EP0833858A1 - Panneau transparent amorphe stabilise vis-a-vis des u.v. en une matiere thermoplastique susceptible de se cristalliser - Google Patents

Panneau transparent amorphe stabilise vis-a-vis des u.v. en une matiere thermoplastique susceptible de se cristalliser

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Publication number
EP0833858A1
EP0833858A1 EP96918681A EP96918681A EP0833858A1 EP 0833858 A1 EP0833858 A1 EP 0833858A1 EP 96918681 A EP96918681 A EP 96918681A EP 96918681 A EP96918681 A EP 96918681A EP 0833858 A1 EP0833858 A1 EP 0833858A1
Authority
EP
European Patent Office
Prior art keywords
plate according
plate
polyethylene terephthalate
range
stabilizer
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Withdrawn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
EP96918681A
Other languages
German (de)
English (en)
Inventor
Ursula Murschall
Wolfgang Gawrisch
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
Hoechst AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hoechst AG filed Critical Hoechst AG
Publication of EP0833858A1 publication Critical patent/EP0833858A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/22—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of indefinite length
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07—Flat, e.g. panels
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07—Flat, e.g. panels
    • B29C48/08—Flat, e.g. panels flexible, e.g. films
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
    • B29C48/911—Cooling
    • B29C48/9135—Cooling of flat articles, e.g. using specially adapted supporting means
    • B29C48/914—Cooling of flat articles, e.g. using specially adapted supporting means cooling drums
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
    • B29C48/911—Cooling
    • B29C48/9135—Cooling of flat articles, e.g. using specially adapted supporting means
    • B29C48/9145—Endless cooling belts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
    • B29C48/90—Thermal treatment of the stream of extruded material, e.g. cooling with calibration or sizing, i.e. combined with fixing or setting of the final dimensions of the extruded article
    • B29C48/906—Thermal treatment of the stream of extruded material, e.g. cooling with calibration or sizing, i.e. combined with fixing or setting of the final dimensions of the extruded article using roller calibration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2067/00—Use of polyesters or derivatives thereof, as moulding material

Definitions

  • the invention relates to an amorphous, transparent, UV-stabilized plate made of a crystallizable thermoplastic, the thickness of which is in the range from 1 to 20 mm.
  • the plate contains at least one UV stabilizer as a light stabilizer and is characterized by very good optical and mechanical properties.
  • the invention further relates to a method for producing this plate and its use.
  • thermoplastics which are processed into sheets, are, for. B. polyvinyl chloride (PVC), polycarbonate (PC) and polymethyl methacrylate (PMMA).
  • PVC polyvinyl chloride
  • PC polycarbonate
  • PMMA polymethyl methacrylate
  • the amorphous thermoplastics can be easily reshaped using smoothing units or other shaping tools due to the steadily increasing viscosity as the temperature decreases.
  • amorphous thermoplastics After molding, amorphous thermoplastics then have sufficient stability, ie a high viscosity, in order to "stand on their own” in the calibration tool. But they are still soft enough to be shaped by the tool.
  • the melt viscosity and inherent stiffness of amorphous thermoplastics is so high in the calibration tool that the semi-finished product does not collapse in the calibration tool before it cools down.
  • easily decomposable materials such.
  • B. PVC are special processing aids for extrusion, such as B. Processing stabilizers against decomposition and lubricants against excessive internal friction and thus uncontrollable heating necessary. External lubricants are required to prevent snagging on walls and rollers.
  • PMMA sheets also have extremely poor impact strength and shatter when broken or subjected to mechanical stress.
  • PMMA panels are highly flammable, so that they must not be used, for example, for indoor applications or in exhibition stand construction.
  • PMMA and PC sheets are also not cold-formable. During cold forming, PMMA sheets break into dangerous fragments. When cold-forming PC sheets, hairline cracks and whitening occur.
  • DE-A-3 531 878 describes plastic films made of thermoplastic polyester which contain a UV stabilizer and have a thickness of 0.5-0.03 mm. These foils are obtained by extrusion blow molding and are therefore partially crystalline. Consequently, the method described in this document cannot be used to obtain an amorphous film with a thickness of 1 mm or more.
  • JP-A-5 320 528 describes a thermoplastic resin composition containing an epoxylated polyester. According to a preferred embodiment, this composition contains PVC as the main component. The plates obtained from this by kneading are transparent and 1 mm thick.
  • EP-A-0 471 528 describes a method for molding an article from a polyethylene terephthalate (PET) plate.
  • the PET plate is heat-treated in a deep-drawing mold on both sides in a temperature range between the glass transition temperature and the melting temperature.
  • the molded PET sheet is taken out of the mold when the degree of crystallization of the molded PET sheet is in the range of 25 to 50%.
  • the PET sheets disclosed in EP-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, Turbidity and light transmission) have the PET plates used. As a rule, the optical properties of these plates are poor and need to be optimized.
  • optical properties e.g. gloss, Turbidity and light transmission
  • these plates do not contain any UV stabilizers as light stabilizers, so that neither the plates nor the moldings made from them are suitable for outdoor use.
  • these plates or molded articles show yellowing and deterioration of the mechanical properties due to photooxidative degradation by sunlight after a short time.
  • US Pat. No. 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 plates also do not contain any light stabilizers and are therefore not suitable for outdoor use.
  • amorphous plates which contain a crystallizable thermoplastic as the main component, with a thickness of 1 mm or more could not be produced in sufficient quality.
  • the object of the present invention was to provide an amorphous, transparent plate with a thickness of 1 to 20 mm which, in addition to good mechanical and optical properties, above all has high UV stability.
  • a high UV stability means that the plates are not or only slightly damaged by sunlight or other UV radiation, so that the plates are suitable for outdoor applications and / or critical indoor applications.
  • the panels should not yellow over several years of outdoor use, should not show embrittlement or cracking of the surface, and should not show any deterioration in the mechanical 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 flame-retardant, so that it can also be used, for example, for interior applications and in exhibition construction.
  • a transparent, amorphous plate with a thickness in the range from 1 to 20 mm, which contains a crystallizable thermoplastic as the main component, which is characterized in that the plate contains at least one UV stabilizer as light stabilizer.
  • the main component of the transparent, amorphous plate is a crystallizable thermoplastic.
  • Suitable crystallizable or partially crystalline thermoplastics are, for example, polyethylene terephthalate,
  • crystallizable thermoplastics are understood to mean crystallizable homopolymers, crystallizable copolymers, crystallizable compounds, crystallizable recyclate and other variations of crystallizable thermoplastics.
  • amorphous plate is understood to mean those plates which, although the crystallizable thermoplastic used preferably has a crystallinity of between 5 and 65%, particularly preferably between 25 and 65%, are not crystalline.
  • Non-crystalline or amorphous means that the degree of crystallinity is generally below 5%, preferably below 2% and particularly preferably 0%.
  • the amorphous plate according to the invention is essentially unoriented.
  • the transparent, amorphous plate further contains at least one UV stabilizer as light stabilizer, the concentration of the UV stabilizer preferably being between 0.01% by weight and 5% by weight, based on the weight of the crystallizable thermoplastic.
  • Light especially the ultraviolet portion of solar radiation, i.e. H. the wavelength range from 280 to 400 nm initiates degradation processes in thermoplastics, as a result of which not only the visual appearance changes as a result of color change or yellowing, but also the mechanical-physical properties are adversely affected.
  • Polyethylene terephthalates for example, begin to absorb UV light below 360 nm, their absorption increases considerably below 320 nm and is very pronounced below 300 nm. The maximum absorption is between 280 and 300 nm.
  • UV stabilizers or UV absorbers as light stabilizers are chemical compounds that can intervene in the physical and chemical processes of light-induced degradation. Soot and other pigments can partially protect against light. However, these substances are unsuitable for transparent plates because they lead to discoloration or color change. For transparent, amorphous plates, only organic and organometallic compounds are suitable, which give the thermoplastic to be stabilized no or only an extremely small color or color change.
  • Suitable UV stabilizers as light stabilizers are, for example, 2-hydroxybenzophenones, 2-hydroxybenzotriazoles, organo-nickel compounds, salicylic acid esters, cinnamic acid ester derivatives, resorcinol monobenzoates, oxalic acid anilides, hydroxybenzoic acid esters, sterically hindered amines and triazines, the 2-hydroxybenzotriazoles being preferred.
  • the transparent, amorphous plate according to the invention contains, as the main constituent, a crystallizable polyethylene terephthalate and 0.01% by weight to 5.0% by weight of 2- (4,6-diphenyl-1,3,5-triazine -2-yl) -5- (hexyl) oxy-phenol (structure in Fig. 1 a) or 0.01 wt% to 5.0 wt% 2,2'-methylene-bis (6- ( 2H-benzotriazol-2-yl) -4- (1, 1, 3,3-tetramethylbutyD-phenol (structure in Fig. 1 b).
  • mixtures of these two UV stabilizers or mixtures of at least one of these can also be used two UV stabilizers, the total concentration of light stabilizers is preferably between 0.01% and 5.0% by weight, based on the weight of crystallizable polyethylene terephthalate.
  • the surface gloss measured according to DIN 67530 (measuring angle 20 °), is greater than 1 20, preferably greater than 140, the light transmission, measured according to ASTM D 1003, is more than 84%, preferably more than 86%, and the cloudiness of the plate, measured according to ASTM D 1003, is less than 15%, preferably less than 11%.
  • the image sharpness of the plate which is also called Clarity and is determined at an angle of less than 2.5 c (ASTM D 1003), is preferably above 96% and particularly preferably above 97%.
  • the notched impact strength a k according to Izod (measured according to ISO 180/1 A) of the plate is in the range from 2.0 to 8.0 kJ / m 2 , preferably in the range from 3.0 to 8.0 kJ / m 2 and particularly preferably in the range from 4.0 to 6.0 kJ / m 2 .
  • Polyethylene terephthalates 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 280 ° C, preferably from 250 ° C to 270 ° C, with a crystallization temperature range T c between 75 ° C and 280 ° C, preferably 75 ° C to 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%, preferably between 25% and 65%, are preferred polymers as starting materials for the production of the plate according to the invention.
  • the standard viscosity SV (DCE) of the polyethylene terephthalate, measured in dichloroacetic acid according to DIN 53728, is between 800 and 1,800, preferably between 950 and 1,250 and particularly preferably between 1000 and 1
  • the intrinsic viscosity IV (DCE) is calculated from the standard viscosity SV (DCE) as follows:
  • the bulk density measured according to DIN 53466, is preferably between 0.75 kg / dm 3 and 1.0 kg / dm 3 , and particularly preferably between 0.80 kg / dm 3 and 0.90 kg / dm 3 .
  • the polydispersity M w / M n of the polyethylene terephthalate measured by means of gel permeation chromatography is preferably between 1.5 and 6.0 and particularly preferably between 2.0 and 3.5.
  • the UV-stabilized plates according to the invention generally have no yellowing, no embrittlement, no loss of gloss on the surface, no cracking on the surface and no deterioration in the mechanical properties.
  • the PET panel according to the invention is flame-retardant and flame-retardant, so that it is suitable, for example, for indoor applications and in exhibition stand construction. Furthermore, the plate according to the invention can be easily recycled without environmental pollution and without loss of the mechanical properties, which makes it suitable, for example, for use as short-lived advertising signs or other promotional items.
  • the transparent, amorphous, UV-stabilized plate according to the invention can be produced, for example, by an extrusion process in an extrusion line.
  • Such an extrusion line is shown schematically in FIG. 2. It essentially comprises an extruder (1) as a plasticizing system, a slot die (2) as a tool for shaping, a smoothing unit / calender (3) as a calibration tool, a cooling bed (4) and / or a roller conveyor (5) for after-cooling, a roller take-off (6), a separating saw (7), a side cutting device (9), and optionally a stacking device (8).
  • the process is characterized in that the crystallizable thermoplastic (for example polyethylene terephthalate) is optionally dried, then melted in the extruder, preferably together with the UV stabilizer, the melt is molded through a nozzle and then calibrated, smoothed and cooled in the calender before being brings the plate to size.
  • the first roller of the smoothing unit has a temperature which is in the range from 50 ° C. to 80 ° C., since it would otherwise be difficult to produce an amorphous transparent plate with a crystallizable thermoplastic in a thickness of 1 mm and more.
  • the light stabilizer can be metered in at the thermoplastic raw material manufacturer or can be metered into the extruder during plate production.
  • the addition of the light stabilizer via masterbatch technology is particularly preferred.
  • the light stabilizer is fully dispersed in a solid carrier material.
  • carrier materials come certain resins, the thermoplastic itself, such as. B. the polyethylene terephthalate or other polymers that are sufficiently compatible with the thermoplastic, in question.
  • the grain size and bulk density of the masterbatch is similar to the grain size and bulk density of the thermoplastic, so that a homogeneous distribution and thus homogeneous UV stabilization can take place.
  • the drying of the polyethylene terephthalate before the extrusion is preferably carried out for 4 to 6 hours at 160 to 180 ° C.
  • the polyethylene terephthalate is then melted in the extruder.
  • the temperature of the PET melt is preferably in the range from 250 to 320 ° C., the temperature of the melt being able to be set essentially both by the temperature of the extruder and by the residence time of the melt in the extruder.
  • the melt then leaves the extruder through a nozzle. This nozzle is preferably a slot die.
  • the PET melted by the extruder and shaped by a slot die is calibrated by smoothing calender rolls, i.e. H. intensely chilled and smoothed.
  • the calender rolls can, for example, be arranged in an I, F, L or S shape (FIG. 3).
  • the PET material can then be cooled on a roller conveyor, cut to the side, cut to length and finally stacked.
  • the thickness of the PET plate is essentially determined by the take-off, which is arranged at the end of the cooling zone, the cooling (smoothing) rolls coupled with it in terms of speed and the conveying speed of the extruder on the one hand and the distance between the rolls on the other hand.
  • Both single-screw and twin-screw extruders can be used as extruders.
  • the slot die preferably consists of the separable tool body, the lips and the dust bar for flow regulation across the width.
  • the dust bar can be bent by tension and pressure screws.
  • the thickness is adjusted by adjusting the lips. It is important to ensure that the temperature of the PET and the lip is even, otherwise the PET melt will flow out to different thicknesses due to the different flow paths.
  • the calibration tool, d. H. the smoothing calender gives the PET melt the shape and dimensions. This is done by freezing below the glass transition temperature by means of cooling and smoothing. Deformation is no longer allowed in this state, otherwise it will be in this cooled state Surface defects would arise. 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 PET melt.
  • the PET melt leaves the slot die at a temperature of 240 to 300 ° C.
  • the first smoothing-cooling roller has a temperature between 50 ° C and 80 ° C depending on the output and plate thickness. The second, somewhat cooler roller cools the second or other surface.
  • the after-cooling device lowers the temperature of the PET 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 the production of PET sheets 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 and amorphous plate according to the invention is excellently suitable for a large number of different uses, for example for interior cladding, for trade fair construction and trade fair articles, as displays, for signs, for protective glazing of machines and vehicles, in the lighting sector, in the store. and shelf construction, as promotional items, as menu card stands, as basketball goal boards, as room dividers, for aquariums, as Information boards and as brochure and newspaper stands.
  • the transparent, amorphous plate according to the invention is also suitable for outdoor applications, such as for greenhouses, roofing, glazing, safety glasses, external cladding, covers, applications in the construction sector, illuminated advertising profiles, balcony cladding, roof hatches and caravan windows.
  • the surface gloss is measured at a measuring angle of 20 ° according to DIN 67530.
  • 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.
  • This size is determined according to ISO 1 79/1 D.
  • the notched 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 53726 in
  • the intrinsic viscosity (IV) is calculated as follows from the standard viscosity (SV)
  • the thermal properties such as crystallite melting point T m , crystallization temperature range T c , post- (cold) crystallization temperature T CN and glass transition temperature T are measured by means of differential scanning calorimetry (DSC) at a heating rate of 10 ° C / min.
  • DSC differential scanning calorimetry
  • the molecular weights M w and M n and the resulting polydispersity 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 61 67. Yellow value G values of ⁇ 5 are not visually visible.
  • a 3 mm thick, transparent, amorphous plate is produced, the main constituent being polyethylene terephthalate and 1.0% by weight of the UV stabilizer 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5- (hexyl) oxyphenol (Tinuvin 1 577 from the company Ciba-Geigy) contains.
  • Tinuvin 1 577 has a melting point of 149 C C and is thermally stable up to approx. 330 ° C.
  • the UV stabilizer is incorporated directly into the polyethylene terephthalate at the raw material manufacturer.
  • the polyethylene terephthalate from which the transparent plate is made has a standard viscosity SV (DCE) of 1010, which corresponds to an intrinsic viscosity IV (DCE) of 0.79 dl / g.
  • 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 258 ° C.
  • the crystallization temperature range T c is between 83 ° C and 258 ° C, the post-crystallization temperature (also cold crystallization temperature) T CN at 144 ° C.
  • the polydispersity M w / M n of the polyethylene terephthalate is 2.14.
  • the glass transition temperature is 83 ° C.
  • the polyethylene terephthalate with a crystallinity of 59% is dried in a dryer at 170 ° C. for 5 hours and then extruded in a single-screw extruder at an extrusion temperature of 286 ° C. through a slot die onto a smoothing calender whose rolls are arranged in an S-shape and smoothed into a 3 mm thick plate.
  • the first calender roll has a temperature of 73 ° C and the subsequent rolls each have a temperature of 67 ° C.
  • the speed of the take-off and the calender rolls is 6.5 m / min.
  • the transparent, 3 mm thick PET sheet is trimmed at the edges with separating saws, cut to length and stacked.
  • the transparent, amorphous PET sheet produced has the following property profile:
  • the PET plate After 1000 hours of weathering per side with Atlas Ci 65 Weather Ometer, the PET plate shows the following properties:
  • Example 2 Analogous to Example 1, a transparent, amorphous plate is produced, the UV stabilizer being 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5- (hexyl) -oxyphenol ( ⁇ Tinuvin 1 577 ) is metered in in the form of a master batch.
  • the masterbatch is composed of 5% by weight of ® Tinuvin 1577 as active ingredient and 95% by weight of the polyethylene terephthalate from Example 1.
  • Example 1 Before the extrusion, 80% by weight of the polyethylene terephthalate from Example 1 and 20% by weight of the masterbatch are dried at 1 70 ° C. for 5 hours. The extrusion and sheet production take place analogously to Example 1.
  • the transparent, amorphous PET sheet produced has the following property profile:
  • the PET plate After 1000 hours of weathering per side with Atlas Ci 65 Weather Ometer, the PET plate shows the following properties:
  • Polyethylene terephthalate which has the following properties:
  • a 6 mm thick, transparent, amorphous plate is produced which, as the main constituent, contains the polyethylene terephthalate described and 0.6% by weight of the UV stabilizer 2,2'-methylene-bis- (6- (2H-benzotriazole-2- yl) -4- (1, 1, 3,3-tetramethylbutyD-phenol ( ⁇ Tinuvin 360 from Ciba-Geigy), based on the weight of the polymer.
  • Tinuvin 360 has a melting point of 1 95 ° C and is thermally stable up to approx. 250 ° C.
  • Example 1 0.6% by weight of the UV stabilizer is incorporated directly into the polyethylene terephthalate at the raw material manufacturer.
  • the extrusion temperature is 280 ° C.
  • the first calender roll has a temperature of 66 ° C and the subsequent rolls have a temperature of 60 ° C.
  • the speed of the take-off and the calender rolls is 2.9 m / min.
  • the transparent PET sheet produced has the following property profile:
  • the PET plate After 1000 hours of weathering per side with Atlas Ci 65 Weather Ometer, the PET plate shows the following properties:
  • a transparent, amorphous plate is produced.
  • the extrusion temperature is 275 ° C.
  • the first calender roll has a temperature of 57 ° C and the subsequent rolls have a temperature of 50 ° C.
  • the speed of the take-off and the calender roll is 1.7 m / min.
  • the plate is stabilized as described in Example 3.
  • the PET sheet produced has the following property profile:
  • the PET plate After 1000 hours of weathering per side with Atlas Ci 65 Weather Ometer, the PET plate shows the following properties:
  • 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 PET sheet produced has the following property profile:
  • the PET plate After 1000 hours of weathering per side with Atlas Ci 65 Weather Ometer, the PET plate shows the following properties:
  • the plate shows a clearly visible "yellow” discoloration.
  • the surfaces are dull and brittle.
  • Example 3 Analogous to example 3, a transparent, amorphous plate is produced. In contrast to Example 3, the plate produced does not contain a UV stabilizer.
  • the polyethylene terephthalate used, the extrusion parameters, the Process parameters and the temperatures are chosen as in Example 3.
  • the transparent PET sheet produced has the following property profile:
  • Thickness 6 mm
  • the PET plate After 1000 hours of weathering per side with Atlas Ci 65 Weather Ometer, the PET plate shows the following properties:
  • the plate shows a clearly visible "yellow” discoloration.
  • the surfaces are badly attacked (blunt, brittle, cracking).
  • Example 3 Analogously to Example 3, a UV-stabilized, transparently colored, translucent plate is produced, the polyethylene terephthalate, the UV stabilizer and the masterbatch from Example 3 also being used.
  • the first calender roll has a temperature of 83 ° C and the subsequent rolls each have a temperature of 77 ° C.
  • the plate produced is extremely cloudy and almost opaque.
  • the light transmission, the clarity and the gloss are significantly reduced.
  • the plate shows surface defects and structures.
  • the optics are unacceptable for a transparent application.
  • the plate produced has the following property profile:

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Thermal Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Laminated Bodies (AREA)
  • Joining Of Glass To Other Materials (AREA)
  • Air Bags (AREA)

Abstract

L'invention concerne un panneau transparent amorphe, d'une épaisseur de 1 à 20 mm, qui contient comme principal élément constitutif une matière thermoplastique susceptible de se cristalliser se caractérise en ce qu'il contient un stabilisant vis-à-vis des U.V. comme agent photoprotecteur. L'invention concerne également un procédé de fabrication de ce panneau et son utilisation.
EP96918681A 1995-06-19 1996-06-10 Panneau transparent amorphe stabilise vis-a-vis des u.v. en une matiere thermoplastique susceptible de se cristalliser Withdrawn EP0833858A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19522118 1995-06-19
DE19522118A DE19522118C1 (de) 1995-06-19 1995-06-19 Amorphe, transparente, UV-stabilisierte Platte aus einem kristallisierbaren Thermoplast, Verfahren zu deren Herstellung sowie deren Verwendung
PCT/EP1996/002514 WO1997000284A1 (fr) 1995-06-19 1996-06-10 Panneau transparent amorphe stabilise vis-a-vis des u.v. en une matiere thermoplastique susceptible de se cristalliser

Publications (1)

Publication Number Publication Date
EP0833858A1 true EP0833858A1 (fr) 1998-04-08

Family

ID=7764642

Family Applications (1)

Application Number Title Priority Date Filing Date
EP96918681A Withdrawn EP0833858A1 (fr) 1995-06-19 1996-06-10 Panneau transparent amorphe stabilise vis-a-vis des u.v. en une matiere thermoplastique susceptible de se cristalliser

Country Status (16)

Country Link
EP (1) EP0833858A1 (fr)
JP (1) JPH11507965A (fr)
KR (1) KR19990028207A (fr)
AU (1) AU6125896A (fr)
BG (1) BG102073A (fr)
BR (1) BR9609412A (fr)
CA (1) CA2225173A1 (fr)
CZ (1) CZ414297A3 (fr)
DE (1) DE19522118C1 (fr)
HU (1) HUP9803029A2 (fr)
NO (1) NO975870D0 (fr)
OA (1) OA10552A (fr)
PL (1) PL324207A1 (fr)
RU (1) RU2169158C2 (fr)
TW (1) TW355717B (fr)
WO (1) WO1997000284A1 (fr)

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US6063464A (en) * 1998-04-23 2000-05-16 Hna Holdings, Inc. Isosorbide containing polyesters and methods for making same
US6140422A (en) * 1998-04-23 2000-10-31 E.I. Dupont De Nemours And Company Polyesters including isosorbide as a comonomer blended with other thermoplastic polymers
US6126992A (en) * 1998-04-23 2000-10-03 E.I. Dupont De Nemours And Company Optical articles comprising isosorbide polyesters and method for making same
US5958581A (en) * 1998-04-23 1999-09-28 Hna Holdings, Inc. Polyester film and methods for making same
US6063495A (en) * 1998-04-23 2000-05-16 Hna Holdings, Inc. Polyester fiber and methods for making same
US6063465A (en) * 1998-04-23 2000-05-16 Hna Holdings, Inc. Polyester container and method for making same
US5959066A (en) * 1998-04-23 1999-09-28 Hna Holdings, Inc. Polyesters including isosorbide as a comonomer and methods for making same
US6025061A (en) * 1998-04-23 2000-02-15 Hna Holdings, Inc. Sheets formed from polyesters including isosorbide
US8669325B1 (en) 1999-06-11 2014-03-11 Sydney Hyman Compositions image making mediums and images
US9744800B2 (en) 1999-06-11 2017-08-29 Sydney Hyman Compositions and image making mediums
US9786194B2 (en) 1999-06-11 2017-10-10 Sydney Hyman Image making medium compositions and images
EP1777255A3 (fr) * 1999-06-11 2007-07-11 Sydney Hyman Support de formation d'image
DE10002171A1 (de) * 2000-01-20 2001-07-26 Mitsubishi Polyester Film Gmbh Transparente, schwerentflammbare, UV-stabile Folie aus einem kristallisierbaren Thermoplasten, Verfahren zu ihrer Herstellung und ihre Verwendung
DE10009246A1 (de) * 2000-02-28 2001-08-30 Mitsubishi Polyester Film Gmbh Weiße, biaxial orientierte und UV-stabilisierte Polyesterfolie mit Cycloolefinocopolymer (COC), Verfahren zu ihrer Herstellung und ihre Verwendung
US7888405B2 (en) 2004-01-30 2011-02-15 E. I. Du Pont De Nemours And Company Aliphatic-aromatic polyesters, and articles made therefrom
US7452927B2 (en) 2004-01-30 2008-11-18 E. I. Du Pont De Nemours And Company Aliphatic-aromatic polyesters, and articles made therefrom
US11355027B2 (en) 2004-04-30 2022-06-07 Sydney Hyman Image making medium compositions and images
DE202005006412U1 (de) * 2004-05-27 2005-06-30 Battenfeld Extrusionstechnik Gmbh Kühlvorrichtung
AU2004100535B4 (en) * 2004-07-05 2004-12-02 Corex Plastics (Aust) Pty Ltd Polymer compositions and uses thereof
US7144972B2 (en) 2004-07-09 2006-12-05 E. I. Du Pont De Nemours And Company Copolyetherester compositions containing hydroxyalkanoic acids and shaped articles produced therefrom
ATE405946T1 (de) 2005-06-10 2008-09-15 Soitec Silicon On Insulator Kalibrierverfahren für apparaturen zur thermischen behandlung
DE102005062687A1 (de) * 2005-12-23 2007-07-05 Röhm Gmbh PMMA-Folie mit besonders hoher Witterungsbeständigkeit und hoher UV-Schutzwirkung
JP5292958B2 (ja) * 2007-07-18 2013-09-18 東レ株式会社 研磨パッド
WO2013149157A1 (fr) 2012-03-30 2013-10-03 E. I. Du Pont De Nemours And Company Polyesters et fibres faites à partir de ceux-ci
JP6709076B2 (ja) * 2016-02-29 2020-06-10 三菱エンジニアリングプラスチックス株式会社 ポリカーボネート樹脂組成物の製造方法
WO2017189552A1 (fr) 2016-04-25 2017-11-02 E I Du Pont De Nemours And Company Procédé de production d'un article en polyester
KR102357178B1 (ko) 2020-01-08 2022-01-28 한세진 플라스틱 복층판

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Also Published As

Publication number Publication date
TW355717B (en) 1999-04-11
CZ414297A3 (cs) 1998-03-18
BR9609412A (pt) 1999-05-18
OA10552A (fr) 2002-05-29
WO1997000284A1 (fr) 1997-01-03
DE19522118C1 (de) 1997-03-13
BG102073A (en) 1998-08-31
JPH11507965A (ja) 1999-07-13
AU6125896A (en) 1997-01-15
KR19990028207A (ko) 1999-04-15
RU2169158C2 (ru) 2001-06-20
CA2225173A1 (fr) 1997-01-03
PL324207A1 (en) 1998-05-11
NO975870L (no) 1997-12-12
MX9710294A (es) 1998-03-29
NO975870D0 (no) 1997-12-12
HUP9803029A2 (hu) 1999-04-28

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