WO1997000284A1 - Amorphe, transparente, uv-stabilisierte platte aus einem kristallisierbaren thermoplast - Google Patents

Amorphe, transparente, uv-stabilisierte platte aus einem kristallisierbaren thermoplast Download PDF

Info

Publication number
WO1997000284A1
WO1997000284A1 PCT/EP1996/002514 EP9602514W WO9700284A1 WO 1997000284 A1 WO1997000284 A1 WO 1997000284A1 EP 9602514 W EP9602514 W EP 9602514W WO 9700284 A1 WO9700284 A1 WO 9700284A1
Authority
WO
WIPO (PCT)
Prior art keywords
plate according
plate
polyethylene terephthalate
range
stabilizer
Prior art date
Application number
PCT/EP1996/002514
Other languages
German (de)
English (en)
French (fr)
Inventor
Ursula Murschall
Wolfgang Gawrisch
Rainer Brunow
Original Assignee
Hoechst Aktiengesellschaft
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 Aktiengesellschaft filed Critical Hoechst Aktiengesellschaft
Priority to BR9609412A priority Critical patent/BR9609412A/pt
Priority to EP96918681A priority patent/EP0833858A1/de
Priority to PL96324207A priority patent/PL324207A1/xx
Priority to JP9502619A priority patent/JPH11507965A/ja
Priority to AU61258/96A priority patent/AU6125896A/en
Publication of WO1997000284A1 publication Critical patent/WO1997000284A1/de
Priority to BG102073A priority patent/BG102073A/xx
Priority to NO975870A priority patent/NO975870L/no
Priority to MXPA/A/1997/010294A priority patent/MXPA97010294A/xx

Links

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C43/00Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/22Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of indefinite length
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03Extrusion 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
    • B29C48/07Flat, e.g. panels
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03Extrusion 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
    • B29C48/07Flat, e.g. panels
    • B29C48/08Flat, e.g. panels flexible, e.g. films
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25Component parts, details or accessories; Auxiliary operations
    • B29C48/88Thermal treatment of the stream of extruded material, e.g. cooling
    • B29C48/911Cooling
    • B29C48/9135Cooling of flat articles, e.g. using specially adapted supporting means
    • B29C48/914Cooling of flat articles, e.g. using specially adapted supporting means cooling drums
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25Component parts, details or accessories; Auxiliary operations
    • B29C48/88Thermal treatment of the stream of extruded material, e.g. cooling
    • B29C48/911Cooling
    • B29C48/9135Cooling of flat articles, e.g. using specially adapted supporting means
    • B29C48/9145Endless cooling belts
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/16Nitrogen-containing compounds
    • C08K5/34Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477Six-membered rings
    • C08K5/3492Triazines
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25Component parts, details or accessories; Auxiliary operations
    • B29C48/88Thermal treatment of the stream of extruded material, e.g. cooling
    • B29C48/90Thermal 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
    • B29C48/906Thermal 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29KINDEXING 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
    • B29K2067/00Use 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:

Landscapes

  • 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)
  • Air Bags (AREA)
  • Joining Of Glass To Other Materials (AREA)
PCT/EP1996/002514 1995-06-19 1996-06-10 Amorphe, transparente, uv-stabilisierte platte aus einem kristallisierbaren thermoplast WO1997000284A1 (de)

Priority Applications (8)

Application Number Priority Date Filing Date Title
BR9609412A BR9609412A (pt) 1995-06-19 1996-06-10 Placa amorfa transparente estabilizada com ultravioleta de um termoplasto cristalizável
EP96918681A EP0833858A1 (de) 1995-06-19 1996-06-10 Amorphe, transparente, uv-stabilisierte platte aus einem kristallisierbaren thermoplast
PL96324207A PL324207A1 (en) 1995-06-19 1996-06-10 Mamorphous transparen panel stabilised in uv radiation, made of crystallisable thermoplastic plastic
JP9502619A JPH11507965A (ja) 1995-06-19 1996-06-10 結晶性熱可塑性樹脂の紫外線安定化した透明な非晶質シート
AU61258/96A AU6125896A (en) 1995-06-19 1996-06-10 Amorphous, transparent, uv-stabilised plate made of thermoplastic capable of crystallising
BG102073A BG102073A (en) 1995-06-19 1997-11-27 Amorphous transparent uv-stabilized plate of cystallizable thermoplast
NO975870A NO975870L (no) 1995-06-19 1997-12-12 Amorf, transparent, UV-stabilisert plate fremstilt av krystalliserbar termoplast
MXPA/A/1997/010294A MXPA97010294A (en) 1995-06-19 1997-12-17 Lamina amorfa transparente stabilizado of ultraviolet light of a crystallized thermoplastic

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19522118.4 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

Publications (1)

Publication Number Publication Date
WO1997000284A1 true WO1997000284A1 (de) 1997-01-03

Family

ID=7764642

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1996/002514 WO1997000284A1 (de) 1995-06-19 1996-06-10 Amorphe, transparente, uv-stabilisierte platte aus einem kristallisierbaren thermoplast

Country Status (16)

Country Link
EP (1) EP0833858A1 (ru)
JP (1) JPH11507965A (ru)
KR (1) KR19990028207A (ru)
AU (1) AU6125896A (ru)
BG (1) BG102073A (ru)
BR (1) BR9609412A (ru)
CA (1) CA2225173A1 (ru)
CZ (1) CZ414297A3 (ru)
DE (1) DE19522118C1 (ru)
HU (1) HUP9803029A2 (ru)
NO (1) NO975870L (ru)
OA (1) OA10552A (ru)
PL (1) PL324207A1 (ru)
RU (1) RU2169158C2 (ru)
TW (1) TW355717B (ru)
WO (1) WO1997000284A1 (ru)

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5958581A (en) * 1998-04-23 1999-09-28 Hna Holdings, Inc. Polyester film and methods 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
US6063465A (en) * 1998-04-23 2000-05-16 Hna Holdings, Inc. Polyester container and method for making same
US6063464A (en) * 1998-04-23 2000-05-16 Hna Holdings, Inc. Isosorbide containing polyesters and methods for making same
US6063495A (en) * 1998-04-23 2000-05-16 Hna Holdings, Inc. Polyester fiber and methods for making same
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
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
EP1127912A1 (de) * 2000-02-28 2001-08-29 Mitsubishi Polyester Film GmbH Weisse, biaxial orientierte und UV-stabilisierte Polyesterfolie mit Cycloolefincopolymer (COC), Verfahren zu ihrer Herstellung und ihre Verwendung
AU2004100535B4 (en) * 2004-07-05 2004-12-02 Corex Plastics (Aust) Pty Ltd Polymer compositions and uses thereof
US7138176B2 (en) * 2000-01-20 2006-11-21 Mitsubishi Polyester Film Gmbh Transparent, low-flammability, UV-resistant film made from a crystallizable thermoplastic, its use and process for its production
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
WO2007074138A1 (de) * 2005-12-23 2007-07-05 Evonik Röhm Gmbh Pmma - folie mit besonders hoher witterungsbeständigkeit und hoher uv-schutzwirkung
US7452927B2 (en) 2004-01-30 2008-11-18 E. I. Du Pont De Nemours And Company Aliphatic-aromatic polyesters, and articles made therefrom
EP2184308A2 (en) 2008-11-06 2010-05-12 E. I. du Pont de Nemours and Company Aliphatic-aromatic polyesters, and articles made therefrom
WO2013149221A1 (en) 2012-03-30 2013-10-03 E. I. Du Pont De Nemours And Company Polyesters and articles made therefrom
WO2017189552A1 (en) 2016-04-25 2017-11-02 E I Du Pont De Nemours And Company Process for producing polyester article

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9744800B2 (en) 1999-06-11 2017-08-29 Sydney Hyman Compositions and image making mediums
EP1208150A4 (en) * 1999-06-11 2005-01-26 Sydney Hyman IMAGE FORMING MATERIAL
US8669325B1 (en) 1999-06-11 2014-03-11 Sydney Hyman Compositions image making mediums and images
US9786194B2 (en) 1999-06-11 2017-10-10 Sydney Hyman Image making medium compositions and images
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
DE602005009159D1 (de) 2005-06-10 2008-10-02 Soitec Silicon On Insulator Kalibrierverfahren für Apparaturen zur thermischen Behandlung
JP5292958B2 (ja) * 2007-07-18 2013-09-18 東レ株式会社 研磨パッド
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
KR102357178B1 (ko) 2020-01-08 2022-01-28 한세진 플라스틱 복층판

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2009768A (en) * 1977-12-12 1979-06-20 Eastman Kodak Co Stabilized Polyester Compositions
US4399265A (en) * 1983-01-19 1983-08-16 Garware Plastics & Polyester Ltd. Process of products UV-stabilized polyester materials
EP0247480A2 (de) * 1986-05-28 1987-12-02 Bayer Ag Verzweigte thermoplastische Polycarbonate mit verbessertem Schutz gegen UV-Licht
WO1988001285A1 (en) * 1986-08-22 1988-02-25 Eastman Kodak Company Thermoformed polyester articles
EP0341588A1 (en) * 1988-05-11 1989-11-15 Mitsubishi Rayon Co., Ltd. Thermoplastic resin composition
US4983653A (en) * 1986-11-12 1991-01-08 Diafoil Company, Ltd. Polyester shrinkable film containing benzotriazole
EP0678376A1 (en) * 1994-04-18 1995-10-25 Axxis N.V. A copolyester-containing plastic sheet, a process for the manufacture of the plastic sheet and mouldings manufactured from the plastic sheet

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IL72879A (en) * 1984-09-06 1988-12-30 Ginegar Kibbutz Plastic sheeting

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2009768A (en) * 1977-12-12 1979-06-20 Eastman Kodak Co Stabilized Polyester Compositions
US4399265A (en) * 1983-01-19 1983-08-16 Garware Plastics & Polyester Ltd. Process of products UV-stabilized polyester materials
EP0247480A2 (de) * 1986-05-28 1987-12-02 Bayer Ag Verzweigte thermoplastische Polycarbonate mit verbessertem Schutz gegen UV-Licht
WO1988001285A1 (en) * 1986-08-22 1988-02-25 Eastman Kodak Company Thermoformed polyester articles
US4983653A (en) * 1986-11-12 1991-01-08 Diafoil Company, Ltd. Polyester shrinkable film containing benzotriazole
EP0341588A1 (en) * 1988-05-11 1989-11-15 Mitsubishi Rayon Co., Ltd. Thermoplastic resin composition
EP0678376A1 (en) * 1994-04-18 1995-10-25 Axxis N.V. A copolyester-containing plastic sheet, a process for the manufacture of the plastic sheet and mouldings manufactured from the plastic sheet

Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5958581A (en) * 1998-04-23 1999-09-28 Hna Holdings, Inc. Polyester film and methods 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
US6063465A (en) * 1998-04-23 2000-05-16 Hna Holdings, Inc. Polyester container and method for making same
US6063464A (en) * 1998-04-23 2000-05-16 Hna Holdings, Inc. Isosorbide containing polyesters and methods for making same
US6063495A (en) * 1998-04-23 2000-05-16 Hna Holdings, Inc. Polyester fiber and methods for making same
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
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
US6359070B1 (en) 1998-04-23 2002-03-19 E. I. Du Pont Nemours And Company Polyesters including isosorbide as a comonomer blended with other thermoplastic polymers
US7138176B2 (en) * 2000-01-20 2006-11-21 Mitsubishi Polyester Film Gmbh Transparent, low-flammability, UV-resistant film made from a crystallizable thermoplastic, its use and process for its production
US6627695B2 (en) 2000-02-28 2003-09-30 Mitsubishi Polyester Film Gmbh White, biaxially oriented and UV-resistant polyester film with cycloolefin copolymer (COC), its use and process for its production
EP1127912A1 (de) * 2000-02-28 2001-08-29 Mitsubishi Polyester Film GmbH Weisse, biaxial orientierte und UV-stabilisierte Polyesterfolie mit Cycloolefincopolymer (COC), Verfahren zu ihrer Herstellung und ihre Verwendung
US7452927B2 (en) 2004-01-30 2008-11-18 E. I. Du Pont De Nemours And Company Aliphatic-aromatic polyesters, and articles made therefrom
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
WO2007074138A1 (de) * 2005-12-23 2007-07-05 Evonik Röhm Gmbh Pmma - folie mit besonders hoher witterungsbeständigkeit und hoher uv-schutzwirkung
WO2007073952A1 (de) * 2005-12-23 2007-07-05 Evonik Röhm Gmbh Pmma-folie mit besonders hoher witterungsbeständigkeit und hoher uv-schutzwirkung
US8088847B2 (en) 2005-12-23 2012-01-03 Evonik Roehm Gmbh PMMA film featuring particularly great weather resistance and great UV protection
EP2184308A2 (en) 2008-11-06 2010-05-12 E. I. du Pont de Nemours and Company Aliphatic-aromatic polyesters, and articles made therefrom
WO2013149221A1 (en) 2012-03-30 2013-10-03 E. I. Du Pont De Nemours And Company Polyesters and articles made therefrom
EP3369846A1 (en) 2012-03-30 2018-09-05 E. I. du Pont de Nemours and Company Articles made from polyester
WO2017189552A1 (en) 2016-04-25 2017-11-02 E I Du Pont De Nemours And Company Process for producing polyester article

Also Published As

Publication number Publication date
RU2169158C2 (ru) 2001-06-20
BG102073A (en) 1998-08-31
NO975870D0 (no) 1997-12-12
DE19522118C1 (de) 1997-03-13
JPH11507965A (ja) 1999-07-13
NO975870L (no) 1997-12-12
CA2225173A1 (en) 1997-01-03
CZ414297A3 (cs) 1998-03-18
MX9710294A (es) 1998-03-29
AU6125896A (en) 1997-01-15
PL324207A1 (en) 1998-05-11
BR9609412A (pt) 1999-05-18
OA10552A (fr) 2002-05-29
HUP9803029A2 (hu) 1999-04-28
TW355717B (en) 1999-04-11
EP0833858A1 (de) 1998-04-08
KR19990028207A (ko) 1999-04-15

Similar Documents

Publication Publication Date Title
DE19522118C1 (de) Amorphe, transparente, UV-stabilisierte Platte aus einem kristallisierbaren Thermoplast, Verfahren zu deren Herstellung sowie deren Verwendung
EP0828596B1 (de) Amorphe, transparente platte aus einem kristallisierbaren thermoplast
WO1996038498A1 (de) Amorphe, transparent eingefärbte platte aus einem kristallisierbaren thermoplast, verfahren zu deren herstellung sowie deren verwendung
EP1265949B1 (de) Transparente, biaxial orientierte, uv-stabilisierte, thermoformbare folie aus kristallisierbaren thermoplasten, verfahren zu ihrer herstellung und ihre verwendung
EP1118635B1 (de) Transparente, schwerentflammbare, UV-stabile Folie aus einem kristallisierbaren Thermoplasten
EP1614707A1 (de) Matte, thermoformbare, IR-reflektierende Polyesterfolie
EP1125968B1 (de) Weiss-opake, UV-stabilisierte Folie mit niedriger Transparanz aus einem kristallisierbaren Thermoplasten
DE19630599A1 (de) Polyethylenterephthalat-Platte mit verbesserter Hydrolysestabilität, Verfahren zur Herstellung und Verwendung
EP0828599B1 (de) Amorphe eingefärbte platte aus einem kristallisierbaren thermoplast
WO1997004948A1 (de) Amorphe, transparente platte aus einem kristallisierbaren thermoplast mit hoher standardviskosität
DE19519578A1 (de) Amorphe, transparent eingefärbte Platte aus einem kristallisierbaren Thermoplast
EP1268645B1 (de) Weisse, uv-stabilisierte, thermoformbare folie aus einem kristallisierbaren thermoplast, verfahren zu ihrer herstellung und ihre verwendung
DE19519577A1 (de) Amorphe, eingefärbte Platte aus einem kristallisierbaren Thermoplast
DE19610956A1 (de) Amorphe Platte aus einem kristallisierbaren Polyalkylennaphthalat
DE19522120A1 (de) Amorphe, transparent eingefärbte, UV-stabilisierte Platte aus einem kristallisierbaren Thermoplast
DE19528334A1 (de) Amorphe, transparent eingefärbte Platte aus einem kristallisierbaren Thermoplast mit hoher Standardviskosität
WO2001053390A1 (de) Amorphe, transparent eingefärbte, uv-licht absorbierende, thermoformbare folie, ein verfahren zu ihrer herstellung und ihre verwendung
EP0960721A2 (de) Platte aus einem Thermoplast
DE19522119A1 (de) Amorphe, eingefärbte, UV-stabilisierte Platte aus einem kristallisierbaren Thermoplast
EP1276794B1 (de) Eingefärbte, schwer entflammbare, uv-stabile, thermoformbare folie aus einem kristallisierbaren thermoplasten, verfahren zu ihrer herstellung und ihre verwendung
DE19528333A1 (de) Amorphe, eingefärbte Platte aus einem kristallisierbaren Thermoplast mit hoher Standardviskosität
DE29623540U1 (de) Amorphe, transparente Platte aus einem kristallisierbaren Thermoplast
DE19630598A1 (de) Mehrschichtige, transparent eingefärbte Platte aus einem kristallisierbaren Thermoplast, Verfahren zu ihrer Herstellung und Verwendung
DE19630597A1 (de) Mehrschichtige Platte aus einem kristallisierbaren Thermoplast, Verfahren zu ihrer Herstellung und Verwendung
DE19913982A1 (de) Transparente, UV-stabilisierte Folie aus einem kristallisierbaren Thermoplast

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 96194872.8

Country of ref document: CN

AK Designated states

Kind code of ref document: A1

Designated state(s): AU BG BR BY CA CN CZ HU JP KR MX NO NZ PL RO RU SG SI UA US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN ML MR NE SN TD TG

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 1996918681

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 97-02351

Country of ref document: RO

WWE Wipo information: entry into national phase

Ref document number: 310459

Country of ref document: NZ

Ref document number: PA/a/1997/010294

Country of ref document: MX

ENP Entry into the national phase

Ref document number: 2225173

Country of ref document: CA

Ref document number: 2225173

Country of ref document: CA

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 1997 502619

Country of ref document: JP

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: PV1997-4142

Country of ref document: CZ

Ref document number: 1019970709518

Country of ref document: KR

WWP Wipo information: published in national office

Ref document number: PV1997-4142

Country of ref document: CZ

WWP Wipo information: published in national office

Ref document number: 1996918681

Country of ref document: EP

WWW Wipo information: withdrawn in national office

Ref document number: PV1997-4142

Country of ref document: CZ

WWP Wipo information: published in national office

Ref document number: 1019970709518

Country of ref document: KR

WWR Wipo information: refused in national office

Ref document number: 1019970709518

Country of ref document: KR

WWW Wipo information: withdrawn in national office

Ref document number: 1996918681

Country of ref document: EP