EP1848770A1 - Polymethylmethacrylate with a nacreous effect - Google Patents

Polymethylmethacrylate with a nacreous effect

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Publication number
EP1848770A1
EP1848770A1 EP06701003A EP06701003A EP1848770A1 EP 1848770 A1 EP1848770 A1 EP 1848770A1 EP 06701003 A EP06701003 A EP 06701003A EP 06701003 A EP06701003 A EP 06701003A EP 1848770 A1 EP1848770 A1 EP 1848770A1
Authority
EP
European Patent Office
Prior art keywords
meth
pearlescent effect
plastic bodies
effect according
acrylate
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Withdrawn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
EP06701003A
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German (de)
French (fr)
Inventor
Volker Mende
Wolfgang Scharnke
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.)
Roehm GmbH Darmstadt
Original Assignee
Roehm GmbH Darmstadt
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Filing date
Publication date
Application filed by Roehm GmbH Darmstadt filed Critical Roehm GmbH Darmstadt
Publication of EP1848770A1 publication Critical patent/EP1848770A1/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Withdrawn legal-status Critical Current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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
    • C08L33/12—Homopolymers or copolymers of methyl methacrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C08L67/025—Polyesters derived from dicarboxylic acids and dihydroxy compounds containing polyether sequences

Definitions

  • the invention relates to polymethylmethacrylate with pearlescent effect.
  • DE 3023964 has already proposed a process for producing colorant-containing zones in acrylic and methacrylic resins near the surface in the course of the polymerization of the monomers and prepolymers forming polymers in forming polymerization chambers, in which first a colorant homogeneously distributed in a binder is applied to the wall of the shaping polymerization chamber is applied as a layer, wherein the binder in the liquid resin or its precursors is soluble or at least swellable and is polymerized after filling of the monomers to be polymerized and / or prepolymers in a conventional manner.
  • EP 0553845 describes a polymer blend of a thermoplastic polyester resin (A) and a resin (B) incompatible therewith.
  • Component (B) is added in amounts of 2-50% by weight.
  • These are polyolefin resins, poly (meth) acrylic resins, polystyrene resins, polycarbonate resins or polyamide resins. An anisotropic glow is observed. It will be on it pointed out that at mixing ratios outside the specified ratios, the optical effect no longer occurs.
  • An anisotropic shimmer or an opalescent effect is used when materials have a pearlescent effect, which is also associated with a depth effect.
  • the object was achieved by a process for the production of plastic bodies with pearlescent effect by extrusion or injection molding, characterized in that a mixture of 5-35% polyethylene terephthalate glycol (PETG) and 65-95% polymethyl methacrylate (PMMA) and optionally 0.01-5, 0% auxiliaries and additives produced and the mixture is extruded into a plastic body and optionally formed or injection-molded.
  • PETG polyethylene terephthalate glycol
  • PMMA polymethyl methacrylate
  • polyethylene terephthalate glycol PET
  • PMMA polymethyl methacrylate
  • the mixture according to the invention can also contain auxiliary substances and additives.
  • Polymethyl methacrylates are generally obtained by free radical polymerization of mixtures containing methyl methacrylate. In general, these mixtures contain at least 65% by weight, preferably at least 80% by weight, based on the weight of the monomers, of methyl methacrylate.
  • these mixtures for the preparation of polymethyl methacrylates may contain further (meth) acrylates which are copolymerizable with methyl methacrylate.
  • (meth) acrylates include methacrylates and acrylates as well as mixtures of both. These monomers are well known. These include, among others
  • Aryl (meth) acrylates such as benzyl (meth) acrylate or
  • Phenyl (meth) acrylate wherein the aryl radicals may each be unsubstituted or substituted up to four times;
  • Cycloalkyl (meth) acrylates such as 3-vinylcyclohexyl (meth) acrylate, bomyl (meth) acrylate;
  • Hydroxylalkyl (meth) acrylates such as
  • Glycol di (meth) acrylates such as 1,4-butanediol (meth) acrylate,
  • Trimethyloylpropantri (meth) acrylate Trimethyloylpropantri (meth) acrylate.
  • compositions to be polymerized may also contain other unsaturated monomers which are copolymerizable with methyl methacrylate and the abovementioned (meth) acrylates.
  • 1-alkenes such as hexene-1, heptene-1
  • branched alkenes such as vinylcyclohexane, 3,3-dimethyl-i-propene, 3-methyl-1-diisobutylene, 4-methylpentene-1
  • 1-alkenes such as hexene-1, heptene-1
  • branched alkenes such as vinylcyclohexane, 3,3-dimethyl-i-propene, 3-methyl-1-diisobutylene, 4-methylpentene-1
  • Vinyl esters such as vinyl acetate
  • Styrene substituted styrenes having an alkyl substituent in the side chain, such as. ⁇ -methylstyrene and ⁇ -ethylstyrene, substituted styrenes having an alkyl substituent on the ring such as vinyltoluene and p-methylstyrene, halogenated styrenes such as monochlorostyrenes, dichlorostyrenes, tribromostyrenes and tetrabromostyrenes; Heterocyclic vinyl compounds, such as 2-vinylpyridine, 3-vinylpyridine, 2-methyl-5-vinylpyridine, 3-ethyl-4-vinylpyridine, 2,3-dimethyl-5-vinylpyridine, vinylpyrimidine, vinylpiperidine, 9-vinylcarbazole, 3-vinylcarbazole, 4-vinylcarbazole, 1-vinylimidazole, 2-methyl-1-vinylimidazole, N-
  • Maleic acid derivatives such as maleic anhydride, methylmaleic anhydride, maleimide, methylmaleimide; and dienes, such as divinylbenzene.
  • these comonomers are used in an amount of 0 to 60 wt .-%, preferably 0 to 40 wt .-% and particularly preferably 0 to 20 wt .-%, based on the weight of the monomers, wherein the compounds individually or can be used as a mixture.
  • the polymerization is generally started with known free-radical initiators.
  • the preferred initiators include the azo initiators well known in the art, such as AIBN and I J-azobiscyclohexanecarbonitrile, and peroxy compounds such as methyl ethyl ketone peroxide, acetylacetone peroxide, dilauryl peroxide, tert-butyl per-2-ethylhexanoate, ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide, dibenzoyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxyisopropyl carbonate, 2,5-bis (2-ethylhexanoylperoxy) -2,5-dimethylhexane, tert-butylperoxy-2-ethylhexanoate, tert-butylperoxy-3,5,5-trimethylhe
  • These compounds are often used in an amount of 0.01 to 10 wt .-%, preferably from 0.5 to 3 wt .-%, based on the weight of the monomers.
  • the weight-average molecular weight M w of the homo- and / or copolymers to be used according to the invention as matrix polymers can vary within wide limits, the molecular weight usually being matched to the intended use and the method of processing of the molding composition. In general, however, it is in the range between 20,000 and 1,000,000 g / mol, preferably 50,000 to 500,000 g / mol, and more preferably 80,000 to 300,000 g / mol, without this being intended to limit this.
  • the mixtures may contain conventional additives of all kinds.
  • additives include, but are not limited to, antistatics, antioxidants, mold release agents, flame retardants, lubricants, dyes, flow improvers, fillers, light stabilizers, UV absorbers, and organic phosphorus compounds such as phosphites or phosphonates, pigments, weathering inhibitors, and plasticizers.
  • antistatics antioxidants, mold release agents, flame retardants, lubricants, dyes, flow improvers, fillers, light stabilizers, UV absorbers, and organic phosphorus compounds such as phosphites or phosphonates, pigments, weathering inhibitors, and plasticizers.
  • additives is limited to the purpose of use.
  • the preferred additives include dyes which, when dissolved in methyl methacrylate at a concentration of 0.01% by weight at 350 nm, exhibit a transmission of at least 30%.
  • dyes are known per se and, for example, under the trade name ® Makrolex blue RR, ® Makrolex violet B, ® Makrolex violet 3R, ® Makrolex green 5B, ® Makrolex green G, from Bayer, ® Sandoplast construction 2B, ® Sandoplast red BB, and ® Sandoplast green G available from Clariant, ® Mikrolitviol BK from Ciba.
  • the inventive method is carried out with commercially available processing machines.
  • Single-screw and twin-screw extruders are suitable for extrusion.
  • degassing extruders are used.
  • the starting materials are usually fed in granulated form to the extruder.
  • the materials are melted and extruded depending on the composition.
  • the inventive mixture of 65-95% polymethacrylate, 5-35% polyethylene terephthalate glycol and optionally 0.01- 5.0% auxiliaries and additives is melted at 160-300 0 C and extruded into semi-finished products.
  • the extruder can be followed by conventional processing machines.
  • a forming process further enhances the pearlescent effect.
  • Forming processes such as deep drawing or compressed air forming are particularly suitable.
  • the semi-finished product is heated to 140-190 0 C and with appropriate Pressure, for example, under vacuum ⁇ 1 bar, brought into the desired shape.
  • the material can be further processed by means of compressed air forming.
  • the extruded semi-finished product is heated and pressed under pressure, for example at 2.5 bar, into a mold.
  • the pearlescent effect of the material is further enhanced by the stretching processes taking place here.
  • the processing by injection molding also leads to materials which have a pearlescent effect.
  • the inventive mixture of 65-95% polymethacrylate, 5-35% polyethylene terephthalate glycol and optionally 0.01-5.0% auxiliaries and additives is fed to an injection molding machine, melted at a temperature of 200-280 0 C and then injection molded.
  • the injection-molded parts show a pronounced pearlescent effect.
  • the plastic bodies according to the invention with pearlescent effect have a wide field of application. They can be used in construction, in the automotive industry, in shipbuilding and aircraft construction, preferably in interior design. However, the pearlescent effect also leads to widespread use for commodities such as e.g. Packaging of all kinds, storage articles (for example, bowls, boxes, mugs, etc.), decorative materials, housing materials for electronic devices (e.g., cell phones, organizers, etc.), toys and office supplies.
  • commodities such as e.g. Packaging of all kinds, storage articles (for example, bowls, boxes, mugs, etc.), decorative materials, housing materials for electronic devices (e.g., cell phones, organizers, etc.), toys and office supplies.
  • 80% polymethyl methacrylate molding compound (Piexiglas molding compound 7H, Röhm, Germany) is placed in an extruder in granular form with 20% polyethylene terephthalate glycol (Spectar copolyester 14471, Kodak Eastman, USA).
  • a temperature of 165 ° C is set.
  • the mixture is melted and reaches a melting temperature of about 278 ° C.
  • the melt is processed via a slot die to a plate with a thickness of 3mm.
  • the plates prepared in Example 1 are formed by means of compressed air molds into shells. For this purpose, the plates are heated for about 9 min to 160 0 C and pressed with a pressure of 2.5 bar in a mold.
  • the plates produced in Example 1 are formed into shells by deep drawing. For this, the plates are heated ca. 9 min to 175 0 C and deep-drawn (1 bar ⁇ ) under vacuum.
  • Example 2 There are obtained in Example 2 and 3 shells with pronounced pearlescent effect.

Abstract

The invention relates to polymethylmethacrylate with a nacreous effect.

Description

Polymethylmethacrylat mit Perlglanzeffekt Polymethyl methacrylate with pearlescent effect
Die Erfindung betrifft Polymethylmethacrylat mit Perlglanzeffekt.The invention relates to polymethylmethacrylate with pearlescent effect.
Die Aufgabe, Kunststoffe einzufärben, ist von der Technik weitgehend in befriedigender Weise gelöst worden. Um Kunststoffen ein höherwertiges Aussehen zu verschaffen werden üblicherweise Farbstoffe oder Pigmente der Polymermischung zugefügt. Dabei können die Materialien vollständig mit den Additiven durchmischt werden, oder aber nur Oberflächen modifiziert werden.The task of coloring plastics has largely been solved satisfactorily by technology. To give plastics a superior appearance, dyes or pigments are usually added to the polymer blend. The materials can be completely mixed with the additives, or only surfaces can be modified.
Auf dem Acrylglas-Sektor beispielsweise steht ein Sortiment von Farbmitteln zur Verfügung, das es erlaubt, Acrylglas in nahezu beliebigen Nuancen homogen einzufärben.On the acrylic glass sector, for example, there is an assortment of colorants available that allows acrylic glass to be homogeneously colored in almost any shade.
In DE 3023964 wurde bereits ein Verfahren zur Erzeugung farbmittelhaltiger Zonen in Acryl- und Methacrylharzen in Oberflächennähe im Zuge der Polymerisation der die Harze bildenden Monomeren und Präpolymeren in formgebenden Polymerisationskammern vorgeschlagen, bei dem zunächst ein in einem Bindemittel homogen verteiltes Farbmittel auf die Wandung der formgebenden Polymerisationskammer als Schicht aufgetragen wird, wobei das Bindemittel im flüssigen Harz bzw. seinen Vorstufen löslich oder zumindest anquellbar ist und nach dem Einfüllen der zu polymerisierenden Monomere und/oder Präpolymere in an sich bekannter Weise polymerisiert wird.DE 3023964 has already proposed a process for producing colorant-containing zones in acrylic and methacrylic resins near the surface in the course of the polymerization of the monomers and prepolymers forming polymers in forming polymerization chambers, in which first a colorant homogeneously distributed in a binder is applied to the wall of the shaping polymerization chamber is applied as a layer, wherein the binder in the liquid resin or its precursors is soluble or at least swellable and is polymerized after filling of the monomers to be polymerized and / or prepolymers in a conventional manner.
In EP 0553845 wird eine Polymermischung aus einem thermoplastischen Polyesterharz (A) und einem damit incompatiblen Harz (B) beschrieben. Die Komponente (B) wird in Mengen von 2-50 Gew.-% zugegeben. Hierbei handelt es sich um Polyolefinharze, Poly(meth)acrylharze, Polystyrolharze, Polycarbonatharze oder Polyamidharze. Es wird ein anisoptroper Schimmer beobachtet. Es wird darauf hingewiesen, dass bei Mischungsverhältnissen außerhalb der angegebenen Verhältnisse, der optische Effekt nicht mehr auftritt.EP 0553845 describes a polymer blend of a thermoplastic polyester resin (A) and a resin (B) incompatible therewith. Component (B) is added in amounts of 2-50% by weight. These are polyolefin resins, poly (meth) acrylic resins, polystyrene resins, polycarbonate resins or polyamide resins. An anisotropic glow is observed. It will be on it pointed out that at mixing ratios outside the specified ratios, the optical effect no longer occurs.
Von einem anisotropen Schimmer bzw. einem opalisierenden Effekt wird gesprochen, wenn Materialien einen Perlglanzeffekt aufweisen, der auch mit einer Tiefenwirkung verbunden ist.An anisotropic shimmer or an opalescent effect is used when materials have a pearlescent effect, which is also associated with a depth effect.
In Anbetracht des hier angegebenen Standes der Technik war es Aufgabe der vorliegenden Erfindung ein Verfahren zur Verfügung zustellen, mit deren Hilfe eine Halbzeug hergestellt werden kann, welches ohne Zumischung von Farbstoffen oder Pigmenten einen Perlglanzeffekt aufweist.In view of the prior art stated here, it was an object of the present invention to provide a method by means of which a semifinished product can be produced which has a pearlescent effect without the admixture of dyes or pigments.
Die Aufgabe wurde gelöst, durch ein Verfahren zur Herstellung von Kunststoffkörpern mit Perlglanzeffekt mittels Extrusion oder Spritzguß, dadurch gekennzeichnet, dass man eine Mischung aus 5-35% Polyethylenterephthalatglycol (PETG) und 65-95% Polymethylmethacrylat (PMMA) und gegebenenfalls 0.01-5,0 % Hilfs- und Zusatzstoffen herstellt und die Mischung zu einem Kunststoffkörper extrudiert und gegebenenfalls umformt oder spritzgießt.The object was achieved by a process for the production of plastic bodies with pearlescent effect by extrusion or injection molding, characterized in that a mixture of 5-35% polyethylene terephthalate glycol (PETG) and 65-95% polymethyl methacrylate (PMMA) and optionally 0.01-5, 0% auxiliaries and additives produced and the mixture is extruded into a plastic body and optionally formed or injection-molded.
Überraschend wurde gefunden, dass bei der Zugabe von unverträglichen Polymeren wie z.B. Polyethylenterephthalatglycol zu Polymethylmethacrylat ein Perlglanzeffekt bei der erhaltenen Formmasse nachgewiesen werden kann. Entgegen der Lehre aus EP 0553845 wird dieser Perlglanzeffekt auch bei Mischungsverhältnissen von unter 50% Polyethylenterephthalatglycol in Polymethylmethacrylat nachgewiesen. Bevorzugt werden Mischungen mit 15-25%, besonders bevorzugt 20%, PETG in PMMA verwendet.Surprisingly, it has been found that when adding incompatible polymers, e.g. Polyethylene terephthalate glycol to polymethyl methacrylate, a pearlescent effect can be detected in the resulting molding composition. Contrary to the teaching of EP 0553845, this pearlescent effect is also detected at mixing ratios of less than 50% polyethylene terephthalate glycol in polymethyl methacrylate. Preference is given to using mixtures with 15-25%, particularly preferably 20%, of PETG in PMMA.
Die erfindungsgemäße Mischung kann neben 5-35% Polyethylenterephthalatglycol (PETG) und 65-95% Polymethylmethacrylat (PMMA) auch weiter Hilfs- und Zusatzstoffe enthalten. Polymethylmethacrylate werden im allgemeinen durch radikalische Polymerisation von Mischungen erhalten, die Methylmethacrylat enthalten. Im allgemeinen enthalten diese Mischungen mindestens 65 Gew.-%, vorzugsweise mindestens 80 Gew.-%, bezogen auf das Gewicht der Monomere, Methylmethacrylat.In addition to 5-35% polyethylene terephthalate glycol (PETG) and 65-95% polymethyl methacrylate (PMMA), the mixture according to the invention can also contain auxiliary substances and additives. Polymethyl methacrylates are generally obtained by free radical polymerization of mixtures containing methyl methacrylate. In general, these mixtures contain at least 65% by weight, preferably at least 80% by weight, based on the weight of the monomers, of methyl methacrylate.
Daneben können diese Mischungen zur Herstellung von Polymethylmethacrylaten weitere (Meth)acrylate enthalten, die mit Methylmethacrylat copolymerisierbar sind.In addition, these mixtures for the preparation of polymethyl methacrylates may contain further (meth) acrylates which are copolymerizable with methyl methacrylate.
Der Ausdruck (Meth)acrylate umfasst Methacrylate und Acrylate sowie Mischungen aus beiden. Diese Monomere sind weithin bekannt. Zu diesen gehören unter anderemThe term (meth) acrylates include methacrylates and acrylates as well as mixtures of both. These monomers are well known. These include, among others
(Meth)acrylate, die sich von gesättigten Alkoholen ableiten, wie beispielsweise(Meth) acrylates derived from saturated alcohols, such as
Methylacrylat, Ethyl(meth)acrylat, Propyl(meth)acrylat, n-Butyl(meth)acrylat, tert.-Butyl(meth)acrylat, Pentyl(meth)acrylat und 2-Ethylhexyl(meth)acrylat;Methyl acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate and 2-ethylhexyl (meth) acrylate;
(Meth)acrylate, die sich von ungesättigten Alkoholen ableiten, wie z. B.(Meth) acrylates derived from unsaturated alcohols, such as. B.
Oleyl(meth)acrylat, 2-Propinyl(meth)acrylat, AIIyI (meth)acrylat, Vinyl(meth)acrylat;Oleyl (meth) acrylate, 2-propynyl (meth) acrylate, allyl (meth) acrylate, vinyl (meth) acrylate;
Aryl(meth)acrylate, wie Benzyl(meth)acrylat oderAryl (meth) acrylates, such as benzyl (meth) acrylate or
Phenyl(meth)acrylat, wobei die Arylreste jeweils unsubstituiert oder bis zu vierfach substituiert sein können;Phenyl (meth) acrylate, wherein the aryl radicals may each be unsubstituted or substituted up to four times;
Cycloalkyl(meth)acrylate, wie 3-Vinylcyclohexyl(meth)acrylat, Bomyl(meth)acrylat;Cycloalkyl (meth) acrylates such as 3-vinylcyclohexyl (meth) acrylate, bomyl (meth) acrylate;
Hydroxylalkyl(meth)acrylate, wieHydroxylalkyl (meth) acrylates, such as
3-Hydroxypropyl(meth)acrylat,3-hydroxypropyl (meth) acrylate,
3,4-Dihydroxybutyl(meth)acrylat,3,4-dihydroxybutyl (meth) acrylate,
2-Hydroxyethyl(meth)acrylat, 2-Hydroxypropyl(meth)acrylat;2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate;
Glycoldi(meth)acrylate, wie 1,4-Butandiol(meth)acrylat,Glycol di (meth) acrylates, such as 1,4-butanediol (meth) acrylate,
(Meth)acrylate von Etheralkoholen, wie(Meth) acrylates of ether alcohols, such as
Tetrahydrofurfuryl(meth)acrylat, Vinyloxyethoxyethyl(meth)acrylat;Tetrahydrofurfuryl (meth) acrylate, vinyloxyethoxyethyl (meth) acrylate;
Amide und Nitrile der (Meth)acrylsäure, wieAmides and nitriles of (meth) acrylic acid, such as
N-(3-Dimethylaminopropyl)(meth)acrylamid,N- (3-dimethylaminopropyl) (meth) acrylamide,
N-(Diethylphosphono)(meth)acrylamid,N- (diethylphosphono) (meth) acrylamide,
1-Methacryloylamido-2-methyl-2-propanol; schwefelhaltige Methacrylate, wie1-Methacryloylamido-2-methyl-2-propanol; Sulfur-containing methacrylates, such as
Ethylsulfinylethyl(meth)acrylat, 4-Thiocyanatobutyl(meth)acrylat,Ethylsulfinylethyl (meth) acrylate, 4-Thiocyanatobutyl (meth) acrylate,
Ethylsulfonylethyl(meth)acrylat,Ethylsulfonylethyl (meth) acrylate,
Thiocyanatomethyl(meth)acrylat,Thiocyanatomethyl (meth) acrylate,
Methylsulfinylmethyl(meth)acrylat,Methylsulfinylmethyl (meth) acrylate,
Bis((meth)acryloyloxyethyl)sulfid; mehrwertige (Meth)acrylate, wieBis ((meth) acryloyloxyethyl) sulfide; polyvalent (meth) acrylates, such as
Trimethyloylpropantri(meth)acrylat.Trimethyloylpropantri (meth) acrylate.
Neben den zuvor dargelegten (Meth)acrylaten können die zu polymerisierenden Zusammensetzungen auch weitere ungesättigte Monomere aufweisen, die mit Methylmethacrylat und den zuvor genannten (Meth)acrylaten copolymerisierbar sind.In addition to the (meth) acrylates set out above, the compositions to be polymerized may also contain other unsaturated monomers which are copolymerizable with methyl methacrylate and the abovementioned (meth) acrylates.
Hierzu gehören unter anderem 1-Alkene, wie Hexen-1 , Hepten-1 ; verzweigte Alkene, wie beispielsweise Vinylcyclohexan, 3,3-Dimethyl-i-propen, 3-Methyl-1-diisobutylen, 4-Methylpenten-1 ;These include, inter alia, 1-alkenes, such as hexene-1, heptene-1; branched alkenes such as vinylcyclohexane, 3,3-dimethyl-i-propene, 3-methyl-1-diisobutylene, 4-methylpentene-1;
Acrylnitril; Vinylester, wie Vinylacetat;acrylonitrile; Vinyl esters, such as vinyl acetate;
Styrol, substituierte Styrole mit einem Alkylsubstituenten in der Seitenkette, wie z. B. α-Methylstyrol und α-Ethylstyrol, substituierte Styrole mit einem Alkylsubstitutenten am Ring, wie Vinyltoluol und p-Methylstyrol, halogenierte Styrole, wie beispielsweise Monochlorstyrole, Dichlorstyrole, Tribromstyrole und Tetrabromstyrole; Heterocyclische Vinylverbindungen, wie 2-Vinylpyridin, 3-Vinylpyridin, 2-Methyl-5- vinylpyridin, 3-Ethyl-4-vinylpyridin, 2,3-Dimethyl-5-vinylpyridin, Vinylpyrimidin, Vinylpiperidin, 9-Vinylcarbazol, 3-Vinylcarbazol, 4-Vinylcarbazol, 1-Vinylimidazol, 2-Methyl-1-vinylimidazol, N-Vinylpyrrolidon, 2-Vinylpyrrolidon, N-Vinylpyrrolidin, 3-Vinylpyrrolidin, N-Vinylcaprolactam, N-Vinylbutyrolactam, Vinyloxolan, Vinylfuran, Vinylthiophen, Vinylthiolan, Vinylthiazole und hydrierte Vinylthiazole, Vinyloxazole und hydrierte Vinyloxazole;Styrene, substituted styrenes having an alkyl substituent in the side chain, such as. Α-methylstyrene and α-ethylstyrene, substituted styrenes having an alkyl substituent on the ring such as vinyltoluene and p-methylstyrene, halogenated styrenes such as monochlorostyrenes, dichlorostyrenes, tribromostyrenes and tetrabromostyrenes; Heterocyclic vinyl compounds, such as 2-vinylpyridine, 3-vinylpyridine, 2-methyl-5-vinylpyridine, 3-ethyl-4-vinylpyridine, 2,3-dimethyl-5-vinylpyridine, vinylpyrimidine, vinylpiperidine, 9-vinylcarbazole, 3-vinylcarbazole, 4-vinylcarbazole, 1-vinylimidazole, 2-methyl-1-vinylimidazole, N-vinylpyrrolidone, 2-vinylpyrrolidone, N-vinylpyrrolidine, 3-vinylpyrrolidine, N-vinylcaprolactam, N-vinylbutyrolactam, vinyloxolane, vinylfuran, vinylthiophene, vinylthiolane, vinylthiazoles and hydrogenated vinylthiazoles, vinyloxazoles and hydrogenated vinyloxazoles;
Vinyl- und Isoprenylether;Vinyl and isoprenyl ethers;
Maleinsäurederivate, wie beispielsweise Maleinsäureanhydrid, Methylmaleinsäureanhydrid, Maleinimid, Methylmaleinimid; und Diene, wie beispielsweise Divinylbenzol. Im allgemeinen werden diese Comonomere in einer Menge von 0 bis 60 Gew.-%, vorzugsweise 0 bis 40 Gew.-% und besonders bevorzugt 0 bis 20 Gew.-%, bezogen auf das Gewicht der Monomeren, eingesetzt, wobei die Verbindungen einzeln oder als Mischung verwendet werden können.Maleic acid derivatives such as maleic anhydride, methylmaleic anhydride, maleimide, methylmaleimide; and dienes, such as divinylbenzene. In general, these comonomers are used in an amount of 0 to 60 wt .-%, preferably 0 to 40 wt .-% and particularly preferably 0 to 20 wt .-%, based on the weight of the monomers, wherein the compounds individually or can be used as a mixture.
Die Polymerisation wird im allgemeinen mit bekannten Radikalinitiatoren gestartet. Zu den bevorzugten Initiatoren gehören unter anderem die in der Fachwelt weithin bekannten Azoinitiatoren, wie AIBN und I J-Azobiscyclohexancarbonitril, sowie Peroxyverbindungen, wie Methylethylketonperoxid, Acetylacetonperoxid, Dilaurylperoxyd, tert.-Butylper-2-ethylhexanoat, Ketonperoxid, Methylisobutylketonperoxid, Cyclohexanonperoxid, Dibenzoylperoxid, tert- Butylperoxybenzoat, tert.-Butylperoxyisopropylcarbonat, 2,5-Bis(2-ethylhexanoyl- peroxy)-2,5-dimethylhexan, tert.-Butylperoxy-2-ethylhexanoat, tert.-Butylperoxy- 3,5,5-trimethylhexanoat, Dicumylperoxid, 1 ,1-Bis(tert.-butylperoxy)cyclohexan, 1 ,1-Bis(tert.-butylperoxy)3,3,5-trimethylcyclohexan, Cumylhydroperoxid, tert.- Butylhydroperoxid, Bis(4-tert.-butylcyclohexyl)peroxydicarbonat, Mischungen von zwei oder mehr der vorgenannten Verbindungen miteinander sowie Mischungen der vorgenannten Verbindungen mit nicht genannten Verbindungen, die ebenfalls Radikale bilden können.The polymerization is generally started with known free-radical initiators. Among the preferred initiators include the azo initiators well known in the art, such as AIBN and I J-azobiscyclohexanecarbonitrile, and peroxy compounds such as methyl ethyl ketone peroxide, acetylacetone peroxide, dilauryl peroxide, tert-butyl per-2-ethylhexanoate, ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide, dibenzoyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxyisopropyl carbonate, 2,5-bis (2-ethylhexanoylperoxy) -2,5-dimethylhexane, tert-butylperoxy-2-ethylhexanoate, tert-butylperoxy-3,5,5-trimethylhexanoate, Dicumyl peroxide, 1, 1-bis (tert-butylperoxy) cyclohexane, 1, 1-bis (tert-butylperoxy) 3,3,5-trimethylcyclohexane, cumyl hydroperoxide, tert-butyl hydroperoxide, bis (4-tert-butylcyclohexyl) peroxydicarbonate, mixtures of two or more of the aforementioned compounds with one another and mixtures of the abovementioned compounds with unspecified compounds which can also form free radicals.
Diese Verbindungen werden häufig in einer Menge von 0,01 bis 10 Gew.-%, vorzugsweise von 0,5 bis 3 Gew.-%, bezogen auf das Gewicht der Monomeren, eingesetzt.These compounds are often used in an amount of 0.01 to 10 wt .-%, preferably from 0.5 to 3 wt .-%, based on the weight of the monomers.
Das Gewichtsmittel des Molekulargewichts Mw der erfindungsgemäss als Matrixpolymere zu verwendenden Homo- und/oder Copolymere kann in weiten Bereichen schwanken, wobei das Molekulargewicht üblicherweise auf den Anwendungszweck und die Verarbeitungsweise der Formmasse abgestimmt wird. Im allgemeinen liegt es aber im Bereich zwischen 20 000 und 1 000 000 g/mol, vorzugsweise 50 000 bis 500 000 g/mol und besonders bevorzugt 80 000 bis 300 000 g/mol, ohne dass hierdurch eine Einschränkung erfolgen soll. Die Mischungen können übliche Zusatzstoffe aller Art enthalten. Hierzu gehören unter anderem Antistatika, Antioxidantien, Entformungsmittel, Flammschutzmittel, Schmiermittel, Farbstoffe, Fliessverbesserungsmittel, Füllstoffe, Lichtstabilisatoren, UV-Absorber und organische Phosphorverbindungen, wie Phosphite oder Phosphonate, Pigmente, Verwitterungsschutzmittel und Weichmacher. Die Menge an Zusatzstoffen ist jedoch auf den Anwendungszweck beschränkt.The weight-average molecular weight M w of the homo- and / or copolymers to be used according to the invention as matrix polymers can vary within wide limits, the molecular weight usually being matched to the intended use and the method of processing of the molding composition. In general, however, it is in the range between 20,000 and 1,000,000 g / mol, preferably 50,000 to 500,000 g / mol, and more preferably 80,000 to 300,000 g / mol, without this being intended to limit this. The mixtures may contain conventional additives of all kinds. These include, but are not limited to, antistatics, antioxidants, mold release agents, flame retardants, lubricants, dyes, flow improvers, fillers, light stabilizers, UV absorbers, and organic phosphorus compounds such as phosphites or phosphonates, pigments, weathering inhibitors, and plasticizers. However, the amount of additives is limited to the purpose of use.
Zu den bevorzugten Additiven gehören Farbstoffe, die gelöst in Methylmethacrylat bei einer Konzentration von 0,01 Gew.-% bei 350 nm eine Transmission von mindestens 30% zeigen. Derartige Farbstoffe sind an sich bekannt und beispielsweise unter dem Handelsnamen ®Makrolex blau RR, ®Makrolex violett B, ®Makrolex violett 3R, ®Makrolex grün 5B, ®Makrolex grün G, von Bayer, ®Sandoplast bau 2B, ®Sandoplast rot BB, sowie ®Sandoplast grün G von Clariant, ®Mikrolitviol B-K von Ciba erhältlich.The preferred additives include dyes which, when dissolved in methyl methacrylate at a concentration of 0.01% by weight at 350 nm, exhibit a transmission of at least 30%. Such dyes are known per se and, for example, under the trade name ® Makrolex blue RR, ® Makrolex violet B, ® Makrolex violet 3R, ® Makrolex green 5B, ® Makrolex green G, from Bayer, ® Sandoplast construction 2B, ® Sandoplast red BB, and ® Sandoplast green G available from Clariant, ® Mikrolitviol BK from Ciba.
Das erfindungsgemäße Verfahren wird mit handelsüblichen Verarbeitungsmaschinen durchgeführt. Zur Extrusion sind Einschnecken- und Doppelschneckenextruder geeignet. Bevorzugt werden Entgasungsextruder verwendet.The inventive method is carried out with commercially available processing machines. Single-screw and twin-screw extruders are suitable for extrusion. Preferably, degassing extruders are used.
Die Ausgangsmaterialien werden üblicherweise in granulierter Form dem Extruder zugeführt. Die Materialien werden in Abhängigkeit von der Zusammensetzung aufgeschmolzen und extrudiert. Die erfindungsgemäße Mischung aus 65-95 % Polymethacrylat, 5-35 % Polyethylenterephthalatglycol und gegebenenfalls 0,01- 5,0 % Hilfs- und Zusatzstoffen wird bei 160-3000C aufgeschmolzen und zu Halbzeugen extrudiert. Dem Extruder können übliche Verarbeitungsmaschinen nachgeschaltet werden.The starting materials are usually fed in granulated form to the extruder. The materials are melted and extruded depending on the composition. The inventive mixture of 65-95% polymethacrylate, 5-35% polyethylene terephthalate glycol and optionally 0.01- 5.0% auxiliaries and additives is melted at 160-300 0 C and extruded into semi-finished products. The extruder can be followed by conventional processing machines.
Es wurde gefunden, dass ein Umformprozeß den Perlglanzeffekt weiter verstärkt. Umformprozesse wie Tiefziehen oder Pressluftformen sind besonders geeignet. Zum Tiefziehen wird das Halbzeug auf 140-1900C erwärmt und mit entsprechendem Druck, z.B. unter Vakuum < 1bar, in die gewünschte Form gebracht. Ebenso kann mittels Pressluftumformen das Material weiterverarbeitet werden. Dazu wird das extrudierte Halbzeug erwärmt und unter Druck, beispielsweise bei 2,5 bar, in eine Form gepresst. Über die hierbei stattfindenden Verstreckungsprozesse wird der Perlglanzeffekt des Materials weiter verstärkt.It has been found that a forming process further enhances the pearlescent effect. Forming processes such as deep drawing or compressed air forming are particularly suitable. For deep drawing, the semi-finished product is heated to 140-190 0 C and with appropriate Pressure, for example, under vacuum <1 bar, brought into the desired shape. Likewise, the material can be further processed by means of compressed air forming. For this purpose, the extruded semi-finished product is heated and pressed under pressure, for example at 2.5 bar, into a mold. The pearlescent effect of the material is further enhanced by the stretching processes taking place here.
Die Verarbeitung über Spritzguß führt ebenfalls zu Materialien die einen Perlglanzeffekt aufweisen.The processing by injection molding also leads to materials which have a pearlescent effect.
Die erfindungsgemäße Mischung aus 65-95 % Polymethacrylat, 5-35 % Polyethylenterephthalatglycol und gegebenenfalls 0,01-5,0 % Hilfs- und Zusatzstoffen wird einer Spritzgussmaschine zugeführt, bei einer Temperatur von 200-2800C geschmolzen und dann spritzgegossen. Die spritzgegossenen Formteile zeigen einen ausgeprägten Perlglanzeffekt.The inventive mixture of 65-95% polymethacrylate, 5-35% polyethylene terephthalate glycol and optionally 0.01-5.0% auxiliaries and additives is fed to an injection molding machine, melted at a temperature of 200-280 0 C and then injection molded. The injection-molded parts show a pronounced pearlescent effect.
Die erfindungsgemäßen Kunststoffkörper mit Perlglanzeffekt haben ein breites Anwendungsgebiet. Sie können im Baubereich, im Automobilbau, im Schiffsbau und im Flugzeugbau, bevorzugt im Innenausbau verwendet werden. Die Perlglanzeffekt führt aber auch zu einer breiten Verwendung für Gebrauchsgegenstände wie z.B. Verpackungen aller Art, Aufbewahrungsgegenstände (z.B. Schalen, Kisten, Becher usw.), Dekorationsmaterialien, Gehäusematerialien für elektronische Geräte (z.B. Handy, Organizer usw.), Spielzeug und Büroartikel.The plastic bodies according to the invention with pearlescent effect have a wide field of application. They can be used in construction, in the automotive industry, in shipbuilding and aircraft construction, preferably in interior design. However, the pearlescent effect also leads to widespread use for commodities such as e.g. Packaging of all kinds, storage articles (for example, bowls, boxes, mugs, etc.), decorative materials, housing materials for electronic devices (e.g., cell phones, organizers, etc.), toys and office supplies.
Die im Folgenden gegebenen Beispiele werden zur besseren Veranschaulichung der vorliegenden Erfindung gegeben, sind jedoch nicht dazu geeignet, die Erfindung auf die hierin offenbarten Merkmale zu beschränken. BeispieleThe examples given below are given for a better illustration of the present invention, but are not intended to limit the invention to the features disclosed herein. Examples
Beispiel 1example 1
80% Polymethylmethacrylat-Formmasse (Piexiglasformmasse 7H, Fa. Röhm, Deutschland) wird mit 20% Polyethylenterephthalatglycol (Spectar Copolyester 14471 , Fa. Kodak Eastman, USA) in Granulatform in einen Extruder gegeben. In der Einzugszone wird eine Temperatur von 165°C eingestellt. Das Gemisch wird aufgeschmolzen und erreicht eine Schmelztemperatur von ca. 278°C. Die Schmelze wird über eine Breitschlitzdüse zu einer Platte mit einer Dicke von 3mm verarbeitet.80% polymethyl methacrylate molding compound (Piexiglas molding compound 7H, Röhm, Germany) is placed in an extruder in granular form with 20% polyethylene terephthalate glycol (Spectar copolyester 14471, Kodak Eastman, USA). In the intake zone, a temperature of 165 ° C is set. The mixture is melted and reaches a melting temperature of about 278 ° C. The melt is processed via a slot die to a plate with a thickness of 3mm.
Beispiel 2Example 2
Die in Beispiel 1 hergestellten Platten werden mittels Preßluftformen zu Schalen umgeformt. Dazu werden die Platten ca. 9 min auf 1600C erwärmt und mit einem Druck von 2,5 bar in eine Form gepresst.The plates prepared in Example 1 are formed by means of compressed air molds into shells. For this purpose, the plates are heated for about 9 min to 160 0 C and pressed with a pressure of 2.5 bar in a mold.
Beispiel 3Example 3
Die in Beispiel 1 hergestellten Platten werden mittels Tiefziehverfahren zu Schalen umgeformt. Dazu werden die Platten ca. 9 min auf 1750C erwärmt und unter Vakuum (< 1bar) tiefgezogen.The plates produced in Example 1 are formed into shells by deep drawing. For this, the plates are heated ca. 9 min to 175 0 C and deep-drawn (1 bar <) under vacuum.
Es werden in den Beispiel 2 und 3 Schalen mit ausgeprägtem Perlglanzeffekt erhalten. There are obtained in Example 2 and 3 shells with pronounced pearlescent effect.

Claims

Patentansprüche claims
1. Verfahren zur Herstellung von Kunststoffkörpern mit Perlglanzeffekt mittels Extrusion oder Spritzguß, dadurch gekennzeichnet, dass man eine Mischung aus 5-35% Polyethylenterephthalatglycol und 65-95% Polymethylmethacrylat und gegebenenfalls 0,01-5,0 % Hilfs- und Zusatzstoffen herstellt und die Mischung zu einem Kunststoffkörper extrudiert und gegebenenfalls umformt oder spritzgießt.1. A process for the production of plastic bodies with pearlescent effect by extrusion or injection molding, characterized in that one produces a mixture of 5-35% polyethylene terephthalate glycol and 65-95% polymethyl methacrylate and optionally 0.01-5.0% auxiliaries and additives and the Extruded mixture to a plastic body and optionally reshaped or injection-molded.
2. Verfahren zur Herstellung von Kunststoffkörpern mit Perlglanzeffekt gemäß Anspruch 1 , dadurch gekennzeichnet, dass Farbstoffe enthalten sind.2. A process for the production of plastic bodies with pearlescent effect according to claim 1, characterized in that dyes are contained.
3. Verfahren zur Herstellung von Kunststoffkörpern mit Perlglanzeffekt gemäß Anspruch 1 , dadurch gekennzeichnet, dass 65-95 % Polymethacrylat, 5-35 % Polyethylenterephthalatglycol und gegebenenfalls 0,01-5,0 % Hilfs- und Zusatzstoffe bei einer Temperatur von 160-3000C zu Halbzeugen extrudiert werden.3. A process for the production of plastic bodies with pearlescent effect according to claim 1, characterized in that 65-95% polymethacrylate, 5-35% polyethylene terephthalate glycol and optionally 0.01-5.0% auxiliaries and additives at a temperature of 160-300 0 C are extruded into semi-finished products.
4. Verfahren zur Herstellung von Kunststoffkörpern mit Perlglanzeffekt gemäß Anspruch 3, dadurch gekennzeichnet, dass die extrudierten Halbzeuge erwärmt und unter Druck umgeformt werden.4. A process for the production of plastic bodies with pearlescent effect according to claim 3, characterized in that the extruded semi-finished products are heated and formed under pressure.
5. Verfahren zur Herstellung von Kunststoffkörpern mit Perlglanzeffekt gemäß Anspruch 1 , dadurch gekennzeichnet, dass 65-95 % Polymethacrylat, 5-35 % Polyethylenterephthalatglycol und gegebenenfalls 0,01-5,0 % Hilfs- und Zusatzstoffe bei einer Schmelzetemperatur von 200 - 28O0C spritzgegossen werden.5. A process for the production of plastic bodies with pearlescent effect according to claim 1, characterized in that 65-95% polymethacrylate, 5-35% polyethylene terephthalate glycol and optionally 0.01-5.0% auxiliaries and additives at a melt temperature of 200 - 28O 0 C injection molded.
6. Mischung enthaltend 65-95 % Polymethacrylat und 5-35 % Polyethylenterephthalatglycol gegebenenfalls 0,01-5,0 % Hilfs- und Zusatzstoffe.6. Mixture containing 65-95% polymethacrylate and 5-35% polyethylene terephthalate glycol optionally 0.01-5.0% auxiliaries and additives.
7. Verwendung von Kunststoffkörpern mit Perlglanzeffekt gemäß Anspruch 1 im Baubereich, im Automobilbereich, im Schiffsbau und Flugzeugbau. 7. Use of plastic bodies with pearlescent effect according to claim 1 in the construction sector, in the automotive sector, in shipbuilding and aircraft construction.
8. Verwendung von Kunststoffkörpern mit Perlglanzeffekt gemäß Anspruch 1 für Verpackungen, Dekorationsmaterialien, Gehäusematerialien für elektronische Geräte, Spielzeug, Büroartikel. 8. Use of plastic bodies with pearlescent effect according to claim 1 for packaging, decorative materials, housing materials for electronic devices, toys, office supplies.
EP06701003A 2005-02-17 2006-01-14 Polymethylmethacrylate with a nacreous effect Withdrawn EP1848770A1 (en)

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