WO1998005496A1 - Plaque multicouche en thermoplastique cristallisable, procede permettant de la produire et utilisation - Google Patents

Plaque multicouche en thermoplastique cristallisable, procede permettant de la produire et utilisation Download PDF

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Publication number
WO1998005496A1
WO1998005496A1 PCT/EP1997/003856 EP9703856W WO9805496A1 WO 1998005496 A1 WO1998005496 A1 WO 1998005496A1 EP 9703856 W EP9703856 W EP 9703856W WO 9805496 A1 WO9805496 A1 WO 9805496A1
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WO
WIPO (PCT)
Prior art keywords
plate
thermoplastic
plate according
layer
range
Prior art date
Application number
PCT/EP1997/003856
Other languages
German (de)
English (en)
Inventor
Ursula Murschall
Rainer Brunow
Original Assignee
Aventis Research & Technologies Gmbh & Co Kg
Hostaglas Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Aventis Research & Technologies Gmbh & Co Kg, Hostaglas Ltd. filed Critical Aventis Research & Technologies Gmbh & Co Kg
Priority to AU40109/97A priority Critical patent/AU4010997A/en
Priority to EP97937502A priority patent/EP0915756A1/fr
Priority to CA002262543A priority patent/CA2262543A1/fr
Publication of WO1998005496A1 publication Critical patent/WO1998005496A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04C—STRUCTURAL ELEMENTS; BUILDING MATERIALS
    • E04C2/00—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels
    • E04C2/54—Slab-like translucent elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2305/00—Condition, form or state of the layers or laminate
    • B32B2305/70—Scrap or recycled material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/412—Transparent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/584—Scratch resistance
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/702—Amorphous
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2367/00—Polyesters, e.g. PET, i.e. polyethylene terephthalate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2607/00—Walls, panels

Definitions

  • Multi-layer sheet made of a crystallizable thermoplastic, process for its production and use
  • the invention relates to an amorphous, transparent, multilayer plate made of a crystallizable thermoplastic, the thickness of which is in the range from 1 to 20 mm.
  • the invention further relates to a method for producing this plate and its use.
  • Multi-layer plates made of plastic materials are known per se.
  • UV-stabilized polycarbonate moldings are known which are composed of polydiorganosiloxane-polycarbonate block copolymers.
  • Multilayer plastic sheets are known from US Pat. No. 5,137,949, with layers of polydiorganosiloxane-polycarbonate block copolymers which contain UV absorbers.
  • EP-A-0 416 404 discloses UV-stabilized, branched polycarbonates made from special diphenols. It is mentioned that such polycarbonates can be used for the production of plates or multi-wall sheets.
  • the applicant has already described single-layer, transparent, amorphous plates with a thickness in the range from 1 to 20 mm, the main constituent of which is a crystallizable thermoplastic such as e.g. Contain polyethylene terephthalate (German Patent Application Nos. 19519579.5, 195221 18.4 and 19528336.8). These plates can have a standard viscosity of 800-6000 and contain a UV stabilizer.
  • a crystallizable thermoplastic such as e.g. Contain polyethylene terephthalate (German Patent Application Nos. 19519579.5, 195221 18.4 and 19528336.8).
  • These plates can have a standard viscosity of 800-6000 and contain a UV stabilizer.
  • EP-A-0 471 528 describes a method for molding an article from a polyethylene terephthalate (PET) plate.
  • the PET sheet is heat-treated on both sides in a deep-drawing mold in a temperature range between the glass transition temperature and the melting temperature.
  • the molded PET sheet is taken out of the mold when the degree of crystallization of the molded PET sheet is in the range of 25 to 50%.
  • the PET sheets disclosed in EP-A-0 471 528 have a thickness of 1 to 10 mm. Since the deep-drawn molded article made from this PET sheet is partially crystalline and therefore no longer transparent and the surface properties of the molded article are determined by the deep-drawing process, the temperatures and shapes given, it is immaterial which optical properties (e.g. gloss, cloudiness and Light transmission) have the PET plates used. As a rule, they are optical properties of these plates poor and in need of optimization.
  • These polyethylene terephthalate plates also have a single-layer structure.
  • US-A-3 496 143 describes the vacuum deep drawing of a 3 mm thick PET sheet, the crystallization of which is said to be in the range from 5 to 25%.
  • the crystallinity of the deep-drawn molded body is greater than 25%. No demands are made on the optical properties of these PET sheets either. Since the crystallinity of the plates used is already between 5 and 25%, these plates are cloudy and opaque.
  • These semi-crystalline PET sheets are also single-layer.
  • the plate or film used as the starting material has been produced from a PET with a crystallization temperature of at least 160 ° C. It follows from this relatively high crystallization temperature that this is not a PET homopolymer, but a glycol-modified PET, PET for short.
  • Called G which is a PET copolymer.
  • PET-G shows due to the additional built-in
  • Glycol units have an extremely low tendency to crystallize and is usually in the amorphous state.
  • the object of the present invention is to provide a multilayer, amorphous, transparent plate with a thickness of 1 mm to 20 mm, which is characterized by good mechanical and optical properties.
  • Good optical properties include, for example, high light transmission, high surface gloss, extremely low haze and high image sharpness (clarity).
  • the good mechanical properties include high impact strength and high breaking strength.
  • the plate according to the invention should be recyclable, in particular without loss of the mechanical properties, and also difficult to burn, so that it can also be used, for example, for interior applications and in trade fair construction.
  • amorphous plate is understood to mean plates which, although the crystallizable thermoplastic used preferably has a crystallinity of between 5 and 65%, are not crystalline. Not crystalline, i.e. essentially amorphous means that the degree of crystallinity is generally below 5%, preferably below 2% and particularly preferably 0% and that the plate has essentially no orientation.
  • crystallizable thermoplastic is understood to mean crystallizable homopolymers, crystallizable copolymers, crystallizable compounds, crystallizable recyclate and other variations of crystallizable thermoplastics.
  • suitable thermoplastics are polyalkylene terephthalates with C1 to C1 2-alkylene radical, such as polyethylene terephthalate and polybutylene terephthalate, polyalkylene naphthalates with C1 to C12 alkylene radical, such as polyethylene naphthalate and polybutylene naphthalate, crystallizable cycloolefin polymers and cycloolefin copolymers, with the thermoplastic and the thermoplastic or the thermoplastic (en) or thermoplastic the thermoplastic or the thermoplastics for the cover layer (s) can be the same or different. Polyolefins have also proven suitable for the top layer.
  • Thermoplastics with a crystallite melting point T m measured with DSC (differential scanning calorimetry) with a heating rate of 10 ° C / min, from 220 ° C to 260 ° C, preferably from 230 ° C to 250 ° C, with a crystallization temperature range T c between 75 ° C and 260 ° C, a glass transition temperature T g 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 5% and 65 % are preferred starting materials for the manufacture of the plate, polymers for the core layer and the top layer.
  • a thermoplastic with a cold (post) crystallization temperature T CN of 1 20 to 158 ° C, in particular 130 to 1 58 ° C, particularly preferred.
  • the bulk density measured according to DIN 53466, is preferably between 0.75 kg / dm 3 and 1.0 kg / dm 3 , and particularly preferably between 0.80 kg / dm 3 and 0.90 kg / dm 3 .
  • the polydispersity of the thermoplastic M w / M n measured by means of GPC, is preferably between 1.5 and 6.0 and particularly preferably between 2.0 and 5.0.
  • a particularly preferred crystallizable thermoplastic for the core layer (s) or the cover layer (s) is polyethylene terephthalate.
  • the invention preferred polyethylene terephthalate consists essentially of monomer units of the following formula
  • thermoplastic or the thermoplastic of the core layer (s) has a higher standard viscosity than the thermoplastic or the thermoplastic of the outer layer (s).
  • the standard viscosities of different core and / or outer layers of a multilayer plate can be different.
  • the standard viscosity SV (DCE) of the crystallizable thermoplastic of the core layer is preferably between 800 and 5000 and particularly preferably between 1000 and 4500.
  • the standard viscosity SV (DCE) of the crystallizable thermoplastic of the top layer is preferably between 500 and 4500 and particularly preferably between 700 and 4000.
  • the intrinsic viscosity IV can be calculated from the standard viscosity SV (DCE) as follows:
  • the crystallizable thermoplastics used according to the invention can be obtained by customary processes known to the person skilled in the art.
  • thermoplastics as used in the invention be obtained by melt polycondensation or by a two-stage polycondensation.
  • the first step is carried out up to an average molecular weight - corresponding to an average intrinsic viscosity IV of about 0.5 to 0.7 - in the melt and the further condensation by means of solid condensation.
  • the polycondensation is usually carried out in the presence of known polycondensation catalysts or catalyst systems.
  • chips made of the thermoplastic are heated to temperatures in the range from 180 to 320 ° C. under reduced pressure or under protective gas until the desired molecular weight is reached.
  • polyethylene terephthalate which is particularly preferred according to the invention, is described in detail in a large number of patent applications, as in JP-A-60-139 71 7, DE-C-2 429 087, DE-A-27 07 491, DE-A-23 19 089, DE-A-1 6 94 461, JP-63-41 528, JP-62-39 621, DE-A-41 1 7 825, DE-A-42 26 737, JP- 60-141 715, DE-A-27 21 501 and US-A-5 296 586.
  • Polyethylene terephthalates with particularly high molecular weights can be e.g. by polycondensation of dicarboxylic acid diol precondensates (oligomers) at elevated temperature in a liquid heat transfer medium in the presence of conventional polycondensation catalysts and, if necessary, co-condensable modifiers if the liquid heat transfer medium is inert and free of aromatic components and a boiling point in the range from 200 to 320 ° C has, the weight ratio of dicarboxylic acid diol precondensate (oligomers) to liquid heat transfer medium is in the range from 20:80 to 80:20, and the polycondensation is carried out in the boiling reaction mixture in the presence of a dispersion stabilizer.
  • the multilayer, transparent, amorphous plate according to the invention can, if desired, also be equipped with suitable additives.
  • This Additives can be added individually or as a mixture to one or more layers of the plate, as required.
  • UV stabilizers and antioxidants as described in German Patent Application No. 195 221 18.4 and the copending application by the same applicant with the title 'Polyethylene terephthalate plate with improved hydrolysis stability'. These applications are cited as part of the disclosure content of the present application.
  • the multilayer, transparent, amorphous plate can additionally contain at least one UV stabilizer as light stabilizer in the top layer (s) and / or the core layer (s).
  • Light especially the ultraviolet portion of solar radiation, i.e. the wavelength range from 280 to 400 nm initiate degradation processes in thermoplastics, as a result of which not only the visual appearance changes as a result of color change or yellowing, but also the mechanical-physical properties are adversely affected.
  • a high UV stability means that the plate is not or only slightly damaged by sunlight or other UV radiation, so that the plate is suitable for outdoor applications and / or critical indoor applications and shows little or no yellowing even after several years of outdoor use.
  • polyethylene terephthalates start below 360 nm Absorbing UV light, its absorption increases considerably below 320 nm and is very pronounced below 300 nm. The maximum absorption is between 280 and 300 nm.
  • UV stabilizers also called light stabilizers or UV absorbers, are chemical compounds that can intervene in the physical and chemical processes of light-induced degradation.
  • UV stabilizers suitable for the present invention are 2-hydroxybenzophenones, 2-hydroxybenzotriazoles, organo-nickel compounds, salicylic acid esters, cinnamic acid ester derivatives, resorcinol monobenzoates, oxalic acid anilides, hydroxybenzoic acid esters, sterically hindered amines and triazines, with 2-hydroxybenzotriazoles and triazines being preferred.
  • UV stabilizers Mixtures of several UV stabilizers can also be used.
  • the UV stabilizer is expediently present in a cover layer in a concentration of 0.01% by weight to 8% by weight, based on the weight of the thermoplastic in the cover layer provided with the stabilizer.
  • the UV stabilizer can also be added to a core layer. In this case, a concentration of 0.01% by weight to 1% by weight, based on the weight of the thermoplastic in the core layer provided with the stabilizer, is sufficient.
  • the core layer (s) can be equipped in order to prevent UV radiation which occurs in the event of possible damage to the outer layer from affecting the underlying core layer.
  • the transparent, amorphous plate according to the invention contains, as the main constituent, a crystallizable polyethylene terephthalate for the core layer and top layer and 0.01% to 8.0% by weight of 2- (4,6-diphenyl-1,3 , 5-triazin-2-yl) -5- (hexyl) oxyphenol or 0.01% by weight to 8.0% by weight of 2,2'-methylene-bis (6- (2H-benzotriazole- 2-yl) -4- (1, 1, 3,3-tetramethylbutyD-phenol in the top layer.
  • the plate according to the invention can also be equipped with at least one antioxidant.
  • Antioxidants are chemical compounds that can delay the signs of oxidation and hydrolysis and the resulting aging.
  • Antioxidants suitable for the plate according to the invention can be divided as follows:
  • Additive group Substance class primary antioxidants sterically hindered phenols and / or secondary, aromatic amines secondary antioxidants phosphites and phosphonites, thioethers, carbondiimides, zinc dibutyl dithiocarbamate
  • the amorphous plate according to the invention contains a phosphite and / or a phosphonite and / or a carbodiimide as a hydrolysis and oxidation stabilizer.
  • antioxidants used according to the invention are 2 - [(2, 4.8, 10-tetrakis (1, 1 -dimethylethyl) dibenzo [d, f] [1, 3.2] dioxaphosphepin-6-yl] oxy) - ethyljethanamine and Tris (2,4-di-tert-butylphenyl) phosphite.
  • the antioxidant is usually present in a concentration of 0.01 to 6% by weight, based on the weight of the thermoplastic of the layer provided with it.
  • the thickness of the multilayer plate according to the invention varies between 1 mm and 20 mm, the thickness of the cover layer (s) depending on the plate thickness being between 10 ⁇ m and 1 mm.
  • the cover layers preferably each have a thickness between 400 to 500 ⁇ m.
  • the plate according to the invention can have a plurality of core and cover layers which are stacked on top of one another in a sandwich.
  • the plate can also consist of only one cover layer and one core layer.
  • a structure with two cover layers and a core layer lying between the cover layers is particularly preferred.
  • the individual cover and core layers can contain different or identical crystallizable thermoplastics as main components, as long as the thermoplastic of a core layer has a higher standard viscosity than the thermoplastics of the cover layers directly adjacent to this core layer.
  • the transparent, amorphous, multilayer plate which optionally contains one or more additives, can be provided on one or more sides with a scratch-resistant surface.
  • US-A-4822828 discloses aqueous radiation-curable coating compositions which, each based on the weight of the dispersion, (A) from 50 to 85% of a silane with vinyl groups, (B) from 15 to 50% of a multifunctional Acrylates and optionally (C) 1 to 3% of a photoinitiator.
  • Ormocere Organic Chemical Modified Ceramics
  • PMMA polymethyl methacrylate
  • PC polycarbonate
  • the hard coatings are bound on the basis of Al 2 O 3 , ZrO 2 , TiO 2 or SiO 2 as network formers and epoxy or methacrylate groups with Si through ⁇ Si-C ⁇ connections.
  • Coating agents for acrylic resin plastics and polycarbonate based on silicone resin in aqueous-organic solution which have a particularly high storage stability, are e.g. in EP-A-0 073 362 and EP-A-0 073 91 1.
  • This technique uses the condensation products of partially hydrolyzed organosilicon compounds as coating agents, especially for glass and especially for acrylic resin plastics and PC.
  • Acrylic coatings such as e.g. the Uvecryl products from UCB Chemicals.
  • Uvecryl 29203 which is hardened with UV light.
  • This material consists of a mixture of urethane acrylate oligomers with monomers and additives. Ingredients are approximately 81% acrylate oligomers and 19% hexanediol diacrylate. These coatings are also described for PC and PMMA.
  • coatings are e.g. Peeraguard from Peerless, Clearlite and Filtalite from Charvo, coating types such as the UVHC series from GE Silicones, Vuegard such as the 900 series from TEC Electrical Components, from the Societ ⁇ Francaise Hoechst Highlink OG series, PPZ products sold by Siber Hegner (manufactured by Idemitsu) and coating materials from Vianova Resins, Toagoshi, Toshiba or Mitsubishi. These coatings are also described for PC and PMMA.
  • Coating methods known from the literature are e.g. Offset printing, pouring, dipping, flooding, spraying or spraying, knife coating or rolling.
  • Coatings applied by the described methods are then cured, for example by means of UV radiation and / or thermally.
  • a primer e.g. based on acrylate or acrylic latex.
  • CVD processes or vacuum plasma processes e.g. Vacuum plasma polymerization, PVD processes, such as coating with electron beam evaporation, resistance-heated evaporator sources or coating by conventional processes in high vacuum, such as in a conventional metallization.
  • Coating systems which are particularly suitable for the purposes of the present invention are systems (1), (2), (4) and (5), with coating system (4) being particularly preferred.
  • Suitable coating processes are e.g. also the casting, the spraying, the spraying, the immersion and the offset method, the spraying method being preferred for the coating system (4).
  • UV curing can take place with UV radiation and / or at temperatures which preferably do not exceed 80 ° C., UV curing being preferred.
  • the coating according to system (4) has the advantage that there is no crystallization which could cause turbidity. Furthermore, the coating shows excellent adhesion, excellent optical properties, very good chemical resistance and does not impair the intrinsic color.
  • the thickness of the scratch-resistant coating is generally between 1 and 50 ⁇ m.
  • the amorphous plate according to the invention which contains a crystallizable thermoplastic such as PET as the main component, has excellent mechanical and optical properties.
  • a n according to Charpy measured according to ISO 179/1 D
  • the notched impact strength a k according to Izod (measured according to ISO 180/1 A) of the plate is preferably in the range from 2.0 to 8.0 kJ / m 2 , particularly preferably in the range from 4.0 to 6.0 kJ / m 2 .
  • the image sharpness of the plate which is also called Clarity and which is determined at an angle of less than 2.5 ° (ASTM D 1003), is preferably above 95% and particularly preferably above 96%.
  • the surface gloss measured in accordance with DIN 67530 (measuring angle 20 °), is greater than 110, preferably greater than 120, the light transmission, measured in accordance with ASTM D 1003, is more than 80%, preferably more than 84%, and the turbidity of the plate, measured according to ASTM D 1003 is less than 15%, preferably less than 11%.
  • UV-stabilized plate according to the invention has no visible yellowing and no visible loss of gloss and no visible surface defects even after 5 to 7 years of outdoor use.
  • the plate according to the invention is flame-retardant and does not drip off with very little smoke, so that it is also particularly suitable for indoor applications and trade fair construction.
  • the plate according to the invention can be easily recycled without any environmental pollution and loss of mechanical properties, which is why it is suitable, for example, for the production of short-lived advertising signs or other promotional items.
  • thermoforming and vacuum forming behavior was found completely unexpectedly.
  • Polycarbonate sheets for example, have to be pre-dried at approx. 125 ° C for 3 to 50 hours, depending on the sheet thickness, before thermoforming.
  • the plate according to the invention can be obtained with very short thermoforming cycle times and at low temperatures during thermoforming. Because of these properties, moldings can be produced economically and with high productivity from the plate according to the invention on conventional thermoforming machines.
  • the multilayered, transparent, amorphous plate according to the invention can be produced in an extrusion line, for example, by the coextrusion process known per se.
  • An extruder for plasticizing and producing the core layer and an additional extruder per cover layer are connected to each coextruder adapter.
  • the adapter is constructed in such a way that the, possibly UV-stabilized, melts forming the cover layers are adhered as thin layers to the melt of the core layer.
  • the multilayer melt strand produced in this way is then shaped in the subsequently connected nozzle and calibrated, smoothed and cooled in the smoothing unit before the plate is cut to length.
  • thermoplastic polymer can be dried before coextrusion.
  • the drying can expediently take place at temperatures in the range from 110 to 190 ° C. over a period of from 1 to 7 hours.
  • the main dryer is connected to the main extruder and one dryer is connected to one coextruder per top layer.
  • the temperature of the melt is preferably in the range from 230 to 330 ° C, the temperature of the melt being able to be set essentially both by the temperature of the extruder and by the residence time of the melt in the extruder.
  • the polyethylene terephthalate preferred according to the invention as the thermoplastic is used, it is usually dried for 4 to 6 hours at 160 to 180 ° C. and the temperature of the melt is set in the range from 250 to 320 ° C.
  • UV stabilizer and / or an antioxidant can be metered in at the raw material manufacturer or metered into the extruder during plate production.
  • additives are fully dispersed in a solid carrier material.
  • Suitable carrier materials are certain resins, the thermoplastic itself or other polymers which are sufficiently compatible with the thermoplastic.
  • the grain size and bulk density of the masterbatch are similar to the grain size and bulk density of the thermoplastic, so that a homogeneous distribution and thus a homogeneous effect of the additives, e.g. UV and hydrolysis stabilization can take place.
  • the main extruder for producing the core layer and the co-extruder or co-extruders are connected to a co-extruder adapter in such a way that the melts forming the outer layers are adhered as thin layers to the melt of the core layer.
  • the multilayer melt strand thus produced is shaped in a connected nozzle.
  • This nozzle is preferably a slot die.
  • the multi-layer melt strand formed by a slot die is then calibrated by smoothing calender rolls, ie intensively cooled and smoothed.
  • the calender rolls used can, for example, be arranged in an I, F, L or S shape.
  • the material can then be cooled on a roller conveyor, cut to the side, cut to length and stacked.
  • the thickness of the plate obtained is essentially determined by the take-off which is arranged at the end of the cooling zone, the cooling (smoothing) rolls coupled to it in terms of speed and the conveying speed of the extruder on the one hand and the distance between the rolls on the other hand.
  • Both single-screw and twin-screw extruders can be used as extruders.
  • the slot die preferably consists of the dismantled tool body, the lips and the control bar for flow regulation across the width.
  • the control bar can be bent using tension and compression screws.
  • the thickness is adjusted by adjusting the lips. It is important to ensure that the temperature of the multilayer melt strand and the lip is uniform, otherwise the melt strand will flow out to different thicknesses through the different flow paths.
  • the calibration tool ie the smoothing calender, gives the melt strand the shape and dimensions. This is done by freezing below the glass transition temperature by cooling and smoothing. In this state, no more deformation should take place, as otherwise surface defects would occur due to the cooling. For this reason, the calender rolls are preferably driven together. The temperature of the calender rolls must be avoided to prevent the melt strand from sticking be less than the crystallite melting temperature.
  • the melt strand leaves the slot die preferably at a temperature of 240 to 300 ° C.
  • the first smoothing-cooling roller has a temperature between 50 ° C and 80 ° C depending on the output and plate thickness. The second, somewhat cooler roller cools the second or other surface.
  • the temperature of the first smoothing roll is 50 to 80 ° C.
  • the post-cooling device lowers the temperature of the plate to almost room temperature. After-cooling can be done on a roller board.
  • the speed of the take-off should be exactly matched to the speed of the calender rolls in order to avoid defects and thickness fluctuations.
  • a separating saw as a cutting device, the side trimming, the stacking system and a control point can be located in the extrusion line for producing the plates according to the invention as additional devices.
  • the side or edge trimming is advantageous because the thickness in the edge area can be uneven under certain circumstances. The thickness and appearance of the plate are measured at the control point.
  • the transparent, amorphous plate according to the invention is excellently suitable for a variety of different applications, for example for interior cladding, for trade fair construction and trade fair items, as displays, for signs, in the lighting sector, in shop and shelf construction, as promotional items, as Menu card stand, as Basketball goal boards, as room dividers, as aquariums, as information boards, as brochure and newspaper stands as well as for outdoor applications such as greenhouses, canopies, outer cladding, covers, for applications in the construction sector, illuminated advertising profiles, balcony cladding and roof hatches.
  • the surface gloss is measured at a measuring angle of 20 ° according to DIN 67530.
  • the reflector value is measured as an optical parameter for the surface of a plate. Based on the standards ASTM-D 523-78 and ISO 2813, the angle of incidence was set at 20 °. A light beam hits the flat test surface at the set angle of incidence and is reflected or scattered by it. The light rays striking the photoelectronic receiver are displayed as a proportional electrical quantity.
  • the measured value is dimensional and must be specified together with the angle of incidence.
  • Haze is the percentage of the transmitted light that deviates by more than 2.5 ° on average from the incident light beam.
  • the image sharpness is determined at an angle of less than 2.5 °.
  • the haze and clarity are measured using the "Hazegard plus" measuring device in accordance with ASTM D 1003.
  • the surface defects are determined visually.
  • This size is determined according to ISO 179/1 D.
  • the impact strength or strength a k according to Izod is measured according to ISO 1 80/1 A.
  • the density is determined according to DIN 53479.
  • the standard viscosity SV (DCE) is based on DIN 53728 in
  • the intrinsic viscosity (IV) is calculated as follows from the standard viscosity (SV)
  • Thermal properties such as crystallite melting point T m , crystallization temperature range T c , post- (cold) crystallization temperature T CN and glass transition temperature T g are measured by differential scanning calorimetry (DSC) at a heating rate of 10 ° C / min.
  • the molecular weights M w and M n and the resulting polydispersity M w / M n are measured by means of gel permeation chromatography (GPC).
  • UV stability is tested according to the test specification ISO 4892 as follows
  • Xenon lamp inner and outer filter made of borosilicate
  • the color change of the samples after artificial weathering is measured with a spectrophotometer according to DIN 5033.
  • the yellowness index G is the deviation from the colorlessness in the "yellow” direction and is measured in accordance with DIN 6167. Yellow value G values of ⁇ 5 are not visually visible.
  • Example 1 is each transparent sheets of different thicknesses which are produced on the extrusion line described.
  • a 4 mm thick, multilayer, transparent, amorphous polyethylene terephthalate plate with the layer sequence ABA is produced by the described coextrusion process, B representing the core layer and A the top layer.
  • the core layer B is 3.5 mm thick and the two outer layers that cover the core layer are each 250 thick.
  • the polyethylene terephthalate used for the core layer B has the following properties:
  • the main layers A contain polyethylene terephthalate and 3.0 wt .-% of the UV stabilizer 2- (4,6-diphenyl-1, 3,5-triazin-2-yl) -5- (hexyloxyphenol ( ® Tinuvin 1577 or Ciba-Geigy).
  • Tinuvin 1577 has a melting point of 140 ° C and is thermally stable up to approx. 330 ° C.
  • the UV stabilizer is incorporated into the polyethylene terephthalate directly at the raw material manufacturer.
  • the polyethylene terephthalate from which the outer layers are made has a standard viscosity SV (DCE) of 1010, which corresponds to an intrinsic viscosity IV (DCE) of 0.79 dl / g.
  • DCE intrinsic viscosity IV
  • 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 259 ° 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 w / M n of the polyethylene terephthalate is 2.14.
  • the glass transition temperature is 83 ° C.
  • the polyethylene terephthalate for the core layer and the UV-stabilized polyethylene terephthalate for the outer layers are each dried in a dryer at 170 ° C. for 5 hours and then coextruded through a slot die onto a smoothing calender, the rollers of which are arranged in an S-shape, and into one three-layer, 4 mm thick plate smoothed.
  • the extrusion temperature of the main extruder for the core layer is 282 ° C.
  • the extrusion temperatures of the two coextruders for the cover layers are 294 ° C.
  • the first calender roll has a temperature of 65 ° C and the subsequent rolls each have a temperature of 58 ° C.
  • the speed of the trigger is 4.2 m / min.
  • the three-layer transparent plate is lined with cut-off saws on the edges, cut to length and stacked.
  • the transparent, amorphous, three-layer PET sheet obtained has the following property profile
  • the PET plate After 1000 hours of weathering per side with the Atlas Ci 65 Weather Ometer, the PET plate shows the following properties:
  • Page 1 66 (measuring angle 20 °) 2. Page 1 64 Light transmission 91, 1% Clarity 100% turbidity 1, 2%
  • Example 2 Analogously to Example 1, a 4 mm thick, transparent, three-layer PET sheet is produced.
  • the core layer B consists of 50% of the polyethylene terephthalate
  • Example 1 and from 50% recycled plate from Example 1 together.
  • the transparent PET sheet obtained has the following property profile:
  • the PET panel After 1000 hours of weathering with Atlas Ci 65 Weather Ometer, the PET panel shows the following properties:
  • the cover layers contain 3.5% by weight of the UV stabilizer 2,2'-methylene-bis- (6- (2H-benzotriazol-2-yl) -4- (1, 1, 3,3-tetramethylbutyl) - phenol ( ® Tinuvin 360 from Ciby-Geigy), based on the weight of the thermoplastic
  • Tinuvin 360 has a melting point of 195 ° C and is thermally stable up to approx. 250 ° C.
  • Example 1 3.5% by weight of the UV stabilizer is incorporated directly into the polyethylene terephthalate at the raw material manufacturer.
  • the first calender roll has a temperature of 59 ° C and the subsequent rolls have a temperature of 51 ° C.
  • the speed of the trigger is 2.5 m / min.
  • the transparent PET sheet obtained has the following property profile:
  • the PET plate After 1000 hours of weathering per side with the Atlas Ci 65 Weather Ometer, the PET plate shows the following properties:
  • Page 1 51 (measuring angle 20 °) 2.
  • Page 150 Light transmission 88.3% Clarity 99.5% Haze 3.1%
  • Example 3 Analogously to example 1, a three-layer, transparent PET sheet is produced. As in Example 3, the top layers contain 3.5% by weight of Tinuvin 360 as UV stabilizer, based on the weight of the thermoplastic of the top layer, which has been incorporated directly at the raw material manufacturer.
  • the polyethylene terephthalate used for the core layer has the following properties:
  • the polyethylene terephthalate for the top layers is the same as in Example 1.
  • the extrusion temperature is 274 ° C.
  • the first calender roll has a temperature of 50 ° C and the subsequent rolls have a temperature of 45 ° C.
  • the speed of the take-off and the calender rolls is 2.4 m / min.
  • the plate produced has the following property profile:
  • the PET panel After 1000 hours of weathering with the Atlas Ci 65 Weather Ometer, the PET panel shows the following properties:
  • Page 1 50 (measuring angle 20 °) 2.
  • Page 149 Light transmission 86.2% Clarity 99, 1% haze 3.2%
  • Example 1 Analogous to example 1, a transparent, amorphous plate is produced. In contrast to example 1, the plate contains no UV stabilizer.
  • the polyethylene terephthalate used, the extrusion parameters, the process parameters and the temperatures are chosen as in Example 1.
  • the transparent, amorphous, three-layer board produced has the following property profile:
  • the PET plate After 1000 hours of weathering per side with the Atlas Ci 65 Weather Ometer, the PET plate shows the following properties:

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  • Engineering & Computer Science (AREA)
  • Architecture (AREA)
  • Civil Engineering (AREA)
  • Structural Engineering (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne une plaque multicouche transparente amorphe comprenant au moins une couche centrale et au moins une couche de recouvrement qui contiennent comme principal constituant un thermoplastique cristallisable. Le thermoplastique de la couche centrale présente une plus grande viscosité standard que celui de la couche de recouvrement. L'invention concerne en outre un procédé permettant de produire ladite plaque et son utilisation. La plaque obtenue selon l'invention peut également contenir au moins un additif tel que des antiultraviolets et des antioxydants et/ou être munie au moins sur une face d'un revêtement résistant aux éraflures.
PCT/EP1997/003856 1996-07-31 1997-07-18 Plaque multicouche en thermoplastique cristallisable, procede permettant de la produire et utilisation WO1998005496A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
AU40109/97A AU4010997A (en) 1996-07-31 1997-07-18 Multilayered crystallizable thermoplastic plate, process for its production and use thereof
EP97937502A EP0915756A1 (fr) 1996-07-31 1997-07-18 Plaque multicouche en thermoplastique cristallisable, procede permettant de la produire et utilisation
CA002262543A CA2262543A1 (fr) 1996-07-31 1997-07-18 Plaque multicouche en thermoplastique cristallisable, procede permettant de la produire et utilisation

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19630597A DE19630597A1 (de) 1996-07-31 1996-07-31 Mehrschichtige Platte aus einem kristallisierbaren Thermoplast, Verfahren zu ihrer Herstellung und Verwendung
DE19630597.7 1996-07-31

Publications (1)

Publication Number Publication Date
WO1998005496A1 true WO1998005496A1 (fr) 1998-02-12

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PCT/EP1997/003856 WO1998005496A1 (fr) 1996-07-31 1997-07-18 Plaque multicouche en thermoplastique cristallisable, procede permettant de la produire et utilisation

Country Status (5)

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EP (1) EP0915756A1 (fr)
AU (1) AU4010997A (fr)
CA (1) CA2262543A1 (fr)
DE (1) DE19630597A1 (fr)
WO (1) WO1998005496A1 (fr)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5976226A (ja) * 1982-10-26 1984-05-01 Kohjin Co Ltd ポリエステル積層フイルム及びその製造方法
US4737389A (en) * 1986-01-31 1988-04-12 Amoco Corporation Dual ovenable frozen food tray/cookware formed from a lainate containing a polymer that is crystallizable at use temperature
WO1994001268A1 (fr) * 1992-07-07 1994-01-20 Continental Pet Technologies, Inc. Procede pour produire une preforme et un recipient multicouche ayant une couche interieure a faible cristallisation
US5292471A (en) * 1990-12-13 1994-03-08 Toray Industries, Inc. Process for forming a polyester film
JPH08156210A (ja) * 1994-12-09 1996-06-18 Kanebo Ltd 滑り性に優れる熱成形ポリエステル容器
JPH08157619A (ja) * 1994-12-08 1996-06-18 Kanebo Ltd 滑り性に優れるポリエステルシート及びその成形品

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3213315C2 (de) * 1982-04-08 1986-10-09 GAO Gesellschaft für Automation und Organisation mbH, 8000 München Verfahren zur Herstellung einer mehrschichtigen Ausweiskarte
DE4214383C2 (de) * 1992-04-30 1996-08-14 Inventa Ag Koextrudiertes Mehrschicht-Polymer-Rohr

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5976226A (ja) * 1982-10-26 1984-05-01 Kohjin Co Ltd ポリエステル積層フイルム及びその製造方法
US4737389A (en) * 1986-01-31 1988-04-12 Amoco Corporation Dual ovenable frozen food tray/cookware formed from a lainate containing a polymer that is crystallizable at use temperature
US5292471A (en) * 1990-12-13 1994-03-08 Toray Industries, Inc. Process for forming a polyester film
WO1994001268A1 (fr) * 1992-07-07 1994-01-20 Continental Pet Technologies, Inc. Procede pour produire une preforme et un recipient multicouche ayant une couche interieure a faible cristallisation
JPH08157619A (ja) * 1994-12-08 1996-06-18 Kanebo Ltd 滑り性に優れるポリエステルシート及びその成形品
JPH08156210A (ja) * 1994-12-09 1996-06-18 Kanebo Ltd 滑り性に優れる熱成形ポリエステル容器

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 8423, Derwent World Patents Index; Class A23, AN 84-143786, XP002048175 *
DATABASE WPI Section Ch Week 9634, Derwent World Patents Index; Class A23, AN 96-338020, XP002048173 *
DATABASE WPI Section Ch Week 9634, Derwent World Patents Index; Class A23, AN 96-339294, XP002048174 *

Also Published As

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EP0915756A1 (fr) 1999-05-19
AU4010997A (en) 1998-02-25
DE19630597A1 (de) 1998-02-05
CA2262543A1 (fr) 1998-02-12

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