecyldimethylammonium chloride are refluxed in 100 ml of water for 30 minutes. Then it is filtered off at about 60 ° C and washed with water at 60 ° C. After drying i. Vac. 14.5 g of the quaternary ammonium salt of the opt. Brightener of the above formula of melting point: 258-259 ° C, which can be recrystallized in n-butanol. The substance is insoluble in water and shows excellent white effects when incorporated into viscose spinning masses on the fiber.

Beispiel 2Example 2

Auf die gleiche Weise wie im Beispiel 1 beschrieben wird der Aufheller der Formel (1) mit 7,5 g Benzyldimethyl-phenylammoniumchlorid umgesetzt. Man erhält 12,2 g hellgelbe Kristalle vom Schmelzpunkt: 259­260°C, die aus Ethylenglykol umkristallisiert werden können.In the same way as described in Example 1, the brightener of the formula (1) is reacted with 7.5 g of benzyldimethylphenylammonium chloride. 12.2 g of light yellow crystals with a melting point of 259260 ° C. are obtained, which can be recrystallized from ethylene glycol.

Die Substanz ist in Wasser praktisch unlöslich und zeigt in Viskose eingearbeitet hervorragende Weißeffekte.The substance is practically insoluble in water and shows excellent white effects when incorporated into viscose.

Beispiel 3Example 3

9,6 g des opt. Aufhellers der Formel

Figure imgb0007
werden mit 6 g Benzyl-dimethyl-phenylammoniumchlorid in 200 ml Wasser 1 Std. am Rückfluß erhitzt. Abfiltrieren bei ca. 50―60°C und Trocknen i. Vak. liefert 8 g hellgelbes Kristallpulver vom Schmp.: 212-215°C, das aus n-Butanol umkristallisiert werden kann. Brillante Weißeffekte auf Reyonfasern.9.6 g of the opt. Brightener of the formula
Figure imgb0007
 are refluxed with 6 g of benzyl-dimethyl-phenylammonium chloride in 200 ml of water for 1 hour. Filter off at approx. 50-60 ° C and dry i. Vac. provides 8 g of light yellow crystal powder, mp: 212-215 ° C, which can be recrystallized from n-butanol. Brilliant white effects on rayon fibers.

Beispiel 4Example 4

6 g des Aufhellers der Formel

Figure imgb0008
werden mit 10 g Benzyldodecyl-dimethylammoniumchlorid in 100 ml Wasser 1 Std. am Rückfluß erhitzt. Abfiltrieren und Trocknen i. Vak. liefert 10,3 g fast farblose Kristalle vom Schmp.: 268-270°C, die aus Ethylenglykol umkristallisiert werden können.6 g of the brightener of the formula
Figure imgb0008
 are refluxed with 10 g of benzyldodecyldimethylammonium chloride in 100 ml of water for 1 hour. Filter off and dry i. Vac. provides 10.3 g of almost colorless crystals of mp: 268-270 ° C, which can be recrystallized from ethylene glycol.

Beispiel 5Example 5

7 g des opt. Aufhellers der Formel

Figure imgb0009
werden mit 10 g Benzyl-dodecyl-dimethylammoniumchlorid in 120 ml Dimethylformamid 2 Stunden am Rückfluß erhitzt und nach dem Abkühlen auf 10°C abfiltriert. Man erhält 8,7 g hellgelbe Kristalle vom Schmp.: 182-184°C, die aus Ethylenglykol umkristallisiert werden können.7 g of the opt. Brightener of the formula
Figure imgb0009
 are refluxed with 10 g of benzyl-dodecyl-dimethylammonium chloride in 120 ml of dimethylformamide for 2 hours and, after cooling to 10 ° C., are filtered off. 8.7 g of light yellow crystals of mp: 182-184 ° C. are obtained, which can be recrystallized from ethylene glycol.

Beispiel 6Example 6

8,5 g des optischen Aufhellers der Formel

Figure imgb0010
werden in 100 ml Wasser gelöst und dann mit 10 g Benzyl-dimethyl-phenyl-ammoniumchlorid 2 Std. am Rückfluß erhitzt. Abkühlen und Absaugen liefert 13 g gelbliche Kristalle vom Schmp.: 224-226°C, die aus Ethylenglykol umkristallisiert werden können.8.5 g of the optical brightener of the formula
Figure imgb0010
 are dissolved in 100 ml of water and then refluxed with 10 g of benzyldimethylphenylammonium chloride for 2 hours. Cooling and suctioning off yields 13 g of yellowish crystals with a melting point of 224-226 ° C., which can be recrystallized from ethylene glycol.

Beispiel 7Example 7

10g des optischen Aufhellers der Formel (1) und 3 g Triethylaminhydrochlorid in 150 ml Wasserwerden 1 Std. am Rückfluß erhitzt, abgekühlt und abfiltriert. Gelbliche Kristalle, die aus Methylglykol umgelöst werden können.10 g of the optical brightener of the formula (1) and 3 g of triethylamine hydrochloride in 150 ml of water are heated under reflux for 1 hour, cooled and filtered off. Yellowish crystals that can be redissolved from methylglycol.

Beispiel 8Example 8

Auf die gleiche Weise, wie in den vorangegangenen Beispielen beschrieben, erhält man weitere schwerlösliche quartäre Ammoniumsalze von opt. Aufhellern, die durch Umsetzung von Verbindungen der Formel

Figure imgb0011
mit Ammoniumsalzen der Formel
Figure imgb0012
erhalten werden können.In the same way as described in the previous examples, further poorly soluble quaternary ammonium salts are obtained from opt. Brightener by implementing compounds of the formula
Figure imgb0011
 with ammonium salts of the formula
Figure imgb0012
 can be obtained.

Die folgende Tabelle erhält die Reste der verwendeten Ausgangsverbindungen (6) und (7).

Figure imgb0013
The following table contains the residues of the starting compounds (6) and (7) used.
Figure imgb0013

Beispiel 9Example 9

20 g des nach Beispiel 1 hergestellten in Wasser unlöslichen Aufhellersalzes werden zusammen mit 20 g Emulgator W und 60 g Wasser homogenisiert und mit einer Zahnkolloidmühle vorzerkleinert. Die Suspension wird dann bei Raumtemperatur mit 4 Durchgängen in einer Perlmühle naßzerkleinert. Die resultierende stabile Dispersion ist leicht in die Spinnmassen einzuarbeiten und zeigt ebenfalls auf der versponnenen Faser hervorragende Weißeffekte.20 g of the water-insoluble brightener salt prepared according to Example 1 are homogenized together with 20 g of emulsifier W and 60 g of water and comminuted with a toothed colloid mill. The suspension is then wet crushed in a bead mill at room temperature with 4 passes. The resulting stable dispersion is easy to incorporate into the spinning masses and also shows excellent white effects on the spun fiber.

Beispiel 10Example 10

16 g des opt. Aufhellers der Formel 1 aus Beispiel 1 werden mit 12,8 g Benzyldimethyl-phenyl- ammoniumchlorid, 16 g Emulgator W und 55,2 g Wasser unter Rühren homogenisiert und mit einer Zahnkolloidmühle vorzerkleinert. Die Suspension wird bei Raumtemperatur und 4 Durchgängen in einer Perlmühle naßzerkleinert. Die resultierende, stabile Dispersion ist leicht in die Spinnmasse einzuarbeiten und zeigt auf der versponnenen Faser hervorragende Weißeffekte.16 g of the opt. Brighteners of the formula 1 from Example 1 are homogenized with 12.8 g of benzyldimethyl-phenylammonium chloride, 16 g of emulsifier W and 55.2 g of water and stirred with a toothed colloid mill. The suspension is wet crushed at room temperature and 4 passes in a bead mill. The resulting stable dispersion is easy to incorporate into the spinning mass and shows excellent white effects on the spun fiber.

Beispiel 11Example 11

16 g des optischen Aufhellers der Formel 1 aus Beispiel 1 werden mit 16 g Benzyl-dodecyl-dimethylammoniumchlorid, 16 g Emulgator W und 52 g Wasser unter Rühren homogenisiert und mit einer Zahnkolloidmühle vorzerkleinert. Die Suspension wird bei Raumtemperatur mit 4 Durchgängen in einer Perlmühle naßzerkleinert.16 g of the optical brightener of formula 1 from Example 1 are homogenized with 16 g of benzyl-dodecyl-dimethylammonium chloride, 16 g of emulsifier W and 52 g of water with stirring and pre-comminuted with a toothed colloid mill. The suspension is wet-crushed at room temperature with 4 passes in a bead mill.

Beispiel 12Example 12

In gleicher Weise wie in Beispiel 9 beschrieben lassen sich die in Wasser schwer- bzw. unlöslichen Aufhellersalze der Beispiel 4, 5 und 6 sowie die im Beispiel 8 beschriebenen Verbindungen (8)-(20) zu stabilen Dispersionen formieren.In the same way as described in Example 9, the brightener salts of Examples 4, 5 and 6, which are sparingly or insoluble in water, and the compounds (8) - (20) described in Example 8 can be formed into stable dispersions.

Beispiel 13Example 13

In gleicher Weise wie in den Beispielen 10 und 11 beschrieben, lassen sich auch die in Beispiel 8 beschriebenen Ausgangsprodukte (8)-(20) umsetzen und zu stabilen Dispersionen formieren.In the same way as described in Examples 10 and 11, the starting products (8) - (20) described in Example 8 can also be converted and formed into stable dispersions.

Beispiel 14Example 14

1 kg Viskose (als Xanthogenat in Natronlauge gelöste 7%ige Cellulose) wird mit 1,2 % der gut geschüttelten Dispersion (16%ig bezogen auf Wirkstoff), deren Herstellung im Beispiel 9 oder 11 beschrieben ist, versetzt; es wird 6 Min. gut gerührt (70 U/Min.), bei ca. 200 Torr (0,26 bar) währen 60 Min. entlüftet und dann in ein Koagulationsbad, bestehend aus Schwefelsäure (8 %), Natriumsulfat (16 %) und Zinksulfat (3 %), abgesponnen und in üblicherweise aufgearbeitet. Eine Beeinflussung der Spinnbäder konnte weder in sauren noch im alkalischen Bereich festgestellt werden.1 kg of viscose (7% cellulose dissolved as xanthate in sodium hydroxide solution) is mixed with 1.2% of the well-shaken dispersion (16% based on active ingredient), the preparation of which is described in Example 9 or 11; it is stirred well for 6 minutes (70 rpm), deaerated at approx. 200 torr (0.26 bar) for 60 minutes and then into a coagulation bath consisting of sulfuric acid (8%), sodium sulfate (16%) and zinc sulfate (3%), spun and usually worked up. An influence on the spinning baths could not be found either in the acidic or in the alkaline range.

Ein Vergleich der Aufhellung mit äquivalenten Mengen der Ausgangsverbindung (1) zeigt, daß man mit den gefällten quartären Ammoniumsalz höhere Weißgrade bekommt.A comparison of the brightening with equivalent amounts of the starting compound (1) shows that the whiteness obtained with the quaternary ammonium salt precipitated.

In gleicher Weise kann auch die entsprechende Menge des reinen Wirkstoffes aus Beispiel 1 eingesetzt und versponnen werden.The corresponding amount of the pure active ingredient from Example 1 can also be used and spun in the same way.

Claims (8)

1. Whitener-containing spinning dopes for the production of regenerated cellulose fibres, characterised in that they contain virtually water-insoluble lowmolecular brightener salts of the formula
Figure imgb0021
wherein
A denotes the anion of a high-affinity anionic whitener for cellulose,
R1 denotes optionally substituted alkyl, alkenyl, aralkyl, aryl or cycloalkyl,
R2, R3 or R4 independently of one another denote hydrogen or R1, or either 2 or 3 of these radicals jointly form, with the inclusion of the N atom, a heterocyclic structure, and
n denotes an integer >0.
2. Spinning dopes according to Claim 1, characterised in that they contain, as brightener salts, those of the formula indicated,
wherein
A represents a radical of the formula
Figure imgb0022
wherein
X1 denotes amino, methylamino, ethylamino, dimethylamino, diethylamino, 2-hydroxyethyla- mino, 3-hydroxypropylamino, di-(2-hydroxyethyl)-amino, di-(2-hydroxypropyl)-amino, 2-sulphoethylamino, morpholino, anilino, chloroanilino, sulphoanilino, methylanilino or 2-disul- phoanilino and
X2 denotes hydroxyl, methoxy, ethoxy, methoxyethoxy, chlorine or X1.
3. Spinning dopes according to Claim 1, characterised in that they contain a compound of the formula
Figure imgb0023
4. Spinning dopes according to Claim 1, characterised in that they contain a compound of the formula
Figure imgb0024
5. Spinning dopes according to Claim 1, characterised in that they contain, as brightener salts, those of the formula indicated,
wherein
A represents a radical of the formula
Figure imgb0025
and
X5 denotes hydrogen, methyl, ethyl, methoxy, ethoxy, chlorine or sulpho.
6. Process for the preparation-of spinning dopes according to Claim 1, characterised in that optical brighteners of the formula
Figure imgb0026
or their water-soluble salts are reacted with n equivalents of a basic nitrogen compound of the formula
Figure imgb0027
wherein
Y denotes a colourless, non-fluorescent anion which imparts solubility in water or OH-,

the virtually water-insoluble brightener salt thus obtained is isolated and incorporated into a viscose spinning dope.
7. Process according to Claim 6, characterised in that the sparingly soluble brightener salt is subjected to a wet-comminution in the presence of surface-active substances.
8. Process according to Claim 6, characterised in that the optical brightener is subjected to a wetcom- minution together with the basic nitrogen compound and surface-active substances.
EP82101612A 1981-03-14 1982-03-03 Spinning mass containing an optical bleaching agent for the preparation of regenerated cellulose fibres Expired EP0060439B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT82101612T ATE11434T1 (en) 1981-03-14 1982-03-03 WHITE SPIN PAST FOR THE MANUFACTURE OF CELLULOSE REGENERATE FIBERS.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3109828 1981-03-14
DE19813109828 DE3109828A1 (en) 1981-03-14 1981-03-14 WHITE-TONED SPIDERS FOR THE PRODUCTION OF CELLULOSE REGENERATE FIBERS

Publications (3)

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EP0060439A2 EP0060439A2 (en) 1982-09-22
EP0060439A3 EP0060439A3 (en) 1983-06-29
EP0060439B1 true EP0060439B1 (en) 1985-01-23

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JPH11130975A (en) * 1997-10-29 1999-05-18 Hakkooru Chemical Kk Fluorescent organic white pigment composition excellent in opacifying properties
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CH449843A (en) * 1964-09-15 1968-01-15 Ciba Geigy Process for the production of optically brightened moldings from regenerated cellulose
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ATE11434T1 (en) 1985-02-15
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DE3109828A1 (en) 1982-09-23
EP0060439A3 (en) 1983-06-29
BR8201336A (en) 1983-01-25

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