EP1532309A1 - Method for brightening synthetic fibres and plastics with granulated optical brighters - Google Patents

Method for brightening synthetic fibres and plastics with granulated optical brighters

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Publication number
EP1532309A1
EP1532309A1 EP03747887A EP03747887A EP1532309A1 EP 1532309 A1 EP1532309 A1 EP 1532309A1 EP 03747887 A EP03747887 A EP 03747887A EP 03747887 A EP03747887 A EP 03747887A EP 1532309 A1 EP1532309 A1 EP 1532309A1
Authority
EP
European Patent Office
Prior art keywords
granulated
plastics
optical brightener
brightener
granules
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP03747887A
Other languages
German (de)
French (fr)
Inventor
Thomas Martini
Jean-Luc Mura
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Clariant Produkte Deutschland GmbH
Original Assignee
Clariant GmbH
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Filing date
Publication date
Application filed by Clariant GmbH filed Critical Clariant GmbH
Publication of EP1532309A1 publication Critical patent/EP1532309A1/en
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0041—Optical brightening agents, organic pigments
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/35—Heterocyclic compounds having nitrogen in the ring having also oxygen in the ring
    • C08K5/353—Five-membered rings
    • 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
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/04—Pigments
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/60—Optical bleaching or brightening
    • D06L4/643—Optical bleaching or brightening wherein the brightener is introduced in a gaseous environment or in solid phase, e.g. by transfer, by use of powders or by use of super-critical fluids
    • 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
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2904—Staple length fiber
    • Y10T428/2907—Staple length fiber with coating or impregnation
    • 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
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2927—Rod, strand, filament or fiber including structurally defined particulate matter

Definitions

  • DE 26 56 406 describes the production of low-dust, preferably water-soluble optical brighteners by adding dust-binding agents, with non-dusting mixtures being produced.
  • DE 39 10 275 describes a process for the production of dye pellets, the dye powder having a water content of 10 to 15% by weight being subjected to an extrusion agglomeration.
  • a solvent together with an insoluble additive for example a wax, must be added to the production of basic dye granules.
  • the processes described in EP 264 049, EP 115 634 or EP 612 557 must be carried out in the presence of auxiliaries.
  • WO 99/05226 describes the granulation of water-soluble dyes or optical brighteners in the presence of an extender or other additives.
  • Lump formation and caking on the walls of the vessel can also occur when metering such powders. Granules or pellets are more suitable for dosing systems because they have a good flow behavior.
  • metering by means of masterbatch is known, with the optical brightener being distributed in polyester or plastic in high concentrations (up to 30%).
  • the production of such masterbatches is very expensive and also has the above-mentioned eco-toxicological problems.
  • a brightener granulate should redisperse well in ethylene glycol if the use of an ethylene glycol / brightener dispersion is required for the system.
  • the invention relates to a method for lightening synthetic fibers and plastics, which consists in incorporating a granulated optical brightener into the synthetic fibers or plastics, the granulated optical brightener being obtained by compacting an optical brightener in powder form in a pressure compaction machine a pressure of 3 to 50 kNewton / cm tube length and subsequent comminution of the compactate obtained.
  • the granulated optical brighteners are produced by compacting in conventional pressure compacting machines between rollers or other pressing units such as, for example, extrusion units, preferably at the temperatures which arise under the pressure conditions and under a pressure of 5 to 50, preferably 10 to 35 kNewton / cm tube length.
  • the resulting plates or strands are then replaced by a Shredding device brought to a desired size.
  • the optical brightener is conveyed onto the rollers via screws, so that precompacting takes place in the screw and the final compaction is carried out between the pressure rollers.
  • the compacting temperature is reached without external temperature supply and can be between 15 and 60 ° C, preferably between 20 and 40 ° C.
  • compacting can be carried out under nitrogen or vacuum with or without roller cooling.
  • the strands, screws or plates obtained by the compacting are comminuted to the desired size by customary methods and the oversize or undersize obtained from the granules obtained by a sieving process with 2 or more sieves.
  • the preferred compacted granules have a diameter of preferably 0.3-3 mm. But granules with smaller or larger diameters can also meet the desired requirements in terms of their properties.
  • the screened oversize or undersize are added to the granulation process again.
  • Compacting pelletizing can be carried out using commercially available pelletizing machines (e.g. compactor series K from BEPEX GmbH in Leingarten or pelletizer WP 50/75, WP 17V Pharma or WP 50/250 from Alexanderwerk AG in Remscheid).
  • commercially available pelletizing machines e.g. compactor series K from BEPEX GmbH in Leingarten or pelletizer WP 50/75, WP 17V Pharma or WP 50/250 from Alexanderwerk AG in Remscheid).
  • the granules obtained in this way are characterized by a dust-free behavior, are free-flowing and stable even during longer transport times. Furthermore, the granules according to the invention are not prone to caking and clumping during metering, which significantly simplifies the processing process. In addition, it was found that the granules according to the invention were stirred into e.g. Ethylene glycol is redispersible again. These dispersions are easy to pump and can be metered in during polyester fiber production.
  • optical brighteners can be granulated using this method. These granules are used to lighten fully synthetic organic polymers (plastics and synthetic fibers) used.
  • the optical brighteners are independent of the chemical structure, characterized in that they absorb in the range from 260 to 400 nm and emit in the visible spectrum from 400 to 450 nm.
  • Preferred optical brighteners are those from the group of benzoxazoles, thiophenes, stilbenes or pyrazolines and coumarins. Particularly preferred optical brighteners are represented by the formulas 1 to 5:
  • R H and / or CH 3
  • optical brighteners based on the plastic to be lightened, are normally between 1 and 1,000 ppm, depending on the plastic or the synthetic fiber and the whiteness to be achieved. Larger quantities are possible in individual cases. Quantities of 0.1 - 30%, based on the total weight of the plastic or synthetic fiber, can also be used in the production of pre-concentrates.
  • the optical brighteners can be used individually or as a mixture. This can also have synergistic effects.
  • the optical brighteners can also be granulated together with shading dyes. Of course, blends of brightener granules with additives that do not interfere with the incorporation or further processing of the plastic or the fiber, e.g. Mixtures with fiber or plastic preservatives can be granulated.
  • the granules can be used to lighten high-molecular organic materials. These can be of natural or synthetic origin. For example, are natural resins, drying oils or rubber or modified natural substances, e.g. Chlorinated rubber, cellulose derivatives.
  • the granules according to the invention are preferably used to lighten polymers which are produced by polymerization, polycondensation or polyaddition. From the class of plastics produced by polymerization, the following are particularly mentioned: polyolefins such as Polyethylene, polypropylene, polyisobutylene, substituted polyolefins such as e.g. Polystyrene, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetals, polyacrylonitrile,
  • Polyacrylic acid and polymethacrylic acid or their esters, or polybutadienes and copolymers thereof From the class of plastics produced by polyaddition and polycondensation, the following may be mentioned: polyesters, polyamides, polyimides, polycarbonates, polyurethanes, polyethers, polyacetals and condensation products of formaldehyde with phenols or urea, thiourea, or melamine.
  • the high-molecular material mentioned can be present individually or as a mixture in the form of plastic compositions or melts.
  • the granules according to the invention can also be added to the respective underlying monomers and the polymerization can then be carried out.
  • the granules according to the invention are particularly preferably suitable for lightening polyester.
  • the optical brightener can be added during transesterification or esterification, during polycondensation or before spinning.
  • the brightener is metered, for example, in ethylene glycol dispersion or as a powder or as a masterbatch.
  • the dosing of powder in the hopper e.g. Tamaki Blender Model 80 D-LC-7K
  • This problem can be avoided by using pellets or granules.
  • the optical brightener in an ethylene glycol dispersion is to be added to the esterification, transesterification or polycondensation, the brightener granules can be stirred, e.g. redisperse well in a 15% brightener setting.
  • the dust behavior of the granules was determined photometrically with the aid of a sedimentation dust measuring device.
  • the dust number was 1.
  • the granules can be redispersed well in ethylene glycol by simple stirring.
  • DMT dimethyl terephthalate
  • II manganese
  • the temperature was increased every 15 minutes by 10 ° C. to 230-235 ° C. and held at this level until all of the methanol had been distilled off.
  • This process was supplemented by increasing the temperature to 250-270 ° C. under a vacuum of at least 0.013 mbar, the stirrer speed being kept constant at 180 rpm. After the desired viscosity was reached, the heating system was removed and the flask, which was blown up during cooling, was protected accordingly.
  • Example 3 The polyester mass was broken hydraulically and ground after CO 2 cooling. The material was dried at 120 ° C. for 5 hours and spun. A homogeneously brightened fiber with excellent white effects was obtained.
  • Example 3 The polyester mass was broken hydraulically and ground after CO 2 cooling. The material was dried at 120 ° C. for 5 hours and spun. A homogeneously brightened fiber with excellent white effects was obtained.
  • Example 2 The procedure was as in Example 2. Instead of the granular optical brightener of formula 1, however, a conventional powder version was used. When opening the storage container and removing the brightener, undesirable dust formation occurred. The white effects are identical to those of Example 1.
  • Example 2 The procedure was as in Example 2. However, the granulated optical brightener of the formula 1 was added to the transesterification without any problem, without the formation of dust, together with the ethylene glycol. Uniformly lightened fibers were obtained, which prove that the granules are distributed homogeneously here too.
  • Example 2 The procedure was as in Example 2. However, a granulate of the brightener of formula 6 was used as the brightener. The metering was carried out without dust formation and homogeneous brightening effects were obtained.

Abstract

The invention relates to a method for brightening synthetic fibres and plastics. According to said inventive method, a granulated optical brightener is incorporated into the synthetic fibres or plastics, wherein the granulated optical brightener is obtained by means of compacting an optical brightener into a powder form in a pressure compacting machine at a pressure of between 3 - 50 kNewton/cm of tubular length and subsequently comminuting the obtained compact.

Description

Beschreibung description
Verfahren zum Aufhellen synthetischer Fasern und Kunststoffe mit granulierten optischen AufhellernProcess for lightening synthetic fibers and plastics with granulated optical brighteners
Granulierte, nicht staubende und rieselfähige nichtionische optische Aufheller für Kunststoffe sind in DE 101 14 696.5-44 beschrieben. Dabei wird die Granulatform des Aufhellers durch eine Belegung des Aufhellerpulvers mit wachsartigen Stoffen erzielt.Granulated, non-dusting and free-flowing nonionic optical brighteners for plastics are described in DE 101 14 696.5-44. The pellet form of the brightener is achieved by covering the brightener powder with wax-like substances.
DE 26 56 406 beschreibt die Herstellung von staubarmen, bevorzugt wasserlöslichen optischen Aufhellern durch Zugabe von Staubbindemittel, wobei nichtstaubende Mischungen entstehen. DE 39 10 275 beschreibt ein Verfahren zur Herstellung von Farbstoffpellets, wobei das Farbstoffpulver mit einem Wassergehalt von 10 bis 15 Gew.-% einer Strangpressagglomerisation unterworfen wird. Auch gemäß US 3,583,877 muss bei der Herstellung von basischen Farbstoffgranulaten ein Lösemittel zusammen mit einem unlöslichen Additiv, beispielsweise ein Wachs, hinzugegeben werden. Ebenso muss bei den in EP 264 049, EP 115 634 oder EP 612 557 beschriebenen Verfahren in Gegenwart von Hilfsstoffen gearbeitet werden. WO 99/05226 beschreibt die Granulierung von wässerlöslichen Farbstoffen oder optischen Aufhellern in Gegenwart eines Extenders oder anderen Additiven.DE 26 56 406 describes the production of low-dust, preferably water-soluble optical brighteners by adding dust-binding agents, with non-dusting mixtures being produced. DE 39 10 275 describes a process for the production of dye pellets, the dye powder having a water content of 10 to 15% by weight being subjected to an extrusion agglomeration. According to US Pat. No. 3,583,877, a solvent together with an insoluble additive, for example a wax, must be added to the production of basic dye granules. Likewise, the processes described in EP 264 049, EP 115 634 or EP 612 557 must be carried out in the presence of auxiliaries. WO 99/05226 describes the granulation of water-soluble dyes or optical brighteners in the presence of an extender or other additives.
Auf diese Art und Weise hergestellte Granulate können jedoch bei der Spinnfaseraufhellung von PES oder PA nicht unbedenklich verwendet werden, da die anhaftenden Additive zu Problemen beim Verspinnen der Fäden führen oder die Laufeigenschaften des versponnenen Fadens beeinträchtigen werden können. Auch bei der Recyclisierung von Ethylenglycol kann es zu unerwünschten Nebeneffekten kommen, so z.B. wenn wachsartige Substanzen aufrahmen und die Qualität des Ethylenglykols beeinträchtigen. Darüber hinaus kann es bei der hohen Temperaturbelastung während der Faserherstellung oder Verspinnung zu Vergilbungserscheinungen der Faser mit reduzierten Weißeffekten kommen. Aus diesen Gründen wurden bisher bei der Faseraufhellung von PET und PA während der Faserproduktion nur Pulverprodukte eingesetzt, welche jedoch nicht fließfähig sind und beim Chargieren zur Staubbildung neigen. Die damit verbundenen ökologischen und toxikologischen Nachteile solcher Stäube sind bekannt. Auch kann es beim Dosieren solcher Pulver zu Klumpenbildung und Anbacken an den Gefässwandungen kommen. Für Dosieranlagen sind Granulate oder Pellets besser geeignet, da sie ein gutes Fliessverhalten aufweisen. In der Praxis kennt man die Dosierung mittels Masterbatch, wobei der optische Aufheller im Polyester oder Kunststoff in hohen Konzentrationen (bis zu 30 %) verteilt ist. Die Herstellung solcher Masterbatche ist jedoch sehr kostenaufwendig und ist ebenfalls mit den oben erwähnte öko-toxikologischen Problemen behaftet. Außerdem soll sich ein Aufhellergranulat in Ethylenglycol gut redispergieren, wenn anlagebedingt der Einsatz einer Ethylenglykol/Aufhellerdispersion gefordert wird.However, granules produced in this way cannot be safely used in the whitening of PES or PA fibers, since the adhering additives can lead to problems when spinning the threads or can impair the running properties of the spun threads. The recycling of ethylene glycol can also have undesirable side effects, for example if wax-like substances cream and impair the quality of the ethylene glycol. In addition, the high temperature load during fiber production or spinning can lead to yellowing of the fiber with reduced white effects. For these reasons, so far only powder products have been used in the fiber lightening of PET and PA during fiber production, which, however, are not flowable and tend to form dust during charging. The associated ecological and toxicological disadvantages of such dusts are known. Lump formation and caking on the walls of the vessel can also occur when metering such powders. Granules or pellets are more suitable for dosing systems because they have a good flow behavior. In practice, metering by means of masterbatch is known, with the optical brightener being distributed in polyester or plastic in high concentrations (up to 30%). However, the production of such masterbatches is very expensive and also has the above-mentioned eco-toxicological problems. In addition, a brightener granulate should redisperse well in ethylene glycol if the use of an ethylene glycol / brightener dispersion is required for the system.
Überraschenderweise wurde nun gefunden, dass man synthetische Fasern und Kunststoffe mit Hilfe von granulierten optischen Aufhellern aufhellen kann, die erhalten werden indem man ein Aufhellerpulver unter erhöhtem Druck verpresst und anschließend zerkleinert.Surprisingly, it has now been found that synthetic fibers and plastics can be brightened with the aid of granulated optical brighteners, which are obtained by pressing a brightener powder under increased pressure and then comminuting it.
Gegenstand der Erfindung ist ein Verfahren zum Aufhellen von synthetischen Fasern und Kunststoffen, das darin besteht, dass man einen granulierten optischen Aufheller in die synthetischen Fasern oder Kunststoffe einarbeitet, wobei der granulierte optische Aufheller erhalten wird durch Kompaktierung eines optischen Aufhellers in Pulverform in einer Druckkompaktierungsmaschine unter einem Druck von 3 bis 50 kNewton/cm Rohrlänge und anschließende Zerkleinerung des erhaltenen Kompaktats.The invention relates to a method for lightening synthetic fibers and plastics, which consists in incorporating a granulated optical brightener into the synthetic fibers or plastics, the granulated optical brightener being obtained by compacting an optical brightener in powder form in a pressure compaction machine a pressure of 3 to 50 kNewton / cm tube length and subsequent comminution of the compactate obtained.
Die Herstellung der granulierten optischen Aufheller erfolgt durch Kompaktierung in herkömmlichen Druckkompaktierungsmaschinen zwischen Walzen oder anderen Pressaggregaten wie z.B. Strangpressaggregaten vorzugsweise bei den sich unter den Druckbedingungen einstellenden Temperaturen und unter einem Druck von 5 bis 50, vorzugsweise 10 bis 35 kNewton/cm Rohrlänge. Die dabei entstehenden Platten oder Strängen werden anschließend durch eine Zerkleinerungsvorrichtung auf eine gewünschte Größe gebracht. Im Falle einer Kompaktierung mittels Druckwalzen wird der optische Aufheller über Schnecken auf die Walzen befördert, so dass ein Vorkompaktierung in der Schnecke erfolgt und die Endkompaktierung zwischen den Druckwalzen durchgeführt wird. Die Kompaktierungstemperatur wird ohne äußere Temperaturzuführung erreicht und kann zwischen 15 und 60°C liegen, vorzugsweise zwischen 20 und 40°C. Je nach Bedarf kann die Kompaktierung unter Stickstoff oder Vakuum mit oder ohne Rollenkühlung durchgeführt werden. Die durch die Kompaktierung erhaltenen Stränge, Schnecken oder Platten werden nach üblichen Verfahren auf die gewünschte Größe zerkleinert und die erhaltenen Granulate von Über- oder Untergrößen durch einen Siebprozess mit 2 oder mehr Sieben befreit. Die bevorzugten kompaktierten Granulate weisen einen Durchmesser von vorzugsweise 0,3 - 3 mm auf. Aber auch Granulate mit kleinerem oder größerem Durchmessern können in ihren Eigenschaften den gewünschten Anforderungen entsprechen. Die abgesiebten Über- oder Untergrößen werden dem Granulierungsprozess erneut zugegeben.The granulated optical brighteners are produced by compacting in conventional pressure compacting machines between rollers or other pressing units such as, for example, extrusion units, preferably at the temperatures which arise under the pressure conditions and under a pressure of 5 to 50, preferably 10 to 35 kNewton / cm tube length. The resulting plates or strands are then replaced by a Shredding device brought to a desired size. In the case of compacting by means of pressure rollers, the optical brightener is conveyed onto the rollers via screws, so that precompacting takes place in the screw and the final compaction is carried out between the pressure rollers. The compacting temperature is reached without external temperature supply and can be between 15 and 60 ° C, preferably between 20 and 40 ° C. Depending on requirements, compacting can be carried out under nitrogen or vacuum with or without roller cooling. The strands, screws or plates obtained by the compacting are comminuted to the desired size by customary methods and the oversize or undersize obtained from the granules obtained by a sieving process with 2 or more sieves. The preferred compacted granules have a diameter of preferably 0.3-3 mm. But granules with smaller or larger diameters can also meet the desired requirements in terms of their properties. The screened oversize or undersize are added to the granulation process again.
Die kompaktierende Granulierung kann mit handelsüblichen Granuliermaschinen durchgeführt werden (z.B. Kompaktor Baureihe K von BEPEX GmbH in Leingarten oder Granulator WP 50/75, WP 17V Pharma oder WP 50/250 von Alexanderwerk AG in Remscheid).Compacting pelletizing can be carried out using commercially available pelletizing machines (e.g. compactor series K from BEPEX GmbH in Leingarten or pelletizer WP 50/75, WP 17V Pharma or WP 50/250 from Alexanderwerk AG in Remscheid).
Die so erhaltenen Granulate zeichnen sich durch ein staubfreies Verhalten aus, sind gut rieselfähig und stabil auch während längerer Transportzeiten. Ferner neigen die erfindungsgemäßen Granulate beim Dosieren nicht zu Verbackungen und Verklumpungen was den Verarbeitungsprozess deutlich erleichtert. Darüber hinaus zeigte sich, dass die erfindungsgemäßen Granulate durch Einrühren in z.B. Ethylenglykol wieder gut redispergierbar sind. Diese Dispersionen sind gut pumpbar und können so während der Polyesterfaserherstellung zudosiert werden.The granules obtained in this way are characterized by a dust-free behavior, are free-flowing and stable even during longer transport times. Furthermore, the granules according to the invention are not prone to caking and clumping during metering, which significantly simplifies the processing process. In addition, it was found that the granules according to the invention were stirred into e.g. Ethylene glycol is redispersible again. These dispersions are easy to pump and can be metered in during polyester fiber production.
Erfindungsgemäß können nach diesem Verfahren alle nichtionischen optischen Aufheller granuliert werden. Diese Granulate werden zum Aufhellen von vollsynthetischen organischen Polymeren (Kunststoffe und Kunstfasern) verwendet. Die optischen Aufheller sind unabhängig von der chemischen Struktur, dadurch gekennzeichnet, dass sie im Bereich von 260 bis 400 nm absorbieren und im sichtbaren Spektrum von 400 bis 450 nm emmitieren. Bevorzugte optische Aufheller sind solche aus der Gruppe der Benzoxazole, Thiophene, Stilbene oder Pyrazoline und Coumarine. Besonders bevorzugte optische Aufheller werden durch die Formeln 1 bis 5 wiedergegeben:According to the invention, all nonionic optical brighteners can be granulated using this method. These granules are used to lighten fully synthetic organic polymers (plastics and synthetic fibers) used. The optical brighteners are independent of the chemical structure, characterized in that they absorb in the range from 260 to 400 nm and emit in the visible spectrum from 400 to 450 nm. Preferred optical brighteners are those from the group of benzoxazoles, thiophenes, stilbenes or pyrazolines and coumarins. Particularly preferred optical brighteners are represented by the formulas 1 to 5:
R = H und/oder CH3 R = H and / or CH 3
Die Mengen an optischen Aufhellern, bezogen auf den aufzuhellenden Kunststoff, betragen normalerweise zwischen 1 und 1.000 ppm, abhängig vom Kunststoff oder der Kunstfaser und dem zu erzielendem Weißgrad. Höhere Mengen sind im Einzelfall möglich. Bei der Herstellung von Vorabkonzentraten können auch Mengen von 0,1 - 30 %, bezogen auf das Gesamtgewicht des Kunststoffes oder der Kunstfaser, eingesetzt werden. Die optischen Aufheller können einzeln oder in Mischung zur Anwendung gelangen. Dabei können sich auch synergistische Effekte ergeben. Auch können die optischen Aufheller gemeinsam mit Nuancierfarbstoffen granuliert werden. Selbstverständlich können auch Abmischungen von Aufhellergranulaten mit Additiven, die bei der Einarbeitung oder Weiterverarbeitung des Kunststoffes oder der Faser nicht stören, z.B. Abmischungen mit Faser- oder Kunststoffschutzmitteln, granuliert werden. Die Granulate können zum Aufhellen von hochmolekularen organischen Materialien eingesetzt werden. Diese können natürlicher oder synthetischer Herkunft sein. Es kann sich z.B. um Naturharze, trocknende Öle oder Kautschuk oder um abgewandelte Naturstoffe handeln, wie z.B. Chlorkautschuk, Zellulosederivate. Bevorzugt dienen die erfindungsgemäßen Granulate zum Aufhellen von Polymeren, die durch Polymerisation, Polykondensation oder Polyaddition hergestellt sind. Aus der Klasse, der durch Polymerisation hergestellten Kunststoffe, seien besonders folgende genannt: Polyolefine wie z.B. Polyethylen, Polypropylen, Polyisobutylen, substituierte Polyolefine wie z.B. Polystyrol, Polyvinylchlorid, Polyvinylidenchlorid, Polyvinylacetale, Polyacrylnitril,The amounts of optical brighteners, based on the plastic to be lightened, are normally between 1 and 1,000 ppm, depending on the plastic or the synthetic fiber and the whiteness to be achieved. Larger quantities are possible in individual cases. Quantities of 0.1 - 30%, based on the total weight of the plastic or synthetic fiber, can also be used in the production of pre-concentrates. The optical brighteners can be used individually or as a mixture. This can also have synergistic effects. The optical brighteners can also be granulated together with shading dyes. Of course, blends of brightener granules with additives that do not interfere with the incorporation or further processing of the plastic or the fiber, e.g. Mixtures with fiber or plastic preservatives can be granulated. The granules can be used to lighten high-molecular organic materials. These can be of natural or synthetic origin. For example, are natural resins, drying oils or rubber or modified natural substances, e.g. Chlorinated rubber, cellulose derivatives. The granules according to the invention are preferably used to lighten polymers which are produced by polymerization, polycondensation or polyaddition. From the class of plastics produced by polymerization, the following are particularly mentioned: polyolefins such as Polyethylene, polypropylene, polyisobutylene, substituted polyolefins such as e.g. Polystyrene, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetals, polyacrylonitrile,
Polyacrylsäure und Polymethacrylsäure bzw. deren Ester, oder Polybutadiene sowie Copolymerisate davon. Aus der Klasse, der durch Polyaddition und Polykondensation hergestellten Kunststoffe, seien genannt: Polyester, Polyamide, Polyimide, Polycarbonate, Polyurethane, Polyether, Polyacetale sowie Kondensationsprodukte von Formaldehyd mit Phenolen oder Harnstoff, Thiohamstoff, oder Melamin.Polyacrylic acid and polymethacrylic acid or their esters, or polybutadienes and copolymers thereof. From the class of plastics produced by polyaddition and polycondensation, the following may be mentioned: polyesters, polyamides, polyimides, polycarbonates, polyurethanes, polyethers, polyacetals and condensation products of formaldehyde with phenols or urea, thiourea, or melamine.
Das genannte hochmolekulare Material kann einzeln oder in Mischung in Form von Kunststoffmassen oder Schmelzen vorliegen. Man kann aber auch das erfindungsgemäße Granulat den jeweils zugrunde liegenden Monomeren zugeben und anschließend die Polymerisation durchführen. Besonders bevorzugt eignen sich die erfindungsgemäßen Granulate zum Aufhellen von Polyester.The high-molecular material mentioned can be present individually or as a mixture in the form of plastic compositions or melts. However, the granules according to the invention can also be added to the respective underlying monomers and the polymerization can then be carried out. The granules according to the invention are particularly preferably suitable for lightening polyester.
Bei der Polyesterfaseraufhellung kann der optische Aufheller bei der Um- oder Veresterung, während der Polykondensation oder vor dem Verspinnen zudosiert werden. Die Dosierung des Aufhellers erfolgt beispielsweise in ethylenglykolischer Dispersion oder als Pulver oder als Masterbatch. Wird z.B. der optische Aufheller kurz vor dem Verspinnen über eine Dosiereinrichtung (hopper) dem mit den getrockneten PET Pellets versehenen Mischaggregat zugegeben, so kann es der Dosierung von Pulver im hopper (z.B. Tamaki Blender Model 80 D-LC-7K) zu Blockierungen kommen was zur Unterbrechung des Dosiervorganges führt. Dieses Problem lässt sich durch die Verwendung von Pellets oder Granulaten vermeiden. Soll der optische Aufheller in einer ethylenglykolischer Dispersion in die Veresterung, Umesterung oder in die Polykondensation zugegeben werden, lassen sich die Aufhellergranulate durch Umrühren z.B. in einer 15 %igen Aufhellereinstellung gut redispergieren.With polyester fiber lightening, the optical brightener can be added during transesterification or esterification, during polycondensation or before spinning. The brightener is metered, for example, in ethylene glycol dispersion or as a powder or as a masterbatch. E.g. If the optical brightener is added to the mixing unit with the dried PET pellets shortly before spinning via a dosing device (hopper), the dosing of powder in the hopper (e.g. Tamaki Blender Model 80 D-LC-7K) can become blocked, which leads to interruption of the dosing process. This problem can be avoided by using pellets or granules. If the optical brightener in an ethylene glycol dispersion is to be added to the esterification, transesterification or polycondensation, the brightener granules can be stirred, e.g. redisperse well in a 15% brightener setting.
Beispiel 1example 1
100 Teile eines Aufhellers der Formel 1 in Pulverform wurden in einer Kompaktier/Granuliermaschine WP 50/75 (Rollenlänge 75 mm, Rollendurchmesser 152 mm) bei einem Rollendruck von 16 kNewton/cmRL und einer Drehgeschwindigkeit von 8 UpM gepresst. Man erhielt einen 2 mm dicken Pressung, welcher granuliert wurde und zu Pellets mit einem Durchmesser von 0,6 - 2 mm führt. Der Rollendurchsatz betrug 31 kg/h, der Ausstoß an Produkt mit 0,6 - 2 mm Durchmesser nach Siebung betrug 85 %. Ca. 4,6 kg wurden der Kompaktierung wieder zugeführt. Das erhaltene Granulat ist gut rieselfähig und staubfrei. Das Staubverhalten des Granulates wurde mit Hilfe eines Sedimentationsstaubmessgerätes fotometrisch ermittelt. Die Staubzahl betrug 1. Die dem Granulat zugrunde liegende pulverförmige Substanz des Aufhellers der Formel 1 besitzt eine Staubzahl von 13. (1 = nicht staubend, 16 = stark staubend) Darüber hinaus lässt sich das Granulat in Ethylenglykol durch einfaches Rühren gut redispergieren.100 parts of a brightener of the formula 1 in powder form were pressed in a compacting / pelletizing machine WP 50/75 (roll length 75 mm, roll diameter 152 mm) at a roll pressure of 16 kNewton / cmRL and a rotation speed of 8 rpm. A 2 mm thick pressing was obtained, which was granulated and turned into pellets with a diameter of 0.6 - 2 mm leads. The roll throughput was 31 kg / h, the output of product with a diameter of 0.6-2 mm after screening was 85%. Approximately 4.6 kg were returned to the compacting. The granules obtained are free-flowing and dust-free. The dust behavior of the granules was determined photometrically with the aid of a sedimentation dust measuring device. The dust number was 1. The powdery substance of the brightener of formula 1 on which the granules are based has a dust number of 13. (1 = not dusting, 16 = heavily dusting) In addition, the granules can be redispersed well in ethylene glycol by simple stirring.
Beispiel 2Example 2
1.000 g Dimethylterephthalat (DMT) 720 g Ethylenglykol 0,23 g Mangan(ll)acetat wurden in einen 2 I Kolben, ausgerüstet mit einem VA-Rührer, einer 20 cm Füllkörperkolonne und einem Kühlersystem, eingetragen. Das Heizbad wurde auf 160°C erhitzt, nach dem Schmelzen des DMT wurde der Rührer gestartet und die Apparatur mit einem N2-Strom gespült.1,000 g of dimethyl terephthalate (DMT) 720 g of ethylene glycol 0.23 g of manganese (II) acetate were introduced into a 2 l flask equipped with a VA stirrer, a 20 cm packed column and a cooler system. The heating bath was heated to 160 ° C., after the DMT had melted, the stirrer was started and the apparatus was flushed with a stream of N 2.
Nach dem Beginn der Abdestillation des Methanols wurde die Temperatur alle 15 Minuten um je 10°C bis auf 230 - 235°C gesteigert und auf diesem Niveau gehalten, bis alles Methanol abdestilliert war.After the methanol had started to be distilled off, the temperature was increased every 15 minutes by 10 ° C. to 230-235 ° C. and held at this level until all of the methanol had been distilled off.
Anschließend wurdenThen were
0,3 g Sb203 0.3 g Sb 2 0 3
4,0 g Ti02 (A-Type) und 0,1 g des granulierten Aufhellers der Formel: 4.0 g of Ti0 2 (A-Type) and 0.1 g of the granulated brightener of the formula:
dispergiert in Ethylenglykol in den 2 I Kolben hineingegeben, der mit einem Kondensator für die Glykoldestillation und mit einer Vakuumpumpe versehen war. Die Dispergierung erhielt man durch Umrühren der Mischung bei Raumtemperatur während 15 Minuten. Die Badtemperatur wurde auf 250°C erhöht und der Kolben mit reinem Stickstoff gespült. Sobald die Viskosität des Kolbeninhaltes es erlaubte, wurde mit dem Rühren begonnen.dispersed in ethylene glycol into the 2 l flask, which was provided with a condenser for glycol distillation and with a vacuum pump. The dispersion was obtained by stirring the mixture at room temperature for 15 minutes. The bath temperature was raised to 250 ° C and the flask was purged with pure nitrogen. As soon as the viscosity of the contents of the flask allowed, stirring was started.
Nach dem vollständigen Aufschmelzen des Umesterungsproduktes wurde der N2- Strom unterbrochen und folgendes Polykondensationsprogramm begonnen.After the transesterification product had melted completely, the N 2 stream was interrupted and the following polycondensation program started.
15 min bei 790 mbar 15 min bei 520 mbar 15 min bei 250 mbar 15 min bei 130 mbar 15 min bei 55 mbar 15 min bei 12 mbar15 min at 790 mbar 15 min at 520 mbar 15 min at 250 mbar 15 min at 130 mbar 15 min at 55 mbar 15 min at 12 mbar
Dieser Vorgang wurde durch Temperaturerhöhung auf 250 - 270°C unter einem Vakuum von mind. 0,013 mbar ergänzt, wobei die Rührergeschwindigkeit mit 180 U/min konstant gehalten wurde. Nachdem die gewünschte Viskosität erreicht war, wurde das Heizsystem entfernt und der Kolben, welcher beim Abkühlen gesprengt wurde, dementsprechend geschützt.This process was supplemented by increasing the temperature to 250-270 ° C. under a vacuum of at least 0.013 mbar, the stirrer speed being kept constant at 180 rpm. After the desired viscosity was reached, the heating system was removed and the flask, which was blown up during cooling, was protected accordingly.
Die Polyestermasse wurde hydraulisch gebrochen und nach C02-Kühlung gemahlen. Das Material wurde 5 h bei 120°C getrocknet und versponnen. Man erhielt eine homogen aufgehellte Faser mit ausgezeichneten Weißeffekten. Beispiel 3The polyester mass was broken hydraulically and ground after CO 2 cooling. The material was dried at 120 ° C. for 5 hours and spun. A homogeneously brightened fiber with excellent white effects was obtained. Example 3
Es wurde wie bei Beispiel 2 gearbeitet. An Stelle des granulierten optischen Aufhellers der Formel 1 wurde jedoch eine herkömmliche Pulverversion verwendet. Beim Öffnen des Vorratsgefäßes und bei der Entnahme des Aufhellers kam es zur unerwünschten Staubbildung. Die Weißeffekte sind identisch mit denjenigen von Beispiel 1.The procedure was as in Example 2. Instead of the granular optical brightener of formula 1, however, a conventional powder version was used. When opening the storage container and removing the brightener, undesirable dust formation occurred. The white effects are identical to those of Example 1.
Beispiel 4Example 4
Es wurde wie bei Beispiel 2 gearbeitet. Der granulierte optische Aufheller der Formel 1 wurde jedoch problemlos ohne Staubbildung zusammen mit dem Ethylenglykol der Umesterung zugegeben. Es wurden gleichmäßig aufgehellte Fasern erhalten, welche beweisen, dass auch hier eine homogene Verteilung des Granulates erfolgt.The procedure was as in Example 2. However, the granulated optical brightener of the formula 1 was added to the transesterification without any problem, without the formation of dust, together with the ethylene glycol. Uniformly lightened fibers were obtained, which prove that the granules are distributed homogeneously here too.
Beispiel 5Example 5
Es wurde wie bei Beispiel 2 gearbeitet. Als Aufheller wurde jedoch ein Granulat des Aufhellers der Formel 6 eingesetzt. Die Dosierung erfolgte ohne Staubbildung und es wurden homogene Aufhelleffekte erhalten.The procedure was as in Example 2. However, a granulate of the brightener of formula 6 was used as the brightener. The metering was carried out without dust formation and homogeneous brightening effects were obtained.

Claims

Patentansprüche claims
1. Verfahren zum Aufhellen von synthetischen Fasern und Kunststoffen, dadurch gekennzeichnet, dass man einen granulierten optischen Aufheller in die synthetischen Fasern oder Kunststoffe einarbeitet, wobei der granulierte optische Aufheller erhalten wird durch Kompaktierung eines optischen Aufhellers in Pulverform in einer Druckkompaktierungsmaschine unter einem Druck von 3 bis 50 kNewton/cm Rohrlänge und anschließende Zerkleinerung des erhaltenen Kompaktats.1. A process for lightening synthetic fibers and plastics, characterized in that a granulated optical brightener is incorporated into the synthetic fibers or plastics, the granulated optical brightener being obtained by compacting an optical brightener in powder form in a pressure compacting machine under a pressure of 3 up to 50 kNewton / cm tube length and subsequent comminution of the compactate obtained.
2. Verfahren nach Anspruch 1 , dadurch gekennzeichnet, dass man einen optischen Aufheller in granulierter Form einarbeitet, der im Bereich von 260 bis 400 nm absorbiert und im sichtbaren Spektrum bei 400 bis 450 emmitiert.2. The method according to claim 1, characterized in that one incorporates an optical brightener in granular form, which absorbs in the range from 260 to 400 nm and emits in the visible spectrum at 400 to 450.
3. Verfahren nach Anspruch 1 , dadurch gekennzeichnet, dass man den granulierten optischen Aufheller den Monomeren, welche den synthetischen Fasern oder Kunststoffen zu Grunde liegen, zugibt und anschließend die Polymerisation durchführt.3. The method according to claim 1, characterized in that the granulated optical brightener is added to the monomers on which the synthetic fibers or plastics are based, and the polymerization is then carried out.
4. Verfahren nach Anspruch 1 , dadurch gekennzeichnet, dass man einen granulierten optischen Aufheller einsetzt, der einen Nuancierfarbstoff enthält.4. The method according to claim 1, characterized in that one uses a granulated optical brightener which contains a shading dye.
5. Verfahren nach Anspruch 1 , dadurch gekennzeichnet, dass man granulierte optische Aufheller einsetzt, die aus einer Mischung mehrerer optischer Aufheller bestehen. 5. The method according to claim 1, characterized in that granulated optical brighteners are used, which consist of a mixture of several optical brighteners.
EP03747887A 2002-08-14 2003-08-08 Method for brightening synthetic fibres and plastics with granulated optical brighters Withdrawn EP1532309A1 (en)

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