EP0915757A1 - Plaque monochrome transparente a couches multiples en matiere thermoplastique cristallisable, procede permettant de la produire et utilisation - Google Patents

Plaque monochrome transparente a couches multiples en matiere thermoplastique cristallisable, procede permettant de la produire et utilisation

Info

Publication number
EP0915757A1
EP0915757A1 EP97934486A EP97934486A EP0915757A1 EP 0915757 A1 EP0915757 A1 EP 0915757A1 EP 97934486 A EP97934486 A EP 97934486A EP 97934486 A EP97934486 A EP 97934486A EP 0915757 A1 EP0915757 A1 EP 0915757A1
Authority
EP
European Patent Office
Prior art keywords
thermoplastic
plate
layer
plate according
range
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP97934486A
Other languages
German (de)
English (en)
Inventor
Ursula Murschall
Rainer Brunow
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hostaglas Ltd
Original Assignee
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 Hostaglas Ltd filed Critical Hostaglas Ltd
Publication of EP0915757A1 publication Critical patent/EP0915757A1/fr
Withdrawn legal-status Critical Current

Links

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
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • 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
    • E04C2/02—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels characterised by specified materials
    • E04C2/10—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels characterised by specified materials of wood, fibres, chips, vegetable stems, or the like; of plastics; of foamed products
    • E04C2/20—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels characterised by specified materials of wood, fibres, chips, vegetable stems, or the like; of plastics; of foamed products of plastics
    • 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
    • B32B2272/00—Resin or rubber layer comprising scrap, waste or recycling 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
    • B32B2307/402—Coloured
    • 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
    • B32B2307/70—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, transparent colored plate made of a crystallizable thermoplastic, process for its production and use
  • the invention relates to an amorphous, transparently colored 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.
  • Multilayer plastic sheets are known from US Pat. No. 5,137,949, with layers of polydiorganosiioxane-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, transparently colored 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 and at least one dye soluble in this thermoplastic (German Patent Application Nos. 19519578.7, 19522120.6 and 19528334.1). These plates can have a standard viscosity of 800-6000 and contain a UV stabilizer. It goes without saying that the plates, starting materials, additives and processes described there can in principle also be used for the present invention, so that these applications belong to the disclosure content of the present application by quotation.
  • 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-0471 528 have a thickness of 1 to 10 mm. Since the deep-drawn molded article made from this PET sheet is semi-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, haze and light transmission) ) have the PET sheets used. Usually the optical properties of these plates are poor and need to be optimized.
  • These polyethylene terephthalate plates also have a single-layer structure and are also not colored.
  • 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 Austrian patent specification No. 304 086 describes a process for the production of transparent moldings by the deep-drawing process, a PET plate or film with a degree of crystallinity below 5% being used as the starting material.
  • 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 rather a glycol-modified PET, or PET-G for short, which is a PET copolymer.
  • PET-G shows an extremely low tendency to crystallize due to the additional built-in glycol units and is usually in the amorphous state.
  • the object of the present invention is to provide a multilayer, amorphous, transparently colored 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.
  • thermoplastics examples include polyalkylene terephthalates with C1 to C12 alkylene radical, such as polyethylene terephthalate and polybutylene terephthalate, Polyalkylene naphthalates with C1 to C12 alkylene radical, crystallizable cycloolefin polymers and cycloolefin copolymers, it being possible for the thermoplastic or the thermoplastics for the core layer (s) and the thermoplastic or the thermoplastics for the cover layer (s) to be the same or different.
  • Thermoplastics with a Kristaliitschmelz Vietnamese T m as measured by DSC (differential scanning calorimetry) at a heating rate of 10 ° C / min, from 220 ° C to 260 ⁇ C, preferably from 230 ° C to 250 ° C, with a crystallization temperature T c between 75 ° C and 260 ° 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 5% and 65% represent preferred polymers for the core layer and the cover layer as starting materials for the production of the plate.
  • a thermoplastic with a cold (post) crystallization temperature T CN of 120 to 158 ° C., in particular 130 to 158 ° 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 ⁇ M , measured by 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 or the cover layer (s) is polyethylene terephthalate.
  • the polyethylene terephthalate preferably used according to the invention essentially consists 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 thermoplastics of different core and / or cover 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:
  • thermoplastics used according to the invention can be obtained by customary processes known to the person skilled in the art.
  • thermoplastics as used according to the invention can 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, such as in JP-A-60-139717, DE-C-2 429087, DE-A-27 07 491, DE-A -23 19 089, DE-A-16 94461, JP-63-41 528, JP-62-39621, DE-A-41 17 825, DE-A-42 26737, JP-60-141 715, DE-A -27 21 501 and US-A-5296 586.
  • Polyethylene terephthalates with particularly high molecular weights can be produced, for example, 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 appropriate, co-condensable modifiers, if the liquid heat transfer medium is inert and free of aromatic components and one Boiling point in the range of 200 to 320 ⁇ C, the weight ratio of dicarboxylic acid diol precondensate (oligomers) to liquid heat transfer medium is in the range of 20:80 to 80:20, and the polycondensation is carried out in the boiling reaction mixture in the presence of a dispersion stabilizer .
  • the amorphous, multilayer plate contains at least one thermoplastic-soluble dye in at least one of the layers.
  • concentration of the soluble dye is preferably in the range from 0.001% by weight to 20% by weight, based on the weight of the thermoplastic of the layer provided with it.
  • Soluble dyes are substances that are molecularly dissolved in the polymer (DIN 55949).
  • the color change as a result of the coloring of the amorphous plate is based on the wavelength-dependent absorption and / or scattering of the light. Dyes can only absorb light, not scatter, since the physical requirement for scattering is a certain minimum particle size.
  • Coloring with dyes is a solution process. As The result of this solution process is that the dye is molecularly dissolved, for example, in the PET polymer. Such coloring is referred to as transparent or translucent or translucent or opal.
  • the fat and aromatic soluble dyes are particularly preferred. These are, for example, azo and anthraquinone dyes. They are particularly suitable for coloring PET because the migration of the dye is restricted due to the high glass transition temperature of PET.
  • Suitable soluble dyes are, for example: solvent yellow 93 a pyrazolone derivative, solvent yellow 16 a fat-soluble azo dye, fluorole green gold a fluorescent polycyclic dye, solvent red 1 an azo dye, azo dyes such as thermoplastic red BS, Sudan red BB, solvent red 138 an anthraquinone derivative, and fluorescent fluorophenane fluorophores such as fluorophenane GK, solvent blue 35 an anthraquinone dye, solvent blue a phthalocyanine dye and many others.
  • the multilayered, transparently colored, amorphous plate according to the invention can, if desired, also be equipped with other suitable additives. Depending on requirements, these additives can be added individually or as a mixture to one or more layers of the plate. These additives can also be mixed with the layer (s) with the dye.
  • UV stabilizers and antioxidants as described in German Patent Application No. 195 221 20.6 and the copending application by the same applicant with the title 'Polyethylene terephthalate plate with improved hydrolysis stability'. These registrations apply by quotation as part of the disclosure content of the present application.
  • the multilayer, transparently colored, 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 no or only slight yellowing even after several years of outdoor use.
  • polyethylene terephthalates begin to absorb UV light below 360 nm, their absorption increases considerably below 320 nm and is very pronounced below 300 nm. The maximum absorption is between 280 and 300 nm.
  • UV stabilizers 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 being preferred. Mixtures of several UV stabilizers can also be used.
  • the UV stabilizer is expediently present in a layer in a concentration of 0.01% by weight to 8% by weight, based on the weight of the thermoplastic in the layer provided with the stabilizer.
  • the UV stabilizer is added to a core layer, 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 generally sufficient.
  • several layers can be equipped with a UV stabilizer at the same time. In general, however, it is sufficient if the layer on which the UV radiation occurs is equipped.
  • the core layer (s) can be equipped in order to prevent UV radiation which occurs in the event of possible damage to the cover layer from affecting the underlying core layer.
  • the transparent-colored, amorphous plate according to the invention contains, as the main component, a crystallizable polyethylene terephthalate for the core layer and the top layer and 0.01% to 8.0% by weight of 2- (4,6-diphenyl-1, 3,5-triazin-2-yl) -5- (hexyl) oxy-phenol or 0.01% to 8.0% by weight of 2,2'-methylene-bis (6- (2H-benzotriazole -2-yl) -4- (1, 1, 3,3-tetramethylbutyl) 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) -ethyethanamine 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 sandwiched one above the other.
  • the plate can only consist of a top layer and a 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 transparently colored, amorphous, multilayer plate 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-Cs compounds.
  • 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-0 073 911 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 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. Components are about 81% acrylate oligomers and 19% hexanediol diacrylate.
  • coatings are, for example, 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 Societe Francaise Hoechst Highlink OG series, PPZ ® Products sold by Siber Hegner (manufactured by Idemitsu) and coating materials by 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 such as 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 conventional metallization.
  • Literature on CVD and PVD is for example: Modern coating processes by H.-D. Steffens and W. Brandl. DGM Information Society Verlag Oberursel. Other literature on coatings: Thin Film Technology by L. Maissei, R. Glang, McGraw-Hill, New York (1983).
  • 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).
  • 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 / 1D
  • the notched impact strength a k according to Izod (measured according to ISO 180 / 1A) of the plate is preferably in the range from 2.0 to 8.0 kJ / m 2 , particularly preferably in the range from 4.0 to 6.0 kJ / m 2nd
  • the image sharpness of the plate which is also called Clarity and is determined at an angle of less than 2.5 ° (ASTM D 1003), is preferably over 83% and particularly preferably over 84%.
  • the surface gloss measured according to DIN 67530 (measuring angle 20 °), is greater than 100, preferably greater than 110, the light transmission, measured according to ASTM D 1003, is generally between 5 and 90%, preferably between 10 and 80%, and the Turbidity of the plate, measured according to ASTM D 1003, is in the range from 2 to 50, preferably from 10 to 35%.
  • 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 were 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, the plate according to the invention can be used Manufacture moldings economically and with high productivity using conventional thermoforming machines.
  • the multilayer, transparently colored, amorphous plates according to the invention can be produced in an extrusion line, for example, by the coextrusion process known per se.
  • One extruder for plasticizing and producing the core layer and one additional extruder per cover layer are connected to each coextruder adapter.
  • the adapter is constructed in such a way that the 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
  • the main dryer is connected to the main extruder and one dryer is connected to one coextruder per top layer.
  • thermoplastic or the thermoplastics for the core layer (s) and the cover layer (s) are melted in the main extruder and in the coextrude.
  • the temperature of the melt is preferably in the range from 230 to 330 ° C, the temperature of the melt being set essentially both by the temperature of the extruder and the residence time of the melt in the extruder can.
  • 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.
  • the dye and optionally the additives such as a UV stabilizer and / or an antioxidant can already be metered in at the raw material manufacturer or metered into the extruder during plate manufacture.
  • the addition of the dye and, if appropriate, the additives via masterbatch technology is particularly preferred.
  • the dye and optionally the 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 the bulk density of the masterbatch are similar to the grain size and the bulk density of the thermoplastic, so that a homogeneous distribution and thus a homogeneous effect of the dye and the additives such as e.g. homogeneous coloring, UV and hydrolysis stabilization can take place.
  • the main extruder for producing the core layer and the coextruder (s) are connected to a coextruder adapter in such a way that the melts forming the outer layers are adhered to the melt of the core layer as thin layers.
  • 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 lower than the crystallite melting temperature in order to avoid sticking of the melt strand.
  • 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.
  • the second, somewhat cooler roller cools the second or other surface.
  • the temperature of the first smooth roller 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 transparently colored, amorphous plate according to the invention is outstandingly suitable for a large number of different applications, for example for interior cladding, for trade fair construction and trade fair articles, as displays, for signs, in the lighting sector, in shop and shelf construction, as promotional articles, as a menu card stand, as a basketball goal board, as a room divider, as aquariums, as information boards, as a brochure and newspaper stand and also for outdoor applications, such as Greenhouses, roofing, external 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 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 D 1003.
  • Haze is the percentage of the transmitted light that deviates by more than 2.5 ° on average from the incident light beam.
  • the image sharpness is determined at an angle of less than 2.5 °.
  • the haze and clarity are measured using the "Hazegard plus" measuring device in accordance with ASTM D 1003.
  • the surface defects are determined visually.
  • the impact strength or strength a k according to Izod is measured according to ISO 180 / 1A.
  • the density is determined according to DIN 53479.
  • the standard viscosity SV (DCE) is measured based on DIN 53728 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 , 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 M .. are measured by means of gel permeation chromatography (GPC).
  • the base layer B is 3.5 mm thick and the two cover layers which cover the base layer are each 250 ⁇ m thick.
  • the polyethylene terephthalate used for the base layer B has the following properties:
  • the main component of the base layer is the polyethylene terephthalate described and 2% by weight of the soluble dye Solventrot 138, an anthraquinone derivative from BASF ( ⁇ Thermoplast G).
  • the soluble dye Solventrot 138 is added in the form of a masterbatch.
  • the masterbatch is composed of 20% by weight of the dye Solventrot 138 as the active ingredient and 80% by weight of the above-described polyethylene terephthalate polymer as the carrier material.
  • the polyethylene terephthalate from which the cover layers are made has a standard viscosity SV (DCE) 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 is 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 MM ⁇ of the polyethylene terephthalate is 2.14.
  • the glass transition temperature is 83 ° C
  • the polyethylene terephthalate for the top layer is also dried in two smaller dryers, which are connected to the two coextrusions, at 170 ° C. for 5 hours.
  • the polyethylene terephthalate for the base or core layer and the masterbatch are melted in the main extruder and the polyethylene terephthalate for the cover layers are melted in the coextruder.
  • the extrusion temperature of the main extruder for the core layer is 281 ⁇ C.
  • the extrusion temperatures of the two coextruders for the cover layers are 294 ° C.
  • the main extruder and the two coextruders are connected to a coextruder adapter which is constructed in such a way that the melts forming the outer layers are adhered to the melt of the core layer as a thin layer.
  • the multilayer melt strand produced in this way is shaped in the connected slot die and smoothed on a smoothing calender, the rollers of which are arranged in an S-shape, to form a three-layer, 4 mm thick plate.
  • 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 added Cutting saws hemmed, cut to length and stacked at the edges.
  • the transparently colored, amorphous, three-layer PET sheet has the following property profile
  • the polyethylene terephthalate used for the base or core layer B has the following properties: SV (DCE) 3173
  • the soluble dye Solventrot 138 is added using masterbatch technology.
  • the base layer contains only 1.0% by weight of the solvent red 138 dye, i.e. only 5% by weight of the masterbatch is metered into the polyethylene terephthalate of the base layer.
  • 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
  • Example 2 Analogously to Example 1, a transparently colored, three-layer, amorphous plate is produced.
  • the base layer of the plate contains 4% by weight of the soluble dye
  • Solventblau 35 a fat-soluble anthraquinone dye from BASF
  • the 4 wt .-% of the dye solvent blue 35 are also in the form of a
  • Base layer composed of Example 1. 80 wt .-% of
  • Polyethylene terephthalate polymers of the base layer from Example 1 are 20
  • the blue-transparent colored plate produced has the following property profile:
  • a transparent colored plate is produced.
  • the outer layers are analogous to the outer layers from Example 1.
  • the polyethylene terephthalate used in the base layer has a standard viscosity SV (DCE) of 760, which corresponds to an intrinsic viscosity IV (DCE) of 0.62 dl / g.
  • DCE intrinsic viscosity IV
  • the other properties are identical to the properties of the polyethylene terephthalate from Example 1 within the scope of the measurement accuracy.
  • the masterbatch used is identical to the masterbatch from example 1.
  • the process parameters and the temperature were chosen as in Example 1. Due to the low viscosity of the base layer, plate production is not possible.
  • the three-layer melt strand shows a large number of flow disorders. The meltdown rate is insufficient.
  • Example 2 Analogously to Example 2, a transparently colored, translucent plate is produced, polyethylene terephthalate and masterbatch from Example 2 also being used.
  • the first calender roll has a temperature of 93 ° C. and the subsequent rolls each have a temperature of 87 ° C.
  • the plate produced is extremely cloudy and almost opaque Light transmission, clarity and gloss are significantly reduced.
  • the plate shows surface defects such as blisters, orange peel or blotchy structures.
  • the optics are unacceptable for a transparent colored application.
  • the plate produced has the following property profile:

Landscapes

  • Engineering & Computer Science (AREA)
  • Architecture (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Civil Engineering (AREA)
  • Structural Engineering (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne une plaque amorphe monochrome transparente à couches multiples d'une épaisseur comprise entre 1 et 20 mm, qui contient comme principal constituant une matière thermoplastique cristallisable et au moins un colorant soluble dans la matière plastique. Cette plaque comprend une couche de revêtement et au moins une couche médiane. La viscosité standard de la matière thermoplastique de la couche médiane est supérieure à celle de la matière thermoplastique constituant la(les) couche(s) de revêtement adjacente(s).
EP97934486A 1996-07-31 1997-07-18 Plaque monochrome transparente a couches multiples en matiere thermoplastique cristallisable, procede permettant de la produire et utilisation Withdrawn EP0915757A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19630598 1996-07-31
DE19630598A DE19630598A1 (de) 1996-07-31 1996-07-31 Mehrschichtige, transparent eingefärbte Platte aus einem kristallisierbaren Thermoplast, Verfahren zu ihrer Herstellung und Verwendung
PCT/EP1997/003854 WO1998005498A1 (fr) 1996-07-31 1997-07-18 Plaque monochrome transparente a couches multiples en matiere thermoplastique cristallisable, procede permettant de la produire et utilisation

Publications (1)

Publication Number Publication Date
EP0915757A1 true EP0915757A1 (fr) 1999-05-19

Family

ID=7801199

Family Applications (1)

Application Number Title Priority Date Filing Date
EP97934486A Withdrawn EP0915757A1 (fr) 1996-07-31 1997-07-18 Plaque monochrome transparente a couches multiples en matiere thermoplastique cristallisable, procede permettant de la produire et utilisation

Country Status (5)

Country Link
EP (1) EP0915757A1 (fr)
AU (1) AU3768197A (fr)
CA (1) CA2261716A1 (fr)
DE (1) DE19630598A1 (fr)
WO (1) WO1998005498A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA3080129A1 (fr) * 2017-10-31 2019-05-09 Flex Films (Usa) Inc. Films thermoplastiques a faible empreinte carbone comprenant des materiaux recycles

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT304086B (de) * 1970-08-07 1972-12-27 Sandoz Ag Verfahren zur Herstellung von transparenten Formkörpern nach dem Tiefzieh-Verfahren
DE3739765A1 (de) * 1987-11-24 1989-06-08 Bayer Ag Beschichtete formkoerper und ein verfahren zu ihrer herstellung
DE4009638C2 (de) * 1990-03-26 2000-11-09 Hoechst Ag Verfahren zur Herstellung einer koextrudierten Folie
JP3378040B2 (ja) * 1993-03-02 2003-02-17 帝人株式会社 写真感光材料用フイルム
JPH081767A (ja) * 1994-06-23 1996-01-09 Kanebo Ltd 耐衝撃性に優れるポリエステル容器
RU2160666C2 (ru) * 1995-05-29 2000-12-20 Хостаглас Лтд. Аморфная прозрачно окрашенная пластина из кристаллизуемого термопласта, способ ее изготовления и ее применение

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9805498A1 *

Also Published As

Publication number Publication date
CA2261716A1 (fr) 1998-02-12
WO1998005498A1 (fr) 1998-02-12
DE19630598A1 (de) 1998-02-05
AU3768197A (en) 1998-02-25

Similar Documents

Publication Publication Date Title
EP1274576B1 (fr) Feuille de polyester coextrudee, thermoformable, stable aux rayons ultraviolets et mate, son procede de production et son utilisation
DE19522118C1 (de) Amorphe, transparente, UV-stabilisierte Platte aus einem kristallisierbaren Thermoplast, Verfahren zu deren Herstellung sowie deren Verwendung
WO2001053089A1 (fr) Feuille polyester matte, stable aux u.v., ignifugeante, coextrudee, son procede de realisation et son utilisation
WO1996038498A1 (fr) Plaque coloree transparente amorphe en thermoplaste cristallisable, son procede de fabrication et son utilisation
WO1998005708A1 (fr) Plaque de polyethylene terephtalate a meilleure stabilite de l'hydrolyse, procede permettant de la produire et utilisation
EP1268206B1 (fr) Feuille polyester matte, stable aux u.v., coextrudee, son procede de realisation et son utilisation
EP0828599B1 (fr) Plaque coloree amorphe en matiere thermoplastique cristallisable
EP0842039A1 (fr) Plaque transparente amorphe en thermoplastique de haute viscosite standard, apte a la cristallisation
DE19630817A1 (de) Mehrschichtige, eingefärbte Platte aus einem kristallisierbaren Thermoplast, Verfahren zu ihrer Herstellung und Verwendung
EP0915757A1 (fr) Plaque monochrome transparente a couches multiples en matiere thermoplastique cristallisable, procede permettant de la produire et utilisation
WO1998005496A1 (fr) Plaque multicouche en thermoplastique cristallisable, procede permettant de la produire et utilisation
WO2002068511A1 (fr) Feuille amorphe fonctionnalisee constituee d'un thermoplaste modifie par dibenzene, son procede de realisation et son utilisation
DE10022946A1 (de) Weisse, zumindest einseitig matte, biaxial orientierte, UV-stabilisierte und schwer entflammbare Polyesterfolie mit Cycloolefincopolymer (COC), Verfahren zu ihrer Herstellung und ihre Verwendung
WO2001060140A2 (fr) Pellicule polyester blanche, scellable, rendue stable aux u.v. et traitee ignifuge, a orientation biaxiale, procede permettant de la produire et utilisation
WO1998050222A1 (fr) Plaque amorphe a surface structuree
DE29712484U1 (de) Amorphe Platte mit strukturierter Oberfläche
EP1274578B1 (fr) Feuille polyester matte, stable aux u.v., peu inflammable, thermoformable, coextrudee, son procede de realisation et son utilisation
DE19528334A1 (de) Amorphe, transparent eingefärbte Platte aus einem kristallisierbaren Thermoplast mit hoher Standardviskosität
DE10043779A1 (de) Matte, mehrschichtige, funktionalisierte Folie aus einem bibenzolmodifizierten Thermoplasten, Verfahren zu ihrer Herstellung und ihre Verwendung
DE19642287A1 (de) Mehrschichtige Platte aus einem kristallisierbaren Thermoplast, ein daraus herstellbarer, kristallisierter Formkörper sowie dessen Verwendung
DE19522119A1 (de) Amorphe, eingefärbte, UV-stabilisierte Platte aus einem kristallisierbaren Thermoplast
DE19522120A1 (de) Amorphe, transparent eingefärbte, UV-stabilisierte Platte aus einem kristallisierbaren Thermoplast
DE19528333A1 (de) Amorphe, eingefärbte Platte aus einem kristallisierbaren Thermoplast mit hoher Standardviskosität

Legal Events

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

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19990225

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB IE IT LI NL PT SE

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

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20030201