CN1216950A - Amorphous plate of crystallizable polyalkylene naphthalate - Google Patents
Amorphous plate of crystallizable polyalkylene naphthalate Download PDFInfo
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- CN1216950A CN1216950A CN97194203A CN97194203A CN1216950A CN 1216950 A CN1216950 A CN 1216950A CN 97194203 A CN97194203 A CN 97194203A CN 97194203 A CN97194203 A CN 97194203A CN 1216950 A CN1216950 A CN 1216950A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C51/00—Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
- B29C43/22—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of indefinite length
- B29C43/222—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of indefinite length characterised by the shape of the surface
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
- B29C48/911—Cooling
- B29C48/9135—Cooling of flat articles, e.g. using specially adapted supporting means
- B29C48/914—Cooling of flat articles, e.g. using specially adapted supporting means cooling drums
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
- B29C48/90—Thermal treatment of the stream of extruded material, e.g. cooling with calibration or sizing, i.e. combined with fixing or setting of the final dimensions of the extruded article
- B29C48/906—Thermal treatment of the stream of extruded material, e.g. cooling with calibration or sizing, i.e. combined with fixing or setting of the final dimensions of the extruded article using roller calibration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
- B29K2995/0037—Other properties
- B29K2995/0072—Roughness, e.g. anti-slip
- B29K2995/0073—Roughness, e.g. anti-slip smooth
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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Abstract
The invention concerns an amorphous plate which is between 1 and 20 mm thick and is characterized in that its main component is at least one polyalkylene naphthalate. The invention further concerns a process for producing this plate.
Description
The present invention relates to a kind of amorphous plate of at least one crystallizable polyalkylene naphthalate, it has 1 to 20mm thickness.This sheet has the characteristic of utmost point good optical and engineering properties.The present invention is further about the method for making of this sheet.
Amorphous plate with 1 to 20mm thickness is known fully.These sheet structures are made of unbodied not crystallizable thermoplastic.The exemplary embodiments of processed in blocks this kind thermoplastic is for example polyvinyl chloride (PVC), Merlon (PC) and polymethyl methacrylate (PMMA).These half-done products are to prepare on the line (referring to polymeric material (Polymer Werkstoffe (Polymericmaterials) so-called extruding, the II volume, 136 pages of technologies 1 (Technology1), Georg ThiemeVerlag, Stuttgart, 1984).Powdery or granular raw material melts in an extruder.After extruding, the viscosity that constantly raises owing to follow the reduction of temperature, by calender or other shaping mould, this amorphous thermoplastic is easy to by reshaping.After moulding, amorphous plate has suitable stability, also is high viscosity, so that can " oneself is stood " (stand by themselves) on die finish.Yet it is still enough soft so that can come moulding with mould.The melt viscosity of the amorphous thermoplastic in die finish and interior rigidity are so high, can not crumble before consequently half-done product cools off in die finish.At the easy material that decomposes, under the situation as PVC, during extruding, need special processing aid, the processing stabilizers and the too high internal friction of antagonism that decompose as antagonism reach the lubricant that does not therefore have controllable heating.Need exterior lubricant to be bonded on wall and the roller to prevent material.
For example in the processing of PMMA, make to spend the volatilization extruder to remove steam.
In amorphous thermoplastic film's preparation, need expensive additive sometimes, it can move in some cases and can cause the preparation problem and cause at the surface deposition of partly finishing on the product because of evaporation.The PVC sheet is difficult to reclaim or only available special neutralization or electrolytic method reclaim.PC and PMMA sheet equally also are difficult to reclaim or are only losing or extremely destroying under the mechanical situation and reclaim.
Except these shortcomings, the PMMA sheet also have extreme difference impact flexibility and can be cracked when being broken or being in mechanical stress following time.In addition, inflammable as PMMA sheet such as the timber, so that for example cannot be applied in internal application or in showing with structure.
In addition, PMMA and PC sheet can't be at cold environment compacted unders.In cold forming, the PMMA sheet is broken into harmful fragment.A meeting generation shape slight crack and white are broken during the cold forming of PC sheet.
EP-A-0471528 describes a kind of method by terephthalic acid (TPA) ethylidene ester (PET) sheet moulding one object.The PET sheet in a thermoforming mould, under the temperature range of glass transition temperature and fusion temperature, on two sides by heat treatment.When the crystallization degree of the PET of moulding sheet is in 25 to 50% scopes, remove in by mould through the PET of moulding sheet.The PET sheet that is disclosed in EP-A-0471528 has 1 to 10mm thickness.Because thus the shaped article of the prepared thermoforming of PET sheet be partially crystallizable and no longer be transparent therefore, and the surface nature of shaped article is determined by thermoforming process and wherein given temperature and shape, the optical property of then used PET sheet (for example gloss, turbidity and light transmission) is unimportant.In principle, the optical property of these sheets be difference and need optimization.
US-A-3,496,143 describe the vacuum thermoforming of the thick PET sheet of 3mm, and its crystallinity must be in 5 to 25% scopes.The degree of crystallinity of the shaped article of thermoforming is greater than 25%.And on these PET sheets, need not limit about optical property.Because the degree of crystallinity of used sheet is between 5 to 25%, these sheets are muddy and opaque.
The objective of the invention is to provide a kind of amorphous plate with 1 to 20mm thickness, it has favorable mechanical and optical property.
Good optical character is decided according to the specific embodiment, comprises for example high light transmission, high lustrous surface, extremely low turbidity and high clarity (Bildschaerfe).
Good mechanical is particularly including high impact flexibility and high fracture strength.
Moreover it should be callable complying with of the present invention, does not particularly lose mechanicalness, and has low combustibility, so that for example can be used in internal application and the displaying structure.
This purpose is reached by an amorphous plate with 1 to 20mm thickness, it is characterized in that this sheet contains at least a crystallizable polyalkylene naphthalate as Main Ingredients and Appearance.
This amorphous plate contains at least a poly-alkylene naphthalate as Main Ingredients and Appearance.The preferably is poly-naphthalenedicarboxylic acid ethylidene ester, poly-naphthalenedicarboxylic acid propylidene ester and poly-naphthalenedicarboxylic acid butylidene ester, especially preferably poly-naphthalenedicarboxylic acid ethylidene ester (PEN).
Amorphous plate can be transparent, and is transparent and coloured or opaque and coloured.
In transparent embodiment, to measure according to DIN 67530 (taking measurement of an angle 20 °), amorphous plate has greater than 110, preferably greater than 120 lustrous surface.According to the measured light transmittance of ASTM D1003 is greater than 80%, and preferably greater than 82%, similarly measured according to ASTM D1003, the turbidity of sheet is less than 15%, preferably is less than 11%.
(ASTM D1003) is preferably greater than 90% in the clarity that is less than the slide of measuring at 2.5 ° of angles (being also referred to as transparency), is preferably greater than 92% especially.
In transparent and coloured embodiment, amorphous plate contains at least one soluble dye.The concentration of soluble dye, the weight based on poly-alkylene naphthalate is preferably in 0.001 to 20wt% scope.
Soluble dye means the material (DIN55949) that can be dissolved in to molecularity in the polymer.
Because of the color change that amorphous plate dyeing is caused is based on absorption relevant with wavelength and/or scattering of light.Dyestuff can only absorb light, and scattered light not, because the necessary condition of the scattering minimum particle size that is some.
By means of the painted of dyestuff is a dissolving method.As the result of this dissolving method, dyestuff by molecularity for example be dissolved in the PEN polymer.This product dyed thereby is called as transparent or translucent or lacteous.
In different types of soluble dye, special preferred aliphatic series and aromatics soluble dye.These are for example azo and castor quinone dyestuff.Because because the high glass transition temperature of PEN, the migration of dyestuff is restricted, so said two devices is particularly suitable for PEN dyeing (literature J.Koerner: the soluble dye in the plastics industry in VDI plastics technology association: dyeing of plastics (Soluble dye in the plastics industry in " VDI-GesellschaftKunstofftechnik:Einfaerben von Kuststoffen VDI-Verlage, Duesseldorf 1975)).
The embodiment of suitable soluble dye is: solvent yellow 93, pyrazolone derivative, solvent yellow 16, fat-soluble azo dyes, Fluorol Green-Gold, the polycyclic dyes of fluorescence, solvent red 1, azo dyes, the red BS of azo dyes class such as thermoplastic, tonyred SB, solvent red 138, castor quinone derivative, the fluorescence benzopyran dyes is as Fluorol Red GK and Fluorol Orange GK, solvent blue 35, castor quinone dyestuff, solvent blue, phthalocyanine dye and a lot of other person.The mixture of two kinds or multiple above these soluble dye also is suitable.
According to the present invention, soluble dye can be added into desired concentration by feedstock production person or can make an addition in the extruder during the sheet preparation.
Yet the dyestuff additive especially preferably adds by the masterbatch mixture technology.Soluble dye is disperseed fully and/or is dissolved in the solid carrier material.The suitable carriers material is some resin, and poly-alkylene naphthalate itself or other can be fully and poly-naphthalene diformazan alkylene ester compatible polymers.
Importantly: the particle size of masterbatch mixture and bulk density are similar to the particle size and the bulk density of poly-alkylene naphthalate, so that can take place to distribute uniformly to reach, the result, and even and transparent is painted.
The surface gloss of the transparent and coloured sheet of measuring according to DIN 67530 (taking measurement of an angle 20 °) is greater than 100, preferably greater than 110, according to the measured light transmittance of ASTM D1003 is in 5 to 80% scopes, preferable in 10 to 70% scopes, and according to the measured turbidity of ASTMD1003 is in 2 to 40% scopes, preferable in 3 to 35% scopes.
In painted embodiment, amorphous plate contains at least one organic and/or inorganic pigment as colouring agent.The concentration of colouring agent, the weight based on poly-alkylene naphthalate is preferably in 0.5 to 30wt% scope.
When considering colouring agent, according to DIN 55944, between dyestuff and pigment be have branch other.Pigment almost is insoluble in the polymer under each concrete processing conditions, yet dyestuff is soluble (DIN 55949).The pigmentation of pigment is to take place by particle itself.The pigment one speech normally particle size with 0.01 μ m to 1.0 μ m is relevant.According to DIN53206, when the definition pigment particles, divide into initial particle, aggregation and agglomerate.
Initial particle is because of normally prepared in synthetic method, so owing to its minimum particle size, it can have the remarkable tendency of gathering.By the aggtegation of initial particle, can produce aggregation, therefore the latter has littler surface area than being equivalent to the long-pending sum person of its initial particle surface.Because initial particle and/or aggregation in the corner or the gathering at edge, form agglomerate, its total surface area only differs from single area sum slightly.Do not have if refer to pigment particle size and to indicate in detail, then be meant the aggregation that exists in painted back essence.
In pulverous pigment, aggregation regular meeting gathers the formation agglomerate, and the latter must make it to disintegrate in coloring process, is aggregated the wetting and even distribution of thing.These simultaneous processes are called dispersion.On the other hand, coming under the painted situation with dyestuff, the process that is involved is a course of dissolution, and consequently dyestuff exists with the molecular melting form.
Opposite with inorganic pigment, under the situation of some organic pigment, insoluble fully is not genuine, particularly all the more so in the example of the pigment with low-molecular-weight simple composition.
Dyestuff is described fully by its chemical constitution.Yet the pigment under each situation of identical chemical composition is to prepare and exist with different crystal habits.This exemplary embodiments is a white pigments titanium dioxide, and it can exist with rutile form and anatase form.
Under the situation of pigment, may be by applying, also promptly by using organic or inorganic reagent to come post processing pigment, with the improvement usability.This improvement is particularly including promoting dispersion and improving light and stablize qualitative and weather resisteant and chemical-resistant.The coating agent that the typical case is used for pigment is for example aliphatic acid, fatty acid amide, siloxanes and aluminium oxide.
The embodiment of suitable inorganic pigment is a white pigments titanium dioxide, zinc sulphide and artificial gold, and it can apply with organic and/or inorganic matter.
TiO 2 particles can comprise anatase and rutile, but preferably mainly comprises rutile, and rutile has bigger opacity than anatase.In preferable embodiment, the TiO 2 particles of 95wt% is made up of rutile at least.It can pass through commonsense method, for example prepares by chloride or sulfate process.Average particle size is quite little and be preferably in 0.10 to 0.30 mu m range.
By using the titanium dioxide of described form, during the preparation of sheet, in polymer substrate, can not form cavity.
TiO 2 particles can have an inorganic oxide coating, as being commonly used in paper as supplying TiO
2The coating of white pigments or coating constituent are to improve fast light jail property.TiO
2Known is photoactive.Under the effect of UV light, free radical forms at particle surface.The film that these free radicals can move to the coating constituent forms on the composition, causes decomposition reaction and flavescence.Particularly suitable oxide comprises aluminium, silicon, the oxide of zinc or magnesium, or the mixture of these compounds more than two kinds.TiO with coating of these compounds more than two kinds
2Particle for example is described among the EP-A-0044515 and EP-A0078633.This coating also can comprise have polarity or nonpolar group because of organic compound.By polymer melt extrude with the preparation sheet during, organic compound must have sufficient heat endurance.The embodiment of polar group is-OH-OR ,-COOX (X=R, H, or Na, the alkyl of R=tool 1 to 34 carbon atom).Preferable organic compound is alkanol and the aliphatic acid that has 8 to 30 carbon atoms in alkyl, the aliphatic acid and the uncle's alphanol that have 12 to 24 carbon atoms especially, and poly-diorganosiloxane and/or poly-organic group hydrogen siloxane (Polyorganohydrogensiloxane), for example dimethyl silicone polymer and polymethyl hydrogen siloxane.
Coating on TiO 2 particles is usually by 1 to 12 gram, and the inorganic oxide of 2 to 6 grams and 0.5 to 3 restrains especially, and 0.7 to 1.5 gram organic compound is formed especially, and this is based on 100 gram TiO 2 particles.Coating is preferable to be coated on the particle with the waterborne suspension form.Inorganic oxide is by water soluble compound, alkali metal aluminate for example, and special sodium aluminate, aluminium hydroxide, aluminum sulfate, aluminum nitrate, sodium metasilicate (waterglass) or silicic acid are settled out in waterborne suspension.
Inorganic oxide one speech is as Al
2O
3And SiO
2Should be understood to include hydroxide or its different water smoking, for example oxide hydrate, but its accurate The Nomenclature Composition and Structure of Complexes of the unknown.For example the oxide hydrate of aluminium and/or silicon grinds postprecipitation at TiO at sintering and in waterborne suspension
2On, pigment then is cleaned and is dry.Behind sintering and wet lapping subsequently, therefore this precipitation can directly occur in the suspension (as prepared in synthetic method).The oxide of each metal and/or the precipitation of oxide hydrate can take place in known pH scope from water-soluble metal salt; For example for aluminium, use aluminum sulfate aqueous solution (pH is less than 4), and oxide hydrate is by preferablely adding ammonia spirit or sodium hydroxide solution precipitates between 5 to 9 in 7 to 8.5 pH scope.Begin the TiO that originally pours into by waterglass or alkali metal aluminate solution
2The pH of suspension should be in the strong basicity scope (pH is greater than 8).In the case, precipitation is to be undertaken by adding inorganic acid such as sulfuric acid in 5 to 8 pH scope.At the metal oxide post precipitation, suspension stirred 15 minutes to 2 hours subsequently, and the beds of precipitation wear out during this period.Through the product of coating in water slurry, isolate and after cleaning at high temperature, under 70 to 110 ℃, be dried especially.
Typical inorganic black pigment be can be coated similarly the carbon black variant, the ash content of Yin Genggao and differ from the carbon pigment of carbon black pigment, and black oxide pigment are as iron oxide black and copper, chromium and ferriferous oxide mixture (mixed dyes of Fe).
Suitable inorganic color color is colored oxide pigment, the pigment of hydroxyl, sulfide pigment and chromate.
The embodiment of colored oxide pigment is an iron oxide red, titanium dioxide-nickel oxide-antimony oxide mixed dyes of Fe, titanium dioxide-chromium oxide-antimony oxide mixed dyes of Fe, the mixture of iron, zinc and titanyl compound, the chromium oxide iron oxide brown, the spinelle of cobalt-aluminium-titanium-nickel-zinc oxide system, reaching with other metal oxide is the mixed dyes of Fe of base.
The embodiment of the pigment of typical hydroxyl is ferric oxide hydroxide such as FeOOH.
The embodiment of sulfide pigment is a cadmium sulfide selenides, and cadmium-zinc sulfide contains the sodium-aluminosilicate of polysulfide type bond sulphur in lattice.
The embodiment of chromate is a plumbous chromate, and its crystal form with monoclinic, orthorhombic and tetragonal exists.
The same with white and black pigment, all color pigments can be not coated or be coated with inorganic and/or organic substance.
Organic color pigment is divided into AZOpigments and so-called non-AZOpigments usually.
The feature of AZOpigments be azo group (N=N-).AZOpigments comprises monoazo pigment, two AZOpigments, two azo condensation pigments, the salt of azo dyes acid and the mixture of AZOpigments.
Amorphous colored pellets contains at least one inorganic and/or organic pigment.In specific embodiments, amorphous plate also can contain the mixture of inorganic and/or organic pigment, and additional soluble dye.In this article, soluble dye concentration is preferably in 0.01 to 20wt% scope, and especially preferably in 0.5 to 10wt% scope, this is the weight based on poly-alkylene naphthalate.
According to the present invention, colouring agent (inorganic and/or organic pigment and optional dyestuff) is added into desired concentration by feedstock production person or can be added in the extruder during the sheet preparation.
Yet color additive is especially preferably by the masterbatch mixture technology or pass through solid pigment preparation and add.Organic and/or inorganic pigment reaches if the soluble dye that needs can fully be dispersed on the solid carrier material.Suitable carriers is some resin, and the polymer of desiring to be colored itself or other are understood and gathered the abundant compatible polymers of alkylene naphthalate.
Importantly, the particle size of solid pigment preparation or masterbatch mixture and bulk density are similar to the particle size and the bulk density of poly-alkylene naphthalate, so that distribution and painted uniformly can take place.
The surface gloss through painted sheet of measuring (taking measurement of an angle 20 °) according to DIN 67530 is preferably greater than 90 and is preferably according to the measured light transmittance of ASTM D1003 and is less than 5%.
Further have by painted sheet opaque, uniform optical property.
In a further preferred embodiment, amorphous plate further contains at least one UV stabilizing agent as light stabilizer, the UV stabilizer concentration, and the weight based on poly-alkylene naphthalate is preferably between 0.01 to 5wt%.
The ultraviolet part of light, particularly solar radiation, also promptly 280 to 400hm wave-length coverage can cause decomposable process in thermoplastic, its result not only has the change of visible outward appearance because of color change or flavescence, and machinery-physical property is also had adverse effect.
The inhibition of these photooxidation decomposable processes has industry and Economic Importance, if not because so, the possible purposes of multiple thermoplastic will be restricted greatly.
Poly-alkylene naphthalate, for example, even can begin to absorb UV light below 360nm, and its absorption is in increase and extremely remarkable below 300nm significantly below the 320nm.The absorption maximum effect is between 280 to 300nm.
In the presence of oxygen, mainly observe chain and split, and non-crosslinked.With amount, carbon monoxide, carbon dioxide and carboxylic acid are main photo-oxidation products.Except the direct photolysis of ester group, the oxidation reaction that can similarly cause carbon dioxide to form by peroxide radical also must be listed consideration in.
By splitting of the hydrogen in ester group α position, the photooxidation of poly-alkylene naphthalate also can obtain hydroperoxides and its catabolite and the relevant chain (H.Day that splits, D.M.Wiles: the 16,1972,203rd page of journal of applied (J.Appl.Polym.Sci.)).
UV stabilizing agent or absorbent as light stabilizer are to disturb by the physics of light-initiated decomposition and the chemical compound of chemical process.Carbon black and other pigment partly have light protection effect.
Yet these materials are not suitable for slide, because it causes fading or color change.
Only organic and organo-metallic compound, it can not give or only give color or color change seldom the thermoplastic of desiring to be stabilized, and is to be suitable for transparent amorphous plate.
The UV stabilizing agent that is suitable as light stabilizer is a 2-dihydroxy benaophenonel for example, the 2-hydroxybenzotriazole, the organic nickel compound, salicylate, cinnamate derivates, resorcinol monobenzoate, the oxalic acid anilid, hydroxybenzoate, bulky amine and triazine are good with 2-hydroxybenzotriazole and triazine.
In a particularly preferred embodiment, contain crystallizable poly-naphthalenedicarboxylic acid ethylidene ester as Main Ingredients and Appearance and 0.01wt% to 5.0wt%2-(4 according to amorphous plate of the present invention, 6-diphenyl-1,3,5-triazine-2-yl)-and 5-(hexyl) oxygen base-phenol or 0.01wt% to 5wt%2,2 '-methylene-two (6-(2H-BTA-2-yl)-4-(1,1,3, the 3-tetramethyl butyl)-phenol.In a preferable embodiment, the mixture of at least a and other UV stabilizing agent of the mixture of this two UV stabilizing agent or this two UV stabilizing agent also can be used, the total concentration of light stabilizer based on crystallizable poly-naphthalenedicarboxylic acid ethylidene ester, is preferably between between 0.01wt% to 5.0wt%.
According to the present invention, crystallizable polyalkylene naphthalate means:
-crystallizable polyalkylene naphthalate homopolymers,
-crystallizable polyalkylene naphthalate copolymer,
-crystallizable polyalkylene naphthalate compound-material,
-crystallizable polyalkylene naphthalate salvage material, and
Other modification of-crystallizable polyalkylene naphthalate.
Preferable in this article copolymer and compound-material are the mixtures of poly-alkylene naphthalate and polyalkylene terephthalates, especially, and the mixture of poly-naphthalenedicarboxylic acid ethylidene ester (PEN) and poly terephthalic acid ethylidene ester (PET).
Amorphous plate in the present invention is meant those amorphism sheets, though the preferable degree of crystallinity that has between 10% to 65% of used crystallizable thermoplastic.Amorphism also promptly amorphously in fact means degree of crystallinity usually below 5%, and is preferable below 2%, and especially preferably 0%.
In addition, finding fully unexpectedly can be by cold forming, but crack-free, and acomia shape slight crack and/or do not have the good capacity that white is broken, so that sheet of the present invention can be by moulding and bending, and need not the effect of temperature.
In addition, measure demonstration poly-alkylene naphthalate of the present invention and be difficult to burning, so that for example can be used in internal application and the displaying structure.
Further can be recovered according to of the present invention, but non-environmental-pollution and do not have the forfeiture of mechanical character, this means it and is fit to, and for example, is used as short-term advertising sign or other advertising items.
In a good especially embodiment, contain crystallizable poly-naphthalenedicarboxylic acid ethylidene ester as Main Ingredients and Appearance according to of the present invention.
Under the situation of poly-naphthalenedicarboxylic acid ethylidene ester, preferably at Charpy impact flexibility a
nMeasurement during (measuring) according to ISO 179/1D on sheet, do not break.Moreover the Ai Zuoshi notch shock toughness ak of sheet (measuring according to SIO 180/1A) is preferably 2.0 to 12.0kJ/m
2, particularly preferably in 3.0 to 8.0kJ/m
2In the scope.
Preferable polymer as the parent material of the preparation that is used for sheet is poly-naphthalenedicarboxylic acid ethylidene ester, and it has 240 ℃ to 300 ℃, preferably 250 ℃ to 290 ℃ crystallite melting point T
m(by DSC (differential scanning calorimetry), measured with 10 ℃/minute the rate of heat addition) is between 100 ℃ to 290 ℃ crystallization range T
c, between 100 ℃ to 140 ℃ glass transition temperature, according to DIN 53479 measured 1.30 to 1.45g/cm
3Density and between 10% to 65% degree of crystallinity.
Normal viscosity SV (DCA) according to DIN 53728 measured poly-naphthalenedicarboxylic acid ethylidene ester in dichloroacetic acid is between 600 to 1400, and is preferable between 750 to 1250, and good for especially 800 to 1100.
It is as follows to calculate inherent viscosity IV (DCA) by normal viscosity:
IV(DCA)=6.67×10
-4SV(DCA)+0.118
Be preferably between 0.75kg/dm according to DIN 53466 measured bulk densitys
3To 1.0kg/dm
3, and especially preferably between 0.80kg/dm
3To 0.90kg/dm
3Between.
Polydispersity Mw/Mn by the measured poly-naphthalenedicarboxylic acid ethylidene ester of GPC is preferably between 1.5 to 4.0, especially goodly between 2.0 to 3.5.
Preparation according to amorphous plate of the present invention is passable, for example, implements by the extrusion method in extruding line.
This kind extruded line and is shown among Fig. 1 with schematic form.Its essence comprises
-as the extruder (1) of plasticising unit,
-as the channel mould (Breitschlitzduese) (2) of shaping mould,
-as calender (the Glaettwerk)/calender (Kalander) (3) of die finish,
Cooling bed (4) and/or the roll-type conveyer belt (5) of-cooling after supplying,
-take out with roller (6),
-separatory saw,
-edge trimming device (9) reaches as if suitable,
-piling apparatus (8).
The method comprises, randomly, dry poly-alkylene naphthalate, then in extruder fusion it, if suitable this is and soluble dye that colouring agent and/or UV stabilizing agent together carry out, and extrude this fused mass by a mould, then before being cut into required size, pressure-sizing in calender, calendering and cooling.
Soluble dye, colouring agent and/or UV stabilizing agent are preferable to be added by the masterbatch mixture technology.In the case, soluble dye, colouring agent and/or UV stabilizing agent are dispersed in the solid carrier material fully.The suitable carriers material is some resin, poly-alkylene naphthalate itself, or other is understood and gathers the abundant compatible polymers of alkylene naphthalate.
At poly-naphthalenedicarboxylic acid ethylidene ester (PEN), be specified in down according to the preparation method of sheet of the present invention.
Before extruding, PEN is preferable following dry 4 to 6 hours at 160 to 180 ℃.
Then PEN and optional additive masterbatch mixture melt in extruder.The temperature of PEN fused mass is preferably in 250 to 320 ℃ of scopes, may be substantially by the temperature of extruder and in extruder the holdup time of fused mass set up melt temperature.
Fused mass then leaves extruder by a mould.This mould is preferably a channel mould.
Melt and the calender rolls (Glaettkalanderwalzen) of the refining usefulness of PEN mat by the moulding of mould institute and pressure-sizing also promptly strong cooling and refining by extruder.Calender rolls can be with for example 1-, F-, and L-or S-shape are arranged.
The PEN material then can be on the roller conveyer back cooling, the trimming edge is with sizing, be cut into the length of wanting and being piled up at last.
PEN sheet thickness is in fact by take out being provided with (it is positioned at the cooling zone end), according to speed and cooling (make with extra care) roller that coupling so far is provided with and, on the one hand, the transfer rate of extruder reaches on the other hand, the distance between roller decides.
Can use single screw rod and double screw extruder as extruder.
Channel mould preferably includes removable die body, lip and by width for the limit rod of Flow-rate adjustment.For this reason, control lever can come crooked by tension spiral and hold-down bolt, and thickness is set by regulating lip.Will guarantee that importantly PEN and lip have a uniform temperature, otherwise the PEN fused mass flows out with different thickness because of different runners.
Die finish, promptly calender makes the PEN fused mass that shape and size be arranged.This is to carry out to be refrigerated under the glass transition temperature by cooling and calendering.In this state, should no longer deform, otherwise in this state of cooling, can form blemish.Reason for this reason, calender rolls is preferably driven jointly.The temperature of calender rolls must be lower than the crystallite fusion temperature to avoid being stained with of PEN fused mass sticking.The PEN fused mass leaves channel mould with 240 to 300 ℃ temperature.First calendering/chill roll has the temperature between 50 ℃ to 80 ℃, and this is according to output quantity and sheet thickness and decide.The second colder slightly roller is with second or other surface cool.
At calibration devices that the PEN surface is freezing as far as possible smoothly and cool off its profile to the degree that makes its dimensionally stable, back cooling device reduces the temperature of PEN sheet to being almost room temperature.Back cooling can take place on the roller plate.Take-off speed should accurately cooperate variation and the defective to avoid thickness with calender rolls speed.
As extra device, extruding line and can comprise that separates saw with the device as Cutting Length, edge trimming device, stacked units and control station for the preparation of PEN sheet.Edge trimming device is favourable, because the thickness in some environment lower limb zone may be inhomogeneous.The thickness of sheet and the character of optics are measured at control station.
Because surprising a large amount of superior character extremely is fit to for multiple different purposes, for example according to poly-alkylene naphthalate sheet of the present invention, be used for inner panelling, be used to show the structure of usefulness and show the object of usefulness, as display, be used for sign, for the protection glazing of machinery and vehicle, in lighting field, in shop finishing and shelf structure, as the advertisement object, as manu-holder, as the basketball backboard, divide the diaphragm thing and supply applications, for example sub of glass as the room.
The present invention is described in more detail hereinafter by means of embodiment embodiment, but is not subject to these embodiment.
The measurement of various character is implemented according to following standard or technology at this.Measuring method: lustrous surface:
According to DIN 67530 decision lustrous surfaces.Measure the reflector value with optical parametric as the sheet surface.According to standard A STM D523-78 and ISO 2813, incidence angle fixes on 20 °.Under the incidence angle of setting, light drops on flat test surfaces and is reflected by this or scattering.Incident ray on optoelectronic receiver is shown as an electricity value that is directly proportional.Measured value be no unit and must together mention with incidence angle.Light transmittance:
Light transmittance means the ratio between the amount of the total amount of transmitted light and incident light.
According to ASTM 1003, in one " Hazegard plus " measurement device, measure light transmittance.
Turbidity and clarity:
Turbidity is to depart from average percentage greater than 2.5 ° transmitted light with incident beam.Clarity is to measure under less than 2.5 ° angle.
According to ASTM 1003, use " Hazegard plus " measurement device to measure turbidity and clarity.Whiteness:
By means of Zeiss, emission again (remission) photometer of Oberkochem (DE), " ELREPHO " standard sources C, 2 ° of normal observers measure whiteness.Whiteness is defined as
WG=RY+3RZ-3RX。
The WG=whiteness, RY, RZ, RX=is when using Y, the reflection factor of being correlated with when Z and X color measuring filter (Farbmessfilter).Used white standard thing is one by the formed compression molded thing of barium sulfate (DIN 5033, the 9 partly).Blemish:
Blemish is measured visually.Charpy impact flexibility a
n:
Measure this value according to ISO 179/1D.Ai Zuoshi notch shock toughness a
k:
Measure Ai Zuoshi notch shock toughness according to ISO 180/1A.Density
Measure density according to DIN 53479.SV(DCA),IV(DCA)：
According to DIN 53726 measurement standard viscosity SV (DCA) in dichloroacetic acid.
It is as follows to calculate inherent viscosity (IV) by normal viscosity:
IV (DCA)=6.67 * 10
-4SV (DCA)+0.118 thermal property:
By differential scanning calorimetry (DSC) (DSC),, measure thermal property, as crystallite melting point T with 10 ℃/minute the rate of heat addition
m, crystallization range T
c, back-(cold) crystallization temperature T
CNAnd glass transition temperature T
gMolecular weight, polydispersity
Polydispersity Mw/Mn by gel permeation chromatography measurement molecular weight Mw and Mn and gained.
Weathering (two-sided), UV stability is as follows according to test specification book ISO 4892 test UV stability: testing equipment: Atlas Ci65 Weather Ometer test condition: ISO 4892, also promptly, the weathering irradiation time of simulation: 1000 hours (every face) irradiation: 05W/m
2340nm temperature: the humidity of 63 ℃ of relative atmosphere: 50% xenon lamp: the inside and outside filter exposure period of borosilicate: 102 minutes UV light, then 18 minutes UV are simultaneously with water spray sample 102 minutes UV light or the like color change once more then:
The change of color sample uses a spectrophotometer to measure according to DIN 5033 after artificial weathering.Symbol has following meaning: Δ L: luminance difference
+ Δ L: sample is brighter than standard items
-Δ L: sample is than the darker Δ A of standard items: the difference on red-Green Zone
+ Δ A: sample is redder than standard items
-Δ A: sample is than the greener Δ B of standard items: the difference in the blue-yellow district
+ Δ B: sample is more yellow than standard items
-Δ B: sample is than the more blue Δ E of standard items: integral color changes
Bigger with the numerical value deviation of standard items, then color distortion is bigger.Numerical value smaller or equal to 0.3 is insignificant and means no significant color change.Yellow value:
Yellow value G colourlessly measures to the deviation between " yellow " and according to DIN6167.Yellow value G smaller or equal to 5 can't discover on visual.
In following examples and comparing embodiment, under each situation, each sheet is the single-layer sheet at the described different-thickness of extruding on the line to be produced.Embodiment 1
The poly-naphthalenedicarboxylic acid ethylidene ester that is used for preparing slide has 810 normal viscosity SV (DCA), is equivalent to the inherent viscosity IV (DCA) of 0.65dl/g.Water content is less than 0.2%, and density (DIN 53479) is 1.33g/cm
3Degree of crystallinity is 15%, is 270 ℃ according to the crystallite melting point of dsc measurement method.The polydispersity M of poly-naphthalenedicarboxylic acid ethylidene ester
w/ M
nBe 2.14.Glass transition temperature is 119 ℃.
Before extruding, poly-naphthalenedicarboxylic acid ethylidene ester is in a drying machine, and drying is 5 hours under 170 ℃, then under 286 ℃ extrusion temperature, in a single screw extrusion machine, squeeze on a calender (its roll row becomes the S shape) by a channel mould, and make it smoothly to obtain the sheet of thick 2mm.First calender rolls has 65 ℃ temperature, and roller subsequently respectively has 58 ℃ temperature.The speed of take-off speed and calender rolls is 4.0m/min.
After the cooling, the clear PE N sheet of thick 2mm uses one to separate the saw finished edge, is cut into the length of wanting and accumulation.
Prepared clear PE N sheet has following character :-thickness: first of 2mm-lustrous surface: second of 170 (at 20 ° of angular measurement): 165-light transmittance: 86%-clarity: the blemish that 98%-turbidity: 1.5%-is every square metre: do not have (spot, tangerine peel, bubble etc.)-Charpy impact flexibility a
n: crack-free-cold formability: good, zero defect-degree of crystallinity: 0% 1 density: 1.31g/cm
3Embodiment 2
To be similar to the mode of embodiment 1, use a poly-naphthalenedicarboxylic acid ethylidene ester with following character to prepare a slide: SV (DCA): 1100IV (DCA): 0.85dl/g density: 1.32g/cm
3Degree of crystallinity: 24% crystallite melting point Tm: 254 ℃ of polydispersity M
w/ M
n: 2.02 glass transition temperatures: 117 ℃
Extrusion temperature is 280 ℃.First calender rolls has 66 ℃ temperature and roller subsequently has 60 ℃ temperature.The speed of take-off speed and calender rolls is 1.9m/min.
Prepared clear PE N sheet has following character: first of-thickness 6mm-lustrous surface: second of 172 (at 20 ° of angular measurement): 170-light transmittance: 88.1%-clarity: the blemish that 99.6%-turbidity: 2.6%-is every square metre: do not have (spot, tangerine peel, bubble etc.)-Charpy impact flexibility a
n: crack-free-cold formability: good, zero defect-degree of crystallinity: 0%-density: 1.32g/cm
3Embodiment 3
Prepare a slide in the mode that is similar to embodiment 2.
Extrusion temperature is 275 ℃.First calender rolls has 57 ℃ temperature, and roller subsequently has 50 ℃ temperature.Take-off speed and calender rolls speed are 1.7m/min.
Prepared PEN sheet has following character :-thickness: first of 10mm-lustrous surface: second of 151 (at 20 ° of angular measurement): 148-light transmittance: 86.5%-clarity: the blemish that 99.2%-turbidity: 4.95%-is every square metre: do not have (spot, tangerine peel, bubble etc.)-Charpy impact flexibility a
n: crack-free-cold formability: good, zero defect-degree of crystallinity: 0.1%-density: 1.33g/cm
3Embodiment 4
Prepare a slide in the mode that is similar to embodiment 2.70% the poly-naphthalenedicarboxylic acid ethylidene ester from embodiment 2 is mixed the poly-thus made salvage material of naphthalenedicarboxylic acid ethylidene ester with 30%.
Prepared clear PE N sheet has following character :-thickness: first of 6mm-lustrous surface: second of 168 (at 20 ° of angular measurement): 166-light transmittance: 87.3%-clarity: the blemish that 99.4%-turbidity: 3.2%-is every square metre: do not have (spot, tangerine peel, bubble etc.)-Charpy impact flexibility a
n: crack-free-cold formability: good, zero defect-degree of crystallinity: 0%-density: 1.32g/cm
3Embodiment 5
Transparent and the coloured amorphous plate for preparing a thick 6mm, it contains from the poly-naphthalenedicarboxylic acid ethylidene ester of embodiment 2 red 138 as the dye solvent of Main Ingredients and Appearance and 2wt% solubility, the latter be a kind of anthraquinone derivative from BASF (
Thermoplast G).
Soluble dye solvent red 138 is added with the masterbatch mixture form.Masterbatch mixture is made up of 20wt% dye solvent red 138 and the above-mentioned poly-naphthalenedicarboxylic acid ethylidene ester of 80wt%.
Before extruding, poly-naphthalenedicarboxylic acid ethylidene ester of 90wt% and 10wt% masterbatch mixture are in a drying machine, drying is 5 hours under 170 ℃, then in a single screw extrusion machine, under 280 ℃ of extrusion temperatures, squeeze on a calender (its roller is arranged in the S shape), and make it smoothly to obtain the sheet of thick 6mm by a channel mould.First calender rolls has 66 ℃ temperature, and roller subsequently respectively has 60 ℃ temperature.The speed of take-off speed and calender rolls is 2.9m/min.
After the cooling, the transparent and coloured PEN sheet of thick 6mm uses a separation saw to come finished edge, is cut into the length of wanting and accumulation.
Prepared red clear PE N sheet has following character :-thickness: first of 6mm-lustrous surface: second of 118 (at 20 ° of angular measurement): 115-light transmittance: 28.1%-clarity: the blemish that 97.1%-turbidity: 9.6%-is every square metre: do not have (spot, tangerine peel, bubble etc.)-Charpy impact flexibility a
n: crack-free-cold formability: good, zero defect-degree of crystallinity: 0%-density: 1.34g/cm
3Embodiment 6
The amorphous plate for preparing the color white of a thick 3mm, it contains poly-naphthalenedicarboxylic acid ethylidene ester from embodiment 2 as Main Ingredients and Appearance and 6wt% titanium dioxide.
Titanium dioxide is rutile-type and has been coated with Al
2O
3The organic coating of inorganic coating and dimethyl silicone polymer.Titanium dioxide has the average grain diameter of 0.2 μ m.
Titanium dioxide adds with the masterbatch mixture form.Masterbatch mixture is made up of described titanium dioxide of 30wt% and the described poly-naphthalenedicarboxylic acid ethylidene ester of 70wt%.
Before extruding, poly-naphthalenedicarboxylic acid ethylidene ester of 80wt% and 20wt% titanium dioxide masterbatch mixture are following dry 5 hours at 170 ℃ in a drying machine, then in a single screw extrusion machine, squeezing on a calender (its roller is arranged in the S shape) and making it by a channel mould under 286 ℃ the extrusion temperature smoothly to obtain the sheet of thick 3mm.First calender rolls has 73 ℃ temperature, and roller subsequently respectively has 67 ℃ temperature.The speed of take-off speed and calender rolls is 6.5m/min.
After the cooling, the white PEN sheet of thick 3mm uses a separation saw to come finished edge, is cut into the length of wanting and accumulation.
Prepared white PEN sheet has following character :-thickness: first of 3mm-lustrous surface: second of 123 (at 20 ° of angular measurement): 122-light transmittance: 0%-whiteness: 110-color: white, evenly-and blemish: there is not (spot, tangerine peel, bubble etc.)-Chalpy impact flexibility a
n: crack-free-cold formability: good-degree of crystallinity: 0% embodiment 7:
Prepare a transparent amorphous of thick 3mm, its contain from the poly-naphthalenedicarboxylic acid ethylidene ester of embodiment 2 as Main Ingredients and Appearance and 1.0wt%VU stabilizing agent 2-(4,6-diphenyl-1,3,5-triazines-2-yl)-5-(hexyl) oxygen base phenol (
Tinuvin 1577, from Ciba-Geigy).
Tinuvin 1577 has 149 ℃ fusing point and is heat-staple under the highest about 330 ℃.
For reaching uniform distribution, the UV stabilizing agent of 1.0wt% is directly incorporated in the poly-naphthalenedicarboxylic acid ethylidene ester by feedstock production person.
Before extruding, poly-naphthalenedicarboxylic acid ethylidene ester is in a drying machine, drying is 5 hours under 170 ℃, then squeezes on a calender (its roller is arranged in the S shape) by a channel mould under 286 ℃ of extrusion temperatures in a single screw extrusion machine, and makes it smoothly to obtain the sheet of thick 3mm.First calender rolls has 73 ℃ temperature, and roller subsequently respectively has 67 ℃ temperature.The speed of take-off speed and calender rolls is 6.5m/min.
After the cooling, the transparent PEN sheet of thick 3mm uses and separates the saw finished edge, is cut into the length of wanting and accumulation.
Prepared transparent amorphous PEN sheet has following character :-thickness: first of 3mm-lustrous surface: second of 168 (at 20 ° of angular measurement): 161-light transmittance: 85%-clarity: the blemish that 97%-turbidity: 1.8%-is every square metre: do not have (spot, tangerine peel, bubble etc.)-Charpy impact flexibility a
n: crack-free-cold formability: good, zero defect-degree of crystallinity: 0%-density: 1.33g/cm
3Passing through the every one side of Altas Ci 65 Weather Ometer weathering after 1000 hours; The PEN sheet has following character :-thickness: 3mm-lustrous surface first surface: second of 162 (at 20 ° of angular measurement): 153-light transmittance: 84.1%-clarity: 96%-turbidity: 2.0%-integral body fade Δ E: 0.22-secretly fade Δ L :-0.18-red-the green Δ A that the fades :-0.08-blue-yellow Δ B that fades: 0.10-blemish: do not have (slight crack, embrittlement)-yellow value G: 4-Charpy impact flexibility an: crack-free-cold formability: good
Claims (12)
1. amorphous plate with the thickness in 1 to 20mm scope, it has at least a poly-alkylene naphthalate as Main Ingredients and Appearance.
2. as claimed in claim 1, wherein it has at least a dyestuff that dissolves in poly-alkylene naphthalate.
3. as the sheet of claim 1 or 2, wherein it has at least a organic and/or inorganic pigment as colouring agent.
4. as at least one sheet among the claim 1-3, wherein it contains at least a UV stabilizing agent as light stabilizer.
5. as at least one sheet among the claim 1-4, wherein use poly-naphthalenedicarboxylic acid ethylidene ester, poly-naphthalenedicarboxylic acid propylidene ester and/or poly-naphthalenedicarboxylic acid butylidene ester as poly-alkylene naphthalate.
6. as at least one sheet among the claim 1-5, wherein use poly-naphthalenedicarboxylic acid ethylidene ester as poly-alkylene naphthalate.
7. each method of amorphous plate for preparing as claim 1-6, it is included in the poly-alkylene naphthalate of fusing in the extruder, extrude this fused mass by a mould, then sheet be cut into want length before, in calender with at least two rollers with its pressure-sizing, calendering and cooling.
8. method as claimed in claim 7, wherein poly-alkylene naphthalate and soluble dye, colouring agent and/or UV stabilizing agent together melt.
9. as the method for claim 7 or 8, wherein in extruder, be dried before the fusion will gathering alkylene naphthalate.
10. as at least one method among the claim 7-9, wherein used poly-alkylene naphthalate is poly-naphthalenedicarboxylic acid ethylidene ester (PEN).
11. as the method for claim 10, wherein the temperature of PEN fused mass is in 250 to 320 ℃ scope.
12. as the method for claim 10 or 11, wherein first roller of calender has 50 to 80 ℃ temperature.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19610956.6 | 1996-03-20 | ||
| DE19610956A DE19610956A1 (en) | 1996-03-20 | 1996-03-20 | Amorphous plate made of a crystallizable polyalkylene naphthalate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1216950A true CN1216950A (en) | 1999-05-19 |
Family
ID=7788857
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97194203A Pending CN1216950A (en) | 1996-03-20 | 1997-03-13 | Amorphous plate of crystallizable polyalkylene naphthalate |
Country Status (11)
| Country | Link |
|---|---|
| EP (1) | EP0889778A2 (en) |
| JP (1) | JP2000507285A (en) |
| KR (1) | KR20000064699A (en) |
| CN (1) | CN1216950A (en) |
| AU (1) | AU2156897A (en) |
| BR (1) | BR9708138A (en) |
| DE (1) | DE19610956A1 (en) |
| PL (1) | PL329028A1 (en) |
| TR (1) | TR199801858T2 (en) |
| TW (1) | TW413689B (en) |
| WO (1) | WO1997034759A2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116476416A (en) * | 2022-12-17 | 2023-07-25 | 青岛新大成塑料机械有限公司 | EVA adhesive film extrusion production line and control method thereof |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA3018516A1 (en) | 2017-09-26 | 2019-03-26 | Davis-Standard, Llc | Casting apparatus for manufacturing polymer film |
| US10661492B2 (en) | 2017-11-17 | 2020-05-26 | Purple Innovation, Llc | Molding systems, mold extractor systems, and related methods |
| US11969932B2 (en) | 2019-06-25 | 2024-04-30 | Omachron Intellectual Property Inc. | Puller apparatus with movable mounting arm |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4175147A (en) * | 1976-10-05 | 1979-11-20 | Allied Chemical Corporation | Method to reduce deposits of terephthalic acid on cooling rolls during sheet extrusion of amorphous polyethylene terephthalate |
| US4996269A (en) * | 1987-03-13 | 1991-02-26 | The Goodyear Tire & Rubber Company | Polyester composition which is particularly suitable for use in thermoforming thin walled articles |
| JPH04142275A (en) * | 1990-09-26 | 1992-05-15 | Mitsui Toatsu Chem Inc | Heat-resistant aerosol container |
| JPH0641330A (en) * | 1992-07-23 | 1994-02-15 | Teijin Ltd | Thermoforming sheet and thermoformed article |
| JPH0639895A (en) * | 1992-07-23 | 1994-02-15 | Unitika Ltd | Reinforced sheet of polyethyene naphthalate |
-
1996
- 1996-03-20 DE DE19610956A patent/DE19610956A1/en not_active Withdrawn
-
1997
- 1997-03-13 EP EP97914249A patent/EP0889778A2/en not_active Withdrawn
- 1997-03-13 BR BR9708138A patent/BR9708138A/en not_active Application Discontinuation
- 1997-03-13 WO PCT/EP1997/001314 patent/WO1997034759A2/en not_active Application Discontinuation
- 1997-03-13 AU AU21568/97A patent/AU2156897A/en not_active Abandoned
- 1997-03-13 JP JP9533135A patent/JP2000507285A/en active Pending
- 1997-03-13 TR TR1998/01858T patent/TR199801858T2/en unknown
- 1997-03-13 KR KR1019980707422A patent/KR20000064699A/en not_active Application Discontinuation
- 1997-03-13 PL PL97329028A patent/PL329028A1/en unknown
- 1997-03-13 CN CN97194203A patent/CN1216950A/en active Pending
- 1997-03-18 TW TW086103368A patent/TW413689B/en active
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116476416A (en) * | 2022-12-17 | 2023-07-25 | 青岛新大成塑料机械有限公司 | EVA adhesive film extrusion production line and control method thereof |
| CN116476416B (en) * | 2022-12-17 | 2024-05-31 | 青岛新大成塑料机械有限公司 | EVA adhesive film extrusion production line and control method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| WO1997034759A2 (en) | 1997-09-25 |
| TR199801858T2 (en) | 1998-12-21 |
| PL329028A1 (en) | 1999-03-01 |
| BR9708138A (en) | 1999-07-27 |
| TW413689B (en) | 2000-12-01 |
| AU2156897A (en) | 1997-10-10 |
| EP0889778A2 (en) | 1999-01-13 |
| DE19610956A1 (en) | 1997-09-25 |
| WO1997034759A3 (en) | 1997-10-30 |
| KR20000064699A (en) | 2000-11-06 |
| JP2000507285A (en) | 2000-06-13 |
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