EP1453907A1 - Granulated optical brightening agents - Google Patents

Granulated optical brightening agents

Info

Publication number
EP1453907A1
EP1453907A1 EP02792852A EP02792852A EP1453907A1 EP 1453907 A1 EP1453907 A1 EP 1453907A1 EP 02792852 A EP02792852 A EP 02792852A EP 02792852 A EP02792852 A EP 02792852A EP 1453907 A1 EP1453907 A1 EP 1453907A1
Authority
EP
European Patent Office
Prior art keywords
wax
brightener
granulated
waxes
parts
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Withdrawn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
EP02792852A
Other languages
German (de)
French (fr)
Inventor
Thomas Martini
Alexander Lerch
Hans Joachim Metz
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
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Clariant GmbH filed Critical Clariant GmbH
Publication of EP1453907A1 publication Critical patent/EP1453907A1/en
Withdrawn legal-status Critical Current

Links

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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/08—Ingredients agglomerated by treatment with a binding agent
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances

Definitions

  • Optical brighteners for plastics are marketed as fine powders that are not flowable and tend to generate dust when charging.
  • the associated ecological disadvantages of such dusts in general are known.
  • irregularities can occur in the lightened plastic due to the fact that, with different grain size of the brightener particles, irregularities can also be observed in the lightened plastic.
  • the powder application of the brightener can lead to an irregularly fluorescent appearance, which is particularly noticeable under UV light (max. 376 nm) due to the formation of dots and stripes.
  • UV light maximum. 376 nm
  • the object of the present invention is to formulate an optical brightener in such a way that it is dust-free and free-flowing to handle on the one hand and on the other hand produces homogeneous brightening effects in plastics.
  • the application technology for loading plastic additives with waxes is state of the art.
  • the easiest way to do this is to premix the brightener with a powdered wax and heat the mixture to the softening point of the wax. Dust-free flowable granules are obtained by slowly cooling to room temperature while rotating the container.
  • wax emulsions or water-dispersible wax formulations with the plastic additive homogeneous to mix in an aqueous medium, possibly at an elevated temperature and with a stirrer, forming a granular form of the additive loaded with wax.
  • JP 10 251533 The methods described in JP 10 251533 are also possible, the wax coating being carried out using an isobutanol finish. The same applies to the use of a fluid bed method described in DE-A1 29 40 156 and WO 92/07912. Wax spraying described in DE 39 35 815 C2 or the wax application described in EP 1 081 195 by means of spray drying are also suitable methods.
  • the brightener wax granules according to the invention have one
  • Granules with a diameter of 0.1 to 2 mm are particularly preferred, since they are very free-flowing, easy to dose and low in dust and, after application, give homogeneous bulges.
  • Waxes are not chemically defined uniformly and form a group of substances with the same or similar usage properties, characterized by special physical properties.
  • the term "wax” describes a series of natural or artificially obtained substances which generally have the following properties: Kneadable at 20 ° C, hard to brittle hard, coarse to fine crystalline, translucent to opaque, but not glassy; Melting above 40 ° C without decomposition, already a little above the melting point, relatively low viscosity and not stringy, strongly temperature-dependent consistency and solubility, can be polished under slight pressure (cf. Ulimanns Encyclopedia of Technical Chemistry, Volume 24, 4th Edition 1983, pp. 1- 49. Verlag Chemie, Weinheim and Römpps Chemie-Lexikon, Volume 6, 8th edition 1988, p. 463, Franck'sche Verlagbuchmaschine).
  • Preferred waxes are: natural waxes, such as plant waxes, e.g. Camauba waxes, candella waxes, animal waxes, e.g. Beeswax, modified natural waxes, e.g. Paraffin wax, micro waxes, semi-synthetic waxes, e.g. Montan ester waxes, or fully synthetic waxes such as polyolefin waxes, e.g. Polyethylene and polypropylene waxes, polyethylene glycol waxes, cycloolefin copolymer waxes, amide waxes such as e.g. N, N'-distearylethylenediamine.
  • natural waxes such as plant waxes, e.g. Camauba waxes, candella waxes
  • animal waxes e.g. Beeswax
  • modified natural waxes e.g. Paraffin wax, micro waxes, semi-synthetic waxe
  • polyolefin waxes and polyolefin waxes containing polar groups formed by subsequent oxidation of the polyolefin wax, by grafting reaction with a monomer containing carboxylic acid, carboxylic acid ester, carboxylic anhydride or hydroxyl groups.
  • High-molecular weight compounds which have a waxy character and are preferably prepared by polycondensation or polyaddition processes are suitable as waxy polymers, for example thermoplastic polyester, epoxy, styrene-acrylate copolymer, styrene-butadiene copolymer, cycloolefin copolymer resins, such as ® Topas.
  • the polymers In order to have sufficient solubility at elevated temperatures in the plastic and in organic solvents, the polymers usually have a number average molecular weight of up to 20,000. Waxes with a number average molecular weight of up to 10,000 are preferred, particularly preferably with a number average molecular weight of up to to 5000.
  • the dropping point of the waxes used according to the invention or the softening temperature of the polymers is preferably in the range from 60 to 180 ° C., particularly preferably in the range from 80 to 140 ° C.
  • the amount and type of wax or polymer can vary, especially to ensure compatibility with the application medium.
  • optical brighteners used are non-ionic and independent of the chemical structure, characterized in that they are in the range of
  • Preferred optical brighteners are represented by formulas 1 to 5.
  • optical brighteners based on the plastic to be lightened, are usually between 1 and 1000 ppm depending on the plastic and the white to be achieved.
  • quantities of 0.1 - 30% based on the total weight of the plastic to be lightened are usually between 1 and 1000 ppm depending on the plastic and the white to be achieved.
  • the optical brighteners can be used individually or in a mixture. Synergistic effects can also be observed.
  • the granules can be used to lighten high-molecular organic materials.
  • These can be of natural or synthetic origin.
  • it can be natural resins, drying oils or rubber.
  • they can also be modified natural substances, such as, for example, chlorinated rubber, cellulose derivatives and, in particular, fully synthetic organic polymers (plastics) which are produced by polymerization, polycondensation or polyaddition.
  • polyolefins such as polyethylene, polypropylene, polyisobutylene, substituted polyolefins such as polystyrene, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetals, polyacrylonitrile, Polyacrylic acid and polymethacrylic acid or their esters, or polybutadienes and copolymers thereof.
  • polyesters From the class of plastics produced by polyaddition and polycondensation, mention may be made of: polyesters, polyamides, polyimides, polycarbonates, polyurethanes, polyethers, polyacetals and also 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. It can also be in the form of its monomers which are polymerized after the brightener dosage.
  • the improvement in levelness can be seen particularly well if the plastic to be lightened is subjected to foaming after the treatment.
  • the high-molecular organic material mentioned can be present individually or in mixtures in the form of plastic compositions or melts. It is also possible to incorporate the shape of the optical brightener according to the invention into the monomers on which the polymers are based and to lighten the corresponding plastic by polymerizing the brightener-containing monomer.
  • the optical brightener is expediently used in an amount of 50 to 99% by weight, preferably 60 to 95% by weight, and the wax or polymer in an amount of 1 to 50% by weight, preferably 5 to 40% by weight .-% of the brightener granules used.
  • Sedimentation dust measuring device determined photometrically.
  • the dust number is 2.
  • Example 2 A mixture consisting of
  • the film thus obtained is viewed under UV light with an intensity maximum at 376 nm.
  • the appearance is not homogeneous and has speck-shaped, selective
  • Example 3 The procedure is as in Example 2. However, 0.046 part of the granules from Example 1 are used as brighteners. The film thus obtained has a uniform fluorescence.
  • Example 4 A mixture consisting of 67.0 parts of polyvinyl chloride and 30.6 parts of diisodecyl phthalate 1.9 parts of dibutyltin thioglycolate
  • titanium dioxide anatase
  • a brightener of formula 2 0.5 part of titanium dioxide (anatase) is mixed with 0.1 part of a brightener of formula 2 in a conventional formulation.
  • the mixture is on the roller mill at 130 ° C for 10min. heated, whereby the best possible distribution of the brightener in the mass is achieved by constant stripping and re-rolling the 1 mm thick film.
  • the removed film is patterned under UV light as described in Example 2 and has recognizable irregularities in the form of streaking.
  • Example 4 The procedure is as in Example 4. However, 0.115 parts of the brightener formulation from test 1 are used as brighteners. A homogeneously fluorescent PVC film is obtained under UV light.
  • the amount of wax used is 500 parts.
  • 500 parts of a commercially available formula 1 product are used as brighteners. A dust-free granulate with excellent flowability is obtained.
  • Example 4 The procedure is as in Example 4. However, 0.02 part of the brightener of formula 1 is incorporated as the brightener. The pattern under UV light shows a recognizable streaking.
  • Example 7 The procedure is as in Example 7. However, 0.04 part of the brightener, prepared according to formula 6, is used as the brightener. A homogeneously fluorescent PVC film is obtained.

Abstract

The invention relates to granulated optical brightening agents that are coated with a wax.

Description

Beschreibungdescription
Granulierte optische AufhellerGranulated optical brighteners
Optische Aufheller für Kunststoffe werden als feine Pulver vermarktet, die nicht fließfähig sind und beim Chargieren stark zur Staubbildung neigen. Die damit verbundenen ökologischen Nachteile solcher Stäube allgemein sind bekannt. Beim direkten Einsatz solcher Pulver besteht darüber hinaus die Gefahr, dass im aufgehellten Kunststoff Unregelmäßigkeiten auftreten können dadurch bedingt, dass bei unterschiedlich anfallender Korngröße der Aufhellerpartikel auch Unegalitäten im aufgehellten Kunststoff zu beobachten sind. So kann beispielsweise beim Aufhellen von Polyethylenvinylacetat und bei Polyvinylchlorid die Pulverapplikation des Aufhellers zu einem unregelmäßig fluoreszierenden Erscheinungsbild führen welches besonders unter UV-Licht (max. 376 nm) durch Punkt- und Streifenbildung erkenntlich macht. Solche Produkte entsprechen nicht den Qualitätsanforderungen des Verbrauchers.Optical brighteners for plastics are marketed as fine powders that are not flowable and tend to generate dust when charging. The associated ecological disadvantages of such dusts in general are known. When such powders are used directly, there is also the risk that irregularities can occur in the lightened plastic due to the fact that, with different grain size of the brightener particles, irregularities can also be observed in the lightened plastic. For example, when lightening polyethylene vinyl acetate and polyvinyl chloride, the powder application of the brightener can lead to an irregularly fluorescent appearance, which is particularly noticeable under UV light (max. 376 nm) due to the formation of dots and stripes. Such products do not meet the quality requirements of the consumer.
Aufgabe der vorliegenden Erfindung ist es, einen optischen Aufheller so zu formulieren, dass er einerseits staubfrei und rieselfähig handhabbar ist und andererseits in Kunststoffen homogene Aufhelleffekte ergibt.The object of the present invention is to formulate an optical brightener in such a way that it is dust-free and free-flowing to handle on the one hand and on the other hand produces homogeneous brightening effects in plastics.
Es wurde nun gefunden, dass granulierte Aufheller, hergestellt durch eine Belegung des Aufhellerpulvers mit einem Wachs, diesen Anforderungen entsprechen.It has now been found that granulated brighteners, produced by covering the brightener powder with a wax, meet these requirements.
Die Applikationstechnologie zur Beladung von Kunststoffadditiven mit Wachsen ist Stand der Technik. Am einfachsten geschieht es durch ein Vormischen des Aufhellers mit einem pulverisierten Wachs und Hochheizen des Gemisches bis zum Erweichungspunkt des Wachses. Durch langsames Abkühlen auf Raumtemperatur unter Rotation des Behälters werden staubfreie fließfähige Granulate erhalten. Auch besteht die Möglichkeit Wachsemulsionen oder in Wasser dispergierbare Wachsformulierungen mit dem Kunststoffadditiv homogen in wässrigem Medium, eventuell bei erhöhter Temperatur und unter Rührer zu vermischen wobei eine mit Wachs beladene Granulatform des Additivs entsteht.The application technology for loading plastic additives with waxes is state of the art. The easiest way to do this is to premix the brightener with a powdered wax and heat the mixture to the softening point of the wax. Dust-free flowable granules are obtained by slowly cooling to room temperature while rotating the container. There is also the possibility of wax emulsions or water-dispersible wax formulations with the plastic additive homogeneous to mix in an aqueous medium, possibly at an elevated temperature and with a stirrer, forming a granular form of the additive loaded with wax.
Möglich sind auch die in JP 10 251533 beschriebenen Verfahren, wobei die Wachsbelegung über einen Isobutanolfinish erfolgt. Gleiches gilt für die in DE-A1 29 40 156 und WO 92/07912 beschriebene Verwendung eines Fliessbettverfahrens. Auch eine in DE 39 35 815 C2 beschriebene Wachsbesprühung oder die in EP 1 081 195 beschriebene Wachsapplikation mittels Sprühtrocknung sind geeignete Verfahren.The methods described in JP 10 251533 are also possible, the wax coating being carried out using an isobutanol finish. The same applies to the use of a fluid bed method described in DE-A1 29 40 156 and WO 92/07912. Wax spraying described in DE 39 35 815 C2 or the wax application described in EP 1 081 195 by means of spray drying are also suitable methods.
Durch die beschriebenen Prozesse werden die Partikel des betreffenden optischen Aufhellers mit dem Wachs oder einem wachsartigen Polymer umhüllt oder belegt.The processes described coat or coat the particles of the optical brightener in question with the wax or a wax-like polymer.
Die erfindungsgemäßen Aufheller-Wachsgranulate weisen einenThe brightener wax granules according to the invention have one
Teilchendurchmesser von 0,05 bis 5 mm auf. Besonders bevorzugt sind Granulate mit einem Durchmesser von 0,1 bis 2 mm da diese sehr gut rieselfähig, gut dosierbar und staubarm sind und nach der Applikation homogene Aufbellungen ergeben.Particle diameter from 0.05 to 5 mm. Granules with a diameter of 0.1 to 2 mm are particularly preferred, since they are very free-flowing, easy to dose and low in dust and, after application, give homogeneous bulges.
Wachse sind nicht einheitlich chemisch definiert und bilden eine Gruppe von Stoffen mit gleichen oder ähnlichen Gebrauchseigenschaften, gekennzeichnet durch besondere physikalische Eigenschaften. So bezeichnet der Begriff "Wachs" eine Reihe natürlicher oder künstlich gewonnener Stoffe, die in der Regel folgende Eigenschaften aufweisen: Bei 20°C knetbar, fest bis brüchig hart, grob bis feinkristallin, durchscheinend bis opak, jedoch nicht glasartig; über 40°C ohne Zersetzung schmelzend, schon wenig oberhalb des Schmelzpunktes verhältnismäßig niedrigviskos und nicht fadenziehend, stark temperaturabhängige Konsistenz und Löslichkeit, unter leichtem Druck polierbar (vgl. Ulimanns Encyclopädie der technischen Chemie, Band 24, 4. Auflage 1983, S. 1-49. Verlag Chemie, Weinheim und Römpps Chemie-Lexikon, Band 6, 8. Auflage 1988, S. 463, Franck'sche Verlagsbuchhandlung).Waxes are not chemically defined uniformly and form a group of substances with the same or similar usage properties, characterized by special physical properties. The term "wax" describes a series of natural or artificially obtained substances which generally have the following properties: Kneadable at 20 ° C, hard to brittle hard, coarse to fine crystalline, translucent to opaque, but not glassy; Melting above 40 ° C without decomposition, already a little above the melting point, relatively low viscosity and not stringy, strongly temperature-dependent consistency and solubility, can be polished under slight pressure (cf. Ulimanns Encyclopedia of Technical Chemistry, Volume 24, 4th Edition 1983, pp. 1- 49. Verlag Chemie, Weinheim and Römpps Chemie-Lexikon, Volume 6, 8th edition 1988, p. 463, Franck'sche Verlagbuchhandlung).
Als Wachse werden bevorzugt: Naturwachse, wie Pflanzenwachse, z.B. Camaubawachse, Candellilawachse, tierische Wachse, z.B. Bienenwachs, modifizierte Naturwachse, wie z.B. Paraffinwachs, Mikrowachse, teilsynthetische Wachse, wie z.B. Montanesterwachse, oder vollsynthetische Wachse wie Polyolefinwachse, z.B. Polyethylen und Polypropylenwachse, Polyethylenglykolwachse, Cycloolefincopolymerwachse, Amidwachse wie z.B. N,N'-Distearylethylendiamin.Preferred waxes are: natural waxes, such as plant waxes, e.g. Camauba waxes, candella waxes, animal waxes, e.g. Beeswax, modified natural waxes, e.g. Paraffin wax, micro waxes, semi-synthetic waxes, e.g. Montan ester waxes, or fully synthetic waxes such as polyolefin waxes, e.g. Polyethylene and polypropylene waxes, polyethylene glycol waxes, cycloolefin copolymer waxes, amide waxes such as e.g. N, N'-distearylethylenediamine.
Besonders bevorzugt sind Polyolefinwachse, sowie polare Gruppen enthaltende Polyolefinwachse, entstanden durch nachträgliche Oxidation des Polyolefinwachses, durch Pfropfreaktion mit Carbonsäure-, Carbonsäureester-, Carbonsäureanhydrid- oder Hydroxygruppen enthaltendem Monomer.Particularly preferred are polyolefin waxes and polyolefin waxes containing polar groups, formed by subsequent oxidation of the polyolefin wax, by grafting reaction with a monomer containing carboxylic acid, carboxylic acid ester, carboxylic anhydride or hydroxyl groups.
Als wachsartige Polymere sind höhermolekulare Verbindungen, die einen wachsartigen Charakter aufweisen und vorzugsweise durch Polykondensations- oder Polyadditionsverfahren hergestellt wurden, geeignet, z.B. thermoplastische Polyester-, Epoxid-, Styrol-Acrylat-Copolymer-, Styrol-Butadien-Copolymer-, Cycloolefincopolymer-Harze, wie z.B. ®Topas.High-molecular weight compounds which have a waxy character and are preferably prepared by polycondensation or polyaddition processes are suitable as waxy polymers, for example thermoplastic polyester, epoxy, styrene-acrylate copolymer, styrene-butadiene copolymer, cycloolefin copolymer resins, such as ® Topas.
Um eine ausreichende Löslichkeit bei erhöhter Temperatur im Kunststoff als auch in organischen Lösungsmitteln zu besitzen, weisen die Polymere meist ein Zahlenmittel des Molekulargewichts von bis zu 20000. Bevorzugt sind Wachse mit einem Zahlenmittel des Molekulargewichts bis zu 10000, besonders bevorzugt mit einem Zahlenmittel des Molekulargewichts bis zu 5000. Der Tropfpunkt der erfindungsgemäß eingesetzten Wachse oder die Erweichungstemperatur der Polymere liegt vorzugsweise im Bereich von 60 bis 180°C, besonders bevorzugt im Bereich von 80 bis 140°C. Je nach Anwendungsgebiet des Granulates kann die Menge und die Art des Wachses oder Polymers variieren, vor allem um die Verträglichkeit mit dem Anwendungsmedium zu gewährleisten.In order to have sufficient solubility at elevated temperatures in the plastic and in organic solvents, the polymers usually have a number average molecular weight of up to 20,000. Waxes with a number average molecular weight of up to 10,000 are preferred, particularly preferably with a number average molecular weight of up to to 5000. The dropping point of the waxes used according to the invention or the softening temperature of the polymers is preferably in the range from 60 to 180 ° C., particularly preferably in the range from 80 to 140 ° C. Depending on the field of application of the granulate, the amount and type of wax or polymer can vary, especially to ensure compatibility with the application medium.
Um ein definiertes Eigenschaftsprofil zu erzeugen, ist es auch möglich, eine Mischung aus zwei oder mehr verschiedenen Wachsen oder Polymeren zu verwenden.To create a defined property profile, it is also possible to use a mixture of two or more different waxes or polymers.
Die zum Einsatz gelangenden Optischen Aufheller sind nichtionisch und unabhängig von der chemischen Struktur, dadurch gekennzeichnet, dass sie im Bereich vonThe optical brighteners used are non-ionic and independent of the chemical structure, characterized in that they are in the range of
270 bis 400 nm absorbieren und im sichtbaren Spektrum von 400 bis 450 nm emmitieren. Bevorzugte optische Aufheller werden durch die Formeln 1 bis 5 wiedergegeben.Absorb 270 to 400 nm and emit in the visible spectrum from 400 to 450 nm. Preferred optical brighteners are represented by formulas 1 to 5.
Die Mengen an optischen Aufhellern, bezogen auf den aufzuhellenden Kunststoff, belaufen sich normalerweise zwischen 1 und 1000 ppm abhängig vom Kunststoff und dem zu erzielendem Weiß. Bei der Herstellung von Vorabkonzentraten können auch Mengen von 0,1 - 30 % bezogen auf das Gesamtgewicht desThe amounts of optical brighteners, based on the plastic to be lightened, are usually between 1 and 1000 ppm depending on the plastic and the white to be achieved. When producing pre-concentrates, quantities of 0.1 - 30% based on the total weight of the
Kunststoffes eingesetzt werden. Die optischen Aufheller können einzeln oder in Mischung zur Anwendung gelangen. Dabei können auch synergistische Effekte beobachtet werden.Plastic are used. The optical brighteners can be used individually or in a mixture. Synergistic effects can also be observed.
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 handeln. Es kann sich aber auch um abgewandelte Naturstoffe handeln, wie z.B. Chlorkautschuk, Zellulosederivate und besonders um vollsynthetische organische Polymere (Kunststoffe), 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, Polyacrylsäure und Polymethacrylsäure bzw. deren Ester, oder Polybutadiene sowie Copolymerisate davon.The granules can be used to lighten high-molecular organic materials. These can be of natural or synthetic origin. For example, it can be natural resins, drying oils or rubber. However, they can also be modified natural substances, such as, for example, chlorinated rubber, cellulose derivatives and, in particular, fully synthetic organic polymers (plastics) which are produced by polymerization, polycondensation or polyaddition. From the class of plastics produced by polymerization, the following may be mentioned in particular: polyolefins such as polyethylene, polypropylene, polyisobutylene, substituted polyolefins such as polystyrene, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetals, polyacrylonitrile, Polyacrylic acid and polymethacrylic acid or their esters, or polybutadienes and copolymers thereof.
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. Das genannte hochmolekulare Material kann einzeln oder in Mischung in Form von Kunststoffmassen oder Schmelzen vorliegen. Es kann auch in Form seiner Monomeren vorliegen welche nach der Aufhellerdosierung polymerisiert werden.From the class of plastics produced by polyaddition and polycondensation, mention may be made of: polyesters, polyamides, polyimides, polycarbonates, polyurethanes, polyethers, polyacetals and also 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. It can also be in the form of its monomers which are polymerized after the brightener dosage.
Ganz besonders gute Effekte werden beim Aufhellen von Copolymerisaten aus Ethylen und Vinylacetat, Polyethylenvinylacetat oder auch bei Polyvinylchlorid erhalten.Particularly good effects are obtained when lightening copolymers of ethylene and vinyl acetate, polyethylene vinyl acetate or also with polyvinyl chloride.
Die Verbesserung der Egalität lässt sich besonders gut konstatieren wenn der aufzuhellende Kunststoff nach der Behandlung dem Schäumen unterworfen wird.The improvement in levelness can be seen particularly well if the plastic to be lightened is subjected to foaming after the treatment.
Das genannte hochmolekulare organische Material kann einzeln oder in Mischungen in Form von Kunststoffmassen oder Schmelzen vorliegen. Auch ist es möglich, die erfindungsgemäße Form der optischen Aufheller in die den Polymeren zugrunde liegenden Monomere einzuarbeiten und den entsprechenden Kunststoff durch Polymerisation des aufhellerhaltigen Monomers aufzuhellen. Zweckmäßigerweise wird der optische Aufheller in einer Menge von 50 bis 99 Gew.-%, vorzugsweise aus 60 bis 95 Gew.-%, und das Wachs oder Polymer in einer Menge von 1 bis 50 Gew.-%, vorzugsweise von 5 bis 40 Gew.-% des Aufhellergranulates, eingesetzt.The high-molecular organic material mentioned can be present individually or in mixtures in the form of plastic compositions or melts. It is also possible to incorporate the shape of the optical brightener according to the invention into the monomers on which the polymers are based and to lighten the corresponding plastic by polymerizing the brightener-containing monomer. The optical brightener is expediently used in an amount of 50 to 99% by weight, preferably 60 to 95% by weight, and the wax or polymer in an amount of 1 to 50% by weight, preferably 5 to 40% by weight .-% of the brightener granules used.
Beispiel 1example 1
Es werden 150 Teile des Montanwachsesters (Säurezahl 13-26 KOH/g) Licolub® WE 40 mit 850 Teilen des Aufhellers der Formel 1 in einem Glasbehälter 2 Stunden auf dem Rollbock bei Raumtemperatur homogen gemischt. Anschließend wird in einer N2 Atmosphäre ohne Bewegung 10 Stunden bei 105°C gelagert. Bei langsamer Rotation mit einer Umdrehungszahl von ca. 16 U/min wird innerhalb von 6 Stunden auf RT abgekühlt. Man erhält ein staubfreies, gut rieselfähiges Granulat mit einer Korngröße von 0,5 - 5 mm Durchmesser. Das Staubverhalten des Granulates wird mit Hilfe einesThere are mixed 150 parts of montan wax ester (acid value 13-26 KOH / g) Licolub ® WE 40 homogeneously with 850 parts of the brightener of the formula 1 in a glass container 2 hours on the roller stand at room temperature. The mixture is then stored in an N2 atmosphere without movement for 10 hours at 105 ° C. With slow rotation with a speed of approx. 16 rpm, inside cooled from 6 hours to RT. A dust-free, free-flowing granulate with a grain size of 0.5-5 mm in diameter is obtained. The dust behavior of the granules is determined using a
Sedimentationsstaubmessgerätes fotometrisch ermittelt. Die Staubzahl beträgt 2. Die dem Granulat zugrunde liegende pulverförmige Substanz des Aufhellers der Formel 1 besitzt eine Staubzahl von 14. (1 = nicht staubend; 16 = stark staubend)Sedimentation dust measuring device determined photometrically. The dust number is 2. The powdery substance of the brightener of formula 1 on which the granules are based has a dust number of 14. (1 = not dusting; 16 = heavily dusting)
Beispiel 2 Eine Mischung bestehend ausExample 2 A mixture consisting of
80,8 Teilen Polyethylenvinylacetat80.8 parts of polyethylene vinyl acetate
16,2 Teilen CaCO3 0,8 Teilen Stearinsäure 0,8 Teilen Zinkoxid 1 ,4 Teilen Schäumungsmittel z.B. Azodicarbonamid sowie 0,04 Teile des Aufhellers der Formel 1 herkömmlicher Formulierung16.2 parts CaCO 3 0.8 parts stearic acid 0.8 parts zinc oxide 1.4 parts foaming agent, for example azodicarbonamide and 0.04 parts of the brightener of formula 1 of conventional formulation
(Reinheitsgrad > 99 %) werden bei 165°C während 10 min auf einem Walzenstuhl so behandelt, dass eine ca. 2 mm dicke Folie entsteht.(Degree of purity> 99%) are treated at 165 ° C for 10 min on a roller mill so that an approximately 2 mm thick film is produced.
Die so erhaltene Folie wird unter UV Licht mit einem Intensitätsmaximum bei 376 nm betrachtet.The film thus obtained is viewed under UV light with an intensity maximum at 376 nm.
Das Erscheinungsbild ist nicht homogen und weist stippenförmige, punktuelleThe appearance is not homogeneous and has speck-shaped, selective
Unregelmäßigkeiten auf.Irregularities on.
Beispiel 3 Es wird wie bei Beispiel 2 gearbeitet. Als Aufheller werden jedoch 0,046 Teile des Granulates von Beispiel 1 eingesetzt. Die so erhaltene Folie weist eine einheitliche Fluoreszenz auf.Example 3 The procedure is as in Example 2. However, 0.046 part of the granules from Example 1 are used as brighteners. The film thus obtained has a uniform fluorescence.
Beispiel 4 Eine Mischung bestehend aus 67,0 Teilen Polyvinylchlorid 30,6 Teilen Diisodecylphthalat 1 ,9 Teilen DibutylzinnthioglykolatExample 4 A mixture consisting of 67.0 parts of polyvinyl chloride and 30.6 parts of diisodecyl phthalate 1.9 parts of dibutyltin thioglycolate
0,5 Teilen Titandioxid (Anatas) wird mit 0,1 Teil eines Aufhellers der Formel 2 in herkömmlicher Formulierung versetzt. Die Mischung wird auf dem Walzenstuhl bei 130°C während 10min. erhitzt, wobei durch ständiges Abstreifen und erneutem Auswalzen der 1 mm dicken Folie die bestmögliche Verteilung des Aufhellers in der Masse erzielt wird.0.5 part of titanium dioxide (anatase) is mixed with 0.1 part of a brightener of formula 2 in a conventional formulation. The mixture is on the roller mill at 130 ° C for 10min. heated, whereby the best possible distribution of the brightener in the mass is achieved by constant stripping and re-rolling the 1 mm thick film.
Die abgezogene Folie wird wie bei Bsp. 2 beschrieben unter UV Licht abgemustert und weist erkennbare Unregelmäßigkeiten in Form von Streifenbildung auf.The removed film is patterned under UV light as described in Example 2 and has recognizable irregularities in the form of streaking.
Beispiel 5Example 5
Es wird wie bei Beispiel 4 gearbeitet. Als Aufheller gelangen jedoch 0,115 Teile der Aufhellerformulierung aus Versuch 1 zur Anwendung. Man erhält unter UV Licht eine homogen fluoreszierende PVC Folie.The procedure is as in Example 4. However, 0.115 parts of the brightener formulation from test 1 are used as brighteners. A homogeneously fluorescent PVC film is obtained under UV light.
Beispiel 6Example 6
Es wird wie bei Beispiel 1 gearbeitet.The procedure is as in Example 1.
Die eingesetzte Wachsmenge beträgt jedoch 500 Teile. Als Aufheller kommen 500 Teile eines handelsüblichen Produktes der Formel 1 zur Anwendung. Es wird ein staubfreies Granulat mit ausgezeichneter Rieselfähigkeit erhalten.However, the amount of wax used is 500 parts. 500 parts of a commercially available formula 1 product are used as brighteners. A dust-free granulate with excellent flowability is obtained.
Beispiel 7Example 7
Es wird wie bei Beispiel 4 gearbeitet. Als Aufheller werden jedoch 0,02 Teile des Aufhellers der Formel 1 eingearbeitet. Die Abmusterung unter UV Licht zeigt eine erkennbare Streifenbildung.The procedure is as in Example 4. However, 0.02 part of the brightener of formula 1 is incorporated as the brightener. The pattern under UV light shows a recognizable streaking.
Beispiel 8Example 8
Es wird wie bei Beispiel 7 gearbeitet. Als Aufheller werden jedoch 0,04 Teile des Aufhellers, hergestellt nach Formel 6 eingesetzt. Man erhält eine homogen fluoreszierende PVC Folie. The procedure is as in Example 7. However, 0.04 part of the brightener, prepared according to formula 6, is used as the brightener. A homogeneously fluorescent PVC film is obtained.

Claims

Patentansprüche: claims:
1. Granulierte optische Aufheller, die mit einem Wachs oder wachsartigen Polymer umhüllt sind.1. Granulated optical brighteners that are coated with a wax or wax-like polymer.
2. Granulierte optische Aufheller nach Anspruch 1 , dadurch gekennzeichnet, dass sie ein Polyolefinwachs enthalten.2. Granulated optical brightener according to claim 1, characterized in that they contain a polyolefin wax.
3. Granulierte optische Aufheller nach Anspruch 1 , dadurch gekennzeichnet, dass sie das Wachs oder wachsartige Polymer in einer Menge von 1 bis3. Granulated optical brightener according to claim 1, characterized in that it contains the wax or wax-like polymer in an amount of 1 to
50 Gew.-% enthalten.Contain 50 wt .-%.
4. Granulierte optische Aufheller nach Anspruch 1 , dadurch gekennzeichnet, dass sie einen Teilchendurchmesser von 0,05 bis 5 mm aufweisen.4. Granulated optical brightener according to claim 1, characterized in that they have a particle diameter of 0.05 to 5 mm.
5. Verfahren zur Herstellung von granulierten optischen Aufhellern nach Anspruch 1 , dadurch gekennzeichnet, dass man den optischen Aufheller und das Wachs oder wachsartige Polymer bei Raumtemperatur homogen vermischt, über den Erweichungspunkt des Wachses erhitzt und anschließend unter langsamer Rotation abkühlt.5. A process for the preparation of granulated optical brighteners according to claim 1, characterized in that the optical brightener and the wax or wax-like polymer are mixed homogeneously at room temperature, heated above the softening point of the wax and then cooled with slow rotation.
6. Verwendung der granulierten Aufheller nach Anspruch 1 zum Aufhellen von hochmolekularen organischen Materialien. 6. Use of the granulated brightener according to claim 1 for brightening high-molecular organic materials.
EP02792852A 2001-12-05 2002-12-02 Granulated optical brightening agents Withdrawn EP1453907A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10159713A DE10159713A1 (en) 2001-12-05 2001-12-05 Granulated optical brighteners
DE10159713 2001-12-05
PCT/EP2002/013590 WO2003048250A1 (en) 2001-12-05 2002-12-02 Granulated optical brightening agents

Publications (1)

Publication Number Publication Date
EP1453907A1 true EP1453907A1 (en) 2004-09-08

Family

ID=7708116

Family Applications (1)

Application Number Title Priority Date Filing Date
EP02792852A Withdrawn EP1453907A1 (en) 2001-12-05 2002-12-02 Granulated optical brightening agents

Country Status (6)

Country Link
US (1) US20050154085A1 (en)
EP (1) EP1453907A1 (en)
JP (1) JP2005511812A (en)
CN (1) CN1599773A (en)
DE (1) DE10159713A1 (en)
WO (1) WO2003048250A1 (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10237186A1 (en) * 2002-08-14 2004-03-18 Clariant Gmbh Process for lightening synthetic fibers and plastics with granulated optical brighteners
EP2556105B1 (en) * 2010-04-09 2015-05-20 Dow Corning Corporation Solid silanes
US9229829B2 (en) * 2012-07-25 2016-01-05 GlobalFoundries, Inc. Synchronous mode replication to multiple clusters

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
LU77235A1 (en) * 1977-04-29 1979-01-18
US4206103A (en) * 1978-05-25 1980-06-03 Borg-Warner Corporation Vinyl chloride polymers having improved stability
US4277288A (en) * 1978-10-06 1981-07-07 Ciba-Geigy Corporation Fluidized granulation of pigments using organic granulating assistant
DE3138020A1 (en) * 1980-10-03 1982-06-24 Sandoz-Patent-GmbH, 7850 Lörrach CUMARINYL-7 COMPOUNDS, THEIR PRODUCTION AND USE
DE4323810A1 (en) * 1992-07-17 1994-01-20 Sandoz Ag Wax and surfactant dispersions, esp. for fabric softening, etc.
JP3635144B2 (en) * 1996-01-25 2005-04-06 富士写真フイルム株式会社 Silver halide photographic light-sensitive material and processing method thereof
DE19727848B4 (en) * 1997-06-26 2005-09-29 Schill & Seilacher (Gmbh & Co) Rubber additive granules, a process for its preparation and its use
ES2198679T3 (en) * 1997-09-29 2004-02-01 Ciba Specialty Chemicals Holding Inc. GRANULATES OF EPOXIDIZED STABILIZERS, EXPENSES OF DUST, AND PROCEDURE FOR MANUFACTURING.
DE19941061A1 (en) * 1999-08-28 2001-03-01 Clariant Gmbh Process for the production of pigment granules
US6492032B1 (en) * 2000-10-12 2002-12-10 Eastman Chemical Company Multi-component optically brightened polyolefin blend
US20030216488A1 (en) * 2002-04-18 2003-11-20 The Procter & Gamble Company Compositions comprising a dispersant and microcapsules containing an active material

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO03048250A1 *

Also Published As

Publication number Publication date
JP2005511812A (en) 2005-04-28
US20050154085A1 (en) 2005-07-14
CN1599773A (en) 2005-03-23
DE10159713A1 (en) 2003-07-10
WO2003048250A1 (en) 2003-06-12

Similar Documents

Publication Publication Date Title
EP1648958B1 (en) Powdery composition of a polymer and a flameproofing agent containing ammonium polyphosphate, method for the production thereof, and moulded body produced from said powder
DE60112967T2 (en) POWDER COAT WITH LOW GLOSS
EP1411087A1 (en) Laser-sinter powder comprising titanium dioxide particles, process for the manufacture thereof and articles made of said laser-sinter powder
DE4426008A1 (en) Hydrophilic, highly-swellable hydrogel coated with non-reactive, water-insol. polymer film
DE19524724A1 (en) Hydrophilic, highly swellable hydrogels
EP1505101A1 (en) Use of organomodified siloxanes as surface modifying agents for polyolefins and for polyamid films
DE4443316A1 (en) Colorant preparation for the production of masterbatches
EP0121759B1 (en) Process for preparing storage-stable plastisols and organosols
EP0970142B1 (en) Use of amphiphiles for permanent improvement of adhesive and/or coating compatibility of polyolefin based shaped bodies
DE10332135A1 (en) Use of waxes as a filler modifier
EP1453907A1 (en) Granulated optical brightening agents
US2489226A (en) Method of making pigmented polystyrene
DE60210339T2 (en) Free-flowing melamine cyanourate agglomerate
DE4235693C1 (en) Process for flame retardant treatment of polyolefin particle foams
EP1339802B1 (en) Method for producing dust-free, pourable pigment concentrations
EP1141110B1 (en) Use of amides of aromatic carboxylic acids for permanently improving the adhesive and/or coating compatibility of polyolefin-based moulded bodies, fibres and films
FR2644794A1 (en) POWDER COATING COMPOSITIONS AND PROCESS FOR PRODUCING THE SAME
EP1242533B1 (en) Use of substituted polyethylenimines for the sustained improvement of the adhesive and/or coating compatibility of polyolefin-based shaped bodies, fibres and films
WO2000029475A2 (en) Utilization of fatty acid amides for the lasting improvement of adhesive and/or coating compatibility of polyolefin-based shaped bodies, fibers and films
EP0866093B1 (en) Solid, storage stable antistaticts mixtures and process for their production
EP1123346B1 (en) Additives for processing plastics
EP0013752B1 (en) Process for preparing finely divided polyolefine compositions with enhanced properties and their use in producing formed articles
EP1419204A1 (en) Thermoplastic coating powder, method for the production thereof and mixing system for coating powder
AT232724B (en) Process for the production of block graft copolymerization from polycondensates and polyolefins
EP2159251B1 (en) Use of block copolymers in polymers for prevention or reduction of adhesion of lime

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20040705

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR IE IT LI LU MC NL PT SE SI SK TR

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: CLARIANT PRODUKTE (DEUTSCHLAND) GMBH

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN

18W Application withdrawn

Effective date: 20090821