EP0889778A2 - Plaque amorphe en naphtalate de polyalkylene cristallisable - Google Patents

Plaque amorphe en naphtalate de polyalkylene cristallisable

Info

Publication number
EP0889778A2
EP0889778A2 EP97914249A EP97914249A EP0889778A2 EP 0889778 A2 EP0889778 A2 EP 0889778A2 EP 97914249 A EP97914249 A EP 97914249A EP 97914249 A EP97914249 A EP 97914249A EP 0889778 A2 EP0889778 A2 EP 0889778A2
Authority
EP
European Patent Office
Prior art keywords
plate
naphthalate
polyalkylene naphthalate
pigments
temperature
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Withdrawn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
EP97914249A
Other languages
German (de)
English (en)
Inventor
Ursula Murschall
Rainer Brunow
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.)
Aventis Research and Technologies GmbH and Co KG
Original Assignee
Hoechst Research and Technology Deutschland GmbH and Co KG
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 Hoechst Research and Technology Deutschland GmbH and Co KG filed Critical Hoechst Research and Technology Deutschland GmbH and Co KG
Publication of EP0889778A2 publication Critical patent/EP0889778A2/fr
Withdrawn legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C51/00—Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/22—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of indefinite length
    • B29C43/222—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of indefinite length characterised by the shape of the surface
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07—Flat, e.g. panels
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07—Flat, e.g. panels
    • B29C48/08—Flat, e.g. panels flexible, e.g. films
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
    • B29C48/911—Cooling
    • B29C48/9135—Cooling of flat articles, e.g. using specially adapted supporting means
    • B29C48/914—Cooling drums
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
    • B29C48/90—Thermal treatment of the stream of extruded material, e.g. cooling with calibration or sizing, i.e. combined with fixing or setting of the final dimensions of the extruded article
    • B29C48/906—Thermal treatment of the stream of extruded material, e.g. cooling with calibration or sizing, i.e. combined with fixing or setting of the final dimensions of the extruded article using roller calibration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037—Other properties
    • B29K2995/0072—Roughness, e.g. anti-slip
    • B29K2995/0073—Roughness, e.g. anti-slip smooth
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds

Definitions

  • the invention relates to an amorphous plate made of at least one crystallizable polyalkylene naphthalate, the thickness of which is in the range from 1 to 20 mm.
  • the plate is characterized by very good optical and mechanical properties.
  • the invention further relates to a method for producing this plate.
  • Amorphous plates with a thickness between 1 and 20 mm are well known. These flat structures consist of amorphous, non-crystallizable thermoplastics. Typical examples of such thermoplastics that are processed into sheets are, for example, polyvinyl chloride (PVC), polycarbonate (PC) and polymethyl methacrylate (PMMA). These semi-finished products are manufactured on so-called extrusion lines (cf. Polymer Maschinentechnik, Volume II, Technologie 1, p. 136, Georg Thieme Verlag, Stuttgart, 1984). The powdered or granular raw material is melted in an extruder.
  • PVC polyvinyl chloride
  • PC polycarbonate
  • PMMA polymethyl methacrylate
  • the amorphous thermoplastics can be easily reshaped using smoothing units or other shaping tools due to the steadily increasing viscosity as the temperature decreases. After shaping, amorphous thermoplastics then have sufficient stability, ie a high viscosity, to "stand by themselves” in the calibration tool. But they are still soft enough to be shaped by the tool. The melt viscosity and inherent stiffness of amorphous thermoplastics is so high in the calibration tool that the semi-finished product does not collapse in the calibration tool before it cools down. With easily decomposable materials such. B. PVC are special processing aids in extrusion, such as. B. Processing stabilizers against decomposition and lubricants against excessive internal friction and thus uncontrollable heating necessary. External lubricants are required to prevent snagging on walls and rollers. When processing PMMA z. B. used a degassing extruder for dehumidification.
  • PMMA sheets also have extremely poor impact strength and shatter when broken or subjected to mechanical stress.
  • PMMA panels such as wood, are flammable, so that they must not be used, for example, for indoor applications or in trade fair construction.
  • PMMA and PC sheets are also not cold-formable. During cold forming, PMMA sheets break into dangerous fragments. When cold-forming PC sheets, hairline cracks and whitening occur.
  • EP-A-0 471 528 describes a method for molding an article from a polyethylene terephthalate (PET) plate.
  • the PET sheet is heat treated in a deep-drawing mold on both sides in a temperature range between the glass transition temperature and the melting temperature.
  • the molded PET sheet is taken out of the mold when the degree of crystallization of the molded PET sheet is in the range of 25 to 50%.
  • the PET sheets disclosed in EP-AO 471 528 have a thickness of 1 to 10 mm. Since the deep-drawn molded article produced from this PET sheet is partially crystalline and therefore no longer transparent, and it is the surface properties of the molded article that are determined by the deep-drawing process, the given temperatures and shapes irrelevant what optical properties (e.g. gloss, haze and light transmission) the PET sheets used have. As a rule, the optical properties of these plates are poor and need to be optimized.
  • US Pat. No. 3,496,143 describes the vacuum deep drawing of a 3 mm thick PET sheet, the crystallization of which should be in the range from 5 to 25%.
  • the crystallinity of the deep-drawn molded body is greater than 25%. No demands are made on the optical properties of these PET sheets either. Since the crystallinity of the plates used is already between 5 and 25%, these plates are cloudy and opaque.
  • the object of the present invention is to provide an amorphous plate with a thickness of 1 to 20 mm, which has both good mechanical and optical properties.
  • the good optical properties include, for example, high light transmission, high surface gloss, extremely low haze and high image sharpness (clarity).
  • the good mechanical properties include high impact strength and high breaking strength.
  • the plate according to the invention should be recyclable, in particular without loss of the mechanical properties, and also flame-retardant, so that it can also be used, for example, for interior applications and in trade fair construction.
  • an amorphous plate with a thickness in the range from 1 to 20 mm which is characterized in that it contains at least one crystallizable polyalkylene naphthalate as the main component.
  • the main component of the amorphous plate contains at least one crystallizable polylakenyl naphthalate.
  • Polyethylene naphthalate, polypropylene naphthalate and pol ⁇ butylene naphthalate are preferred, with polyethylene naphthalate (PEN) being particularly preferred.
  • the amorphous plate can be colored transparent, transparent or opaque.
  • the amorphous plate has a surface gloss, measured according to DIN 67530 (measuring angle 20 °), which is greater than 110, preferably greater than 120.
  • the light transmission, measured according to ASTM D 1003, is more than 80%, preferably more than 82% and the haze of the plate, also measured according to ASTM D 1003, is less than 15%, preferably less than 11%.
  • the image sharpness of the transparent plate which is also called Clarity, and is determined at an angle of less than 2.5 ° (ASTM D 1003), is preferably over 90% and particularly preferably over 92%.
  • the amorphous plate contains at least one soluble dye.
  • concentration of soluble dye is preferably in the range from 0.001 to 20% by weight, based on the weight of the polyalkylene naphthalate.
  • Soluble dyes are substances that are molecularly dissolved in the polymer (DIN 55949).
  • the color change as a result of the coloring of the amorphous plate is based on the wavelength-dependent absorption and / or scattering of the light. Dyes can only absorb light, not scatter, since the physical requirement for scattering is a certain minimum particle size. Coloring with dyes is a solution process. As a result of this solution process, the dye is molecularly dissolved in the PEN polymer, for example. Such coloring is referred to as transparent or translucent or translucent or opal.
  • the fat and aromatic soluble dyes are particularly preferred. These are, for example, azo and anthraquinone dyes. They are particularly suitable for coloring PEN, because due to the high glass transition temperature of PEN, the migration of the dye is restricted (literature J. Koerner: Soluble dyes in the plastics industry in "VDI-Gesellschaft Kunststofftechnik: coloring plastics, VDI-Veriag, Düsseldorf 1975).
  • Suitable soluble dyes are, for example: solvent yellow 93 a pyrazolone derivative, solvent yellow 16 a fat-soluble azo dye, fluorole green gold a fluorescent polycyclic dye, solvent red 1 an azo dye, azo dyes such as thermoplastic red BS, Sudan red BB, solvent red 138 an anthraquinone derivative, and fluorescent fluorophenane fluorophores such as fluorophenane GK, solvent blue 35 an anthraquinone dye, solvent blue a phthalocyanine dye and many others. Mixtures of two or more of these soluble dyes are also suitable.
  • the soluble dye in the desired concentration can already be metered in from the raw material manufacturer or metered into the extruder during plate manufacture.
  • the soluble dye is fully dispersed and / or dissolved in a solid carrier material.
  • the grain size and the bulk density of the masterbatch are similar to the grain size and the bulk density of the polyalkylene naphthalate, so that a homogeneous distribution and thus a homogeneous, transparent coloring can take place.
  • the surface gloss of the transparent colored plate, measured according to DIN 67530 (measuring angle 20 °) is greater than 100, preferably greater than 110, the light transmission, measured according to ASTM D 1003, is in the range from 5 to 80%, preferably in the range from 10 to 70% and the turbidity of the plate, measured according to ASTM D 1003, is in the range from 2 to 40%, preferably in the range from 3 to 35%.
  • the amorphous plate contains at least one organic and / or inorganic pigment as a colorant.
  • concentration of the colorant is preferably in the range from 0.5 to 30% by weight, based on the weight of the polyalkylene naphthalate.
  • pigments are almost insoluble in the polymer under the respective processing conditions, while dyes are soluble (DIN 55949).
  • the coloring effect of the pigments is caused by the particles themselves.
  • the term pigment is generally linked to a particle size of 0.01 ⁇ m to 1.0 ⁇ m. According to DIN 53206, a distinction is made in the definition of pigment particles between primary particles, aggregates and agglomerates.
  • the aggregates are always stored together to form agglomerates that have to be broken up during coloring, wetted by the plastic and distributed homogeneously. These simultaneous processes are called dispersion.
  • coloring with dyes is a solution process, as a result of which the dye is present in molecular solution.
  • Dyes are adequately described by their chemical structure. However, pigments of the same chemical composition can be produced and present in different crystal modifications. A typical example of this is the white pigment titanium dioxide, which can be in the rutile form and in the anatase form.
  • pigments an improvement in the properties of use can be achieved by coating, ie by post-treatment of the pigment particle surface, with organic or inorganic agents. This improvement lies in particular in facilitating the dispersion and increasing the resistance to light, weather and chemicals.
  • Typical coating agents for pigments are, for example, fatty acids, fatty acid amides, siloxanes and aluminum oxides.
  • Suitable inorganic pigments are, for example, the white pigments titanium dioxide, zinc sulfide and tin sulfide, which can optionally be coated organically and / or inorganically.
  • the titanium dioxide particles can consist of anatase or rutile, preferably predominantly rutile, which has a higher covering power than anatase. In a preferred embodiment, the titanium dioxide particles consist of at least 95% by weight of rutile. You can by a usual procedure, e.g. by the chloride or sulfate process.
  • the average particle size is relatively small and is preferably in the range from 0.10 to 0.30 ⁇ m.
  • Titanium dioxide of the type described does not produce any vacuoles within the polymer matrix during plate production.
  • the titanium dioxide particles can have a coating of inorganic oxides, as is usually used as a coating for TiO 2 white pigment in papers or paints to improve the lightfastness.
  • Ti0 2 is photoactive. When exposed to UV rays, free radicals form on the surface of the particles. These free radicals can migrate to the film-forming components of the paint, which leads to degradation reactions and yellowing.
  • the particularly suitable oxides include the oxides of aluminum, silicon, zinc or magnesium or mixtures of two or more of these compounds.
  • TiO 2 particles with a coating of several of these compounds are described, for example, in EP-A-0 044 515 and EP-A-0 078 633.
  • the coating can contain organic compounds with polar and non-polar groups.
  • the organic compounds must be sufficiently thermostable in the manufacture of the plate by extrusion of the polymer melt.
  • Preferred organic compounds are alkanols and fatty acids with 8 to 30 carbon atoms in the alkyl group, in particular fatty acids and primary n-alkanols with 12 to 24 carbon atoms, and also polydiorganosiloxanes and / or polyorganohydrogensiloxanes such as, for example, polydimethylsiloxane and polymethylhydrogensiioxane.
  • the coating on the titanium dioxide particles usually consists of 1 to 12, in particular 2 to 6 g of inorganic oxides and 0.5 to 3, in particular 0.7 to 1.5 g of organic compound, based on 100 g of titanium dioxide particles.
  • the coating is preferably applied to the particles in an aqueous suspension.
  • the inorganic oxides are made from water-soluble compounds, e.g. Alkali, in particular sodium aluminate, aluminum hydroxide, aluminum sulfate, aluminum nitrate, sodium silicate (water glass) or silica precipitated in the aqueous suspension.
  • Inorganic oxides such as Al 2 O 3 and SiO 2 are also to be understood as the hydroxides or their various dewatering stages such as oxide hydrates, without knowing their exact composition and structure.
  • the oxide hydrates for example of aluminum and / or silicon, are precipitated onto the Ti0 2 pigment, and the pigments are then washed and dried. This precipitation can thus take place directly in a suspension, such as is obtained in the manufacturing process after annealing and the subsequent wet grinding.
  • Precipitation of the oxides and / or oxide hydrate of the respective metals takes place from the water-soluble metal salts in the known pH range, for the aluminum, for example, aluminum sulfate in aqueous solution (pH less than 4) is used and in the pH range between by adding aqueous ammonia solution or sodium hydroxide solution 5 and 9, preferably between 7 and 8.5, the oxide hydrate precipitates.
  • aqueous ammonia solution or sodium hydroxide solution 5 and 9 preferably between 7 and 8.5
  • the oxide hydrate precipitates.
  • the pH of the TiO 2 suspension presented should be in the strongly alkaline range (pH greater than 8).
  • the precipitation then takes place by adding mineral acid such as sulfuric acid in the pH range from 5 to 8.
  • the suspension was stirred for a further 15 minutes to about 2 hours, the precipitated layers undergoing aging.
  • the coated product is separated from the aqueous dispersion and, after washing at elevated temperature, in particular at 70 to 110 ° C., is dried.
  • Typical inorganic black pigments are carbon black modifications, which can also be coated, carbon pigments that differ from the carbon black pigments in their higher ash content and oxidic black pigments such as iron oxide black as well as copper, chromium and iron oxide mixtures (mixed phase pigments).
  • Suitable inorganic colored pigments are oxidic colored pigments, hydroxyl-containing pigments, sulfidic pigments and chromates.
  • colored oxide pigments are iron oxide red, titanium dioxide-nickel oxide-antimony oxide mixed-phase pigments, titanium dioxide-chromium oxide-antimony oxide mixed-phase pigments, mixtures of the oxides of iron, zinc and titanium, chromium oxide iron oxide brown, spinels of the cobalt-aluminum-titanium-nickel-zinc oxide system and mixed-phase pigments based on other metal oxides.
  • Typical hydroxyl-containing pigments are, for example, oxide hydroxides of trivalent iron such as FeOOH.
  • sulfidic pigments examples include cadmium sulfide selenides, cadmium zinc sulfides, sodium aluminum silicate with sulfur bound in polysulfide form in the lattice.
  • chromates examples are the lead chromates, which can be monoclinic, rhombic and tetragonal in the crystal forms.
  • all colored pigments can uncoated as well as inorganic and / or organically coated.
  • the organic colored pigments are generally divided into azo pigments and so-called non-azo pigments.
  • Azo pigments can be monoazo pigments, diazo pigments, diazo condensation pigments, salts of azo color acids and mixtures of the azo pigments.
  • the amorphous colored plate contains at least one inorganic and / or organic pigment.
  • the amorphous plate can also contain mixtures of inorganic and / or organic pigments and additionally soluble dyes.
  • the concentration of the soluble dye is preferably in the range from 0.01 to 20% by weight, particularly preferably in the range from 0.5 to 10% by weight, based on the weight of the polyalkylene naphthalate.
  • the colorants inorganic and / or organic pigments and optionally dyes
  • the colorants can be metered in at the desired concentration at the raw material manufacturer or metered into the extruder during plate manufacture.
  • the addition of the color additive (s) via the masterbatch technology or via the solid pigment preparation is particularly preferred.
  • the organic and / or inorganic pigment and optionally the soluble dye are fully dispersed in a solid carrier material.
  • Suitable carriers are certain resins, the polymer to be colored itself or other polymers which are sufficiently compatible with the polyalkylene naphthalate. It is important that the grain size and the bulk density of the solid pigment preparation or the masterbatch are similar to the grain size and the bulk density of the polylactic naphthalate, so that a homogeneous distribution and thus coloring can take place.
  • the surface gloss of the colored plate measured according to DIN 67530 (measuring angle 20 °) is preferably greater than 90 and the light transmission, measured according to ASTM D 1003, is preferably less than 5%.
  • the colored plate has a muted, homogeneous look.
  • the amorphous plate further contains at least one UV stabilizer as light stabilizer, the concentration of the UV stabilizer preferably being between 0.01 and 5% by weight, based on the weight of the polyalkylene naphthalate.
  • Light especially the ultraviolet portion of solar radiation, i.e. H. the wavelength range from 280 to 400 nm initiates degradation processes in thermoplastics, as a result of which not only the visual appearance changes as a result of color change or yellowing, but also the mechanical-physical properties are adversely affected.
  • polyalkylene naphthalates begin to absorb UV light below 360 nm, their absorption increases considerably below 320 nm and is very pronounced below 300 nm. The maximum absorption is between 280 and 300 nm.
  • UV stabilizers or UV absorbers as light stabilizers are chemical compounds that can intervene in the physical and chemical processes of light-induced degradation. Soot and other pigments can partially protect against light. However, these substances are unsuitable for transparent plates because they lead to discoloration or color change. For transparent, amorphous plates, only organic and organometallic compounds are suitable, which give the thermoplastic to be stabilized no or only an extremely small color or color change.
  • Suitable UV stabilizers as light stabilizers are, for example, 2-hydroxybenzophenones, 2-hydroxybenzotriazoles, organo-nickel compounds, salicylic acid esters, cinnamic acid ester derivatives, resorcinol monobenzoates, oxalic acid anilides, hydroxybenzoic acid esters, sterically hindered amines and triazines, the 2-hydroxybenzotriazoles being preferred.
  • the amorphous plate according to the invention contains, as the main component, a crystallizable polyethylene naphthalate and 0.01% by weight to 5.0% by weight of 2- (4,6-diphenyl-1,3,5-triazine-2 -yl) -5- (hexyl) oxy-phenol or 0.01% by weight to 5.0% by weight of 2,2'-methylene-bis (6- (2H-benzotriazol-2-yl) -4 - (1, 1, 3,3-tetramethylbutyl) phenol
  • mixtures of these two UV stabilizers can also be used or mixtures of at least one of these two UV stabilizers with other UV stabilizers, the total concentration of light stabilizer preferably being between 0.01% by weight and 5.0% by weight, based on the weight of crystallizable polyethylene naphthalate .
  • crystallizable polyalkylene naphthalate is understood to mean crystallizable polyalkylene naphthalate homopolymers, crystallizable polyalkylene naphthalate copolymers, crystallizable polyalkylene naphthalate compounds, crystallizable polyalkylene naphthalate recyclate and other variations of crystallizable polyalkylene naphthalate.
  • Preferred copolymers or compounds are mixtures of polyalkylene naphthalates and polyalkylene terephthalates, in particular mixtures of polyethylene naphthalate (PEN) and polyethylene terephthalate (PET).
  • PEN polyethylene naphthalate
  • PET polyethylene terephthalate
  • amorphous plate is understood to mean those plates which, although the crystallizable thermoplastic used preferably has a crystallinity of between 10 and 65%, are not crystalline. Not crystalline, i.e. H. essentially amorphous means that the degree of crystallinity is generally below 5%, preferably below 2% and particularly preferably 0%.
  • the polyalkylene naphthalate plate according to the invention is flame-retardant and flame-retardant, so that it is suitable, for example, for interior applications and in trade fair construction. Furthermore, the plate according to the invention can be easily recycled without environmental pollution and without loss of the mechanical properties, which makes it suitable, for example, for use as short-lived advertising slider or other promotional items.
  • the amorphous plate according to the invention contains crystallizable polyethylene naphthalate as the main constituent.
  • a n occurs Charpy (measured according to ISO 179 / 1D) on the board preferably no fracture.
  • the notched impact strength a k according to Izod (measured according to ISO 180 / 1A) of the plate is preferably in the range from 2.0 to 12.0 kJ / m 2 , particularly preferably in the range from 3.0 to 8.0 kJ / m 2nd
  • Polyethylene naphthalates with a crystallite melting point T m measured with DSC (differential scanning calorimetry) with a heating rate of 10 ⁇ C / min, from 240 ° C to 300 ° C, preferably from 250 ° C to 290 ° C, with a crystallization temperature range T c between 100 ° C and 290 ° C, a glass transition temperature T fl between 100 ⁇ C and 140 ° C and with a density, measured according to DIN 53479, of 1, 30 to 1, 45 g / cm 3 and a crystallinity between 10% and 65 % represent preferred polymers as starting materials for the production of the plate.
  • DSC differential scanning calorimetry
  • the standard viscosity SV (DCE) of the polyethylene naphthalate, measured in dichloroacetic acid according to DIN 53728, is between 600 and 1400, preferably between 750 and 1250 and particularly preferably between 800 and 1100.
  • the intrinsic viscosity IV (DCE) is calculated as follows from the standard viscosity SV (DCE):
  • the bulk density measured according to DIN 53466, is preferably between 0.75 kg / dm 3 and 1.0 kg / dm 3 , and particularly preferably between 0.80 kg / dm 3 and 0.90 kg / dm 3 .
  • the polydispersity of the polyethylene naphthalate M w / M n measured by GPC is preferably between 1.5 and 4.0 and particularly preferably between 2.0 and 3.5.
  • the amorphous plate according to the invention can be produced, for example, by an extrusion process in an extrusion line.
  • Such an extrusion line is shown schematically in FIG. 1. It essentially comprises an extruder (1) as a plasticizing system, a slot die (2) as a tool for shaping, a smoothing unit / calender (3) as a calibration tool, a cooling bed (4) and / or a roller conveyor (5) for after-cooling, a roller take-off (6), a separating saw (7), a side cutting device (9), and optionally a stacking device (8).
  • the process is characterized in that the polyalkylene naphthalate is optionally dried, then melted in the extruder, optionally together with the soluble dye, the colorant and / or the UV stabilizer, the melt is shaped through a nozzle and then calibrated, smoothed and cooled in the calender before you get the plate to size.
  • the soluble dye, the colorant and / or the UV stabilizer are preferably added using masterbatch technology.
  • the soluble dye, the colorant and / or the UV stabilizer are combined in one solid carrier material fully dispersed.
  • Suitable carrier materials are certain resins, the polyalkylene naphthalate itself or other polymers which are sufficiently compatible with the polyalkylene naphthalate.
  • the PEN is dried before extrusion, preferably for 4 to 6 hours at 160 to 180 ° C.
  • the PEN and optionally the additive masterbatches are then melted in the extruder.
  • the temperature of the PEN melt is preferably in the range from 250 to 320 ° C., the temperature of the melt being able to be set essentially both by the temperature of the extruder and by the residence time of the melt in the extruder.
  • the melt then leaves the extruder through a nozzle.
  • This nozzle is preferably a slot die.
  • the PEN melted by the extruder and shaped by a slot die is calibrated by smoothing calender rolls, i.e. H. intensely chilled and smoothed.
  • the calender rolls can for example be arranged in an I, F, L or S shape.
  • the PEN material can then be cooled on a roller conveyor, cut to the side, cut to length and finally stacked.
  • the thickness of the PEN plate is essentially determined by the take-off, which is arranged at the end of the cooling zone, the cooling (smoothing) rolls coupled with it in terms of speed and the conveying speed of the extruder on the one hand and the distance between the rolls on the other hand.
  • the take-off which is arranged at the end of the cooling zone, the cooling (smoothing) rolls coupled with it in terms of speed and the conveying speed of the extruder on the one hand and the distance between the rolls on the other hand.
  • Both single-screw and twin-screw extruders can be used as extruders.
  • the slot die preferably consists of the separable tool body, the lips and the dust bar for flow regulation across the width.
  • the control bar can be bent using tension and compression screws. The thickness is adjusted by adjusting the lips. It is important to ensure that the temperature of the PEN and lip is even, otherwise the PEN melt will flow out to different thicknesses through the different flow paths.
  • the calibration tool, d. H. the smoothing calender gives the PEN melt the shape and dimensions. This is done by freezing below the glass transition temperature by cooling and smoothing. Deformation should no longer occur in this state, since otherwise surface defects would occur in this cooled state. For this reason, the calender rolls are preferably driven together. The temperature of the calender rolls must be lower than the crystallite melting temperature in order to avoid sticking of the PEN melt.
  • the PEN melt leaves the slot die at a temperature of 240 to 300 ° C.
  • the first smoothing-cooling roller has a temperature between 50 ° C and 80 ° C depending on the output and plate thickness. The second, somewhat cooler roller cools the second or other surface.
  • the post-cooling device lowers the temperature of the PEN plate to almost room temperature. After-cooling can be done on a roll board.
  • the speed of the take-off should be exactly matched to the speed of the quayander rollers in order to avoid defects and thickness fluctuations.
  • a separating saw as a cutting device, the side trimming, the stacking system and a control point can be located in the extrusion line for the production of PEN plates as additional devices.
  • the side or edge trimming is advantageous because the thickness in the edge area can be uneven under certain circumstances. The thickness and appearance of the plate are measured at the control point.
  • the amorphous polyalkylene naphthalate plate according to the invention is excellently suitable for a large number of different uses, for example for interior cladding, for trade fair construction and trade fair articles, as displays, for signs, for protective glazing of machines and vehicles, in the lighting sector, in the store. and shelf construction, as a promotional item, as a menu card stand, as a basketball goal board, as a room divider and for outdoor applications, for example as a glass replacement.
  • the surface gloss is determined in accordance with DIN 67 530.
  • the reflector value is measured as an optical parameter for the surface of a plate. Based on the standards ASTM-D 523-78 and ISO 2813, the angle of incidence was set at 20 °. A light beam hits the flat test surface at the set angle of incidence and is reflected or scattered by it. The light rays striking the photoelectronic receiver are displayed as a proportional electrical quantity. The measured value is dimensionless and must be specified together with the angle of incidence.
  • the light transmission is measured with the "Hazegard plus" measuring device in accordance with ASTM 1003.
  • Haze is the percentage of the transmitted light that deviates by more than 2.5 ° on average from the incident light beam.
  • the image sharpness is determined at an angle of less than 2.5 °.
  • the haze and clarity are measured using the "Hazegard plus" measuring device in accordance with ASTM 1003.
  • the degree of whiteness is determined using the electrical reflectance photometer "ELREPHO” from Zeiss, Oberkochem (DE), standard illuminant C, 2 ° normal observer.
  • the whiteness is defined as
  • WG whiteness
  • RY, RZ, RX corresponding reflection factors when using the Y, Z and X color measurement filter.
  • a barium sulfate compact (DIN 5033, part 9) is used as the white standard.
  • the surface defects are determined visually.
  • This size is determined according to ISO 179/1 D.
  • the notched impact strength or strength a k according to Izod is measured according to ISO 180/1 A.
  • the density is determined according to DIN 53479.
  • the standard viscosity SV (DCE) is based on DIN 53726 in
  • the intrinsic viscosity (IV) is calculated as follows from the standard viscosity (SV)
  • the thermal properties such as crystallite melting point T m , crystallization temperature range T c , post- (cold) crystallization temperature T CN and glass transition temperature T g are measured by differential scanning calorimetry (DSC) at a heating rate of 10 ° C / min.
  • the molecular weights M w and M n and the resulting polydispersity M w / M n are measured by means of gel permeation chromatography (GPC). Weathering (both sides), UV stability:
  • UV stability is tested according to the test specification ISO 4892 as follows
  • Xenon lamp inner and outer filter made of borosilicate
  • the color change of the samples after artificial weathering is measured with a spectrophotometer according to DIN 5033.
  • the yellowness index G is the deviation from the colorlessness in the "yellow” direction and is measured in accordance with DIN 6167. Yellow value G values of ⁇ 5 are not visually visible.
  • the polyethylene naphthalate from which the transparent plate is made has a standard viscosity SV (DCE) of 810, which corresponds to an intrinsic viscosity IV (DCE) of 0.65 dl / g.
  • DCE intrinsic viscosity IV
  • the moisture content is ⁇ 0.2% and the density (DIN 53479) is 1.33 g / cm 3 .
  • the crystallinity is 15%, the crystallite melting point according to DSC measurements being 270 ° C.
  • the polydispersity M w / M n of the polyethylene naphthalate is 2.14.
  • the glass transition temperature is 1 19 "C.
  • the polyethylene naphthalate is dried in a dryer at 170 ° C for 5 hours and then extruded in a single-screw extruder at an extrusion temperature of 286 ° C through a slot die onto a smoothing calender, the rollers of which are arranged in an S-shape, and into a 2 mm thick plate smoothed.
  • the first calender roll has a temperature of 65 ⁇ C and the subsequent rollers each have a temperature of 58 ° C.
  • the speed of the take-off and the calender rolls is 4.0 m / min.
  • the transparent, 2 mm thick PET plate is trimmed at the edges with separating saws, cut to length and stacked.
  • the transparent PEN sheet produced has the following property profile:
  • Polyethylene naphthalate is used, which has the following properties:
  • the extrusion temperature is 280 ° C.
  • the first calender roll has a temperature of 66 ° C and the subsequent rolls have a temperature of 60 ° C.
  • the speed of the take-off and the calender rolls is 1.9 m / min.
  • the transparent PEN sheet produced has the following property profile:
  • a transparent plate is produced.
  • the extrusion temperature is 275 ° C.
  • the first calender roll has a temperature of 57 ° C and the subsequent rolls have a temperature of 50 ° C.
  • the speed of the take-off and the calender rolls is 1.7 m / min.
  • the PEN board produced has the following property profile:
  • a transparent plate is produced. 70% polyethylene naphthalate from Example 2 are mixed with 30% recyclate from this polyethylene naphthalate.
  • the transparent PEN sheet produced has the following property profile:
  • a 6 mm thick, transparently colored, amorphous plate is produced, the main component of which is the polyethylene naphthalate from Examples 2 and 2 wt. % of the soluble dye S michell Rot 138, an anthraquinone derivative from BASF ("Thermoplast G) contains.
  • the soluble dye Solventrot 138 is added in the form of a masterbatch.
  • the masterbatch is composed of 20% by weight of the solvent red 138 dye and 80% by weight of the polyethylene naphthalate described above.
  • the first calender roll has a temperature of 66 ° C. and the subsequent rolls each have a temperature of 60 ° C.
  • the speed of the take-off and the calender rolls is 2.9 m / min.
  • the transparently colored, 6 mm thick PEN plate is trimmed at the edges with separating saws, cut to length and stacked.
  • the manufactured, red-transparent colored PEN plate has the following property professional !:
  • a 3 mm thick, white-colored, amorphous plate is produced, which contains the polyethylene naphthalate from Example 2 and 6% by weight of titanium dioxide as the main constituent.
  • the titanium dioxide is of the rutile type and is coated with an inorganic coating made of Al 2 0 3 and with an organic coating made of polydimethylsiloxane.
  • the titanium dioxide has an average particle diameter of 0.2 ⁇ m.
  • the titanium dioxide is added in the form of a master batch.
  • the masterbatch is composed of 30% by weight of the titanium dioxide described and 70% by weight of the polyethylene naphthalate described.
  • Prior to extrusion are wt .-% of the polyethylene naphthalate 80 and 20% by weight of the titanium dioxide masterbatch for 5 hours at 170 C ⁇ dried in a dryer and then in a single screw extruder at an extrusion temperature of 286 ° C through a slot die onto a polishing calender, whose rollers are arranged in an S-shape, extruded and smoothed into a 3 mm thick plate.
  • the first Kaianderwalze has a temperature of 73 ° C and the subsequent rolls each have a temperature of 67 C C.
  • the speed of the draw-off and of the calender rolls is 6.5 m / min.
  • the white, 3 mm thick PEN plate is trimmed at the edges with separating saws, cut to length and stacked.
  • the white colored plate produced shows the following properties:
  • a 3 mm thick, transparent, amorphous plate is produced, which as
  • the main component is the polyethylene naphthalate from Example 2 and 1.0% by weight of the
  • UV stabilizer contains 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5- (hexyl) oxyphenol® (Tinuvin 1577 from Ciba-Geig ⁇ ).
  • Tinuvin 1577 has a melting point of 149 ° C and is thermally stable up to approx. 330 ° C.
  • UV stabilizer For the purpose of homogeneous distribution, 1.0% by weight of the UV stabilizer is incorporated directly into the polyethylene naphthalate at the raw material manufacturer.
  • the polyethylene naphthalate is dried for 5 hours at 170 ° C in a dryer and then extruded in a single-screw extruder at an extrusion temperature of 286 ° C through a slot die onto a smoothing calender, the rollers of which are arranged in an S-shape, and extruded to form a 3 mm thick plate smoothed.
  • the first calender roll has a temperature of 73 ° C and the subsequent rollers each have a temperature of 67 ° C.
  • the speed of the take-off and the calender rolls is 6.5 m / min.
  • the transparent, 3 mm thick PEN plate is trimmed at the edges with separating saws, cut to length and stacked.
  • the transparent, amorphous PEN plate produced has the following
  • the PEN plate After 1000 hours of weathering per side with Atlas Ci 65 Weather Ometer, the PEN plate shows the following properties:

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  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Laminated Bodies (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)
  • Reinforced Plastic Materials (AREA)

Abstract

L'invention concerne une plaque amorphe en naphtalate de polyalkylène, d'une épaisseur comprise entre 1 et 20 mm, qui se caractérise en ce qu'elle contient pour principal constituant au moins un naphtalate de polyalkylène. L'invention concerne par ailleurs un procédé permettant de la produire.
EP97914249A 1996-03-20 1997-03-13 Plaque amorphe en naphtalate de polyalkylene cristallisable Withdrawn EP0889778A2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19610956A DE19610956A1 (de) 1996-03-20 1996-03-20 Amorphe Platte aus einem kristallisierbaren Polyalkylennaphthalat
DE19610956 1996-03-20
PCT/EP1997/001314 WO1997034759A2 (fr) 1996-03-20 1997-03-13 Plaque amorphe en naphtalate de polyalkylene cristallisable

Publications (1)

Publication Number Publication Date
EP0889778A2 true EP0889778A2 (fr) 1999-01-13

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EP (1) EP0889778A2 (fr)
JP (1) JP2000507285A (fr)
KR (1) KR20000064699A (fr)
CN (1) CN1216950A (fr)
AU (1) AU2156897A (fr)
BR (1) BR9708138A (fr)
DE (1) DE19610956A1 (fr)
PL (1) PL329028A1 (fr)
TR (1) TR199801858T2 (fr)
TW (1) TW413689B (fr)
WO (1) WO1997034759A2 (fr)

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Publication number Priority date Publication date Assignee Title
CA3018516A1 (fr) 2017-09-26 2019-03-26 Davis-Standard, Llc Appareil de coulage destine a la fabrication d'une pellicule de polymere
US10661492B2 (en) 2017-11-17 2020-05-26 Purple Innovation, Llc Molding systems, mold extractor systems, and related methods
CA3079153C (fr) 2019-06-25 2022-08-02 Omachron Intellectual Property Inc. Appareil de tirage dote d`un bras de statif mobile
CN220052780U (zh) * 2022-12-17 2023-11-21 青岛新大成塑料机械有限公司 膜片用挤出模头组件及挤出生产线

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US4175147A (en) * 1976-10-05 1979-11-20 Allied Chemical Corporation Method to reduce deposits of terephthalic acid on cooling rolls during sheet extrusion of amorphous polyethylene terephthalate
US4996269A (en) * 1987-03-13 1991-02-26 The Goodyear Tire & Rubber Company Polyester composition which is particularly suitable for use in thermoforming thin walled articles
JPH04142275A (ja) * 1990-09-26 1992-05-15 Mitsui Toatsu Chem Inc 耐熱性エアゾール容器
JPH0639895A (ja) * 1992-07-23 1994-02-15 Unitika Ltd ポリエチレンナフタレート樹脂強化シート
JPH0641330A (ja) * 1992-07-23 1994-02-15 Teijin Ltd 熱成形用シート及び熱成形体

Non-Patent Citations (1)

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Title
See references of WO9734759A2 *

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Publication number Publication date
DE19610956A1 (de) 1997-09-25
WO1997034759A2 (fr) 1997-09-25
CN1216950A (zh) 1999-05-19
KR20000064699A (ko) 2000-11-06
AU2156897A (en) 1997-10-10
TW413689B (en) 2000-12-01
WO1997034759A3 (fr) 1997-10-30
TR199801858T2 (xx) 1998-12-21
JP2000507285A (ja) 2000-06-13
PL329028A1 (en) 1999-03-01
BR9708138A (pt) 1999-07-27

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