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WO1998016381A2 - Plaque multicouche en matiere thermoplastique cristallisable, fabrication d'un moule cristallise a partir d'une telle plaque et utilisation - Google Patents

Plaque multicouche en matiere thermoplastique cristallisable, fabrication d'un moule cristallise a partir d'une telle plaque et utilisation Download PDF

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Publication number
WO1998016381A2
WO1998016381A2 PCT/EP1997/005311 EP9705311W WO9816381A2 WO 1998016381 A2 WO1998016381 A2 WO 1998016381A2 EP 9705311 W EP9705311 W EP 9705311W WO 9816381 A2 WO9816381 A2 WO 9816381A2
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WO
WIPO (PCT)
Prior art keywords
thermoplastic
shaped body
plate
layer
crystallization
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP1997/005311
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German (de)
English (en)
Other versions
WO1998016381A3 (fr
Inventor
Ursula Murschall
Rainer Brunow
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Aventis Research and Technologies GmbH and Co KG
Original Assignee
Aventis Research and Technologies GmbH and Co KG
Hoechst Research and Technology Deutschland GmbH and Co KG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Aventis Research and Technologies GmbH and Co KG, Hoechst Research and Technology Deutschland GmbH and Co KG filed Critical Aventis Research and Technologies GmbH and Co KG
Priority to AU47787/97A priority Critical patent/AU4778797A/en
Publication of WO1998016381A2 publication Critical patent/WO1998016381A2/fr
Publication of WO1998016381A3 publication Critical patent/WO1998016381A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • 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
    • B32B2605/00—Vehicles

Definitions

  • Multi-layer plate made of a crystallizable thermoplastic, a crystallized molded body that can be produced therefrom and its use
  • the invention relates to an amorphous, multilayer plate made of a crystallizable thermoplastic, the thickness of which is in the range from 1 to 20 mm.
  • Multi-layer plates made of plastic materials are known per se.
  • Multi-layer plastic sheets are known from US Pat. No. 5,137,949, with layers of polydiorganosiloxane-polycarbonate block copolymers which contain UV absorbers.
  • EP-A-0416404 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.
  • All of these plates are made of polycarbonate, an amorphous thermoplastic that cannot be crystallized.
  • Polycarbonate sheets have the disadvantage that they often show efflorescence in the form of white spots and surface coverings, especially in the UV-stabilized embodiment (cf. EP-A-0649 724).
  • EP-A-0 649 724 for example, UV absorber evaporation is strongly linked to the average molecular weight.
  • Amorphous plates also have the disadvantage that they become dimensionally unstable even at relatively low temperatures.
  • amorphous objects sheets, moldings
  • PET polyethylene terephthalate
  • thermoform an article from a layer of PET material and to crystallize the article during thermoforming, which increases the heat resistance.
  • US-A-3,496,143 describes a process for thermoforming a PET sheet using a deep-drawing device.
  • the PET plate has a thickness of 3 mm and an area of 370 mm x 280 mm.
  • the PET plate must already have an initial degree of crystallization of 5% to 25%.
  • the process also requires that the PET sheet be subjected to a lengthy heat treatment before being vacuum formed. After molding, the plate is subjected to further heat treatment while it is still in the mold. The plate is held in the mold until the degree of crystallization of the molded plate is greater than 25%.
  • the patent indicates that the molded article obtained remains dimensionally stable at a temperature of 160 ° C. for 60 minutes.
  • the articles produced by this method show a strong fluctuation in light transmission, which is a sign that the article is only incompletely and unevenly crystallized.
  • the heat resistance also fluctuates in accordance with the fluctuating degree of crystallization.
  • a multi-layer, amorphous plate with a thickness of 1 to 20 mm which contains a crystallizable thermoplastic as the main component and which has at least one core layer and at least one cover layer, the standard viscosity of the crystallizable thermoplastic of the core layer being higher than the standard viscosity of the crystallizable thermoplastic of the top layer, and which contains at least one nucleating agent.
  • the nucleating agent is homogeneously distributed and causes the initiation of crystallization during the thermoforming process and the increase in Crystallization rate during the thermoforming process, so that a crystallized shaped body with the required property profile results after the thermoforming process.
  • the invention therefore also relates to a shaped body obtainable from the plate according to the invention.
  • a homogeneous degree of crystallization means that the degree of crystallization of the shaped article is in a range between 20% and 60%, preferably 30% and 50%, and particularly preferably 35% and 45%, and that the degree of crystallization is within a shaped one Object fluctuates by no more than 10 units in crystallinity.
  • Uniform light transmission (measured in accordance with ASTM D 1003) is understood to mean that the light transmission is less than 50%, preferably less than 40% and particularly preferably less than 30% depending on the wall thickness of the molded article and does not vary by more than 10 units within the molded article.
  • the light transmission of a shaped article (shaped body) according to the invention with a wall thickness of more than 3 mm is generally below 20%.
  • the light transmission is not only dependent on the wall thickness, but also on the degree of crystallization.
  • the heat resistance of the shaped article according to the invention should be uniform in all areas at greater than 100 ° C., preferably at greater than 120 ° C. and particularly preferably at greater than 140 ° C. and should not fluctuate within the molded article by more than 20 ° C, preferably 10 ° C.
  • a homogeneous, glossy surface is understood to mean that the surface gloss of the shaped object on the surface which does not come into contact with the deep-drawing mold, measured in accordance with DIN 67530 (measuring angle 20 °), is greater than 70, preferably greater than 80 and particularly preferably greater 90 and is in particular greater than 95.
  • the surface gloss should not fluctuate by more than 20 gloss points on this surface.
  • Homogeneous haze is understood to mean that the haze of the shaped object, measured in accordance with ASTM D 1003, is more than 50%, preferably more than 60% and particularly preferably more than 70%. The haze should not fluctuate more than 10 cloud points within the molded article.
  • the object according to the invention is distinguished by excellent chemical resistance.
  • 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 also consist of only one cover layer and one core layer.
  • a structure with two cover layers and a core layer lying between the cover layers is particularly preferred.
  • the individual cover and core layers can contain different or identical crystallizable thermoplastics as main components, as long as the thermoplastic of a core layer has a higher standard viscosity than the thermoplastics of the cover layers directly adjacent to this core layer.
  • 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 radicals, such as polyethylene terephthalate and polybutylene terephthalate, polyalkylene naphthalates with C1 to C12 alkylene radicals, such as polyethylene naphthalate and polybutylene naphthalate, crystallizable cycloolefin polymers and cycloolefin copolymers, the thermoplastic and the thermoplastic or the (en) the thermoplastic or thermoplastic Thermoplastic or the thermoplastics for the cover layer (s) can be the same or different. Polyolefins have also proven suitable for the top layer.
  • Thermoplastics with a crystallite melting point T m measured with DSC (Differential Scanning Calorimetry) with a heating rate of 10 ° C / min, from 220 ° C to 280 ° C, preferably from 230 ° C to 270 ° C, with a crystallization temperature range T c between 75 ° C and 280 ° C, a glass transition temperature T_ between 65 ° C and 90 ° C and with a density, measured according to DIN 53479, of 1, 30 to 1, 45 g / cm 3 and a crystallinity between 5% and 65% , preferably between 25% and 65%, are preferred starting materials for the production of the plate, which are polymers for the core layer and the top layer.
  • thermoplastic with a cold (post) crystallization temperature T CN of 120 to 158 ° C., in particular 130 to 158 ° C., is particularly preferred for the purposes of the invention.
  • the bulk density 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 MM n measured by means of GPC, is preferably between 1.5 and 6.0 and particularly preferably between 2.0 and 5.0.
  • a particularly preferred crystallizable thermoplastic for the core layer (s) or the cover layer (s) is polyethylene terephthalate.
  • the 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 different core and / or outer layers of a multilayer plate can be different.
  • the standard viscosity SV (DCE) of the crystallizable thermoplastic of the core layer is preferably between 800 and 5000 and particularly preferably between 1000 and 4500.
  • the standard viscosity SV (DCE) of the crystallizable thermoplastic of the top layer is preferably between 500 and 4500 and particularly preferably between 700 and 4000.
  • the intrinsic viscosity IV can be calculated from the standard viscosity SV (DCE) as follows:
  • the crystallizable thermoplastics used according to the invention can be obtained by customary processes known to the person skilled in the art.
  • thermoplastics as used according to the invention can 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, as in JP-A-60-139717, DE-C-2 429 087, DE-A-27 07 491, DE- A-23 19 089, DE-A-16 94 461, JP-63-41 528, JP-62- 39 621, DE-A-41 17 825, DE-A-42 26 737, JP-60-141 715 , DE-A-27 21 501 and US-A-5296 586.
  • Polyethylene terephthalates with particularly high molecular weights can be e.g. by polycondensation of dicarboxylic acid diol precondensates (oligomers) at elevated temperature in a liquid heat transfer medium in the presence of conventional polycondensation catalysts and, if necessary, co-condensable modifiers if the liquid heat transfer medium is inert and free of aromatic components and a boiling point in the range from 200 to 320 ° C has, the weight ratio of dicarboxylic acid diol precondensate (oligomers) to liquid heat transfer medium is in the range from 20:80 to 80:20, and the polycondensation is carried out in the boiling reaction mixture in the presence of a dispersion stabilizer.
  • Multilayer amorphous plates suitable for the present invention which contain a crystallizable thermoplastic as the main constituent, have been described by the applicant in their German patent applications DE 196 30 597.7, 196 30 598.5 and 196 30 817.8, to which express reference is made here and which are incorporated by reference into the content of this application.
  • the multilayer amorphous plate contains at least one nucleating agent, the concentration of the nucleating agent depending on the type of nucleating agent can vary widely.
  • thermoplastics with a low to medium crystal growth rate
  • Polymers with a low to medium crystal growth rate such as the thermoplastics used here respond very well to the so-called homogeneous, heterogeneous, athermal and / or spontaneous nucleation (nucleation) with the help of foreign substances - the nucleating agents.
  • thermoforming into a crystalline object since the crystallization only takes place at high temperatures and long cycle times can be achieved.
  • the thermoforming of these amorphous thermoplastics with extremely heated molds and a lot of heat - to accelerate the crystallization - only leads to crystallized finished parts with a strongly fluctuating degree of crystallization and strongly fluctuating properties, e.g. Light transmission, haze, surface gloss and heat resistance. These finished parts are very difficult to remove from the mold and are sometimes too soft. Due to the z. T. very long and uneconomical cycle times at extreme temperatures also form large spherulites in the shaped objects, which makes the object very brittle.
  • the added nucleating agent may be used in plate production in the Extrusion line with relatively rapid cooling does not lead to crystallization in the plate.
  • thermoforming to a crystallized object proves to be inadequate and very time-consuming since the crystalline components first have to be melted during deep-drawing, which requires a lot of time and energy.
  • the nucleating agent in the thermoforming process must increase the rate of crystallization and ensure that numerous small spherulites are quickly formed.
  • Suitable nucleating agents are, for example, inert mineral fillers such as silicates with an average particle size of less than 5 ⁇ m and talc, clay, kaolin, mica with average particle sizes of less than 6 ⁇ m, metal oxides such as silicon dioxide, titanium dioxide and magnesium oxide, carbonates and sulfates, preferably of alkaline earth metals, Boron nitride and sodium fluoride with average particle diameters of less than 4 ⁇ m.
  • inert mineral fillers such as silicates with an average particle size of less than 5 ⁇ m and talc, clay, kaolin, mica with average particle sizes of less than 6 ⁇ m, metal oxides such as silicon dioxide, titanium dioxide and magnesium oxide, carbonates and sulfates, preferably of alkaline earth metals, Boron nitride and sodium fluoride with average particle diameters of less than 4 ⁇ m.
  • organic compounds are suitable alone or with insoluble, inert solids such as, for example, montan wax, montan ester salts, salts of mono- and polycarboxylic acids, epoxides and alkali aryl and alkyl sulfonates, and also polymeric compounds alone or with insoluble, inert solids such as polyethylene, polypropylene, polyamides, Poly-4-methylpentene-1, polymethylbutene-1, copolymers of ethylene with unsaturated carboxylic acid residues, ionic copolymers of ethylene with salts of unsaturated carboxylic acids, copolymers of styrene derivatives with conjugated dienes, the crystallizable thermoplastic itself with a significantly lower or a significantly higher intrinsic viscosity, oxidatively degraded polymers, regranulate (recyclate) from the crystallizable thermoplastic and mixtures of these as nucleating agents.
  • the amount of inorganic nucleating agent is preferably from 0.01 to
  • the amount of organic nucleating agent is usually 0.5 to 40% by weight, based on the weight of the thermoplastic of the layer to be finished with it.
  • regenerate is added to a core layer as an organic nucleating agent, the amount in this case can be up to 100% by weight.
  • the core layer essentially consists of a regenerate.
  • the core layer (hereinafter also referred to as the base layer) contains regrind and the crystallizable thermoplastics contained in the cover layers are the original raw material, i. H. the cover layers are essentially free of regenerated material.
  • An additive consisting of up to 100% by weight of regrind of a thermoplastic and 0.01 to 3% by weight of silicon dioxide, preferably with an average particle diameter of 1 to 3 ⁇ m, or from up to 100, has proven particularly suitable for nucleation %
  • regenerate and a mixture of the above-mentioned inorganic nucleating agents is particularly advantageous, the total concentration of the inorganic nucleating agents preferably being between 0.1% by weight and 3% by weight.
  • the quantities given relate to the weight of the thermoplastic contained in the layer. If regrind is used, it is advantageous for the formation of small and numerous spherulites during the subsequent deep-drawing process if the intrinsic viscosity of the regrind from the crystallizable thermoplastic is lower or higher than the intrinsic viscosity of the crystallizable thermoplastic itself, which is the main component in the amorphous plate is included.
  • the intrinsic viscosity of the regrind preferably differs by at least 2%, preferably at least 5% and particularly preferably by at least 10% from the intrinsic viscosity of the layer-forming thermoplastics.
  • the intrinsic viscosity of the regenerate is preferably lower.
  • the multilayer, amorphous plate according to the invention can, if desired, also be equipped with further additives. These additives can, depending on
  • Suitable additives are UV stabilizers, antioxidants and
  • the multilayer, amorphous plate can additionally contain at least one UV stabilizer as light stabilizer in the top layer (s) and / or the core layer (s).
  • thermoplastics Light, in particular the ultraviolet portion of solar radiation, ie the wavelength range from 280 to 400 nm, initiate degradation processes in thermoplastics, as a result of which not only the visual appearance changes as a result of color change or yellowing, but also the mechanical-physical properties are adversely affected.
  • a high UV stability means that the plate is not or only slightly damaged by sunlight or other UV radiation, so that the plate is suitable for outdoor applications and / or critical indoor applications and shows little or no yellowing even after several years of outdoor use.
  • 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.
  • Certain pigments such as Soot can partially protect against light. However, these substances can cause discoloration or color change. It is therefore expedient to use only such UV stabilizers, e.g. from the class of organic and organometallic compounds used, which cause no or only an extremely slight discoloration or color change in the thermoplastic to be stabilized.
  • 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.
  • Preferred examples are 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5- (hexyl) oxyphenol and 2,2'-methylene-bis (6- (2H-benzothazole- 2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol). Mixtures of several UV stabilizers can also be used.
  • the UV stabilizer is expediently present in a cover layer in a concentration of 0.01% by weight to 8% by weight, based on the weight of the thermoplastic in the cover layer provided with the stabilizer.
  • the UV stabilizer can also be added to a core layer. In this case, a concentration of 0.01% by weight to 1% by weight, based on the weight of the thermoplastic in the core layer provided with the stabilizer, is sufficient.
  • 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 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:
  • 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) -ethyl] - ethanamine 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 mixture of the thermoplastics of this layer.
  • the plates according to the invention can be colored by adding colorants.
  • the colorants are differentiated into dyes and pigments according to DIN 55 949.
  • the colorant can optionally be added to one or more layers.
  • the concentration of colorant is usually between 0.001 to 20% by weight for dyes, between 0.1 to 30% by weight for pigments and in the event that a mixture of pigments and dye is used between 0.1 to 30% by weight for the pigment and between 0.01 to 20% by weight, preferably between 0.5 to 10% by weight, for the dye.
  • 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 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 Thermaplastrot BS, Sudan red BB, solvent red 138 an anthraquinone derivative, fluorescent agents such as fluorophenane and fluorophenane , Solvent blue 35 an anthraquinone dye, solvent blue a phthalocyanine dye and many others.
  • Suitable inorganic pigments are, for example, the white pigments titanium dioxide, zinc sulfide and tin sulfide, which can be coated organically and / or inorganically.
  • the titanium dioxide particles can consist of anatase or rutile, preferably predominantly rutile, which has a higher covering power than anatase. In a preferred embodiment, the titanium dioxide particles consist of at least 95% by weight of rutile. You can by a conventional procedure, e.g. B. after the chloride or sulfate process.
  • the average particle size is relatively small and is preferably in the range from 0.10 to 0.30 ⁇ m.
  • Titanium dioxide of the type described does not produce any vacuoles within the polymer matrix during plate production.
  • Typical inorganic black pigments are carbon black modifications, which can also be coated, carbon pigments that differ from the carbon black pigments in their higher ash content, and oxidic black pigments such as iron oxide black and copper, chromium and iron oxide mixtures (mixed phase pigments).
  • Suitable inorganic colored pigments are oxidic colored pigments, hydroxyl-containing pigments, sulfidic pigments and chromates.
  • colored oxide pigments are iron oxide red, titanium dioxide-nickel oxide-antimony oxide mixed-phase pigments, titanium dioxide-chromium oxide-antimony oxide mixed-phase pigments, mixtures of the oxides of iron, zinc and titanium, chromium oxide-iron oxide brown, spinels of the cobalt-aluminum-titanium-nickel-zinc oxide system and Mixed phase pigments based on other metal oxides.
  • Typical hydroxyl-containing pigments are, for example, oxide hydroxides of trivalent iron such as FeOOH.
  • sulfidic pigments examples include cadmium sulfide selenides, cadmium zinc sulfides, sodium aluminum silicate with sulfur bound in polysulfide form in the lattice.
  • chromates examples are the lead chromates, which can be monoclinic, rhombic and tetragonal in the crystal forms.
  • all colored pigments can be both uncoated and also inorganic and / or organically coated.
  • the organic colored pigments are generally divided into azo pigments and so-called non-azo pigments.
  • Azo pigments can be monoazo pigments, diazo pigments, diazo condensation pigments, salts of azo color acids and mixtures of the azo pigments.
  • coating i.e. H. an improvement in the performance properties can be achieved by post-treatment of the pigment particle surface, with organic or inorganic agents. This improvement lies in particular in facilitating the dispersion and increasing the resistance to light, weather and chemicals.
  • Typical coating agents for pigments are, for example, fatty acids, fatty acid amides, siloxanes and aluminum oxides.
  • the inventive one from that described above multi-layer plate producible moldings can be equipped on one or more sides with a scratch-resistant surface.
  • the thickness of the scratch-resistant coating is generally between 1 and 50 ⁇ m.
  • Suitable coating systems and materials are e.g. those in the
  • Coating compositions disclosed each based on the weight of the dispersion, (A) 50 to 85% of a silane with vinyl groups, (B) 15 to 50% of a multifunctional acrylate and optionally (C) 1 to 3% of a photoinitiator.
  • Ormocere Organic Chemical Modified Ceramics
  • the hard coatings are bound on the basis of Al 2 O 3 , ZrO 2 , TiO 2 or SiO 2 as network formers and epoxy or methacrylate groups with Si through ⁇ Si-C ⁇ connections.
  • Coating agents for example for acrylic resin plastics and polycarbonate, based on silicone resin in aqueous-organic solution, which have a particularly high storage stability, are described in EP-A-0 073 362 and EP-A-0 073 911. These include coating agents Condensation products of partially hydrolyzed organosilicon compounds.
  • Acrylic-containing 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. Ingredients are approximately 81% acrylate oligomers and 19% hexanediol diacrylate.
  • CVD or PVD coating technologies using a polymerizing plasma and diamond-like coatings are also described in the literature (thin-film technology, edited by Dr. Hartmut Frey and Dr. Gerhard Kienel, VDI Verlag, Düsseldorf, 1987).
  • coatings are e.g. Peeraguard from Peerless, Clearlite and Filtalite from Charvo, coating types such as the UVHC series from GE Silicones, Vuegard such as the 900 series from TEC Electrical Components, from the Societe Francaise Hoechst Highlink OG series, PPZ® products sold by Siber Hegner (manufactured by Idemitsu) and coating materials from Vianova Resins, Toagoshi , Toshiba or Mitsubishi.
  • 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 from Vianova Resins, Toagoshi , Toshiba or Mitsubishi.
  • Known coating methods suitable for the present invention include e.g. Offset printing, pouring, dipping, flooding, spraying or spraying, knife coating or rolling.
  • CVD processes or vacuum plasma processes e.g. Vacuum plasma polymerization, PVD processes, coating with electron beam evaporation, resistance-heated evaporator sources or coating by conventional processes in a high vacuum, such as in a conventional metallization.
  • 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 Acry Ilatex.
  • the multilayer, amorphous plate according to the invention can be produced by a conventional coextrusion process. Suitable methods and devices are e.g. described in German patent applications DE 196 30 597.7, 196 30 598.5 and 196 30 817.3 by the same applicant, to which reference is expressly made here.
  • An extruder for plasticizing and producing the core layer and an additional extruder per cover layer are connected to each coextruder adapter.
  • the adapter is constructed in such a way that the melts which form the cover layer, optionally with additives, are applied as thin layers adhering 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.
  • the first smoothing cooling roll, over which the extruded thermoplastic melt is guided for shaping has a temperature between 50 ° C and 80 ° C.
  • the nucleating agents used in the manufacture of the plate it is important to ensure precise temperature control and exact roller temperatures. If the roll temperatures are too high, the nucleation process can cause crystallization can be initiated during the extrusion, which leads to enormous problems during the subsequent thermoforming.
  • the nucleating agent and, if appropriate, further additives such as UV stabilizer, antioxidant, colorant, etc. can be metered in at the thermoplastic raw material manufacturer or metered into the extruder during plate production.
  • additives via masterbatch technology is particularly preferred.
  • the additives such as the nucleating agent, are fully dispersed in a solid carrier material.
  • 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 of the additives, in particular the nucleating agent, is ensured and thus homogeneous nucleation and crystallization can take place.
  • the homogeneously crystallized shaped body according to the invention can be obtained from the above-described, nucleating agent-containing, multi-layer, amorphous plate by a thermoforming method known per se with the usual devices and measures. It has a particularly homogeneous degree of crystallization and a high and uniform heat resistance.
  • Thermoforming generally includes
  • the heating or heating of the plate to the forming temperature can be carried out with all heating devices known to the person skilled in the art for deep drawing, such as hot-air ovens or infrared heaters. In order to heat the plate as quickly and uniformly as possible, heating is preferably carried out on both sides, ie with top and bottom heat.
  • the plate temperature is advantageously below 140 ° C., preferably below 130 ° C. and particularly preferably below 120 ° C.
  • the deformation is preferably carried out by means of a vacuum deformation process under the influence of heat.
  • the mold When forming, it is essential that the mold has a temperature of at least 100 ° C and preferably at least 120 ° C.
  • the molding tool can be heated using conventional heating devices such as heated oil, electrically operated cassette heaters or the like.
  • the already formed, still essentially amorphous plate is kept in the mold after the forming, preferably under vacuum, and is subjected to a heat treatment at temperatures in the range from 100 to 200 ° C., preferably from 120 to 180 ° C., for crystallization.
  • the same heating devices can be used for the heat treatment as for the heating or heating of the plate.
  • the progress of the crystallization in the course of the heat treatment of the shaped body can be monitored visually, since the initially largely transparent shaped body becomes increasingly milky white in color.
  • the light transmission of the transparent plate used initially decreases homogeneously from about 90% as a result of the crystallization and takes on values which are less than 50%, preferably less than 40% and particularly preferably less than 30%.
  • the duration of the heat treatment is generally 30 seconds to 6 minutes for the process described here using the amorphous plate according to the invention with homogeneously distributed nucleating agents, the duration depending on the plate thickness.
  • the crystallized shaped body obtained is cooled and demolded as usual.
  • the crystallization takes place rapidly and uniformly over the entire area of the shaped body, so that a shaped body is obtained which has the properties described above, which are desirable according to the invention, such as a homogeneous degree of crystallinity and, as a result, improved heat resistance and improved optical and mechanical properties.
  • the tensile modulus measured in accordance with ISO 527-1, 2, is below 3600 MPa, in particular below 3400 MPa. This is further proof that the crystallization took place homogeneously and that numerous small spherulites have formed due to the nucleating agent used, i.e. despite crystallization, the object is not brittle.
  • the light transmission of the amorphous plate according to the invention at wavelengths of 2000 nm or 2300 nm and more is less than 10%, the deviation for colored plates being only slight, i.e. the absorption is extremely high in these wavelength ranges.
  • the absorbed radiation is converted into heat, which is evenly distributed over the entire molded body and, with the participation of the nucleating agents, initiates and continues the crystallization evenly over the entire molded body.
  • the heating (heating) of the plate takes considerably less time - usually 1-2 seconds are sufficient - than the heat treatment for crystallization, the heating can also be carried out with an IR radiator with a wavelength of 2000 ⁇ m or more, without in this case premature Crystallization is to be feared.
  • the shaping is not limited to the vacuum shaping, but can also be carried out by means of another, conventional shaping process such as the pressing or blowing process.
  • the molded body according to the invention can be produced by any known method suitable for this purpose, such as e.g. injection molding, as long as a material is used as the starting material which contains at least one nucleating agent as the main constituent of the crystallizable thermoplastic described above and essentially homogeneously distributed therein.
  • the injection molding process is particularly advantageous for the production of thin-walled crystallized moldings, for example for wall thicknesses ⁇ 1 mm, with very short cycle times being possible.
  • the starting material used is granulate (pellets) which contains the thermoplastic described above and at least one of the nucleating agents described as the main constituent.
  • These granules can be processed into a shaped body according to a known injection molding process.
  • the shaped bodies obtained by this process can be amorphous or already partially crystallized.
  • the amorphous or insufficiently crystallized moldings can be crystallized after the injection molding.
  • An IR radiator with a wavelength of 2000 nm or more is also preferably used for this, as a result of which particularly homogeneously crystallized shaped bodies with numerous small spherulites are obtained.
  • the shot volume and cylinder volume are preferably matched to one another so that a residence time of the mass in the plasticizing unit of 5 to 10 minutes is not exceeded, depending on the material composition. In the case of longer dwell times due to interruptions during processing, the melt remaining in the plasticizing unit should be pumped out before starting up again.
  • melt temperatures are usually between 260 and 290 ° C. Temperatures above 295 ° C thermal damage to the melt should be avoided because of the danger.
  • the injection speed and the injection and holding pressure are generally adapted to the particular shape of the molding desired.
  • thin-walled parts should be manufactured at high spray speeds and high spray pressure in order to avoid premature solidification of the melt during the mold filling process and thus poor surface formation.
  • a medium to high pressure is recommended to exclude sink marks.
  • the mold wall temperature should not exceed 60 ° C.
  • the amorphous or partially crystallized moldings obtained in this way are subjected to a thermal aftertreatment, preferably with the above-described IR radiators with a wavelength of 2000 nm and more, for complete crystallization.
  • the crystalline shaped body according to the invention is suitable for numerous different applications, for example for trade fair construction and trade fair articles, for chemicals and transport containers, for sanitary articles, and in shop and shelf construction.
  • the moldings according to the invention are extremely suitable for use in the automotive industry, for. B. for the production of motor vehicle body parts such as fenders.
  • the surface gloss is determined 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 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 heat resistance is called HDT B (Heat Deflection Temperature)
  • the Vicat softening temperature is measured at 50 N load according to ISO 306. Density:
  • the density is determined according to DIN 53479.
  • the standard viscosity SV (DCE) is measured based on DIN 53726 in dichloroacetic acid.
  • the intrinsic viscosity (IV) is calculated as follows from the standard viscosity (SV)
  • the thermal properties such as crystallite melting point T m , degree of crystallization,
  • Crystallization temperature range T c Crystallization temperature range T c , post (cold) crystallization temperature T CN and
  • Glass transition temperature T_ 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 tensile modulus is measured at 23 ° C according to ISO 527-1, 2.
  • a 4 mm thick, multilayer, transparent, amorphous polyethylene terephthalate plate with the layer sequence A-B-A is produced according to the coextrusion process described, wherein B represents the core layer and A the cover layer.
  • the core layer B is 3.5 mm thick and the two outer layers that cover the core layer are each 250 ⁇ m thick.
  • the core layer B contains 19.9% by weight of polyethylene terephthalate, 80% by weight Regenerate from this polyethylene terephthalate as a nucleating agent and 0.1 wt .-% silicon dioxide as a nucleating agent.
  • the polyethylene terephthalate used for the core layer B has the following properties:
  • the regenerate from this polyethylene terephthalate as a nucleating agent has a standard viscosity 990, which corresponds to an intrinsic viscosity of 0.78 dl / g.
  • the silicon dioxide is metered in in the form of a master batch.
  • the masterbatch is composed of 1.0% by weight of silicon dioxide as a nucleating agent with an average particle diameter of 1 ⁇ m and 99.0% by weight of the polyethylene terephthalate described above.
  • the main layers of A contain polyethylene terephthalate and 3.0% by weight of the UV stabilizer 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-hexyloxyphenol ( ⁇ Tinuvin 1577 from the company Ciba-Geigy).
  • Tinuvin 1577 has a melting point of 140 ° C and is thermally stable up to approx. 330 ° C.
  • the UV stabilizer is incorporated into the polyethylene terephthalate directly at the raw material manufacturer.
  • the polyethylene terephthalate from which the top layers are made has a standard viscosity SV (DCE) of 890, which corresponds to an intrinsic viscosity IV (DCE) of 0.71 dl / g.
  • DCE intrinsic viscosity IV
  • the moisture content is ⁇ 0.2% and the density (DIN 53479) is 1.41 g / cm 3 .
  • the crystallinity is 59%, the crystallite melting point according to DSC measurements being 259 ° C.
  • the crystallization temperature range T c is between 83 ° C and 258 ° C, the post-crystallization temperature (also crystallization temperature) T CN at 144 ° C.
  • the polydispersity M ⁇ / M., Of the polyethylene terephthalate is 2.14.
  • the glass transition temperature is 83 ° C.
  • 10% by weight of polyethylene terephthalate, 80% by weight of regrind and 10% by weight of the silicon dioxide masterbatch for the core layer and the UV-stabilized polyethylene terephthalate for the cover layers are each 5 hours at 170 ° C in one Dryer dried and then co-extruded through a slot die onto a smoothing calender, the rollers of which are arranged in an S-shape, and smoothed into a three-layer, 4 mm thick plate.
  • the extrusion temperature of the main extruder for the core layer is 282 ° C.
  • the extrusion temperatures of the two coextruders for the cover layers are 294 ° C.
  • the first calender roll has a temperature of 65 ° C and the subsequent rolls each have a temperature of 58 ° C.
  • the speed of the trigger is 3.2 m / min.
  • the three-layer transparent plate is lined with cut-off saws on the edges, cut to length and stacked.
  • the transparent, amorphous, three-layer PET sheet obtained has the following property profile
  • Thickness of the outer layers each 0.25 mm - Surface gloss on page 185
  • the transparent, amorphous, three-layer plate is thermoformed on a vacuum thermoforming machine, which is equipped with adjustable infrared rays with a wavelength of 2000 nm to 4000 nm as heat sources, with the following parameters:
  • the fender which was colored homogeneously white due to the crystallization, was washed for 3 days at a temperature of 40 ° C in lubricating oil, alkaline washing solution, diluted hydrochloric acid, alcohol and petrol stored and proved to be absolutely chemically stable.
  • the crystallized fender was left in an autoclave at a temperature of 160 ° C. for 48 h and proved to be completely and homogeneously stable over the molded body.
  • the crystallized fender is characterized by the following properties:
  • the crystallinity, the HDT-B (0.45 MPa) and the Vicat softening temperature were measured at 15 different locations on the crystallized, white shaped body.
  • the crystallinity only fluctuated between 49% and 52%, i.e. H. by 3 units.
  • the HDT-B (0.45 MPa) and the Vicat softening temperature fluctuated by only 5% to 6%.
  • Xenon lamp inner and outer filters made of borosilicate
  • the crystallized fender After 3000 hours of artificial weathering, the crystallized fender showed no measurable difference in the property profile.
  • the crystallized fender was painted under industrial conditions.
  • the molded body proved to be absolutely dimensionally stable and showed no surface defects or inhomogeneities in the paint layer after painting.
  • Example 1 Analogously to Example 1, a transparent, three-layer, amorphous, UV-stabilized plate is produced.
  • the property profile is identical to the property profile of the plate from example 1.
  • the amorphous polyethylene terephthalate plate with the layer structure A-B-A is deep-drawn analogously to example on a vacuum thermoforming machine, which is equipped with adjustable infrared radiators as a heat source, to form a crystallized fender.
  • the infrared radiators have a wavelength of 1000-1500 nm.
  • the fender had to be held under vacuum in the mold for 290 seconds with heating on both sides with IR radiators with a wavelength of 1000 nm to 1500 nm.
  • the crystallized fender shows high chemical resistance, excellent UV stability and good, homogeneous heat resistance.
  • the fender is characterized by the following additional properties:
  • Crystallinity, HDT-B (0.45 MPa) and Vicat softening temperature were measured at 15 different locations on the crystallized, white, UV-stabilized fender.
  • the crystallinity fluctuated between 45% and 51%, i.e. by 6 units.
  • the HDT-B (0.45 MPa) and the Vicat softening temperature fluctuated by only 7 ° C to 8 ° C.
  • Example 2 Analogously to Example 1, a polyethylene terephthalate plate with the layer structure A-B-A is produced.
  • the core layer B is 5.5 mm thick and the two outer layers that cover the core layer are each 250 ⁇ m thick.
  • the core layer B consists of 100% regenerated polyethylene terephthalate.
  • the regenerated polyethylene terephthalate has the following properties - SV (DCE) 990 - IV (DCE) 0.78 dl / g
  • the outer layers A are identical to the outer layers from Example 1, but do not contain any UV stabilizer.
  • regenerate of the core layer B and the polyethylene terephthalate of the outer layers A are coextruded analogously to Example 1 to a 6 mm thick plate with the layer structure A-B-A.
  • the transparent, amorphous, three-layer plate obtained has the following property profile:
  • Layer structure ABA total thickness 6 mm thickness of the core layer 5.5 mm thickness of the outer layers each 0.25 mm surface gloss 1st side 176 (measuring angle 20 °) 2nd side 172 • Light transmission 83% ⁇ Clarity 97.8%
  • the transparent, three-layer, amorphous plate is thermoformed on a vacuum thermoforming machine, which is equipped with adjustable infrared radiators with a wavelength of 2000 nm to 4000 nm as heat sources, with the following parameters:
  • the chemical collection container which was colored homogeneously white due to the crystallization, was each 48 hours with 30% formic acid, with 20% sulfuric acid, with 10% hydrofluoric acid, with 20% hydrochloric acid, with toluene, with gasoline, with isopropanol, with cyclohexanol, with ethanol , filled with transformer oil and with hydrogen superoxide and proved to be absolutely chemically stable.
  • the crystallized shaped body was left in an autoclave at a temperature of 160 ° C. for 48 hours and proved to be completely and homogeneously stable over the entire shaped body.
  • the crystallized chemical collecting container is characterized by the following properties:
  • Crystallinity, HDT-B (0.45 MPa) and Vicat softening temperature were measured at 15 different locations on the crystallized container. The crystallinity only fluctuated between 49% and 51%. The HDT-B (0.45 MPa) and the Vicat softening temperature only fluctuated by 5 ° C.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention concerne, d'une part, une plaque multicouche ayant comme principal composant une matière thermoplastique cristallisable et au moins un agent de nucléation et, d'autre part, un moule réalisable à partir d'une telle plaque, le mode de fabrication et l'utilisation.
PCT/EP1997/005311 1996-10-14 1997-09-29 Plaque multicouche en matiere thermoplastique cristallisable, fabrication d'un moule cristallise a partir d'une telle plaque et utilisation Ceased WO1998016381A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU47787/97A AU4778797A (en) 1996-10-14 1997-09-29 Cristallizable thermoplastic multilayer plate, manufacturing from same a cristallizable mould, and its use

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19642287.6 1996-10-14
DE19642287A DE19642287A1 (de) 1996-10-14 1996-10-14 Mehrschichtige Platte aus einem kristallisierbaren Thermoplast, ein daraus herstellbarer, kristallisierter Formkörper sowie dessen Verwendung

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WO1998016381A2 true WO1998016381A2 (fr) 1998-04-23
WO1998016381A3 WO1998016381A3 (fr) 1998-07-30

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EP2177575A1 (fr) 2008-10-20 2010-04-21 Nanogate AG Revêtement résistant aux égratignures pour objets sanitaires

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DK120505B (da) * 1964-12-03 1971-06-07 Glanzstoff Ag Fremgangsmåde til fremstilling ved vakuumdybtrækningsmetoden af formlegemer af polyætylentereftalat.
DE3147881A1 (de) * 1981-12-03 1983-06-16 Basf Ag Warmverformbares flaechiges halbzeug aus faserverstaerktem polyethylenterephthalat
JPS5976226A (ja) * 1982-10-26 1984-05-01 Kohjin Co Ltd ポリエステル積層フイルム及びその製造方法
DE3688313D1 (de) * 1985-10-03 1993-05-27 Ppg Industries Inc Laminate aus mit glasfasern verstaerkten polyaethylenterephthalaten fuer pressstoffe.
US4737389A (en) * 1986-01-31 1988-04-12 Amoco Corporation Dual ovenable frozen food tray/cookware formed from a lainate containing a polymer that is crystallizable at use temperature
US4824718A (en) * 1987-12-04 1989-04-25 Minnesota Mining And Manufacturing Company Porous film
IT1216472B (it) * 1988-02-29 1990-03-08 Montefibre Spa Composizioni poliestere a rapida cristallizzazione.
DE4009638C2 (de) * 1990-03-26 2000-11-09 Hoechst Ag Verfahren zur Herstellung einer koextrudierten Folie
IE68430B1 (en) * 1990-08-12 1996-06-12 Polysheet Ireland Ltd A method and apparatus for forming an article of PET material
US5292471A (en) * 1990-12-13 1994-03-08 Toray Industries, Inc. Process for forming a polyester film
HU213531B (en) * 1992-07-07 1997-07-28 Continental Pet Technologies Method of forming multilayer product, especially container, bottle, and multilayer container, bottle, made from multilayer material and preform forming the container, the bottle
US5318810A (en) * 1992-12-30 1994-06-07 Welex Incorporated Food tray and method of making the same
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
US5497562A (en) * 1995-03-03 1996-03-12 Hosokawa Bepex Corporation Radiant heater system for solid phase crystallization and polymerization of polymers
EP0828785A1 (fr) * 1995-05-29 1998-03-18 Hoechst Aktiengesellschaft Plaque coloree transparente amorphe en thermoplaste cristallisable, son procede de fabrication et son utilisation

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AU4778797A (en) 1998-05-11
DE19642287A1 (de) 1998-04-30

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