EP0833858A1 - Amorphe, transparente, uv-stabilisierte platte aus einem kristallisierbaren thermoplast - Google Patents
Amorphe, transparente, uv-stabilisierte platte aus einem kristallisierbaren thermoplastInfo
- Publication number
- EP0833858A1 EP0833858A1 EP96918681A EP96918681A EP0833858A1 EP 0833858 A1 EP0833858 A1 EP 0833858A1 EP 96918681 A EP96918681 A EP 96918681A EP 96918681 A EP96918681 A EP 96918681A EP 0833858 A1 EP0833858 A1 EP 0833858A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- plate according
- plate
- polyethylene terephthalate
- range
- stabilizer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 229920001169 thermoplastic Polymers 0.000 title claims description 36
- 239000004416 thermosoftening plastic Substances 0.000 title claims description 36
- 238000000034 method Methods 0.000 claims abstract description 18
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 74
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 71
- -1 2H-benzotriazol-2-yl Chemical group 0.000 claims description 44
- 239000012963 UV stabilizer Substances 0.000 claims description 26
- 230000005540 biological transmission Effects 0.000 claims description 21
- 238000001125 extrusion Methods 0.000 claims description 18
- 239000004611 light stabiliser Substances 0.000 claims description 12
- 238000002425 crystallisation Methods 0.000 claims description 11
- 230000008025 crystallization Effects 0.000 claims description 10
- 238000009499 grossing Methods 0.000 claims description 10
- 230000008018 melting Effects 0.000 claims description 10
- 238000002844 melting Methods 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 7
- JXTHNDFMNIQAHM-UHFFFAOYSA-N dichloroacetic acid Chemical compound OC(=O)C(Cl)Cl JXTHNDFMNIQAHM-UHFFFAOYSA-N 0.000 claims description 6
- 239000000155 melt Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- FQUNFJULCYSSOP-UHFFFAOYSA-N bisoctrizole Chemical compound N1=C2C=CC=CC2=NN1C1=CC(C(C)(C)CC(C)(C)C)=CC(CC=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)N2N=C3C=CC=CC3=N2)O)=C1O FQUNFJULCYSSOP-UHFFFAOYSA-N 0.000 claims description 4
- AIXMJTYHQHQJLU-UHFFFAOYSA-N chembl210858 Chemical compound O1C(CC(=O)OC)CC(C=2C=CC(O)=CC=2)=N1 AIXMJTYHQHQJLU-UHFFFAOYSA-N 0.000 claims description 4
- UXWKVPJOPVIIRU-UHFFFAOYSA-N (6-methylsulfanylpyridin-3-yl)boronic acid Chemical compound CSC1=CC=C(B(O)O)C=N1 UXWKVPJOPVIIRU-UHFFFAOYSA-N 0.000 claims description 3
- PHBCDAHASFSLMJ-UHFFFAOYSA-N 2-hydroxybenzotriazole Chemical group C1=CC=CC2=NN(O)N=C21 PHBCDAHASFSLMJ-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- 229960005215 dichloroacetic acid Drugs 0.000 claims description 3
- 238000005516 engineering process Methods 0.000 claims description 3
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 2
- 150000003918 triazines Chemical class 0.000 claims description 2
- 239000003381 stabilizer Substances 0.000 abstract description 2
- 239000003223 protective agent Substances 0.000 abstract 1
- 239000012815 thermoplastic material Substances 0.000 abstract 1
- 238000002845 discoloration Methods 0.000 description 28
- 230000007547 defect Effects 0.000 description 26
- 238000001816 cooling Methods 0.000 description 9
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 8
- 239000004926 polymethyl methacrylate Substances 0.000 description 8
- 238000010276 construction Methods 0.000 description 6
- 230000009477 glass transition Effects 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 238000000113 differential scanning calorimetry Methods 0.000 description 4
- 229920000515 polycarbonate Polymers 0.000 description 4
- 239000004417 polycarbonate Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000004800 polyvinyl chloride Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 3
- 238000005253 cladding Methods 0.000 description 3
- 238000003776 cleavage reaction Methods 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229920000915 polyvinyl chloride Polymers 0.000 description 3
- 230000007017 scission Effects 0.000 description 3
- 239000011265 semifinished product Substances 0.000 description 3
- 238000004383 yellowing Methods 0.000 description 3
- LEVFXWNQQSSNAC-UHFFFAOYSA-N 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-hexoxyphenol Chemical compound OC1=CC(OCCCCCC)=CC=C1C1=NC(C=2C=CC=CC=2)=NC(C=2C=CC=CC=2)=N1 LEVFXWNQQSSNAC-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 238000009966 trimming Methods 0.000 description 2
- HJIAMFHSAAEUKR-UHFFFAOYSA-N (2-hydroxyphenyl)-phenylmethanone Chemical class OC1=CC=CC=C1C(=O)C1=CC=CC=C1 HJIAMFHSAAEUKR-UHFFFAOYSA-N 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- PQJZHMCWDKOPQG-UHFFFAOYSA-N 2-anilino-2-oxoacetic acid Chemical class OC(=O)C(=O)NC1=CC=CC=C1 PQJZHMCWDKOPQG-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 239000004605 External Lubricant Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 229930016911 cinnamic acid Natural products 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000007791 dehumidification Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000010101 extrusion blow moulding Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 150000005165 hydroxybenzoic acids Chemical class 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000007539 photo-oxidation reaction Methods 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- GDESWOTWNNGOMW-UHFFFAOYSA-N resorcinol monobenzoate Chemical class OC1=CC=CC(OC(=O)C=2C=CC=CC=2)=C1 GDESWOTWNNGOMW-UHFFFAOYSA-N 0.000 description 1
- 239000005336 safety glass Substances 0.000 description 1
- 150000003902 salicylic acid esters Chemical class 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
- B29C43/22—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of indefinite length
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
- B29C48/911—Cooling
- B29C48/9135—Cooling of flat articles, e.g. using specially adapted supporting means
- B29C48/914—Cooling of flat articles, e.g. using specially adapted supporting means cooling drums
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
- B29C48/911—Cooling
- B29C48/9135—Cooling of flat articles, e.g. using specially adapted supporting means
- B29C48/9145—Endless cooling belts
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
- B29C48/90—Thermal treatment of the stream of extruded material, e.g. cooling with calibration or sizing, i.e. combined with fixing or setting of the final dimensions of the extruded article
- B29C48/906—Thermal treatment of the stream of extruded material, e.g. cooling with calibration or sizing, i.e. combined with fixing or setting of the final dimensions of the extruded article using roller calibration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
Definitions
- the invention relates to an amorphous, transparent, UV-stabilized plate made of a crystallizable thermoplastic, the thickness of which is in the range from 1 to 20 mm.
- the plate contains at least one UV stabilizer as a light stabilizer and is characterized by very good optical and mechanical properties.
- the invention further relates to a method for producing this plate and its use.
- thermoplastics which are processed into sheets, are, for. B. polyvinyl chloride (PVC), polycarbonate (PC) and polymethyl methacrylate (PMMA).
- PVC polyvinyl chloride
- PC polycarbonate
- PMMA polymethyl methacrylate
- the amorphous thermoplastics can be easily reshaped using smoothing units or other shaping tools due to the steadily increasing viscosity as the temperature decreases.
- amorphous thermoplastics After molding, amorphous thermoplastics then have sufficient stability, ie a high viscosity, in order to "stand on their own” in the calibration tool. But they are still soft enough to be shaped by the tool.
- the melt viscosity and inherent stiffness of amorphous thermoplastics is so high in the calibration tool that the semi-finished product does not collapse in the calibration tool before it cools down.
- easily decomposable materials such.
- B. PVC are special processing aids for extrusion, such as B. Processing stabilizers against decomposition and lubricants against excessive internal friction and thus uncontrollable heating necessary. External lubricants are required to prevent snagging on walls and rollers.
- PMMA sheets also have extremely poor impact strength and shatter when broken or subjected to mechanical stress.
- PMMA panels are highly flammable, so that they must not be used, for example, for indoor applications or in exhibition stand construction.
- PMMA and PC sheets are also not cold-formable. During cold forming, PMMA sheets break into dangerous fragments. When cold-forming PC sheets, hairline cracks and whitening occur.
- DE-A-3 531 878 describes plastic films made of thermoplastic polyester which contain a UV stabilizer and have a thickness of 0.5-0.03 mm. These foils are obtained by extrusion blow molding and are therefore partially crystalline. Consequently, the method described in this document cannot be used to obtain an amorphous film with a thickness of 1 mm or more.
- JP-A-5 320 528 describes a thermoplastic resin composition containing an epoxylated polyester. According to a preferred embodiment, this composition contains PVC as the main component. The plates obtained from this by kneading are transparent and 1 mm thick.
- EP-A-0 471 528 describes a method for molding an article from a polyethylene terephthalate (PET) plate.
- the PET plate is heat-treated in a deep-drawing mold on both sides in a temperature range between the glass transition temperature and the melting temperature.
- the molded PET sheet is taken out of the mold when the degree of crystallization of the molded PET sheet is in the range of 25 to 50%.
- the PET sheets disclosed in EP-A-0 471 528 have a thickness of 1 to 10 mm. Since the deep-drawn molded article made from this PET sheet is partially crystalline and therefore no longer transparent and the surface properties of the molded article are determined by the deep-drawing process, the temperatures and shapes given, it is immaterial which optical properties (e.g. gloss, Turbidity and light transmission) have the PET plates used. As a rule, the optical properties of these plates are poor and need to be optimized.
- optical properties e.g. gloss, Turbidity and light transmission
- these plates do not contain any UV stabilizers as light stabilizers, so that neither the plates nor the moldings made from them are suitable for outdoor use.
- these plates or molded articles show yellowing and deterioration of the mechanical properties due to photooxidative degradation by sunlight after a short time.
- US Pat. No. 3,496,143 describes the vacuum deep drawing of a 3 mm thick PET sheet, the crystallization of which is said to be in the range from 5 to 25%. The crystallinity of the deep-drawn molded body is greater than 25%. No demands are made on the optical properties of these PET sheets either. Since the crystallinity of the plates used is already between 5 and 25%, these plates are cloudy and opaque. These plates also do not contain any light stabilizers and are therefore not suitable for outdoor use.
- amorphous plates which contain a crystallizable thermoplastic as the main component, with a thickness of 1 mm or more could not be produced in sufficient quality.
- the object of the present invention was to provide an amorphous, transparent plate with a thickness of 1 to 20 mm which, in addition to good mechanical and optical properties, above all has high UV stability.
- a high UV stability means that the plates are not or only slightly damaged by sunlight or other UV radiation, so that the plates are suitable for outdoor applications and / or critical indoor applications.
- the panels should not yellow over several years of outdoor use, should not show embrittlement or cracking of the surface, and should not show any deterioration in the mechanical properties.
- Good optical properties include, for example, high light transmission, high surface gloss, extremely low haze and high image sharpness (clarity).
- the good mechanical properties include high impact strength and high breaking strength.
- the plate according to the invention should be recyclable, in particular without loss of the mechanical properties, and also flame-retardant, so that it can also be used, for example, for interior applications and in exhibition construction.
- a transparent, amorphous plate with a thickness in the range from 1 to 20 mm, which contains a crystallizable thermoplastic as the main component, which is characterized in that the plate contains at least one UV stabilizer as light stabilizer.
- the main component of the transparent, amorphous plate is a crystallizable thermoplastic.
- Suitable crystallizable or partially crystalline thermoplastics are, for example, polyethylene terephthalate,
- crystallizable thermoplastics are understood to mean crystallizable homopolymers, crystallizable copolymers, crystallizable compounds, crystallizable recyclate and other variations of crystallizable thermoplastics.
- amorphous plate is understood to mean those plates which, although the crystallizable thermoplastic used preferably has a crystallinity of between 5 and 65%, particularly preferably between 25 and 65%, are not crystalline.
- Non-crystalline or amorphous means that the degree of crystallinity is generally below 5%, preferably below 2% and particularly preferably 0%.
- the amorphous plate according to the invention is essentially unoriented.
- the transparent, amorphous plate further contains at least one UV stabilizer as light stabilizer, the concentration of the UV stabilizer preferably being between 0.01% by weight and 5% by weight, based on the weight of the crystallizable thermoplastic.
- Light especially the ultraviolet portion of solar radiation, i.e. H. the wavelength range from 280 to 400 nm initiates degradation processes in thermoplastics, as a result of which not only the visual appearance changes as a result of color change or yellowing, but also the mechanical-physical properties are adversely affected.
- Polyethylene terephthalates for example, begin to absorb UV light below 360 nm, their absorption increases considerably below 320 nm and is very pronounced below 300 nm. The maximum absorption is between 280 and 300 nm.
- UV stabilizers or UV absorbers as light stabilizers are chemical compounds that can intervene in the physical and chemical processes of light-induced degradation. Soot and other pigments can partially protect against light. However, these substances are unsuitable for transparent plates because they lead to discoloration or color change. For transparent, amorphous plates, only organic and organometallic compounds are suitable, which give the thermoplastic to be stabilized no or only an extremely small color or color change.
- Suitable UV stabilizers as light stabilizers are, for example, 2-hydroxybenzophenones, 2-hydroxybenzotriazoles, organo-nickel compounds, salicylic acid esters, cinnamic acid ester derivatives, resorcinol monobenzoates, oxalic acid anilides, hydroxybenzoic acid esters, sterically hindered amines and triazines, the 2-hydroxybenzotriazoles being preferred.
- the transparent, amorphous plate according to the invention contains, as the main constituent, a crystallizable polyethylene terephthalate and 0.01% by weight to 5.0% by weight of 2- (4,6-diphenyl-1,3,5-triazine -2-yl) -5- (hexyl) oxy-phenol (structure in Fig. 1 a) or 0.01 wt% to 5.0 wt% 2,2'-methylene-bis (6- ( 2H-benzotriazol-2-yl) -4- (1, 1, 3,3-tetramethylbutyD-phenol (structure in Fig. 1 b).
- mixtures of these two UV stabilizers or mixtures of at least one of these can also be used two UV stabilizers, the total concentration of light stabilizers is preferably between 0.01% and 5.0% by weight, based on the weight of crystallizable polyethylene terephthalate.
- the surface gloss measured according to DIN 67530 (measuring angle 20 °), is greater than 1 20, preferably greater than 140, the light transmission, measured according to ASTM D 1003, is more than 84%, preferably more than 86%, and the cloudiness of the plate, measured according to ASTM D 1003, is less than 15%, preferably less than 11%.
- the image sharpness of the plate which is also called Clarity and is determined at an angle of less than 2.5 c (ASTM D 1003), is preferably above 96% and particularly preferably above 97%.
- the notched impact strength a k according to Izod (measured according to ISO 180/1 A) of the plate is in the range from 2.0 to 8.0 kJ / m 2 , preferably in the range from 3.0 to 8.0 kJ / m 2 and particularly preferably in the range from 4.0 to 6.0 kJ / m 2 .
- Polyethylene terephthalates with a crystallite melting point T m measured with DSC (differential scanning calorimetry) with a heating rate of 10 ° C / min, from 220 ° C to 280 ° C, preferably from 250 ° C to 270 ° C, with a crystallization temperature range T c between 75 ° C and 280 ° C, preferably 75 ° C to 260 ° C, a glass transition temperature T g between 65 ° C and 90 ° C and with a density, measured according to DIN 53479, of 1.30 to 1.45 g / cm 3 and a crystallinity between 5% and 65%, preferably between 25% and 65%, are preferred polymers as starting materials for the production of the plate according to the invention.
- the standard viscosity SV (DCE) of the polyethylene terephthalate, measured in dichloroacetic acid according to DIN 53728, is between 800 and 1,800, preferably between 950 and 1,250 and particularly preferably between 1000 and 1
- the intrinsic viscosity IV (DCE) is calculated from the standard viscosity SV (DCE) as follows:
- the bulk density measured according to DIN 53466, is preferably between 0.75 kg / dm 3 and 1.0 kg / dm 3 , and particularly preferably between 0.80 kg / dm 3 and 0.90 kg / dm 3 .
- the polydispersity M w / M n of the polyethylene terephthalate measured by means of gel permeation chromatography is preferably between 1.5 and 6.0 and particularly preferably between 2.0 and 3.5.
- the UV-stabilized plates according to the invention generally have no yellowing, no embrittlement, no loss of gloss on the surface, no cracking on the surface and no deterioration in the mechanical properties.
- the PET panel according to the invention is flame-retardant and flame-retardant, so that it is suitable, for example, for indoor applications and in exhibition stand construction. Furthermore, the plate according to the invention can be easily recycled without environmental pollution and without loss of the mechanical properties, which makes it suitable, for example, for use as short-lived advertising signs or other promotional items.
- the transparent, amorphous, UV-stabilized plate according to the invention can be produced, for example, by an extrusion process in an extrusion line.
- Such an extrusion line is shown schematically in FIG. 2. It essentially comprises an extruder (1) as a plasticizing system, a slot die (2) as a tool for shaping, a smoothing unit / calender (3) as a calibration tool, a cooling bed (4) and / or a roller conveyor (5) for after-cooling, a roller take-off (6), a separating saw (7), a side cutting device (9), and optionally a stacking device (8).
- the process is characterized in that the crystallizable thermoplastic (for example polyethylene terephthalate) is optionally dried, then melted in the extruder, preferably together with the UV stabilizer, the melt is molded through a nozzle and then calibrated, smoothed and cooled in the calender before being brings the plate to size.
- the first roller of the smoothing unit has a temperature which is in the range from 50 ° C. to 80 ° C., since it would otherwise be difficult to produce an amorphous transparent plate with a crystallizable thermoplastic in a thickness of 1 mm and more.
- the light stabilizer can be metered in at the thermoplastic raw material manufacturer or can be metered into the extruder during plate production.
- the addition of the light stabilizer via masterbatch technology is particularly preferred.
- the light stabilizer is fully dispersed in a solid carrier material.
- carrier materials come certain resins, the thermoplastic itself, such as. B. the polyethylene terephthalate or other polymers that are sufficiently compatible with the thermoplastic, in question.
- the grain size and bulk density of the masterbatch is similar to the grain size and bulk density of the thermoplastic, so that a homogeneous distribution and thus homogeneous UV stabilization can take place.
- the drying of the polyethylene terephthalate before the extrusion is preferably carried out for 4 to 6 hours at 160 to 180 ° C.
- the polyethylene terephthalate is then melted in the extruder.
- the temperature of the PET melt is preferably in the range from 250 to 320 ° C., the temperature of the melt being able to be set essentially both by the temperature of the extruder and by the residence time of the melt in the extruder.
- the melt then leaves the extruder through a nozzle. This nozzle is preferably a slot die.
- the PET melted by the extruder and shaped by a slot die is calibrated by smoothing calender rolls, i.e. H. intensely chilled and smoothed.
- the calender rolls can, for example, be arranged in an I, F, L or S shape (FIG. 3).
- the PET material can then be cooled on a roller conveyor, cut to the side, cut to length and finally stacked.
- the thickness of the PET plate is essentially determined by the take-off, which is arranged at the end of the cooling zone, the cooling (smoothing) rolls coupled with it in terms of speed and the conveying speed of the extruder on the one hand and the distance between the rolls on the other hand.
- Both single-screw and twin-screw extruders can be used as extruders.
- the slot die preferably consists of the separable tool body, the lips and the dust bar for flow regulation across the width.
- the dust bar can be bent by tension and pressure screws.
- the thickness is adjusted by adjusting the lips. It is important to ensure that the temperature of the PET and the lip is even, otherwise the PET melt will flow out to different thicknesses due to the different flow paths.
- the calibration tool, d. H. the smoothing calender gives the PET melt the shape and dimensions. This is done by freezing below the glass transition temperature by means of cooling and smoothing. Deformation is no longer allowed in this state, otherwise it will be in this cooled state Surface defects would arise. For this reason, the calender rolls are preferably driven together. The temperature of the calender rolls must be lower than the crystallite melting temperature in order to avoid sticking of the PET melt.
- the PET melt leaves the slot die at a temperature of 240 to 300 ° C.
- the first smoothing-cooling roller has a temperature between 50 ° C and 80 ° C depending on the output and plate thickness. The second, somewhat cooler roller cools the second or other surface.
- the after-cooling device lowers the temperature of the PET plate to almost room temperature. After-cooling can be done on a roller board.
- the speed of the take-off should be exactly matched to the speed of the calender rolls in order to avoid defects and thickness fluctuations.
- a separating saw as a cutting device, the side trimming, the stacking system and a control point can be located in the extrusion line for the production of PET sheets as additional devices.
- the side or edge trimming is advantageous because the thickness in the edge area can be uneven under certain circumstances. The thickness and appearance of the plate are measured at the control point.
- the transparent and amorphous plate according to the invention is excellently suitable for a large number of different uses, for example for interior cladding, for trade fair construction and trade fair articles, as displays, for signs, for protective glazing of machines and vehicles, in the lighting sector, in the store. and shelf construction, as promotional items, as menu card stands, as basketball goal boards, as room dividers, for aquariums, as Information boards and as brochure and newspaper stands.
- the transparent, amorphous plate according to the invention is also suitable for outdoor applications, such as for greenhouses, roofing, glazing, safety glasses, external cladding, covers, applications in the construction sector, illuminated advertising profiles, balcony cladding, roof hatches and caravan windows.
- the surface gloss is measured at a measuring angle of 20 ° according to DIN 67530.
- the light transmission is measured with the "Hazegard plus" measuring device in accordance with ASTM D 1003.
- Haze is the percentage of the transmitted light that deviates by more than 2.5 ° on average from the incident light beam.
- the image sharpness is determined at an angle of less than 2.5 °.
- the haze and clarity are measured using the "Hazegard plus" measuring device in accordance with ASTM D 1003.
- the surface defects are determined visually.
- This size is determined according to ISO 1 79/1 D.
- the notched impact strength or strength a k according to Izod is measured according to ISO 1 80/1 A.
- the density is determined according to DIN 53479.
- the standard viscosity SV (DCE) is based on DIN 53726 in
- the intrinsic viscosity (IV) is calculated as follows from the standard viscosity (SV)
- the thermal properties such as crystallite melting point T m , crystallization temperature range T c , post- (cold) crystallization temperature T CN and glass transition temperature T are measured by means of differential scanning calorimetry (DSC) at a heating rate of 10 ° C / min.
- DSC differential scanning calorimetry
- the molecular weights M w and M n and the resulting polydispersity M w / M n are measured by means of gel permeation chromatography (GPC).
- UV stability is tested according to the test specification ISO 4892 as follows
- Xenon lamp inner and outer filter made of borosilicate
- the color change of the samples after artificial weathering is measured with a spectrophotometer according to DIN 5033.
- the yellowness index G is the deviation from the colorlessness in the "yellow” direction and is measured in accordance with DIN 61 67. Yellow value G values of ⁇ 5 are not visually visible.
- a 3 mm thick, transparent, amorphous plate is produced, the main constituent being polyethylene terephthalate and 1.0% by weight of the UV stabilizer 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5- (hexyl) oxyphenol (Tinuvin 1 577 from the company Ciba-Geigy) contains.
- Tinuvin 1 577 has a melting point of 149 C C and is thermally stable up to approx. 330 ° C.
- the UV stabilizer is incorporated directly into the polyethylene terephthalate at the raw material manufacturer.
- the polyethylene terephthalate from which the transparent plate is made has a standard viscosity SV (DCE) of 1010, which corresponds to an intrinsic viscosity IV (DCE) of 0.79 dl / g.
- DCE intrinsic viscosity IV
- the moisture content is ⁇ 0.2% and the density (DIN 53479) is 1.41 g / cm 3 .
- the crystallinity is 59%, the crystallite melting point according to DSC measurements being 258 ° C.
- the crystallization temperature range T c is between 83 ° C and 258 ° C, the post-crystallization temperature (also cold crystallization temperature) T CN at 144 ° C.
- the polydispersity M w / M n of the polyethylene terephthalate is 2.14.
- the glass transition temperature is 83 ° C.
- the polyethylene terephthalate with a crystallinity of 59% is dried in a dryer at 170 ° C. for 5 hours and then extruded in a single-screw extruder at an extrusion temperature of 286 ° C. through a slot die onto a smoothing calender whose rolls are arranged in an S-shape and smoothed into a 3 mm thick plate.
- the first calender roll has a temperature of 73 ° C and the subsequent rolls each have a temperature of 67 ° C.
- the speed of the take-off and the calender rolls is 6.5 m / min.
- the transparent, 3 mm thick PET sheet is trimmed at the edges with separating saws, cut to length and stacked.
- the transparent, amorphous PET sheet produced has the following property profile:
- the PET plate After 1000 hours of weathering per side with Atlas Ci 65 Weather Ometer, the PET plate shows the following properties:
- Example 2 Analogous to Example 1, a transparent, amorphous plate is produced, the UV stabilizer being 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5- (hexyl) -oxyphenol ( ⁇ Tinuvin 1 577 ) is metered in in the form of a master batch.
- the masterbatch is composed of 5% by weight of ® Tinuvin 1577 as active ingredient and 95% by weight of the polyethylene terephthalate from Example 1.
- Example 1 Before the extrusion, 80% by weight of the polyethylene terephthalate from Example 1 and 20% by weight of the masterbatch are dried at 1 70 ° C. for 5 hours. The extrusion and sheet production take place analogously to Example 1.
- the transparent, amorphous PET sheet produced has the following property profile:
- the PET plate After 1000 hours of weathering per side with Atlas Ci 65 Weather Ometer, the PET plate shows the following properties:
- Polyethylene terephthalate which has the following properties:
- a 6 mm thick, transparent, amorphous plate is produced which, as the main constituent, contains the polyethylene terephthalate described and 0.6% by weight of the UV stabilizer 2,2'-methylene-bis- (6- (2H-benzotriazole-2- yl) -4- (1, 1, 3,3-tetramethylbutyD-phenol ( ⁇ Tinuvin 360 from Ciba-Geigy), based on the weight of the polymer.
- Tinuvin 360 has a melting point of 1 95 ° C and is thermally stable up to approx. 250 ° C.
- Example 1 0.6% by weight of the UV stabilizer is incorporated directly into the polyethylene terephthalate at the raw material manufacturer.
- the extrusion temperature is 280 ° C.
- the first calender roll has a temperature of 66 ° C and the subsequent rolls have a temperature of 60 ° C.
- the speed of the take-off and the calender rolls is 2.9 m / min.
- the transparent PET sheet produced has the following property profile:
- the PET plate After 1000 hours of weathering per side with Atlas Ci 65 Weather Ometer, the PET plate shows the following properties:
- a transparent, amorphous plate is produced.
- the extrusion temperature is 275 ° C.
- the first calender roll has a temperature of 57 ° C and the subsequent rolls have a temperature of 50 ° C.
- the speed of the take-off and the calender roll is 1.7 m / min.
- the plate is stabilized as described in Example 3.
- the PET sheet produced has the following property profile:
- the PET plate After 1000 hours of weathering per side with Atlas Ci 65 Weather Ometer, the PET plate shows the following properties:
- Example 1 Analogous to example 1, a transparent, amorphous plate is produced. In contrast to example 1, the plate contains no UV stabilizer.
- the polyethylene terephthalate used, the extrusion parameters, the process parameters and the temperatures are chosen as in Example 1.
- the transparent PET sheet produced has the following property profile:
- the PET plate After 1000 hours of weathering per side with Atlas Ci 65 Weather Ometer, the PET plate shows the following properties:
- the plate shows a clearly visible "yellow” discoloration.
- the surfaces are dull and brittle.
- Example 3 Analogous to example 3, a transparent, amorphous plate is produced. In contrast to Example 3, the plate produced does not contain a UV stabilizer.
- the polyethylene terephthalate used, the extrusion parameters, the Process parameters and the temperatures are chosen as in Example 3.
- the transparent PET sheet produced has the following property profile:
- Thickness 6 mm
- the PET plate After 1000 hours of weathering per side with Atlas Ci 65 Weather Ometer, the PET plate shows the following properties:
- the plate shows a clearly visible "yellow” discoloration.
- the surfaces are badly attacked (blunt, brittle, cracking).
- Example 3 Analogously to Example 3, a UV-stabilized, transparently colored, translucent plate is produced, the polyethylene terephthalate, the UV stabilizer and the masterbatch from Example 3 also being used.
- the first calender roll has a temperature of 83 ° C and the subsequent rolls each have a temperature of 77 ° C.
- the plate produced is extremely cloudy and almost opaque.
- the light transmission, the clarity and the gloss are significantly reduced.
- the plate shows surface defects and structures.
- the optics are unacceptable for a transparent application.
- the plate produced has the following property profile:
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Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19522118A DE19522118C1 (de) | 1995-06-19 | 1995-06-19 | Amorphe, transparente, UV-stabilisierte Platte aus einem kristallisierbaren Thermoplast, Verfahren zu deren Herstellung sowie deren Verwendung |
DE19522118 | 1995-06-19 | ||
PCT/EP1996/002514 WO1997000284A1 (de) | 1995-06-19 | 1996-06-10 | Amorphe, transparente, uv-stabilisierte platte aus einem kristallisierbaren thermoplast |
Publications (1)
Publication Number | Publication Date |
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EP0833858A1 true EP0833858A1 (de) | 1998-04-08 |
Family
ID=7764642
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP96918681A Withdrawn EP0833858A1 (de) | 1995-06-19 | 1996-06-10 | Amorphe, transparente, uv-stabilisierte platte aus einem kristallisierbaren thermoplast |
Country Status (16)
Country | Link |
---|---|
EP (1) | EP0833858A1 (de) |
JP (1) | JPH11507965A (de) |
KR (1) | KR19990028207A (de) |
AU (1) | AU6125896A (de) |
BG (1) | BG102073A (de) |
BR (1) | BR9609412A (de) |
CA (1) | CA2225173A1 (de) |
CZ (1) | CZ414297A3 (de) |
DE (1) | DE19522118C1 (de) |
HU (1) | HUP9803029A2 (de) |
NO (1) | NO975870L (de) |
OA (1) | OA10552A (de) |
PL (1) | PL324207A1 (de) |
RU (1) | RU2169158C2 (de) |
TW (1) | TW355717B (de) |
WO (1) | WO1997000284A1 (de) |
Families Citing this family (27)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6025061A (en) * | 1998-04-23 | 2000-02-15 | Hna Holdings, Inc. | Sheets formed from polyesters including isosorbide |
US5958581A (en) * | 1998-04-23 | 1999-09-28 | Hna Holdings, Inc. | Polyester film and methods for making same |
US6063464A (en) * | 1998-04-23 | 2000-05-16 | Hna Holdings, Inc. | Isosorbide containing polyesters and methods for making same |
US6140422A (en) * | 1998-04-23 | 2000-10-31 | E.I. Dupont De Nemours And Company | Polyesters including isosorbide as a comonomer blended with other thermoplastic polymers |
US6126992A (en) * | 1998-04-23 | 2000-10-03 | E.I. Dupont De Nemours And Company | Optical articles comprising isosorbide polyesters and method for making same |
US5959066A (en) * | 1998-04-23 | 1999-09-28 | Hna Holdings, Inc. | Polyesters including isosorbide as a comonomer and methods for making same |
US6063465A (en) * | 1998-04-23 | 2000-05-16 | Hna Holdings, Inc. | Polyester container and method for making same |
US6063495A (en) * | 1998-04-23 | 2000-05-16 | Hna Holdings, Inc. | Polyester fiber and methods for making same |
US9744800B2 (en) | 1999-06-11 | 2017-08-29 | Sydney Hyman | Compositions and image making mediums |
EP1208150A4 (de) * | 1999-06-11 | 2005-01-26 | Sydney Hyman | Bildformungsmaterial |
US8669325B1 (en) | 1999-06-11 | 2014-03-11 | Sydney Hyman | Compositions image making mediums and images |
US9786194B2 (en) | 1999-06-11 | 2017-10-10 | Sydney Hyman | Image making medium compositions and images |
DE10002171A1 (de) * | 2000-01-20 | 2001-07-26 | Mitsubishi Polyester Film Gmbh | Transparente, schwerentflammbare, UV-stabile Folie aus einem kristallisierbaren Thermoplasten, Verfahren zu ihrer Herstellung und ihre Verwendung |
DE10009246A1 (de) * | 2000-02-28 | 2001-08-30 | Mitsubishi Polyester Film Gmbh | Weiße, biaxial orientierte und UV-stabilisierte Polyesterfolie mit Cycloolefinocopolymer (COC), Verfahren zu ihrer Herstellung und ihre Verwendung |
US7452927B2 (en) | 2004-01-30 | 2008-11-18 | E. I. Du Pont De Nemours And Company | Aliphatic-aromatic polyesters, and articles made therefrom |
US7888405B2 (en) | 2004-01-30 | 2011-02-15 | E. I. Du Pont De Nemours And Company | Aliphatic-aromatic polyesters, and articles made therefrom |
US11355027B2 (en) | 2004-04-30 | 2022-06-07 | Sydney Hyman | Image making medium compositions and images |
DE202005006412U1 (de) * | 2004-05-27 | 2005-06-30 | Battenfeld Extrusionstechnik Gmbh | Kühlvorrichtung |
AU2004100535B4 (en) * | 2004-07-05 | 2004-12-02 | Corex Plastics (Aust) Pty Ltd | Polymer compositions and uses thereof |
US7144972B2 (en) | 2004-07-09 | 2006-12-05 | E. I. Du Pont De Nemours And Company | Copolyetherester compositions containing hydroxyalkanoic acids and shaped articles produced therefrom |
DE602005009159D1 (de) | 2005-06-10 | 2008-10-02 | Soitec Silicon On Insulator | Kalibrierverfahren für Apparaturen zur thermischen Behandlung |
DE102005062687A1 (de) * | 2005-12-23 | 2007-07-05 | Röhm Gmbh | PMMA-Folie mit besonders hoher Witterungsbeständigkeit und hoher UV-Schutzwirkung |
JP5292958B2 (ja) * | 2007-07-18 | 2013-09-18 | 東レ株式会社 | 研磨パッド |
WO2013149157A1 (en) | 2012-03-30 | 2013-10-03 | E. I. Du Pont De Nemours And Company | Polyesters and fibers made therefrom |
JP6709076B2 (ja) * | 2016-02-29 | 2020-06-10 | 三菱エンジニアリングプラスチックス株式会社 | ポリカーボネート樹脂組成物の製造方法 |
CN109071927A (zh) | 2016-04-25 | 2018-12-21 | 纳幕尔杜邦公司 | 用于生产聚酯制品的方法 |
KR102357178B1 (ko) | 2020-01-08 | 2022-01-28 | 한세진 | 플라스틱 복층판 |
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CA1096534A (en) * | 1977-12-12 | 1981-02-24 | Wayne P. Pruett | Polyesters having unobvious weatherability characteristics |
US4399265A (en) * | 1983-01-19 | 1983-08-16 | Garware Plastics & Polyester Ltd. | Process of products UV-stabilized polyester materials |
IL72879A (en) * | 1984-09-06 | 1988-12-30 | Ginegar Kibbutz | Plastic sheeting |
DE3617978A1 (de) * | 1986-05-28 | 1987-12-03 | Bayer Ag | Verzweigte thermoplastische polycarbonate mit verbessertem schutz gegen uv-licht |
EP0328528B1 (de) * | 1986-08-22 | 1993-11-24 | Eastman Chemical Company | Warm geformte polyester-gegenstände |
US4983653A (en) * | 1986-11-12 | 1991-01-08 | Diafoil Company, Ltd. | Polyester shrinkable film containing benzotriazole |
JPH01284543A (ja) * | 1988-05-11 | 1989-11-15 | Mitsubishi Rayon Co Ltd | 熱可塑性樹脂組成物 |
BE1008335A3 (nl) * | 1994-04-18 | 1996-04-02 | Axxis Nv | Kunststofplaat die een copolyester bevat, een werkwijze voor de vervaardiging van de kunststofplaat en vormdelen vervaardigd uit de kunststofplaat. |
-
1995
- 1995-06-19 DE DE19522118A patent/DE19522118C1/de not_active Expired - Fee Related
-
1996
- 1996-06-10 HU HU9803029A patent/HUP9803029A2/hu unknown
- 1996-06-10 CZ CZ974142A patent/CZ414297A3/cs unknown
- 1996-06-10 PL PL96324207A patent/PL324207A1/xx unknown
- 1996-06-10 BR BR9609412A patent/BR9609412A/pt not_active Application Discontinuation
- 1996-06-10 AU AU61258/96A patent/AU6125896A/en not_active Abandoned
- 1996-06-10 RU RU98101098/04A patent/RU2169158C2/ru active
- 1996-06-10 EP EP96918681A patent/EP0833858A1/de not_active Withdrawn
- 1996-06-10 KR KR1019970709518A patent/KR19990028207A/ko not_active Application Discontinuation
- 1996-06-10 CA CA002225173A patent/CA2225173A1/en not_active Abandoned
- 1996-06-10 JP JP9502619A patent/JPH11507965A/ja not_active Ceased
- 1996-06-10 WO PCT/EP1996/002514 patent/WO1997000284A1/de not_active Application Discontinuation
- 1996-06-17 TW TW085107307A patent/TW355717B/zh active
-
1997
- 1997-11-27 BG BG102073A patent/BG102073A/xx unknown
- 1997-12-12 NO NO975870A patent/NO975870L/no unknown
- 1997-12-19 OA OA70167A patent/OA10552A/fr unknown
Non-Patent Citations (1)
Title |
---|
See references of WO9700284A1 * |
Also Published As
Publication number | Publication date |
---|---|
RU2169158C2 (ru) | 2001-06-20 |
BG102073A (en) | 1998-08-31 |
NO975870D0 (no) | 1997-12-12 |
DE19522118C1 (de) | 1997-03-13 |
JPH11507965A (ja) | 1999-07-13 |
NO975870L (no) | 1997-12-12 |
CA2225173A1 (en) | 1997-01-03 |
CZ414297A3 (cs) | 1998-03-18 |
MX9710294A (es) | 1998-03-29 |
AU6125896A (en) | 1997-01-15 |
PL324207A1 (en) | 1998-05-11 |
BR9609412A (pt) | 1999-05-18 |
OA10552A (fr) | 2002-05-29 |
HUP9803029A2 (hu) | 1999-04-28 |
WO1997000284A1 (de) | 1997-01-03 |
TW355717B (en) | 1999-04-11 |
KR19990028207A (ko) | 1999-04-15 |
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