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WO1998009799A1 - Amorphous, transparent, crystallisable plate and a moulded body produced therefrom with a high and uniform dimensional stability when exposed to heat - Google Patents

Amorphous, transparent, crystallisable plate and a moulded body produced therefrom with a high and uniform dimensional stability when exposed to heat Download PDF

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Publication number
WO1998009799A1
WO1998009799A1 PCT/EP1997/004689 EP9704689W WO9809799A1 WO 1998009799 A1 WO1998009799 A1 WO 1998009799A1 EP 9704689 W EP9704689 W EP 9704689W WO 9809799 A1 WO9809799 A1 WO 9809799A1
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WO
WIPO (PCT)
Prior art keywords
plate
amorphous
heat
polyethylene terephthalate
crystallization
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.)
Ceased
Application number
PCT/EP1997/004689
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German (de)
French (fr)
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
Aventis Research and Technologies GmbH and Co KG
Hoechst Research and Technology Deutschland GmbH and Co KG
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Filing date
Publication date
Application filed by Aventis Research and Technologies GmbH and Co KG, Hoechst Research and Technology Deutschland GmbH and Co KG filed Critical Aventis Research and Technologies GmbH and Co KG
Priority to AU46190/97A priority Critical patent/AU4619097A/en
Publication of WO1998009799A1 publication Critical patent/WO1998009799A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing 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
    • 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
    • B29C51/002—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 characterised by the choice of material
    • 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
    • B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
    • B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
    • B29C35/0805—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation
    • B29C2035/0822—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation using IR radiation
    • 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
    • B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
    • 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
    • B29K2995/0041—Crystalline

Definitions

  • the invention relates to a plate which contains a crystallizable thermoplastic as the main component, a molded article which can be produced from this amorphous plate, a process for its production and its use
  • Amorphous plates made of a crystallizable thermoplastic become dimensionally stable at relatively low temperatures.
  • amorphous objects for example made of amorphous polyethylene terephthalate (PET) material, become dimensionally unstable at temperatures of about 70 ° C., so that it is recommended that such objects not have temperatures of Expose above 65 ° C. It is known that increasing the degree of crystallization increases the temperature stability
  • thermoforming an object from a layer of PET material It is known to thermoform an object from a layer of PET material and to crystallize the object during thermoforming, which increases the heat resistance.
  • US Pat. No. 3,496,143 describes a method for thermoforming a PET plate using a deep-drawing device
  • the PET plate has a thickness of 3 mm and an area of 370 mm x 280 mm
  • the US document requires that the PET sheet should have an initial degree of installation of 5% to 25%.
  • the process requires that the PET sheet be subjected to a lengthy heat treatment before being formed in the vacuum mold still in the mold, subjected to further heat treatment.
  • the plate is held in the mold until the degree of crystallization of the molded plate is greater than 25%.
  • the patent indicates that the molded article is at a temperature of 160 ° C and 60 minutes remains dimensionally stable
  • a disadvantage of the process of US Pat. No. 3,496,143 is that no precise and well-shaped objects can be produced, since the starting plate already has a degree of crystallization of 5% to 25% and can hardly be shaped.
  • the objects are not homogeneously crystallized and the amorphous regions which are still present only remain dimensionally stable up to approximately 70 ° C.
  • the proposed method with the proposed plate with a degree of crystallization of 5 to 25% is extremely uneconomical in terms of time.
  • EP-A-0 471 528 (Polysheet Ireland Limited) describes a method and apparatus for molding an article from a PET sheet so that the molded article is at temperatures above 70 ° C and preferably up to 200 ° C remains dimensionally stable.
  • this method can only produce objects whose light transmission fluctuates greatly, which is a sign that the object is incomplete and unevenly crystallized. Likewise, the dimensional stability under heat fluctuates in accordance with the fluctuating degree of crystallization.
  • the object of the present invention is therefore to provide a plate made of an amorphous, crystallizable thermoplastic, and an object formed therefrom with a uniform degree of crystallization, a homogeneous light transmission and a homogeneous heat resistance. Furthermore, the shaped object is to be distinguished by a homogeneous, glossy surface, a homogeneous cloudiness and by economical production.
  • a uniform degree of crystallization means that the degree of crystallization of the shaped object is greater than 20% and less than 60%, preferably greater than 30% and less than 50%, and that the degree of crystallization within a shaped object is not more than 10% fluctuates in crystallinity.
  • Uniform light transmission (measured according to ASTM D 1003) is understood to mean that the light transmission, depending on the wall thickness of the shaped object, is less than 50%, preferably less than 40% and particularly preferably less than 30%. The light transmission within the shaped object must not exceed 10 units fluctuate
  • the heat resistance of the molded article should be homogeneous in all areas at a high 100 ° C, preferably at a high 120 ° C and particularly preferably at a high 140 C
  • the heat resistance should not fluctuate more than 20 ° C within the molded article
  • a homogeneous, glossy surface is understood to mean that the surface gloss of the shaped object on the surface which does not come into contact with the deep-drawing mold, measured in accordance with DIN 67530 (measuring angle 20 °) at 70, preferably at 80 and particularly preferably at 90
  • the surface gloss should not fluctuate more than 20 gloss points on this surface
  • Homogeneous haze is understood to mean that the haze of the shaped article, measured according to ASTM D 1003, is more than 50%, preferably more than 60% and particularly preferably more than 70%. The haze should not fluctuate more than 10 cloud points within the shaped article
  • the planned item should have an excellent chemical resistance
  • a transparent, amorphous plate with a thickness in the range of 1 to 20 mm, which contains at least one crystallizable thermoplastic as the main component, and is characterized in that the plate is characterized by at least one homogeneously distributed nucleating agent for initiating crystallization during the thermoforming process and to increase the installation speed during the thermoforming process, so that after the thermoforming process, a crystallized article with the required property profile results.
  • the transparent, amorphous plate contains at least one crystallizable thermoplastic as the main component.
  • Suitable crystallizable or semi-crystalline thermoplastics are, for example, polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polybutylene naphthalate, cycloolefin homopolymers and cycloolefin copolymers and mixtures of these thermoplastics, polyethylene terephthalate being particularly preferred.
  • the transparent, amorphous plate also contains at least one nucleating agent, wherein the concentration of the nucleating agent can vary widely depending on the type of nucleating agent.
  • Polymers with a low to medium crystal growth rate like the thermoplastics mentioned respond very well to the so-called homogeneous, heterogeneous, athermal and / or spontaneous nucleation (nucleation) with the help of foreign substances - the nucleating agents.
  • thermoforming leads to the amorphous Thermoplastics with extremely heated molds and a lot of heat - to accelerate the crystallization - to partially crystalline finished parts with a strongly fluctuating degree of crystallization and strongly fluctuating properties such as light transmission, turbidity, surface gloss and heat resistance.
  • the finished parts are very difficult to remove from the mold and are sometimes too soft.
  • inert, insoluble additives, organic compounds with or without an inert additive and polymeric compounds with or without an inert additive as nucleating agents in these crystallizable thermoplastics can overcome these difficulties in deep-drawing.
  • the added nucleating agent is subject to the requirements that it must not lead to crystallization in the plate during plate production in the extrusion line with relatively rapid cooling. It is essential to the invention that the plate must be amorphous. In the case of plates which only have a low crystallization of more than 5%, thermoforming to a crystallized object proves to be inadequate and very time-consuming, since the crystalline components first have to be melted during deep-drawing, which requires a lot of time and energy.
  • the nucleating agent in the thermoforming process must increase the rate of crystallization and ensure that numerous small spherulites are quickly formed.
  • Suitable nucleating agents are, for example, inert, mineral fillers such as silicates with an average particle size of less than 5 ⁇ m and talc, clay, kaolin, mica with average particle sizes of less than 6 ⁇ m, metal oxides such as silicon dioxide, titanium dioxide and magnesium oxide, carbonates and sulfates, preferably of alkaline earth metals , Boron nitride and sodium fluoride with average particle diameters of less than 4 ⁇ m.
  • mineral fillers such as silicates with an average particle size of less than 5 ⁇ m and talc, clay, kaolin, mica with average particle sizes of less than 6 ⁇ m
  • metal oxides such as silicon dioxide, titanium dioxide and magnesium oxide
  • carbonates and sulfates preferably of alkaline earth metals
  • Boron nitride and sodium fluoride with average particle diameters of less than 4 ⁇ m.
  • Organic compounds are also suitable on their own or with insoluble, inert solids such as, for example, montan wax, montan ester salts, salts of mono- and polycarboxylic acids, epoxides and alkali metal aryl and alkylsulfonates, and also polymeric compounds alone or with insoluble, inert solids, such as polyethylene, polypropylene, polyamides Poly-4-methylpentene-1, polymethylbutene-1, copolymers of ethylene with unsaturated carboxylic acid residues, ionic copolymers of ethylene with salts of unsaturated carboxylic acids, copolymers of styrene derivatives with conjugated dienes, the crystallizable thermoplastic itself with an essential lower or a substantially higher intrinsic viscosity, oxidatively degraded polymers, regranulate from the crystallizable thermoplastic and mixtures of these nucleating agents.
  • insoluble, inert solids such as, for example, montan wax, montan ester
  • the transparent, amorphous plate according to the invention contains, as the main component, a crystallizable polyethylene terephthalate, 1 to 40% by weight.
  • a crystallizable polyethylene terephthalate 1 to 40% by weight.
  • the amorphous plate in addition to the crystallizable polyethylene terephthalate, the regrind from the crystallizable polyethylene terephthalate as nucleating agent, can also contain mixtures of the two inorganic nucleating agents, the total concentration of inorganic nucleating agent preferably between 0.01% by weight and 3.0% by weight. -% is based on the weight of the crystallizable polyethylene terephthalate.
  • the intrinsic viscosity of the regrind from the crystallizable thermoplastic is lower than the intrinsic viscosity of the crystallizable polyethylene terephthalate itself, which is contained as the main component in the amorphous plate.
  • Polyethylene terephthalate 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 280 ° C, preferably from 250 ° C to 270 ° C, with a crystallization temperature range T c between 75 ° C and 280 ° C, a glass transition temperature T between 65 ° C and 90 ° C and with a density, measured according to DIN 53479, of 1, 30 to 1, 45 g / cm 3 and a crystallinity between 25% and 65% provide as starting materials for the production of Plate preferred polymers.
  • DSC differential scanning calorimetry
  • the standard viscosity SV (DCE) of the polyethylene terephthalate, measured in dichloroacetic acid according to DIN 53728, is between 600 and 1800, preferably between 700 and 1250 and particularly preferably between 800 and 1 200.
  • the intrinsic viscosity IV (DCE) is calculated 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 M ⁇ M p of the polyethylene terephthalate measured by means of gel permeation chromatography is preferably between 1.5 and 4.0 and particularly preferably between 2.0 and 3.5.
  • crystallizable polyethylene terephthalate means: crystallizable polyethylene terephthalate homopolymers, crystallizable polyethylene terephthalate copolymers, crystallizable polyethylene terephthalate compounds, crystallizable polyethylene terephthalate recyclate and other variations of crystallizable polyethylene terephthalate.
  • amorphous plate is understood to mean plates which, although the crystallizable thermoplastic used preferably has a crystallinity of between 25 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 plate according to the invention can be thermoformed on a conventional vacuum thermoforming machine with upper and lower heating to form a homogeneously crystallized object. It is essential that the molding tool is heated to temperatures of at least 100 ° C., preferably at least 120 ° C., for heating of the mold, in addition to heated oil, it is also possible, for example, to use electrically operated cassette heaters or the like.
  • the plate temperature should be below 140 ° C., preferably below 130 ° C. and particularly preferably below 120 ° C.
  • radiant heaters are suitable as a heat source for heating the plate to the preform temperature and for crystallizing the shaped object, but that infrared radiators with a wavelength of large 2000 nm provide a higher installation speed and an even higher and more homogeneous degree of crystallization, which also has a positive effect on the other physical properties such as light transmission, haze, surface gloss, heat resistance, chemical resistance and mechanical properties
  • the light transmission of the amorphous plate according to the invention is less than 10%, that is to say the absorption is extremely high in this wavelength range, which means that radiation with these wavelengths is converted into heat during deep drawing, as a result of which the crystallization is initiated and continued homogeneously with the participation of the nucleating agents
  • the deep-drawing process comprises the steps of heating with a heat source, vacuum forming under the action of heat, heat treatment, cooling and subsequent demolding
  • the amorphous PET plate according to the invention which contains the nucleating agents described contains is subjected to this deep-drawing process, whereby radiant heaters or other heating elements can serve as the heat source, but preferably infrared radiators with wavelengths of large 2000 nm are used
  • the already formed, still essentially amorphous and still substantially transparent layer is held in the mold under vacuum and, depending on the plate thickness, is preferably heat-treated for 30 seconds to 6 minutes at temperatures preferably in the range from 100 to 200 ° C., for which purpose preferably infrared radiators with wavelengths of larger 2000 nm are used
  • temperatures preferably in the range from 100 to 200 ° C., for which purpose preferably infrared radiators with wavelengths of larger 2000 nm are used
  • the transparent object turns milky white, ie the light transmission of the originally amorphous, transparent plate decreases homogeneously from about 90% due to the onset of crystallization and assumes values that are less than 50 %, preferably less than 40% and particularly preferably less than 30%, after the crystallization has taken place, the person skilled in the art being able to set the desired degree of crystallization via the light transmission which can be visually observed and / or measured by measurement technology, the shaped object is cooled and removed from the mold
  • the crystallized object thermoformed from the amorphous, transparent PET plate equipped with nucleating agents has a degree of crystallization from 20% to 60%, preferably from 30% to 50% and particularly preferably from 35% to 45% due to the nucleating agents used, which Initiate crystallization homogeneously and ensure that small, numerous spherulites are formed, the crystallization within the shaped object is extremely homogeneous and fluctuates less than 10 units in the degree of crystallization
  • the heat resistance of the molded article is homogeneous in all areas and greater than 100 ° C, preferably greater than 120 ° C, particularly preferably greater than 140 ° C and in particular greater than 160 ° C
  • the light transmission measured according to ASTM D 1003, by means of which the degree of crystallization can be set, is of course homogeneous and is below 50%, preferably below 40% and particularly preferably below 30%, since the light transmission depends on the degree of crystallization but also on the wall thickness of the molded Depends on the body, the light transmission is particularly less than 20% for wall thicknesses of large 3 mm
  • the shaped, crystallized object has a surface gloss on the surface that does not come into contact with the deep-drawing mold, measured in accordance with DIN 67530 (measuring angle 20 °) of greater than 70, preferably greater than 80, particularly preferably greater than 90 and in particular greater than 95
  • the haze of the shaped object measured in accordance with ASTM D 1003, is generally above 50%, preferably above 60% and particularly preferably above 70%. Since the haze, like the light transmission, depends not only on the degree of crystallization but also on the wall thickness of the shaped body, the haze is included Wall thicknesses of large 3 mm over 80%
  • the shaped and crystallized object according to the invention shows an even higher chemical resistance than the amorphous, transparent plate according to the invention
  • the tensile modulus measured in accordance with ISO 527-1, 2, is below 3600 MPa, preferably below 3400 MPa, which is further evidence that the crystallization is homogeneous and that numerous, small spherulites are due to the used Have formed nucleating agent, ie the object is not brittle despite crystallization
  • the nucleating agent can be metered in at the thermoplastic raw material manufacturer or metered into the extruder during plate production.
  • the addition of the nucleating agent via masterbatch technology is particularly preferred.
  • the nucleating agent is fully dispersed in a solid carrier material.
  • Certain resins, the polyethylene terephthalate itself or other polymers which are sufficiently compatible with the polyethylene terephthalate, are suitable as carrier material.
  • the grain size and the bulk density of the masterbatch is similar to the grain size and the bulk density of the polyethylene terephthalate, so that a homogeneous distribution and thus a homogeneous nucleation and crystallization can take place.
  • the crystallized object according to the invention is suitable for a large number of different applications, for example for trade fair construction and trade fair articles, for chemical and transport containers, for sanitary articles, and in shop and shelf construction.
  • the surface gloss is determined in accordance with DIN 67530.
  • the reflector value is measured as the 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 proportional electrical values. 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 sharpness of the image is determined at an angle of less than 2.5 °
  • the heat resistance is called HDT B (Heat Deflection Temperature)
  • the Vicat softening temperature is measured at 50 N load according to ISO 306 Density:
  • the density is determined according to DIN 53479.
  • the standard viscosity SV (DCE) is measured based on DIN 53726 in dichloroacetic acid.
  • the intrinsic viscosity (IV) is calculated as follows from the standard viscosity (SV)
  • the thermal properties such as crystallite melting point T m , degree of crystallization, crystallization temperature range T c , post- (cold) crystallization temperature T CN and glass transition temperature T are measured by means of differential scanning calorimetry (DSC) at a heating rate of 10 ° C./min.
  • DSC differential scanning calorimetry
  • the molecular weights M w and M n and the resulting polydispersity MM n are measured by means of gel permeation chromatography (GPC).
  • the tensile modulus is measured at 23 ° C according to ISO 527-1, 2.
  • the polyethylene terephthalate from which the transparent plate is made has a standard viscosity SV (DCE) of 1010, which corresponds to an intrinsic viscosity IV (DCE) of 0.79 dl / g.
  • the moisture content is ⁇ 0.2% and the density (DIN 53479) is 1.41 g / cm 3 .
  • the crystallinity is 59%, the crystallite melting point according to DSC measurements being 258 ° C.
  • the crystallization temperature range T c is between 83 ° C and 258 ° C, the post-crystallization temperature (also cold crystallization temperature) T CN at 144 ° C
  • the polydispersity M ⁇ / M ,, of the polyethylene terephthalate polymer is 2.14
  • the masterbatch is composed of 2% by weight of silicon dioxide as nucleating agent with an average particle diameter of 1.0 ⁇ m and 98% by weight of polyethylene terephthalate, the main constituent of the plate
  • the regenerated polyethylene terephthalate as a nucleating agent has a standard viscosity SV (DCE) of 890, which corresponds to an internal viscosity IV (DCE) of 0.71 dl / g
  • the raw material mixture is then extruded in a single-screw extruder at an extrusion temperature of 280 ° C through a slot die on a smooth calender, the rolls of which are arranged in an S-shape, and smoothed to form a 4 mm thick plate.
  • the first calender roll has a temperature of 65 ° C and that subsequent rollers each have a temperature of 58 C C.
  • the speed of the take-off is 2.8 m / mm
  • the transparent, amorphous, 4 mm thick PET sheet is lined with cut-off saws on the edges, cut to length and stacked
  • the transparent, amorphous plate produced has the following property profile
  • the transparent, amorphous PET is thermoformed on a vacuum thermoforming machine from Geiss / Sesslach, using the following parameters, to form a chemical collecting container
  • Heating source upper and lower heating IR radiators with a wavelength of 2200 nm to 3200 nm
  • the molded chemical container has the following properties
  • the chemical container was loaded 150 times with a wide variety of chemicals for 24 hours and longer and proved to be absolutely stable.
  • the chemical container was left in an autoclave at a temperature of 162 ° C for 48 hours and was completely and homogeneously stable over the object
  • the molded body according to the invention is characterized by a high and uniform heat resistance, a defined and uniform light transmission, an extreme chemical resistance, by a homogeneous, glossy, corrosion-resistant surface and by an economical production

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

A plate contains as main component a crystallisable thermoplastic and at least one nucleating agent. Also disclosed is a moulded body produced from this amorphous plate, a process for producing the same and its use.

Description

Beschreibungdescription

Amorphe, transparente, kπstallisierbare Platte und ein daraus hergestellter Formkorper mit einer hohen und gleichmäßigen WarmeformbestandigkeitAmorphous, transparent, installable plate and a molded body made from it with a high and uniform heat resistance

Die Erfindung betrifft eine Platte, die als Hauptbestandteil einen kristallisierbaren Thermoplast enthalt, einen Formkorper herstellbar aus dieser amorphen Platte, ein Verfahren zu dessen Herstellung sowie dessen VerwendungThe invention relates to a plate which contains a crystallizable thermoplastic as the main component, a molded article which can be produced from this amorphous plate, a process for its production and its use

Amorphe Platten aus einem kristallisierbaren Thermoplasten werden bei relativ niedrigen Temperaturen formmstabil Insbesondere werden amorphe Gegenstande (Platten, Formkorper) beispielsweise aus amorphem Polyethylenterephthalat- (PET)-Mateπal bei Temperaturen von etwa 70°C forminstabil, so daß empfohlen wird, solche Gegenstande nicht Temperaturen von über 65°C auszusetzen Es ist bekannt, daß durch Erhohen des Kristallisationsgrades die Temperaturstabilitat erhöht wirdAmorphous plates made of a crystallizable thermoplastic become dimensionally stable at relatively low temperatures. In particular, amorphous objects (plates, moldings), for example made of amorphous polyethylene terephthalate (PET) material, become dimensionally unstable at temperatures of about 70 ° C., so that it is recommended that such objects not have temperatures of Expose above 65 ° C. It is known that increasing the degree of crystallization increases the temperature stability

Es ist bekannt, einen Gegenstand aus einer Lage aus PET-Mateπal warmzuformen und beim Warmformen den Gegenstand zu kristallisieren, wodurch die Warmeformbestandigkeit erhöht wird So wird beispielsweise in der US-A-3,496,143 ein Verfahren zum Warmeformen einer PET-Platte unter Verwendung einer Tiefziehvorrichtung beschrieben Die PET-Platte hat ein Dicke von 3 mm und eine Flache von 370 mm x 280 mmIt is known to thermoform an object from a layer of PET material and to crystallize the object during thermoforming, which increases the heat resistance. For example, US Pat. No. 3,496,143 describes a method for thermoforming a PET plate using a deep-drawing device The PET plate has a thickness of 3 mm and an area of 370 mm x 280 mm

Die US-Schrift fordert, daß die PET-Platte einen Anfangskπstallisationsgrad von 5% bis 25% besitzen sollte Das Verfahren erfordert, daß die PET-Platte vor dem Formen in der Vakuumform einer langwierigen Wärmebehandlung unterworfen wird Nach dem Formen wird die Platte, wahrend sie noch in der Form ist, einer weiteren Wärmebehandlung ausgesetzt Die Platte wird in der Form gehalten, bis der Kristallisationsgrad der geformten Platte größer als 25% ist In der Patentschrift wird darauf hingewiesen, daß der geformte Gegenstand bei einer Temperatur von 160°C und 60 Minuten formstabil bleibt Nachteilig beim Verfahren der US-A-3,496,143 ist, daß keine exakt und gut geformten Gegenstände herstellbar sind, da die Ausgangsplatte bereits einen Kristallisationsgrad von 5% bis 25% besitzt und kaum noch formbar ist. Desweiteren hat sich gezeigt, daß die Gegenstände nicht homogen kristallisiert sind und die noch vorhandenen amorphen Bereiche lediglich bis ca. 70°C formstabil bleiben. Außerdem ist das vorgeschlagene Verfahren mit der vorgeschlagenen Platte mit einem Kristallisationsgrad von 5 bis 25% von der Zeit her extrem unwirtschaftlich.The US document requires that the PET sheet should have an initial degree of installation of 5% to 25%. The process requires that the PET sheet be subjected to a lengthy heat treatment before being formed in the vacuum mold still in the mold, subjected to further heat treatment. The plate is held in the mold until the degree of crystallization of the molded plate is greater than 25%. The patent indicates that the molded article is at a temperature of 160 ° C and 60 minutes remains dimensionally stable A disadvantage of the process of US Pat. No. 3,496,143 is that no precise and well-shaped objects can be produced, since the starting plate already has a degree of crystallization of 5% to 25% and can hardly be shaped. Furthermore, it has been shown that the objects are not homogeneously crystallized and the amorphous regions which are still present only remain dimensionally stable up to approximately 70 ° C. In addition, the proposed method with the proposed plate with a degree of crystallization of 5 to 25% is extremely uneconomical in terms of time.

Die EP-A-0 471 528 (Polysheet Irland Limited) beschreibt ein Verfahren und eine Vorrichtung zum Formen eines Gegenstandes aus einer PET-Platte, so daß der geformte Gegenstand bei Temperaturen von über 70°C und bevorzugt bis zu Temperaturen von 200°C formstabil bleibt.EP-A-0 471 528 (Polysheet Ireland Limited) describes a method and apparatus for molding an article from a PET sheet so that the molded article is at temperatures above 70 ° C and preferably up to 200 ° C remains dimensionally stable.

Mit diesem Verfahren lassen sich allerdings nur Gegenstände herstellen, deren Lichttransmission stark schwankt, was ein Zeichen dafür ist, daß der Gegenstand unvollständig und ungleichmäßig kristallisiert ist. Ebenso schwankt entsprechend des schwankenden Kristallisationsgrades die Wärmeformstabilität.However, this method can only produce objects whose light transmission fluctuates greatly, which is a sign that the object is incomplete and unevenly crystallized. Likewise, the dimensional stability under heat fluctuates in accordance with the fluctuating degree of crystallization.

Weder mit dem in der US-A-3,496,143 noch mit dem in der EP-A-0 471 528 offenbarten Verfahren, lassen sich Gegenstände mit homogener Lichttransmission und Gleichmäßigkeit der Kristallisation herstellen.Neither with the method disclosed in US-A-3,496,143 nor with the method disclosed in EP-A-0 471 528 can objects with homogeneous light transmission and uniformity of crystallization be produced.

Aufgabe der vorliegen Erfindung ist es daher, eine Platte aus einem amorphen, kristallisierbaren Thermoplasten, und einen daraus geformten Gegenstand mit einem gleichmäßigen Kristallisationsgrad, einer homogenen Lichttransmission und einer homogenen Wärmeformbeständigkeit zur Verfügung zu stellen. Desweiteren soll sich der geformte Gegenstand durch eine homogene, glänzende Oberfläche, eine homogene Trübung sowie durch eine wirtschaftliche Herstellung auszeichnen.The object of the present invention is therefore to provide a plate made of an amorphous, crystallizable thermoplastic, and an object formed therefrom with a uniform degree of crystallization, a homogeneous light transmission and a homogeneous heat resistance. Furthermore, the shaped object is to be distinguished by a homogeneous, glossy surface, a homogeneous cloudiness and by economical production.

Unter gleichmäßigem Kristallisationgrad wird im Rahmen der vorliegenden Erfindung verstanden, daß der Kristallisationsgrad des geformten Gegenstandes bei größer 20% und kleiner 60% liegt, vorzugsweise bei größer 30% und kleiner 50% liegt und daß der Kristallisationsgrad innerhalb eines geformten Gegenstandes nicht mehr als 10% in der Kristallinität schwankt. Unter gleichmäßiger Lichttransmission (gemessen nach ASTM D 1003) wird verstanden, daß die Lichttransmission je nach Wanddicke des geformten Gegenstandes bei kleiner 50%, vorzugsweise bei kleiner 40% und besonders bevorzugt bei kleiner 30% liegt Die Lichttransmission darf innerhalb des geformten Gegenstandes nicht mehr als 10 Einheiten schwankenIn the context of the present invention, a uniform degree of crystallization means that the degree of crystallization of the shaped object is greater than 20% and less than 60%, preferably greater than 30% and less than 50%, and that the degree of crystallization within a shaped object is not more than 10% fluctuates in crystallinity. Uniform light transmission (measured according to ASTM D 1003) is understood to mean that the light transmission, depending on the wall thickness of the shaped object, is less than 50%, preferably less than 40% and particularly preferably less than 30%. The light transmission within the shaped object must not exceed 10 units fluctuate

Die Warmeformbestandigkeit des geformten Gegenstandes, gemessen nach ISO 75-1 ,2 (HDTB, 0,45 MPa), sollte in allen Bereichen homogen bei großer 100°C, vorzugsweise bei großer 120°C und besonders bevorzugt bei großer 140CC liegen Die Warmeformbestandigkeit sollte innerhalb des geformten Gegenstandes nicht mehr als 20°C schwankenThe heat resistance of the molded article, measured according to ISO 75-1, 2 (HDTB, 0.45 MPa), should be homogeneous in all areas at a high 100 ° C, preferably at a high 120 ° C and particularly preferably at a high 140 C The heat resistance should not fluctuate more than 20 ° C within the molded article

Unter homogener, glänzender Oberflache wird verstanden, daß der Oberflachenglanz des geformten Gegenstandes an der Oberflache, die nicht mit der Tiefziehform in Berührung kommt, gemessen nach DIN 67530 (Meßwinkel 20°) bei großer 70, vorzugsweise bei großer 80 und besonders bevorzugt bei großer 90 liegt Der Oberflachenglanz sollte auf dieser Oberflache nicht mehr als 20 Glanzpunkte schwankenA homogeneous, glossy surface is understood to mean that the surface gloss of the shaped object on the surface which does not come into contact with the deep-drawing mold, measured in accordance with DIN 67530 (measuring angle 20 °) at 70, preferably at 80 and particularly preferably at 90 The surface gloss should not fluctuate more than 20 gloss points on this surface

Unter homogener Trübung wird verstanden, daß die Trübung des geformten Gegenstandes, gemessen nach ASTM D 1003 mehr als 50%, vorzugsweise mehr als 60% und besonders bevorzugt mehr als 70% betragt Die Trübung sollte nicht mehr als 10 Trubungspunkte innerhalb des geformten Gegenstandes schwankenHomogeneous haze is understood to mean that the haze of the shaped article, measured according to ASTM D 1003, is more than 50%, preferably more than 60% and particularly preferably more than 70%. The haze should not fluctuate more than 10 cloud points within the shaped article

Darüber hinaus sollte sich der geplante Gegenstand durch eine hervorragende Chemiekalienbestandigkeit auszeichnenIn addition, the planned item should have an excellent chemical resistance

Gelost wird diese Aufgabe durch eine transparente, amorphe Platte mit einer Dicke im Bereich von 1 bis 20 mm, die als Hauptbestandteil mindestens einen kristallisierbaren Thermoplasten enthalt, und dadurch gekennzeichnet ist, daß die Platte mindestens einen homogen verteilten Keimbildner zur Initiierung der Kristallisation wahrend des Thermoformprozesses und zur Erhöhung der Kπstallisationsgeschwindigkeit wahrend des Thermoformprozesses enthalt, so daß nach dem Thermoformprozeß ein kristallisierter Gegenstand mit dem geforderten Eigenschaftsprofil resultiert.This object is achieved by a transparent, amorphous plate with a thickness in the range of 1 to 20 mm, which contains at least one crystallizable thermoplastic as the main component, and is characterized in that the plate is characterized by at least one homogeneously distributed nucleating agent for initiating crystallization during the thermoforming process and to increase the installation speed during the thermoforming process, so that after the thermoforming process, a crystallized article with the required property profile results.

Die transparente, amorphe Platte enthält als Hauptbestandteil mindestens einen kristallisierbaren Thermoplasten. Geeignete kristallisierbare bzw. teilkristalline Thermoplaste sind beispielsweise Polyethylenterephthalat, Polyethylennaphthalat, Polybutylenterephthalat, Polybutylennaphthalat, Cycloolefinhomopolymere und Cycloolefincopolymere sowie Mischungen aus diesen Thermoplasten, wobei Polyethylenterephthalat besonders bevorzugt ist.The transparent, amorphous plate contains at least one crystallizable thermoplastic as the main component. Suitable crystallizable or semi-crystalline thermoplastics are, for example, polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polybutylene naphthalate, cycloolefin homopolymers and cycloolefin copolymers and mixtures of these thermoplastics, polyethylene terephthalate being particularly preferred.

Die transparente, amorphe Platte enthält ferner mindestens einen Keimbildner, wobei die Konzentration des Keimbildners je nach Art des Keimbildners stark variieren kann.The transparent, amorphous plate also contains at least one nucleating agent, wherein the concentration of the nucleating agent can vary widely depending on the type of nucleating agent.

Polymere mit einer niedrigen bis mittleren Kristallwachstumsgeschwindigkeit wie die genannten Thermoplaste sprechen auf die sogenannte homogene, heterogene, athermische und/oder spontane Keimbildung (Nukleierung) mit Hilfe von Fremdsubstanzen - den Keimbildnern - sehr gut an.Polymers with a low to medium crystal growth rate like the thermoplastics mentioned respond very well to the so-called homogeneous, heterogeneous, athermal and / or spontaneous nucleation (nucleation) with the help of foreign substances - the nucleating agents.

Die niedrige bis mittlere Kristallwachstumsgeschwindigkeit und die langsam ablaufende Keimbildung von den genannten Thermoplasten sind einerseits sehr vorteilhaft für die Herstellung der hoch transparenten, amorphen Platten, andererseits stellen diese Eigenschaften jedoch ein ernsthaftes Problem beim Thermoformen zu einem kristallinen Gegenstand dar. So führt das Thermoformen der amorphen Thermoplasten mit extrem beheizten Formen und viel Wärme - zur Beschleunigung der Kristallisation - zu teilweise kristallinen Fertigteilen mit stark schwankendem Kristallisationsgrad und stark schwankenden Eigenschaften wie z.B. Lichttransmission, Trübung, Oberflächenglanz und Wärmeformbeständigkeit. Die Fertigteile lassen sich nur sehr schwer aus der Form lösen und sind teilweise zu weich. Infolge der teilweise sehr langen und dazu unwirtschaftlichen Zykluszeiten bei extremen Temperaturen erhält man aufgrund der gebildeten, großen Sphärolithe sehr spröde Gegenstände. Es wurde nun gefunden, daß man mit Hilfe von inerten, unlöslichen Additiven, von organischen Verbindungen ohne oder mit inertem Additiv sowie mit polymeren Verbindungen ohne oder mit inertem Additiv als Keimbildner in diesen kristallisierbaren Thermoplasten diese Schwierigkeiten beim Tiefziehen beheben kann.The low to medium crystal growth rate and the slow nucleation of the thermoplastics mentioned are on the one hand very advantageous for the production of the highly transparent, amorphous plates, but on the other hand these properties represent a serious problem in thermoforming to a crystalline object. This is how thermoforming leads to the amorphous Thermoplastics with extremely heated molds and a lot of heat - to accelerate the crystallization - to partially crystalline finished parts with a strongly fluctuating degree of crystallization and strongly fluctuating properties such as light transmission, turbidity, surface gloss and heat resistance. The finished parts are very difficult to remove from the mold and are sometimes too soft. As a result of the sometimes very long and uneconomical cycle times at extreme temperatures, very large objects are obtained due to the large spherulites formed. It has now been found that inert, insoluble additives, organic compounds with or without an inert additive and polymeric compounds with or without an inert additive as nucleating agents in these crystallizable thermoplastics can overcome these difficulties in deep-drawing.

An den zugesetzten Keimbildner werden erfindungsgemäß die Anforderungen gestellt, daß er bei der Plattenherstellung in der Extrusionsstraße bei relativ schneller Abkühlung nicht zu einer Kristallisation in der Platte führen darf. Erfindungswesentlich ist, daß die Platte amorph sein muß. Bei Platten, die nur eine geringe Kristallisation von größer 5% aufweisen, erweist sich das Thermoformen zu einem kristallisierten Gegenstand als unzureichend und sehr zeitaufwendig, da während des Tiefziehens die kristallinen Anteile erst aufgeschmolzen werden müssen, wozu viel Zeit und Energie erforderlich ist.According to the invention, the added nucleating agent is subject to the requirements that it must not lead to crystallization in the plate during plate production in the extrusion line with relatively rapid cooling. It is essential to the invention that the plate must be amorphous. In the case of plates which only have a low crystallization of more than 5%, thermoforming to a crystallized object proves to be inadequate and very time-consuming, since the crystalline components first have to be melted during deep-drawing, which requires a lot of time and energy.

Auf der anderen Seite muß der Keimbildner bei dem Thermoformprozeß die Kristallisationsgeschwindigkeit erhöhen und dafür Sorge tragen, daß schnell zahlreiche, kleine Sphärolithe gebildet werden.On the other hand, the nucleating agent in the thermoforming process must increase the rate of crystallization and ensure that numerous small spherulites are quickly formed.

Geeignete Keimbildner sind beispielsweise inerte, mineralische Füllstoffe wie Silikate mit einer mittleren Teilchengröße von kleiner 5 μm sowie Talkum, Ton, Kaolin, Glimmer mit mittleren Teilchengrößen von kleiner 6 μm, Metalloxide wie z.B. Siliciumdioxid, Titandioxid und Magnesiumoxid, Carbonate und Sulfate, bevorzugt von Erdalkalimetallen, Bornitrid und Natriumfluorid mit mittleren Teilchendurchmessern von kleiner 4 μm. Desweiteren eignen sich organische Verbindungen alleine oder mit unlöslichen, inerten Feststoffen wie beispielsweise Montanwachs, Montanestersalze, Salze von Mono- und Polycarbonsäuren, Epoxide und Alkaliaryl- und -alkylsulfonate sowie polymere Verbindungen alleine oder mit unlöslichen, inerten Feststoffen wie beispielsweise Polyethylen, Polypropylen, Polyamide, Poly-4-methylpenten-1 , Polymethylbuten-1 , Copolymerisate aus Ethylen mit ungesättigten Carbonsäurerestem, ionische Copolymerisate aus Ethylen mit Salzen ungesättigter Carbonsäuren, Copolymerisate aus Styrolderivaten mit konjugierten Dienen, der kristallisierbare Thermoplast selbst mit einer wesentlich niedrigeren oder einer wesentlich höheren intrinsischen Viskosität, oxidativ abgebaute Polymere, Regranulat aus dem kristallisierbaren Thermoplast sowie Mischungen von diesen Keimbildnern.Suitable nucleating agents are, for example, inert, mineral fillers such as silicates with an average particle size of less than 5 μm and talc, clay, kaolin, mica with average particle sizes of less than 6 μm, metal oxides such as silicon dioxide, titanium dioxide and magnesium oxide, carbonates and sulfates, preferably of alkaline earth metals , Boron nitride and sodium fluoride with average particle diameters of less than 4 μm. Organic compounds are also suitable on their own or with insoluble, inert solids such as, for example, montan wax, montan ester salts, salts of mono- and polycarboxylic acids, epoxides and alkali metal aryl and alkylsulfonates, and also polymeric compounds alone or with insoluble, inert solids, such as polyethylene, polypropylene, polyamides Poly-4-methylpentene-1, polymethylbutene-1, copolymers of ethylene with unsaturated carboxylic acid residues, ionic copolymers of ethylene with salts of unsaturated carboxylic acids, copolymers of styrene derivatives with conjugated dienes, the crystallizable thermoplastic itself with an essential lower or a substantially higher intrinsic viscosity, oxidatively degraded polymers, regranulate from the crystallizable thermoplastic and mixtures of these nucleating agents.

In einer besonders bevorzugten Ausführungsform enthält die erfindungsgemäße, transparente, amorphe Platte als Hauptbestandteil ein kristallisierbares Polyethylenterephthalat, 1 bis 40 Gew.-%. Regenerat aus dem kristallisierbaren Polyethylenterephthalat und 0,01 bis 3 Gew.-% Siliciumdioxid mit einem mittleren Teilchendurchmesser von 1 bis 3 μm oder 1 bis 40 Gew.-% Regenerat aus dem kristallisierbaren Thermoplast und 0,01 bis 3,0 Gew.-% Kaolin mit einem mittleren Teilchendurchmesser von 1 ,0 bis 5,0 μm, bezogen auf das Gewicht an kristallisierbarem Polyethylenterephthalat. In einer bevorzugten Ausführungsform kann die amorphe Platte neben dem kristallisierbaren Polyethylenterephthalat, dem Regenerat aus dem kristallisierbaren Polyethylenterephthalat als Keimbildner auch Mischungen der beiden anorganischen Keimbildner enthalten, wobei die Gesamtkonzentration an anorganischem Keimbildner vorzugsweise zwischen 0,01 Gew.-% und 3,0 Gew.-% liegt, bezogen auf das Gewicht des kristallisierbaren Polyethylenterephthalats.In a particularly preferred embodiment, the transparent, amorphous plate according to the invention contains, as the main component, a crystallizable polyethylene terephthalate, 1 to 40% by weight. Regenerate from the crystallizable polyethylene terephthalate and 0.01 to 3% by weight silicon dioxide with an average particle diameter of 1 to 3 μm or 1 to 40% by weight regenerate from the crystallizable thermoplastic and 0.01 to 3.0% by weight Kaolin with an average particle diameter of 1.0 to 5.0 μm, based on the weight of crystallizable polyethylene terephthalate. In a preferred embodiment, in addition to the crystallizable polyethylene terephthalate, the regrind from the crystallizable polyethylene terephthalate as nucleating agent, the amorphous plate can also contain mixtures of the two inorganic nucleating agents, the total concentration of inorganic nucleating agent preferably between 0.01% by weight and 3.0% by weight. -% is based on the weight of the crystallizable polyethylene terephthalate.

Zwecks Bildung von kleinen und zahlreichen Sphärolithen beim späteren Tiefziehprozeß ist es bevorzugt, wenn die intrinsische Viskosität des Regenerates aus dem kristallisierbaren Thermoplast niedriger liegt als die intrinsische Viskosität des kristallisierbaren Polyethylenterephthalats selbst, was als Hauptbestandteil in der amorphen Platte enthalten ist.In order to form small and numerous spherulites in the subsequent deep-drawing process, it is preferred if the intrinsic viscosity of the regrind from the crystallizable thermoplastic is lower than the intrinsic viscosity of the crystallizable polyethylene terephthalate itself, which is contained as the main component in the amorphous plate.

Polyethylenterephthalate mit einem Kristallitschmelzpunkt Tm, gemessen mit DSC (Differential Scanning Calorimetry) mit einer Aufheizgeschwindigkeit von 10°C/min, von 240°C bis 280°C, vorzugsweise von 250°C bis 270°C, mit einem Kristallisationstemperaturbereich Tc zwischen 75°C und 280°C, einer Glasübergangstemperatur T zwischen 65°C und 90°C und mit einer Dichte, gemessen nach DIN 53479, von 1 ,30 bis 1 ,45 g/cm3 und einer Kristallinität zwischen 25 % und 65 % stellen als Ausgangsmaterialien zur Herstellung der Platte bevorzugte Polymere dar.Polyethylene terephthalate 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 280 ° C, preferably from 250 ° C to 270 ° C, with a crystallization temperature range T c between 75 ° C and 280 ° C, a glass transition temperature T between 65 ° C and 90 ° C and with a density, measured according to DIN 53479, of 1, 30 to 1, 45 g / cm 3 and a crystallinity between 25% and 65% provide as starting materials for the production of Plate preferred polymers.

Die Standardviskosität SV (DCE) des Polyethylenterephthalats, gemessen in Dichloressigsäure nach DIN 53728, liegt zwischen 600 und 1800, vorzugsweise zwischen 700 und 1250 und besonders bevorzugt zwischen 800 und 1 200.The standard viscosity SV (DCE) of the polyethylene terephthalate, measured in dichloroacetic acid according to DIN 53728, is between 600 and 1800, preferably between 700 and 1250 and particularly preferably between 800 and 1 200.

Die intrinsische Viskosität IV (DCE) berechnet sich aus der Standardviskosität SV (DCE):The intrinsic viscosity IV (DCE) is calculated from the standard viscosity SV (DCE):

IV (DCE) = 6,67 ■ 10"4 SV (DCE) + 0, 1 18IV (DCE) = 6.67 ■ 10 "4 SV (DCE) + 0.118

Das Schüttgewicht, gemessen nach DIN 53466, liegt vorzugsweise zwischen 0,75 kg/dm3 und 1 ,0 kg/dm3, und besonders bevorzugt zwischen 0,80 kg/dm3 und 0,90 kg/dm3.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 .

Die Polydispersität M^ Mp des Polyethylenterephthalats gemessen mittels Gelpermeationschromatographie liegt vorzugsweise zwischen 1 ,5 und 4,0 und besonders bevorzugt zwischen 2,0 und 3,5. Erfindungsgemäß versteht man unter kristallisierbarem Polyethylenterephthalat: kristallisierbare Polyethylenterephthalat-Homopolymere, kristallisierbare Polyethylenterephthalat-Copolymere, kristallisierbare Polyethylenterephthalat-Compounds, kristallisierbares Polyethylenterephthalat-Recyklat und andere Variationen von kristallisierbarem Polyethylenterephthalat.The polydispersity M ^ M p of the polyethylene terephthalate measured by means of gel permeation chromatography is preferably between 1.5 and 4.0 and particularly preferably between 2.0 and 3.5. According to the invention, crystallizable polyethylene terephthalate means: crystallizable polyethylene terephthalate homopolymers, crystallizable polyethylene terephthalate copolymers, crystallizable polyethylene terephthalate compounds, crystallizable polyethylene terephthalate recyclate and other variations of crystallizable polyethylene terephthalate.

Unter amorpher Platte werden im Sinne der vorliegenden Erfindung solche Platten verstanden, die, obwohl der eingesetzte kristallisierbare Thermoplast vorzugsweise eine Kristallinität zwischen 25 und 65 % besitzt, nicht kristallin sind. Nicht kristallin, d. h. im wesentlichen amorph bedeutet, daß der Kristallinitätsgrad im allgemeinen unter 5 %, vorzugsweise unter 2 % liegt und besonders bevorzugt 0 % beträgt .For the purposes of the present invention, amorphous plate is understood to mean plates which, although the crystallizable thermoplastic used preferably has a crystallinity of between 25 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%.

Daneben ergaben Messungen, daß die erfindungsgemäße PET-Platte schwer brennbar und schwer entflammbar ist, so daß folglich der aus dieser Platte tiefgezogene, kristallisierte Gegenstand ebenfalls schwer entflammbar istIn addition, measurements showed that the PET panel according to the invention was heavy is flammable and flame-retardant, so that consequently the crystallized object drawn from this plate is also flame-retardant

Desweiteren laßt sich die erfindungsgemaße Platte auf einer herkömmlichen Vakuum-Thermoformmaschine mit Ober- und Unterheizung zu einem homogen kristallisierten Gegenstand tiefziehen Wesentlich ist, daß das Formwerkzeug auf Temperaturen von mindestens 100°C, vorzugsweise mindestens 120°C, zu erwarmen ist, wobei zum Erwarmen des Formwerkzeuges neben erwärmten öl beispielsweise auch elektrisch betriebene Kassettenheizer oder dergleichen verwendet werden können Die Plattentemperatur sollte dabei unter 140°C, vorzugsweise unter 130°C und besonders bevorzugt unter 120°C liegenFurthermore, the plate according to the invention can be thermoformed on a conventional vacuum thermoforming machine with upper and lower heating to form a homogeneously crystallized object. It is essential that the molding tool is heated to temperatures of at least 100 ° C., preferably at least 120 ° C., for heating of the mold, in addition to heated oil, it is also possible, for example, to use electrically operated cassette heaters or the like. The plate temperature should be below 140 ° C., preferably below 130 ° C. and particularly preferably below 120 ° C.

Daneben wurde völlig überraschend gefunden, daß zwar Heizstrahler als Wärmequelle zur Erwärmung der Platte auf die Vorformtemperatur und zur Kristallisation des geformten Gegenstandes geeignet sind, daß aber Infrarotstrahler mit einer Wellenlange von großer 2000 nm eine höhere Kπstallisationsgeschwindigkeit und einen nochmals höheren und homogeneren Kristallisationsgrad liefern, was sich ebenfalls positiv auf die übrigen physikalischen Eigenschaften, wie beispielsweise Lichttransmission, Trübung, Oberflachenglanz, Warmeformbestandigkeit, Chemikahenbestandigkeit und mechanische Eigenschaften auswirktIn addition, it was found, completely surprisingly, that radiant heaters are suitable as a heat source for heating the plate to the preform temperature and for crystallizing the shaped object, but that infrared radiators with a wavelength of large 2000 nm provide a higher installation speed and an even higher and more homogeneous degree of crystallization, which also has a positive effect on the other physical properties such as light transmission, haze, surface gloss, heat resistance, chemical resistance and mechanical properties

Bei Wellenlangen von großer 2000 nm, insbesondere großer 2300 nm egt die Lichttransmission der erfmdungsgemaßen, amorphen Platte bei kleiner 10%, d h die Absorption ist in diesem Wellenlangenbereich extrem hoch, was bedeutet, daß Strahlung mit diesen Wellenlangen beim Tiefziehen in Warme umgewandelt wird, wodurch die Kristallisation unter Mitwirkung der Keimbildner homogen initiiert und fortgesetzt wirdAt wavelengths of large 2000 nm, in particular large 2300 nm, the light transmission of the amorphous plate according to the invention is less than 10%, that is to say the absorption is extremely high in this wavelength range, which means that radiation with these wavelengths is converted into heat during deep drawing, as a result of which the crystallization is initiated and continued homogeneously with the participation of the nucleating agents

Der Tiefziehprozeß umfaßt wie dem Fachmann bekannt die Schritte Aufheizen mit einer Wärmequelle, Vakuumformen unter Wärmeeinwirkung, Wärmebehandlung, Abkühlen und anschließendes EntformenAs is known to the person skilled in the art, the deep-drawing process comprises the steps of heating with a heat source, vacuum forming under the action of heat, heat treatment, cooling and subsequent demolding

Die erfindungsgemaße, amorphe PET-Platte, die die beschriebenen Keimbildner enthalt, wird diesem Tiefziehprozeß unterzogen, wobei als Wärmequelle Heizstrahler oder andere Heizelemente dienen können, bevorzugt aber Infrarotstrahler mit Wellenlangen von großer 2000 nm eingesetzt werdenThe amorphous PET plate according to the invention which contains the nucleating agents described contains, is subjected to this deep-drawing process, whereby radiant heaters or other heating elements can serve as the heat source, but preferably infrared radiators with wavelengths of large 2000 nm are used

Die bereits geformte, noch im wesentlichen amorphe und noch im wesentlichen transparente Lage wird unter Vakuum in der Form gehalten und je nach Plattendicke vorzugsweise 30 Sekunden bis 6 Minuten bei Temperaturen vorzugsweise im Bereich von 100 bis 200°C warmebehandelt, wozu vorzugsweise Infrarotstrahler mit Wellenlangen von großer 2000 nm eingesetzt werden Wahrend der Wärmebehandlung kann visuell beobachtet werden, wie sich der transparente Gegenstand milchig weiß verfärbt, d h die Lichttransmission der ursprunglich amorphen, transparenten Platte nimmt von ca 90% infolge der einsetzenden Kristallisation homogen ab und nimmt Werte an, die kleiner 50%, vorzugsweise kleiner 40 % und besonders bevorzugt kleiner 30% sind Nach erfolgter Kristallisation, wobei der Fachmann den gewünschten Kristallisationsgrad über die visuell zu beobachtende und/oder auch meßtechnisch zu erfassende Lichttransmission einstellen kann, wird der geformte Gegenstand abgekühlt und entformtThe already formed, still essentially amorphous and still substantially transparent layer is held in the mold under vacuum and, depending on the plate thickness, is preferably heat-treated for 30 seconds to 6 minutes at temperatures preferably in the range from 100 to 200 ° C., for which purpose preferably infrared radiators with wavelengths of larger 2000 nm are used During the heat treatment it can be visually observed how the transparent object turns milky white, ie the light transmission of the originally amorphous, transparent plate decreases homogeneously from about 90% due to the onset of crystallization and assumes values that are less than 50 %, preferably less than 40% and particularly preferably less than 30%, after the crystallization has taken place, the person skilled in the art being able to set the desired degree of crystallization via the light transmission which can be visually observed and / or measured by measurement technology, the shaped object is cooled and removed from the mold

Der aus der amorphen, transparenten, mit Keimbildnern ausgerüsteten PET-Platte thermogeformte, kristallisierte Gegenstand hat einen Kristallisationsgrad von 20% bis 60%, vorzugsweise von 30% bis 50% und besonders bevorzugt von 35% bis 45% Aufgrund der eingesetzten Keimbildner, die die Kristallisation homogen initiieren und dafür sorgen, daß kleine, zahlreiche Sphärolithe gebildet werden, ist die Kristallisation innerhalb des geformten Gegenstandes extrem homogen und schwankt weniger als 10 Einheiten im KristallisationsgradThe crystallized object thermoformed from the amorphous, transparent PET plate equipped with nucleating agents has a degree of crystallization from 20% to 60%, preferably from 30% to 50% and particularly preferably from 35% to 45% due to the nucleating agents used, which Initiate crystallization homogeneously and ensure that small, numerous spherulites are formed, the crystallization within the shaped object is extremely homogeneous and fluctuates less than 10 units in the degree of crystallization

Infolge der homogenen Kristallisation ist ebenfalls die Warmeformbestandigkeit, gemessen nach ISO 75-1 ,2 [HDT= Heat Deflection Temperature, 0,45 MPa], des geformten Gegenstandes extrem homogen und schwankt nicht mehr als 20°C, vorzugsweise nicht mehr als 10°C innerhalb des geformten Gegenstandes Die Warmeformbestandigkeit des geformten Gegenstandes ist in allen Bereichen homogen und großer als 100°C, vorzugsweise großer als 120°C, besonders bevorzugt großer als 140°C und insbesondere großer als 160°CAs a result of the homogeneous crystallization, the heat resistance, measured according to ISO 75-1, 2 [HDT = Heat Deflection Temperature, 0.45 MPa], of the shaped object is also extremely homogeneous and does not fluctuate by more than 20 ° C., preferably not more than 10 ° C within the molded article The heat resistance of the molded article is homogeneous in all areas and greater than 100 ° C, preferably greater than 120 ° C, particularly preferably greater than 140 ° C and in particular greater than 160 ° C

Die Lichttransmission, gemessen nach ASTM D 1003, über die der Kristallisationsgrad eingestellt werden kann, ist naturlich homogen und liegt unter 50%>, vorzugsweise unter 40% und besonders bevorzugt unter 30% Da die Lichttraπsmission von dem Kristallisationsgrad aber auch von der Wanddicke des geformten Korpers abhangt, liegt die Lichttransmission bei Wandstarken von großer 3 mm insbesondere unter 20%The light transmission, measured according to ASTM D 1003, by means of which the degree of crystallization can be set, is of course homogeneous and is below 50%, preferably below 40% and particularly preferably below 30%, since the light transmission depends on the degree of crystallization but also on the wall thickness of the molded Depends on the body, the light transmission is particularly less than 20% for wall thicknesses of large 3 mm

Der geformte, kristallisierte Gegenstand zeigt an der Oberflache, die nicht mit der Tiefziehform in Berührung kommt, einen Oberflachenglanz, gemessen nach DIN 67530 (Meßwinkel 20°) von großer 70, vorzugsweise von großer 80, besonders bevorzugt von großer 90 und insbesondere von großer 95The shaped, crystallized object has a surface gloss on the surface that does not come into contact with the deep-drawing mold, measured in accordance with DIN 67530 (measuring angle 20 °) of greater than 70, preferably greater than 80, particularly preferably greater than 90 and in particular greater than 95

Die Trübung des geformten Gegenstandes, gemessen nach ASTM D 1003 liegt im allgemeinen über 50%, vorzugsweise über 60% und besonders bevorzugt über 70% Da die Trübung wie die Lichttransmission neben dem Kristallisationsgrad auch von der Wandstarke des geformten Korpers abhangt, liegt die Trübung bei Wandstarken von großer 3 mm über 80%The haze of the shaped object, measured in accordance with ASTM D 1003, is generally above 50%, preferably above 60% and particularly preferably above 70%. Since the haze, like the light transmission, depends not only on the degree of crystallization but also on the wall thickness of the shaped body, the haze is included Wall thicknesses of large 3 mm over 80%

Daneben zeigt der erfindungsgemaße, geformte und kristallisierte Gegenstand eine noch höhere Chemikalienbestandigkeit als die erfindungsgemaße, amorphe, transparente PlatteIn addition, the shaped and crystallized object according to the invention shows an even higher chemical resistance than the amorphous, transparent plate according to the invention

Ganz überraschend wurde festgestellt, daß das Zugmodul, gemessen nach ISO 527-1 ,2, unter 3600 MPa, vorzugsweise unter 3400 MPa liegt, was ein weiterer Beweis dafür ist, daß die Kristallisation homogen ist und daß sich zahlreiche, kleine Sphärolithe aufgrund des eingesetzten Keimbildners gebildet haben, d h der Gegenstand ist trotz Kristallisation nicht sprödeQuite surprisingly, it was found that the tensile modulus, measured in accordance with ISO 527-1, 2, is below 3600 MPa, preferably below 3400 MPa, which is further evidence that the crystallization is homogeneous and that numerous, small spherulites are due to the used Have formed nucleating agent, ie the object is not brittle despite crystallization

Die Herstellung der amorphen, kristallisierbaren Platten wird beispielsweise in den nicht offengelegten, deutschen Patentanmeldungen 195 19 579 5, 195 19 578 7, 195 19 577 9, 195 22 118 4, 195 22 1206, 195 22 119 2, 195 28 336 8, 195 28 334.1 und 195 28 333.3 beschrieben.The production of the amorphous, crystallizable plates is described, for example, in the unpublished German patent applications 195 19 579 5, 195 19 578 7, 195 19 577 9, 195 22 118 4, 195 22 1206, 195 22 119 2, 195 28 336 8, 195 28 334.1 and 195 28 333.3.

Aufgrund der eingesetzten Keimbildner ist bei der Herstellung der Platte auf eine genaue Temperaturführung und auf exakte Walzentemperaturen zu achten. Bei zu hohen Walzentemperaturen wird die Kristallisation durch die Keimbildner bereits während der Extrusion initiiert, was zu enormen Problemen beim Tiefziehen führt.Due to the nucleating agents used, precise temperature control and exact roller temperatures must be ensured when manufacturing the plate. If the roll temperatures are too high, the nucleating agents initiate crystallization during the extrusion, which leads to enormous problems in deep drawing.

Erfindungsgemäß kann der Keimbildner bereits beim Thermoplast-Rohstoffhersteller zudosiert werden oder bei der Plattenherstellung in den Extruder dosiert werden.According to the invention, the nucleating agent can be metered in at the thermoplastic raw material manufacturer or metered into the extruder during plate production.

Besonders bevorzugt ist die Zugabe des Keimbildners über die Masterbatchtechnologie. Der Keimbildner wird in einem festen Trägermaterial voll dispergiert. Als Trägermaterial kommen gewisse Harze, das Polyethylenterephthalat selbst oder auch andere Polymere, die mit dem Polyethylenterephthalat ausreichend verträglich sind, in Frage.The addition of the nucleating agent via masterbatch technology is particularly preferred. The nucleating agent is fully dispersed in a solid carrier material. Certain resins, the polyethylene terephthalate itself or other polymers which are sufficiently compatible with the polyethylene terephthalate, are suitable as carrier material.

Wichtig ist, daß die Korngröße und das Schüttgewicht des Masterbatches ähnlich der Korngröße und dem Schüttgewicht des Polyethylenterephthalats ist, so daß eine homogene Verteilung und damit eine homogene Keimbilduπg und Kristallisation erfolgen kann.It is important that the grain size and the bulk density of the masterbatch is similar to the grain size and the bulk density of the polyethylene terephthalate, so that a homogeneous distribution and thus a homogeneous nucleation and crystallization can take place.

Durch die Vielzahl ausgezeichneter Eigenschaften eignet sich der erfindungsgemäße, kristallisierte Gegenstand für eine Vielzahl verschiedener Anwendungen, beispielsweise für Messebau und Messeartikel, für Chemikalien- und Transportbehälter, für Sanitärartikel, sowie im Laden- und Regalbau.Due to the large number of excellent properties, the crystallized object according to the invention is suitable for a large number of different applications, for example for trade fair construction and trade fair articles, for chemical and transport containers, for sanitary articles, and in shop and shelf construction.

Die Erfindung wird im folgenden anhand eines Ausführungsbeispiels näher erläutert, ohne dadurch beschränkt zu werden.The invention is explained in more detail below using an exemplary embodiment, without being restricted thereby.

Die Messung der einzelnen Eigenschaften erfolgt dabei gemäß den folgenden Normen bzw. Verfahren. MeßmethodenThe individual properties are measured in accordance with the following standards and procedures. Measurement methods

OberflachenglanzSurface gloss

Der Oberflachenglanz wird nach DIN 67530 bestimmt Gemessen wird der Reflektorwert als optische Kenngroße für die Oberflache einer Platte Angelehnt an die Normen ASTM-D 523-78 und ISO 2813 wurde der Einstrahlwinkel mit 20° eingestellt Ein Lichtstrahl trifft unter dem eingestellten Einstrahlwinkel auf die ebene Prufflache und wird von dieser reflektiert beziehungsweise gestreut Die auf den photoelektronischen Empfanger auffallenden Lichtstrahlen werden als proportionale elektrische Große angezeigt Der Meßwert ist dimensionslos und muß mit dem Einstrahlwinkel zusammen angegeben werdenThe surface gloss is determined in accordance with DIN 67530. The reflector value is measured as the 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 proportional electrical values. The measured value is dimensionless and must be specified together with the angle of incidence

LichttransmissionLight transmission

Unter der Lichttransmission ist das Verhältnis des insgesamt durchgelassenenUnder the light transmission is the ratio of the total let through

Lichtes zur einfallenden Lichtmenge zu verstehenTo understand light to the incident amount of light

Die Lichttransmission wird mit dem Meßgerat "Hazegard plus" nach ASTM 1003 gemessenThe light transmission is measured with the "Hazegard plus" measuring device in accordance with ASTM 1003

Trübung und ClarityTurbidity and Clarity

Trübung ist der prozentuale Anteil des durchgelassenen Lichtes, der vom eingestrahlten Lichtbundel im Mittel um mehr als 2,5° abweicht Die Bildscharfe wird unter einem Winkel kleiner als 2,5° ermitteltHaze is the percentage of the transmitted light that deviates by more than 2.5 ° on average from the incident light beam. The sharpness of the image is determined at an angle of less than 2.5 °

Die Trübung und die Clarity werden mit dem Meßgerat "Hazegard plus" nach ASTMThe haze and clarity are measured using the "Hazegard plus" measuring device according to ASTM

1003 gemessen1003 measured

WarmeformbestandigkeitHeat resistance

Die Warmeformbestandigkeit wird als HDT B (Heat Deflection Temperature) mitThe heat resistance is called HDT B (Heat Deflection Temperature)

0,45 MPa nach ISO 75-1 ,2 gemessen0.45 MPa measured according to ISO 75-1, 2

Vicat-ErweichungstemperaturVicat softening temperature

Die Vicat-Erweichungstemperatur wird bei 50 N Belastung nach ISO 306 gemessen Dichte:The Vicat softening temperature is measured at 50 N load according to ISO 306 Density:

Die Dichte wird nach DIN 53479 bestimmt.The density is determined according to DIN 53479.

SV (DCE), IV (DCE):SV (DCE), IV (DCE):

Die Standardviskosität SV (DCE) wird angelehnt an DIN 53726 in Dichloressigsäure gemessen.The standard viscosity SV (DCE) is measured based on DIN 53726 in dichloroacetic acid.

Die intrinsische Viskosität (IV) berechnet sich wie folgt aus der Standardviskosität (SV)The intrinsic viscosity (IV) is calculated as follows from the standard viscosity (SV)

IV (DCE) = 6,67 * 10"4 SV (DCE) + 0,118IV (DCE) = 6.67 * 10 "4 SV (DCE) + 0.118

Thermische Eigenschaften:Thermal properties:

Die thermischen Eigenschaften wie Kristallitschmelzpunkt Tm, Kristallisationsgrad, Kristallisationstemperaturbereich Tc, Nach-(Kalt-) Kristallisationstemperatur TCN und Glasübergaπgstemperatur T werden mittels Differential Scanning Calorimetrie (DSC) bei einer Aufheizgeschwindigkeit von 10°C/min gemessen.The thermal properties such as crystallite melting point T m , degree of crystallization, crystallization temperature range T c , post- (cold) crystallization temperature T CN and glass transition temperature T are measured by means of differential scanning calorimetry (DSC) at a heating rate of 10 ° C./min.

Molekulargewicht, Polydispersität:Molecular weight, polydispersity:

Die Molekulargewichte Mw und Mn und die resultierende Polydispersität M Mn werden mittels Gelpermeationschromatographie (GPC) gemessen.The molecular weights M w and M n and the resulting polydispersity MM n are measured by means of gel permeation chromatography (GPC).

Zugmodul:Train module:

Das Zugmodul wird bei 23°C nach ISO 527-1 ,2 gemessen.The tensile modulus is measured at 23 ° C according to ISO 527-1, 2.

Beispiel 1 :Example 1 :

Das Polyethylenterephthalat, aus dem die transparente Platte hergestellt wird, hat eine Standardviskosität SV (DCE) von 1010, was einer intrinsischen Viskosität IV (DCE) von 0,79 dl/g entspricht. Der Feuchtigkeitsgehalt liegt bei < 0,2 % und die Dichte (DIN 53479) bei 1 ,41 g/cm3. Die Kristallinität beträgt 59%, wobei der Kristallitschmelzpunkt nach DSC-Messungen bei 258°C liegt. Der Kristallisationstemperaturbereich Tc liegt zwischen 83°C und 258°C, wobei die Nachkristallisationstemperatur (auch Kaltkristallisationstemperatur) TCN bei 144°C liegt Die Polydispersität M^/M,, des Polyethylenterephthalat-Polymeren betragt 2,14The polyethylene terephthalate from which the transparent plate is made has a standard viscosity SV (DCE) of 1010, which corresponds to an intrinsic viscosity IV (DCE) of 0.79 dl / g. The moisture content is <0.2% and the density (DIN 53479) is 1.41 g / cm 3 . The crystallinity is 59%, the crystallite melting point according to DSC measurements being 258 ° C. The crystallization temperature range T c is between 83 ° C and 258 ° C, the post-crystallization temperature (also cold crystallization temperature) T CN at 144 ° C The polydispersity M ^ / M ,, of the polyethylene terephthalate polymer is 2.14

Vor der Extrusion werden 60 Gew -% des Polyethylenterephthalats mit 30 Gew -% Regenerat aus dem Polyethylenterephthalat und 10 Gew -% Masterbatch 5 Stunden bei 170°C getrocknetBefore the extrusion, 60% by weight of the polyethylene terephthalate with 30% by weight of regenerate from the polyethylene terephthalate and 10% by weight of masterbatch are dried at 170 ° C. for 5 hours

Das Masterbatch setzt sich aus 2 Gew -% Siliciumdioxid als Keimbildner mit einem mittleren Teilchendurchmesser von 1 ,0 μm und 98 Gew -% Polyethylenterephthalat, dem Hauptbestandteil der Platte, zusammenThe masterbatch is composed of 2% by weight of silicon dioxide as nucleating agent with an average particle diameter of 1.0 μm and 98% by weight of polyethylene terephthalate, the main constituent of the plate

Das Polyethylenterephthalat-Regenerat als Keimbildner hat eine Standardviskositat SV(DCE) von 890, was einer intπnsischen Viskosität IV (DCE) von 0,71 dl/g entsprichtThe regenerated polyethylene terephthalate as a nucleating agent has a standard viscosity SV (DCE) of 890, which corresponds to an internal viscosity IV (DCE) of 0.71 dl / g

Die Rohstoffmischung wird dann in einem Einschneckenextruder bei einer Extrusionstemperatur von 280°C durch eine Breitschlitzduse auf einem Glattkalander, dessen Walzen S-formig angeordnet sind, extrudiert und zu einer 4 mm dicken Platte geglättet Die erste Kalanderwalze hat eine Temperatur von 65°C und die nachfolgenden Walzen haben jeweils eine Temperatur von 58CC Die Geschwindigkeit des Abzuges liegt bei 2,8 m/mmThe raw material mixture is then extruded in a single-screw extruder at an extrusion temperature of 280 ° C through a slot die on a smooth calender, the rolls of which are arranged in an S-shape, and smoothed to form a 4 mm thick plate.The first calender roll has a temperature of 65 ° C and that subsequent rollers each have a temperature of 58 C C. The speed of the take-off is 2.8 m / mm

Im Anschluß an die Nachkuhlung wird die transparente, amorphe, 4 mm dicke PET- Platte mit Trennsagen an den Randern gesäumt, abgelangt und gestapeltFollowing the after-cooling, the transparent, amorphous, 4 mm thick PET sheet is lined with cut-off saws on the edges, cut to length and stacked

Die hergestellte transparente, amorphe Platte hat folgendes EigenschaftsprofilThe transparent, amorphous plate produced has the following property profile

- Dicke 4 mm- thickness 4 mm

- Oberflachenglanz 1 Seite 180 (Meßwinkel 20") 2 Seite 176- Surface gloss 1 page 180 (measuring angle 20 ") 2 page 176

- Lichttransmission 89%- light transmission 89%

- Clarity 98%- Clarity 98%

- Trübung 2,4 %- turbidity 2.4%

- Oberflachendefekte pro m2 keine - Kristallmitat 0% - Dichte 1 ,33 g/cm3 - Surface defects per m 2 none - crystal mitate 0% - density 1.33 g / cm 3

- Zugmodul (23°C) 2450 MPa- tensile modulus (23 ° C) 2450 MPa

- HDT B (0,45 MPa) 73°C- HDT B (0.45 MPa) 73 ° C

- Vicat-Erweichungsmodul 75°C- Vicat softening module 75 ° C

Die transparente, amorphe PET wird auf einer Vakuum-Thermoformmaschine der Fa Geiss / Sesslach, mit folgenden Parametern zu einem Chemikalienauffangbehalter tiefgezogenThe transparent, amorphous PET is thermoformed on a vacuum thermoforming machine from Geiss / Sesslach, using the following parameters, to form a chemical collecting container

- Plattengroße 1000 mm x 700 mm- Panel size 1000 mm x 700 mm

- Plattendicke 4 mm- Panel thickness 4 mm

- Formflache 960 mm x 660 mm- 960 mm x 660 mm molded surface

- Ziehtiefe 200 mm- Depth of drawing 200 mm

- Vortrocknen nicht erforderlich- Pre-drying is not necessary

- Temperatur des Formwerkzeuges 145°C- Mold temperature 145 ° C

- Heizquelle Ober- und Unterheizung IR Strahter mit einer Wellenlange von 2200 nm bis 3200 nm- Heating source upper and lower heating IR radiators with a wavelength of 2200 nm to 3200 nm

- Vakuum ja- vacuum yes

- Temperatur der Platte 1 15°C- Temperature of the plate 1 15 ° C

- Zeitdauer in der Form bei beidseitiger- Duration in the form with bilateral

Beheizung mit den IR Strahlern 150 sekHeating with the IR emitters 150 sec

- Kühlung 90 sek- cooling 90 sec

Der geformte Chemikalienauffangbehalter hat folgende EigenschaftenThe molded chemical container has the following properties

- Farbe Weiß- Color white

- Oberflachenglanz, der Seite, die nicht mit der Form in Berührung kam 110- surface gloss, the side that did not come into contact with the mold 110

- Lichttransmission 12%- light transmission 12%

- Clarity 0%- Clarity 0%

- Trübung 100 %- turbidity 100%

- Oberflachendefekte keine- Surface defects none

- Kristallmitat 49%- crystal mitate 49%

- Dichte 1 ,39 g/cm - Zugmodul (23°C) 3250 MPa- Density 1.39 g / cm - tensile modulus (23 ° C) 3250 MPa

- HDT B (0,45 MPa) 164°C - 168°C- HDT B (0.45 MPa) 164 ° C - 168 ° C

- Vicat-Erweichungstemperatur 168°C - 172°C- Vicat softening temperature 168 ° C - 172 ° C

Der Chemikalienauffangbehalter wurde 150-mal mit den unterschiedlichsten Chemikalien für 24 Stunden und langer belastet und erwies sich als absolut stabil Der Chemikalienbehälter wurde 48 Stunden in einem Autoklaven bei einer Temperatur von 162°C belassen und erwies sich vollständig und homogen über den Gegenstand als formstabilThe chemical container was loaded 150 times with a wide variety of chemicals for 24 hours and longer and proved to be absolutely stable. The chemical container was left in an autoclave at a temperature of 162 ° C for 48 hours and was completely and homogeneously stable over the object

Alles in allem zeichnet sich der erfindungsgemaße Formkorper durch eine hohe und gleichmäßige Warmeformbestandigkeit, eine definierte und gleichmäßige Lichttransmission, eine extreme Chemikahenbestandigkeit, durch eine homogene, glanzende, korrosionsfeste Oberflache sowie durch eine wirtschaftliche Herstellung aus All in all, the molded body according to the invention is characterized by a high and uniform heat resistance, a defined and uniform light transmission, an extreme chemical resistance, by a homogeneous, glossy, corrosion-resistant surface and by an economical production

Claims

Patentansprüche claims 1. Amorphe, transparente Platte mit einer Dicke im Bereich von 1 bis 20 mm, die als Hauptbestandteil einen kristallisierbaren Thermoplast enthält, dadurch gekennzeichnet, daß die Platte mindestens einen im wesentlichen homogen verteilten Keimbildner enthält.1. Amorphous, transparent plate with a thickness in the range from 1 to 20 mm, which contains a crystallizable thermoplastic as the main component, characterized in that the plate contains at least one essentially homogeneously distributed nucleating agent. 2. Platte gemäß Anspruch 1 , dadurch gekennzeichnet, daß der kristallisierbare Thermoplast Polyethylenterephthalat, Polybutylenterephthalat, Polyethylennaphthalat, Polybutylennaphthalat, ein Cycloolefinhomopolymer oder ein Cycloolefincopolymer oder eine Mischung aus diesen Thermoplasten ist.2. Plate according to claim 1, characterized in that the crystallizable thermoplastic is polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, a cycloolefin homopolymer or a cycloolefin copolymer or a mixture of these thermoplastics. 3 Platte gemäß Anspruch 2, dadurch gekennzeichnet, daß der kristallisierbare3 plate according to claim 2, characterized in that the crystallizable Thermoplast Polyethylenterephthalat ist.Thermoplastic is polyethylene terephthalate. 4. Platte gemäß mindestens einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß als Keimbildner anorganische und/oder organische Keimbildner verwendet werden.4. Plate according to at least one of the preceding claims, characterized in that inorganic and / or organic nucleating agents are used as nucleating agents. 5 Platte gemäß Anspruch 4, dadurch gekennzeichnet, daß die5 plate according to claim 4, characterized in that the Gesamtkonzentration an anorganischen Keimbildnern im Bereich von 0,01 bis 3,0 Gew.-% liegt, bezogen auf das Gewicht des kristallisierbaren Thermoplasten.Total concentration of inorganic nucleating agents is in the range from 0.01 to 3.0% by weight, based on the weight of the crystallizable thermoplastic. 6. Platte gemäß Anspruch 4, dadurch gekennzeichnet, daß die Gesamtkonzentration an organischen Keimbildnern im Bereich von 0,5 bis 40,0 Gew -% liegt, bezogen auf das Gewicht des kristallisierbaren Thermoplasten.6. Plate according to claim 4, characterized in that the total concentration of organic nucleating agents is in the range from 0.5 to 40.0% by weight, based on the weight of the crystallizable thermoplastic. 7. Platte gemäß mindestens einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß sie als Hauptbestandteil ein kristallisierbares Polyethylenterephthalat, 0,5 bis 40,0 Gew.-% Regenerat aus dem kristallisierbaren Polyethylenterephthalat mit einer wesentlich niedrigeren oder einer wesentlich höheren intrinsischen Viskosität als organischen Keimbildner sowie 0,01 bis 3,0 Gew -% Siliciumdioxid und/oder Kaolin als anorganischen Keimbildner enthalt7. Plate according to at least one of the preceding claims, characterized in that it is a crystallizable polyethylene terephthalate, 0.5 to 40.0 wt .-% of regrind from the main component contains crystallizable polyethylene terephthalate with a substantially lower or a substantially higher intrinsic viscosity than organic nucleating agents and 0.01 to 3.0% by weight of silicon dioxide and / or kaolin as inorganic nucleating agents Verfahren zur Herstellung eines Formkorpers aus einer amorphen, transparenten Platte gemäß mindestens einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß man die Platte mittels Wärmequelle aufheizt, die aufgeheizte Platte zwecks Formung tiefzieht, die tiefgezogene Platte warmebehandelt, die warmebehandelte Platte abkühlt und anschließend entformtA process for producing a molded body from an amorphous, transparent plate according to at least one of Claims 1 to 7, characterized in that the plate is heated by means of a heat source, the heated plate is deep-drawn for the purpose of shaping, the deep-drawn plate is heat-treated, the heat-treated plate is cooled and then demolded Verfahren gemäß Anspruch 8, dadurch gekennzeichnet, daß zum Aufheizen und/oder zur Wärmebehandlung Infrarotstrahler mit einer Wellenlange von großer 2000 nm verwendet werdenA method according to claim 8, characterized in that infrared radiators with a wavelength of greater than 2000 nm are used for heating and / or for heat treatment Verfahren gemäß Anspruch 8 oder 9, dadurch gekennzeichnet, daß die Wärmebehandlung bei einer Temperatur im Bereich von 100 bis 200°C für die Dauer von 30 Sekunden bis 6 Minuten durchgeführt wirdA method according to claim 8 or 9, characterized in that the heat treatment is carried out at a temperature in the range from 100 to 200 ° C for a period of 30 seconds to 6 minutes Formkorper erhältlich nach einem Verfahren gemäß mindestens einem der Ansprüche 8 bis 10, dadurch gekennzeichnet, daß der Kristallisationsgrad im Bereich von 20 bis 60 % hegt und die Schwankungen des Kristallisationsgrades innerhalb des Formkorpers weniger als 10 % betragenShaped bodies obtainable by a process according to at least one of claims 8 to 10, characterized in that the degree of crystallization is in the range from 20 to 60% and the fluctuations in the degree of crystallization within the shaped body are less than 10% Formkorper gemäß Anspruch 11 , dadurch gekennzeichnet, daß er eine Warmeformbestandigkeit von mehr als 100°C aufweist und die Schwankungen der Warmeformbestandigkeit innerhalb des Formkorpers nicht mehr als 20CC betragen Formkorper gemäß Anspruch 11 oder 2, dadurch gekennzeichnet, daß er eine Lichttransmission aufweist, die unter 50% hegtShaped body according to claim 11, characterized in that it has a heat resistance of more than 100 ° C and the fluctuations in the heat resistance within the molded body are not more than 20 C C. Shaped body according to claim 11 or 2, characterized in that it has a light transmission which is less than 50% Formkorper gemäß mindestens einem der Ansprüche 11 bis 13, dadurch gekennzeichnet, daß er einen Oberflachenglanz von großer 70 aufweistShaped body according to at least one of claims 11 to 13, characterized in that it has a surface gloss greater than 70 Formkorper gemäß mindestens einem der Ansprüche 11 bis 14, dadurch gekennzeichnet, daß er eine Trübung von über 50% aufweistShaped body according to at least one of claims 11 to 14, characterized in that it has a haze of over 50% Verwendung eines Formkorpers gemäß mindestens einem der Ansprüche 11 bis 15 für Messebau und Messeartikel, für Chemikalien- und Transportbehälter, für Sanitarartikel sowie im Laden- und Regalbau Use of a molded body according to at least one of claims 11 to 15 for stand construction and trade fair articles, for chemical and transport containers, for sanitary articles and in shop and shelf construction
PCT/EP1997/004689 1996-09-09 1997-08-28 Amorphous, transparent, crystallisable plate and a moulded body produced therefrom with a high and uniform dimensional stability when exposed to heat Ceased WO1998009799A1 (en)

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AU46190/97A AU4619097A (en) 1996-09-09 1997-08-28 Amorphous, transparent, crystallisable plate and a moulded body produced therefrom with a high and uniform dimensional stability when exposed to heat

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DE1996136541 DE19636541A1 (en) 1996-09-09 1996-09-09 Amorphous, transparent, crystallizable plate and a molded body made from it with a high and uniform heat resistance
DE19636541.4 1996-09-09

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GB0505967D0 (en) * 2005-03-23 2005-04-27 Imerys Minerals Ltd Infrared absorbing polymer compositions and films
CN101376690B (en) * 2007-08-30 2011-06-15 中国石化上海石油化工股份有限公司 Preparation of flame-retardant polyester for preparing fiber

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3496143A (en) * 1964-12-03 1970-02-17 Glanzstoff Ag Process for sheet forming polyethylene terephthalate
DE2420407A1 (en) * 1973-04-26 1974-11-14 Horizons Research Inc MOLDED BODIES AND METHOD FOR MANUFACTURING THEREOF
DE2748654A1 (en) * 1976-11-03 1978-05-11 Allied Chem SHEET MATERIAL, METHOD FOR MANUFACTURING IT, AND ITS USE
EP0471528A1 (en) * 1990-08-12 1992-02-19 Polysheet (Ireland) Limited A method and apparatus for forming an article of PET material

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3496143A (en) * 1964-12-03 1970-02-17 Glanzstoff Ag Process for sheet forming polyethylene terephthalate
DE2420407A1 (en) * 1973-04-26 1974-11-14 Horizons Research Inc MOLDED BODIES AND METHOD FOR MANUFACTURING THEREOF
DE2748654A1 (en) * 1976-11-03 1978-05-11 Allied Chem SHEET MATERIAL, METHOD FOR MANUFACTURING IT, AND ITS USE
EP0471528A1 (en) * 1990-08-12 1992-02-19 Polysheet (Ireland) Limited A method and apparatus for forming an article of PET material

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AU4619097A (en) 1998-03-26

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