CA2225173A1 - Amorphous, transparent, uv-stabilized sheet of a crystallizable thermoplastic - Google Patents
Amorphous, transparent, uv-stabilized sheet of a crystallizable thermoplastic Download PDFInfo
- Publication number
- CA2225173A1 CA2225173A1 CA002225173A CA2225173A CA2225173A1 CA 2225173 A1 CA2225173 A1 CA 2225173A1 CA 002225173 A CA002225173 A CA 002225173A CA 2225173 A CA2225173 A CA 2225173A CA 2225173 A1 CA2225173 A1 CA 2225173A1
- Authority
- CA
- Canada
- Prior art keywords
- sheet
- polyethylene terephthalate
- measured
- range
- accordance
- 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.)
- Abandoned
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 17
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 71
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 70
- -1 polyethylene terephthalate Polymers 0.000 claims description 38
- JXTHNDFMNIQAHM-UHFFFAOYSA-N dichloroacetic acid Chemical compound OC(=O)C(Cl)Cl JXTHNDFMNIQAHM-UHFFFAOYSA-N 0.000 claims description 36
- 238000005259 measurement Methods 0.000 claims description 20
- 230000005540 biological transmission Effects 0.000 claims description 19
- 229960005215 dichloroacetic acid Drugs 0.000 claims description 18
- 238000001125 extrusion Methods 0.000 claims description 18
- 230000008018 melting Effects 0.000 claims description 12
- 238000002844 melting Methods 0.000 claims description 12
- 238000002425 crystallisation Methods 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 239000000470 constituent Substances 0.000 claims description 8
- 238000009499 grossing Methods 0.000 claims description 8
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 7
- 230000008025 crystallization Effects 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 239000000155 melt Substances 0.000 claims description 6
- 238000005498 polishing Methods 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 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 4
- 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
- 238000010438 heat treatment Methods 0.000 claims description 4
- PHBCDAHASFSLMJ-UHFFFAOYSA-N 2-hydroxybenzotriazole Chemical group C1=CC=CC2=NN(O)N=C21 PHBCDAHASFSLMJ-UHFFFAOYSA-N 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- 238000005520 cutting process Methods 0.000 claims description 3
- 238000005516 engineering process Methods 0.000 claims description 3
- 150000003918 triazines Chemical class 0.000 claims description 3
- IYAZLDLPUNDVAG-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 IYAZLDLPUNDVAG-UHFFFAOYSA-N 0.000 claims description 2
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 2
- 239000012963 UV stabilizer Substances 0.000 claims 5
- 239000013036 UV Light Stabilizer Substances 0.000 claims 1
- 229920001707 polybutylene terephthalate Polymers 0.000 claims 1
- 239000003381 stabilizer Substances 0.000 abstract description 15
- 239000003223 protective agent Substances 0.000 abstract 1
- 239000012815 thermoplastic material Substances 0.000 abstract 1
- 238000002845 discoloration Methods 0.000 description 27
- 230000007547 defect Effects 0.000 description 26
- 208000010392 Bone Fractures Diseases 0.000 description 16
- 206010017076 Fracture Diseases 0.000 description 16
- 239000004611 light stabiliser Substances 0.000 description 11
- 230000003287 optical effect Effects 0.000 description 9
- 239000004926 polymethyl methacrylate Substances 0.000 description 8
- 238000005336 cracking Methods 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000009477 glass transition Effects 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 238000007493 shaping process Methods 0.000 description 5
- 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 4
- 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
- 230000006735 deficit Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 239000004417 polycarbonate Substances 0.000 description 4
- 229920000515 polycarbonate Polymers 0.000 description 4
- 239000004800 polyvinyl chloride Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920000915 polyvinyl chloride Polymers 0.000 description 3
- 239000011265 semifinished product Substances 0.000 description 3
- 238000003856 thermoforming Methods 0.000 description 3
- 238000004383 yellowing Methods 0.000 description 3
- 241000518994 Conta Species 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000007707 calorimetry Methods 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
- 238000003776 cleavage reaction Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000007539 photo-oxidation reaction Methods 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000007017 scission Effects 0.000 description 2
- 230000002087 whitening effect Effects 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
- 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
- 239000004698 Polyethylene Substances 0.000 description 1
- 206010041662 Splinter Diseases 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006229 carbon black Substances 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
- 238000005253 cladding Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination 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
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000011521 glass Substances 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
- 230000005764 inhibitory process Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000005457 optimization 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
- 230000036961 partial effect Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 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
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000002829 reductive 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
- 238000000926 separation method Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000007787 solid 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
- 230000002311 subsequent effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 238000009966 trimming Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
Abstract
A transparent, amorphous plate with a thickness in a range from 1 to 20 mm that contains as main component a thermoplastic material capable of crystallising is characterised in that it contains at least one UV stabiliser as light protective agent. Also disclosed is a process for producing the same and its use.
Description
.... . ..
WO 97/00284 ~ PCT/~P96/02514 Amorphous, transparent, W-stabilized sheet of a crys-tallizable thermoplastic The invention relates to an amorphous, transparent, W-stabilized sheet of a crystallizable thermoplastic whose thickness is in the range from 1 to 20 mm. The sheet contains at least one W light stabilizer and is distin-guished by very good optical and mechanical properties.
The invention furthermore relates to a process for the production of this sheet, and to the use of the sheet.
Amorphous, transparent sheets having a thickness of from 1 to 20 mm are well known. These two-dimensional struc-tures comprise amorphous, non-crystallizable thermoplastics. Typical examples of such thermoplastics which can be converted into sheets are, for example, polyvinyl chloride (PVC), polycarbonate (PC) and poly-methyl methacrylate (PMMA). These semifinished products are produced on so-called extrusion lines (cf. Polymer Werkstoffe, Volume II, Technologie 1, p. 136, Georg Thieme Verlag, Stuttgart, 1984). The pulverulent or granular raw material is melted in an extruder. After extrusion, the amorphous thermoplastics can easily be shaped via polishing stacks or other shaping tools as a consequence of their viscosity, which continuously increases with decreasing temperature. After shaping, amorphous thermoplastics then have adequate stability, i.e. a high viscosity, in order to be self-supporting in the calibration die. However, they are still sufficiently soft to be shaped by the die. The melt viscosity and inherent rigidity of amorphous thermoplastics is 80 high in the calibration die that the semifinished product does not collapse in the calibration die before cooling. In the case of easily decomposed materials, for example PVC, special processing aids, for example processing stabi-lizers against decomposition and lubricants against excessive internal friction and thus uncontrollable warming, are necessary during extrusion. External lubricants are necessary to prevent sticking to walls and CA 0222~173 1997-12-18 rolls.
The processing of PMMA is carried out using, for example, a vented extruder to enable removal of moisture.
The production of transparent sheets from amorphous thermoplastics sometimes requires expensive additives, which can migrate and can cause production problems owing to evaporations and surface coatings on the semifinished product. PVC sheets can be recycled only with difficulty or using special neutralization or electrolysis process-es. PC and PMMA sheets can likewise only be recycled withdifficulty and only with 1088 or extreme impairment of the mechanical properties.
In addition to these disadvantages, PMMA sheets also have extremely poor impact strength and splinter on fracture or mechanical loading. Furthermore, PMMA sheets are readily combustible, which means that they cannot be employed, for example, for internal applications and in exhibitions.
PMMA and PC sheets furthermore cannot be shaped when cold; PMMA sheets disintegrate to form dangerous splin-ters, while PC sheets undergo hairline cracking and stress whitening.
DE-A-3 531 878 describes plastic films made from thermo-plastic polyesters and cont~;n;ng a W stabilizer and having a thickness of 0.5 - 0.03 mm.
These films are obtained by extrusion blow molding and are thus partially crystalline. Consequently, the process described in this specification cannot give an amorphous film having a thickness of 1 mm or greater.
JP-A-5 320 528 describes a thermoplastic resin composi-tion cont~;n;ng an epoxidized polyester. According to a preferred embodiment, this composition contains PVC as CA 0222~173 1997-12-18 principal constituent. The sheets obtained therefrom by compo~n~;~g are transparent and have a thickness of 1 mm.
EP-A-0 471 528 describes a process for shaping an article from a polyethylene terephthalate (PET) sheet. The PET
sheet is heat-treated on both sides in the thermofilming mold in a temperature range between the glass transition temperature and the melting point. The shaped PET sheet is removed from the mold when the degree of crystalliza-tion of the shaped PET sheet is in the region of 25 to 50%. The PET sheets disclosed in EP-A-0 471 528 have a thickness of from 1 to 10 mm. Since the thermoformed molding produced from the PET sheet is partially crystal-line and thus no longer transparent and the surface properties of the molding are determined by the thermo-forming process and by the thermoforming temperature and mold, it is unimportant what optical properties (for example gloss, haze and light transmission) the PET
sheets employed have. In general, the optical properties of these sheets are poor and in need of optimization.
In addition, these sheets contain no W light stabiliz-ers, 80 that neither the sheets nor the moldings produced therefrom are suitable for external applications. If used externally, these sheets or moldings exhibit, after only a short time, yellowing and an impairment in the mechani-cal properties as a consequence of photooxidative degra-dation by sunlight.
US-A-3,496,143 describes the vacuum thermoforming of a 3 mm thick PET sheet whose degree of crystallization is said to be in the range from 5 to 25%. However, the crystallinity of the thermoformed molding is greater than 25%. Again, no requirements regarding optical properties are made of these PET sheets. Since the crystallinity of the sheets employed is already between 5 and 25%, these sheets are hazy and non-transparent. These sheets again contain no light stabilizer and consequently are unsuit-able for external applications.
CA 0222~173 1997-12-18 The processes known hitherto do not allow the production of amorphous sheets contA; n; ng a crystallizable thermo-plastic as principal constituent in a thickness of 1 mm or greater in adequate quality.
The object of the present invention was to provide an amorphous, transparent sheet having a thickness of from 1 to 20 mm which, in addition to good mechanical and optical properties, also has, in particular, high W
stability.
High W stability means that the sheets experience extremely little damage, or none at all, due to sunlight or other W radiation, 80 that the sheets are suitable for outdoor applications and/or critical indoor applica-tions. In particular, after several years of use outside, lS the sheets do not yellow or exhibit embrittlement or cracking of the surface or impairment of the mechanical properties.
The good optical properties include, for example, high light transmission, high surface gloss, extremely low haze and high clarity.
The good mechanical properties include, inter alia, high impact strength and high bre~k; ng strength.
In addition, the novel sheet should be recyclable, in particular without 1088 of the mechanical properties, and have low combustibility 80 that it can also be employed, for example, for indoor applicat~ons and in exhibitions.
This object is achieved by a transparent, amorphous sheet having a thickness in the range from 1 to 20 mm which contains, as principal constituent, a crystallizable thermoplastic, wherein the sheet contains at least one W
light stabilizer.
The transparent, amorphous sheet contains, as principal CA 0222~173 1997-12-18 constituent, a crystallizable thermoplastic. Suitable crystallizable or partially crystalline thermoplastics are, for example, polyethylene terephthalate, polybuty-lene terephthalate, cycloolefin polymers and cycloolefin copolymers, preference being given to polyethylene terephthalate.
For the purposes of the invention, the term crystal-lizable thermoplastics is taken to mean - crystallizable homopolymers, - crystallizable copolymers, - crystallizable compounds, - crystallizable recyclate and - other variations of crystallizable thermoplastics.
For the purposes of the present invention, the term amorphous sheet is taken to mean a sheet which is non-crystalline, although the crystallizable thermoplastic employed preferably has a crystallinity of from 5 to 65%, particularly preferably from 25 to 65%. Non-crystalline or amorphous means that the degree of crystallinity is generally less than 5%, preferably less than 2%, particu-larly preferably 0%. The novel amorphous sheet is essentially unoriented.
The transparent, amorphous sheet furthermore contains at least one W light stabilizer, of which the concentration is preferably from 0.01 to 5% by weight, based on the weight of the crystallizable thermoplastic.
Light, in particular the ultra-violet part of sunlight, i.e. having a wavelength in the range of 280 to 400 nm, initiates degradation processes in thermoplastics, resulting not only in a change in the visual appearance as a consequence of color change or yellowing, but also adversely affecting the mechanical-physical properties.
The inhibition of these photooxidative degradation processes is of considerable industrial and economic CA 0222~173 1997-12-18 importance, since otherwise the potential uses of numer-ous thermoplastics are drastically limited.
Polyethylene terephthalates begin to absorb W light, for example, even at below 360 nm, their absorption increases considerably below 320 nm and is very pronounced at below 300 nm. The maximum absorption is between 280 and 300 nm.
In the presence of oxygen, principally chain cleavage, but no crossl;nk;ng is observed. Carbon monoxide, carbon dioxide and carboxylic acids represent the predominant photooxidation products in terms of amount. Besides direct photolysis of the ester groups, consideration must also be given to oxidation reactions, which likewise result in the formation of carbon dioxide via peroxide free radicals.
The photooxidation of polyethylene terephthalates can also result, by elimination of hydrogen in the ~-position of the ester groups, in hydroperoxides and decomposition products thereof, and associated chain cleavage (H. Day, D. M. Wiles: J. Appl. Polym. Sci 16, 1972, page 203).
W stabilizers and W absorbers as light stabilizers are chemical compounds which can engage in the physical and chemical processes of photoinduced degradation. Carbon black and other pigments can provide partial protection from light. However, the substances are unsuitable for transparent sheets since they result is discoloration or a color change. For transparent, amorphous sheets, the only suitable compounds are organic and organometallic compounds which impart only an extremely weak color or color change, or none at all, in the thermoplastics to be stabilized.
Examples of suitable W light stabilizers are 2-hydroxy-benzophenones, 2-hydroxybenzotriazoles, organonickel compounds, salicylic esters, c;nnA~;c ester derivatives, resorcinol monobenzoates, oxanilides, hydroxybenzoic CA 0222~173 1997-12-18 esters, sterically hindered amines and triazines, prefer-ence being given to 2-hydroxybenzotriazoles and tri-azines .
In a particularly preferred embodiment, the novel trans-parent, amorphous sheet contains, as principle constitu-ents, a crystallizable polyethylene terephthalate and from 0.01 to 5.0% by weight of 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-(hexyl)oxyphenol (structure in Fig. la) or from 0.01 to 5.0% by weight of 2,2'-methylene-bis(6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol (structure in Fig. lb). In a preferred ~mhodiment, it is also possible to employ mixtures of these two W stabi-lizers or mixtures of at least one of these two W
stabilizers with other W stabilizers, with a total concentration of light stabilizers, preferably from 0.01 to 5.0% by weight, based on the weight of crystallizable polyethylene terephthalate.
The surface gloss, measured in accordance with DIN 67530 (measurement angle 20~), is greater than 120, preferably greater than 140, the light transmission, measured in accordance with ASTM D 1003, being greater than 84%, preferably greater than 86%, and the haze of the sheet, measured in accordance with ASTM D 1003, being less than 15%, preferably less than 11%.
The clarity of the sheet measured at an angle of less than 2.5~ (ASTM D 1003) is preferably greater than 96%, particularly preferably greater than 97~.
In the case of polyethylene terephthalate, measurement of the Charpy impact strength an (measured in accordance with ISO 179/lD) of the sheet is preferably not accompa-nied by a fracture. In addition, the Izod notched impact strength ak (measured in accordance with ISO 180/lA) of the sheet is in the range from 2.0 to 8.0 kJ/m2, prefer-ably from 3.0 to 8.0 kJ/m2, particularly preferably in the range from 4.0 to 6.0 kJ/m2.
CA 0222~173 1997-12-18 Polyethylene terephthalate polymers having a crystalline melting point Tm~ as measured by DSC (differential sc~nn;ng calorimetry) at a heating rate of 10~C/min, of from 220~ to 280~C, preferably from 250~C to 270~C, a crystallization temperature range Tc from 75~C to 280~C, preferably from 75~C to 260~C, a glass transition temper-ature Tg of from 65~C to 90~C and a density, measured in accordance with DIN 53479, of from 1.30 to 1.45 g/cm3 and a crystallinity of from 5 to 65%, preferably from 25% to 65%, are preferred polymers as starting materials for production of the novel sheet.
The st~n~rd viscosity SV (DCA) of the polyethylene terephthalate, measured in dichloroacetic acid in accordance with DIN 53728, is from 800 to 1800, prefera-bly from 950 to 1250, particularly preferably from 1000 to 1200.
The intrinsic viscosity IV (DCA) is calculated from the st~n~rd viscosity SV (DCA) as follows:
IV (DCA) = 6.67 ~ 10-4 SV (DCA) + 0.118 The bulk density, measured in accordance with DIN 53466, is preferably from 0.75 to 1.0 kg/dm3, particularly preferably from 0.80 to 0.90 kg/dm3.
The polydispersity of the polyethylene terephthalate MW/Mn, measured by gel permeation chromatography, is preferably from 1.5 to 6.0, particularly preferably from 2.0 to 3.5.
Weathering tests have shown that the novel W -stabilized sheets exhibit no yellowing, no ~brittlement, no 1088 in gloss on the surface, no cracking on the surface and no impairment of the mechanical properties even after use outside for from five to seven years.
Besides excellent W stability, entirely unexpectedly, CA 0222~173 1997-12-18 good cold formability without fracture, hairline cracking and/or stress whitening was observed, me~n; ng that the novel sheet can be shaped and bent without the action of heat.
In addition, measurements showed that the novel PET sheet has low combustibility and low flammability, 80 that it is suitable, for example, for internal applications and in exhibitions.
Furthermore, the novel sheet can easily be recycled without environmental pollution and without 1088 of the mechanical properties, me~ning that it is suitable, for example, for use as short-term advertising hoardings or other advertising articles.
The novel transparent, amorphous, W-stabilized sheet can be produced, for example, by extrusion in an extrusion line.
An extrusion line of this type is shown diagrammatically in Fig. 2. It essentially comprises - an extruder (1) as plastication unit, - a sheet die (2) as shaping tool, - a polishing stack/calender (3) as calibration die, - a cooling bed (4) and/or a roller conveyor (5) for aftercooling, - a take-off roll (6), - a separating saw (7), - an edge trimming device (9), and, if desired, - a stacking unit (8).
The process for the production of the novel sheet is described in detail below using the example of polyethy-lene terephthalate as thermoplastic.
The process comprises drying the crystallizable thermo-plastic (e.g. polyethylene terephthalate) if necessary, then melting the dry polymer in the extruder, preferably CA 0222~173 1997-12-18 together with the W stabilizer, extruding the melt through a die, calibrating, smoothing and cooling the sheet in the polishing stack and then cutting the sheet to size.
It is essential in the novel process that the first roll of the polishing stack has a temperature in the range from 50~C to 80~C, since it is otherwise difficult to obtain an amorphous transparent sheet contA; n; ng a crystallizable thermoplastic in a thickness of 1 mm or greater.
In accordance with the invention, it is possible for the light stabilizer already to have been added by the producer of the thermoplastic raw material or to be metered into the extruder during production of the sheet.
The light stabilizer is particularly preferably added via masterbatch technology, where the light stabilizer is fully dispersed in a solid carrier material. Suitable carrier materials are certain resins, the thermoplastic itself, such as for example, polyethylene terephthalate, or alternatively other polymers which are sufficiently compatible with the thermoplastic.
It is important that the particle size and bulk density of the masterbatch are similar to the particle size and bulk density of the thermoplastic, 80 that a homogeneous distribution and thus homogeneous W stabilization can take place.
The polyethylene terephthalate is preferably dried at from 160 to 180~C for from 4 to 6 hours before extrusion.
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, it being possible for the temperature of the melt to be adjusted essentially both through the temperature of the extruder and through the CA 0222~173 1997-12-18 residence time of the melt in the extruder.
The melt then leaves the extruder through a die. This die is preferably a sheet die.
The PET melted by the extruder and shaped by a sheet die is calibrated, i.e. intensively cooled and smoothed, by smoothing calender rolls. The calender rolls can be arranged, for example, in an I-, F-, L- or S-shape (see Fig. 3).
The PET material can then be cooled on a roller conveyor, cut to size in width, cut into appropriate lengths and finally stacked.
The thickness of the PET sheet is determined essentially by the take-off unit, which is arranged at the end of the cooling zone, the chill (smoothing) rolls, which are coupled to the take-off unit with respect to speed, and the conveying rate of the extruder on the one hand and the separation between the rolls on the other hand.
The extruders employed can be either single-screw or twin-screw extruders.
The sheet die preferably comprises a collapsible die body, the lips and the restrictor bar for flow regulation over the width. To this end, the restrictor bar can be bent by means of tension and pressure screws. The thick-ness is set by adjusting the lips. It i8 important to ensure a uniform temperature of the PET and of the lip, since otherwise the PET melt flows out through the various flow channels in different thicknesses.
The calibration tool, ie. the smoothing calender, gives the PET melt shape and dimensions. This is achieved by freezing at below the glass transition temperature by cooling and smoothing. Shaping should not be carried out in this state, since otherwise surface defects would form CA 0222~l73 l997-l2-l8 in this cooled state. For this reason, the calender rolls are preferably driven jointly. The temperature of the calender rolls must be lower than the crystalline melting point in order to avoid sticking of the PFT melt. The PET
melt leaves the sheet die at a temperature of from 240 to 300~C. The first smoothing/chill roll is at a temperature of from 50~C to 80~C, dep~n~;ng on the output rate and sheet thickness. The second, somewhat colder roll cools the second or other surface.
While the calibration unit freezes the PET surfaces as smoothly as possible and cools the profile until it is rigid in shape, the aftercooling device lowers the temperature of the PET sheet virtually to room tempera-ture. The aftercooling can be carried out on a roller board. The take-off rate should be matched accurately to the calender roll speed in order to prevent defects and thickness variations.
As additional equipment, the extrusion line for the production of PET sheets can also include a separating saw for cutting the sheet to length, a side trimmer, a stacking unit and a monitoring station. The side or edge trimmer is advantageous since the thickness in the edge region may under certain circumstances not be uniform. At the monitoring station, the thickness and optical proper-ties of the sheet are measured.
The surprising multiplicity of excellent properties makesthe novel, transparent, amorphous sheet highly suitable for a multiplicity of different uses, for example for interior room panels, for exhibitions and exhibition articles, as displays, for signs, for protective glazing of machines and vehicles, in the lighting sector, in shop fitting and shelf construction, as advertizing articles, as menu holders, as basketball backboards, as room divid-ers, for aquaria, as information panels and as brochure and newspaper stands.
- CA 0222~173 1997-12-18 Owing to the good W stability, the novel transparent, amorphous sheet is likewise suitable for external appli-cations, such as, for example, for greenhouse~, roofing systems, glazing systems, safety glass, external clad-ding, covers, applications in the construction sector,illuminated advertising profiles, balcony clA~;ng, roof exit doors and caravan windows.
The invention is described in greater detail below with reference to working examples without this representing a limitation.
The individual properties are measured in accordance with the following stAn~Ands or by the following processes.
Measurement methods Surface gloss:
The surface gloss is measured at a measurement angle of 20~ in accordance with DIN 67530.
Light transmission:
The light transmission is taken to mean the ratio between the total amount of transmitted light and the amount of incident light.
The light transmission is measured using a "Hazegard plus" instrument in accordance with ASTM D 1003.
Eaze and clarity:
Haze is the percentage of transmitted light deflected from the incident ray bundle by an average of more than 2.5~. The clarity is measured at an angle of less than 2.5~.
The haze and clarity are measured using a "Hazegard plus"
instrument in accordance with ASTM D 1003.
CA 0222~173 1997-12-18 Surface defects:
The surface defects are determined visually.
Charpy impact strength an:
This parameter is determined in accordance with IS0 179/lD.
Izod notched impact strength ak:
The Izod notched impact strength ak i8 measured in accordance with IS0 180/lA.
Density:
The density is determined in accordance with DIN 53479.
SV (DCA) and IV (DCA):
The stAn~Ard viscosity SV (DCA) is measured in accordance with DIN 53726 in dichloroacetic acid.
The intrinsic viscosity (IV) is calculated as follows from the stAn~Ard viscosity (SV):
IV (DCA) = 6.67 x 10-4 SV (DCA) + 0.118.
Thermal properties:
The thermal properties, such as crystalline melting point Tm~ crystallization temperature range Tc, after- or cold-crystallization temperature TCN and glass transitiontemperature Tg are measured by differential 8cAnn;ng calorimetry (DSC) at a heating rate of 10~C/min.
Molecular weight and polydispersity:
The molecular weights Mw and Mn and the resultant poly-dispersity MW/Mn are measured by gel permeation chroma-tography (GPC).
Weathering (on both sides), W stability:
The W stability is tested as follows in accordance with IS0 4892 test ~pecification:
CA 0222~173 1997-12-18 Test instrument : Atlas Ci 65 Weather-O-meter Test conditions : ISO 4892, i.e. artificial weathering Exposure time : 1000 hours, (per side) Exposure : 0.5 W/m2, 340 nm Temperature : 63~C
Relative atmospheric humidity : 50%
Xenon lamp : inner and outer filters made of borosilicate Exposure cycles : 102 minutes W light, then 18 minutes W light with water spraying of the samples, then a further 102 minutes W light, etc.
Color change:
The color change of the samples after artificial weather-ing is measured in accordance with DIN 5033 using a spectrophotometer.
The following symbols are used:
~L: Difference in brightness +~L: The sample is brighter than the stAn~Ard -AL: The sample is darker than the stAn~Ard ~A: Difference in the red-green region +~A: The sample is redder than the stAn~Ard -~A: The sample is greener than the stAn~Ard ~B: Difference in the blue-yellow region +~B: The sample i6 yellower than the stAn~lArd -~B: The sample is bluer than the stAn~Ard ~E: Overall color change ~E = ~L2 + AA2 + ~B2 The larger the numerical deviation from the stAn~Ard, the greater the color difference.
CA 0222~173 1997-12-18 Numerical values of 5 0.3 can be neglected and mean that there is no significant color change.
Yellow value:
The yellow value G is a deviation from colorlessness toward "yellow" and is measured in accordance with DIN
6167. Yellow values of 5 5 are invisible.
The examples and comparative example~ below each relate to single-layer transparent sheets of various thicknesses produced on the extrusion line described.
All sheets were weathered in accordance with IS0 4892 test specification on both sides for 1000 hours per side using the Atlas Ci 65 Weather-0-meter and subsequently tested for their mechanical properties discoloration, surface defects, haze and gloss.
Example 1:
A transparent, amorphous sheet with a thickness of 3 mm is produced which contains, as principal constituents, polyethylene terephthalate and 1.0% by weight o$ W
stabilizer 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-(hexyl)-oxyphenol (~Tinuvin 1577 from Ciba-Geigy).
Tinuvin 1577 has a melting point of 149~C and is thermal-ly stable up to about 330~C.
In order to ensure homogeneous distribution, 1.0% by weight of the W stabilizer are incorporated into the polyethylene terephthalate directly by the raw material producer. The polyethylene terephthalate from which the transparent sheet is produced has a st~n~rd viscosity SV
(DCA) of 1010, which corresponds to an intrinsic visco-~ity IV (DCA) of 0.79 dl/g. The moisture content is c 0.2% and the density (DIN 53479) is 1.41 g/cm3. The crystallinity is 59%, and the crystalline melting point, according to DSC measurements, is 258~C. The crystal-CA 0222~173 1997-12-18 lization temperature range Tc i8 between 83~C and 258~C, and the after- crystallization temperature (also known as cold-crystallization temperature) TCN i8 144~C. The polydispersity MW/Mn of the polyethylene terephthalate is 2.14. The glass transition temperature is 83~C.
Before extrusion, the polyethylene terephthalate with a crystallinity of 59% is dried in a drier for 5 hours at 170~C and then extruded in a single-screw extruder at an extrusion temperature of 286~C through a sheet die onto a smoothing calender whose rolls are arranged in an S-shape, and smoothed to give a sheet with a thickness of 3 mm. The first calender roll has a temperature of 73~C
and the subsequent rolls each ha~e a temperature of 67~C.
The take-off rate and the calender roll speed are 6.5 m/min.
Following aftercooling, the transparent PET sheet with a thickness of 3 mm is trimmed at the edges using separating saws, cut to length and stacked.
The transparent, amorphous PET sheet produced has the following property profile:
- thickness : 3 mm - surface gloss, 1st side : 198 (measurement angle 20~) 2nd side : 196 - light transmission : 91%
- clarity : 100%
- haze : 1.5%
- surface defects per m2 : none (fisheyes, orange peel, bubbles, etc) - Charpy impact strength an : no fracture - Izod notched impact strength ak : 4.2 kJ/m2 CA 0222~l73 l997-l2-l8 - cold formability : good, no defects - crystallinity : 0%
- density : 1.33 g/cm3 After weathering for 1000 hours per side using the Atlas Ci 65 Weather-O-meter, the PET sheet exhibits the follow-ing properties:
- thickness : 3 mm - surface gloss, 1st side : 196 (measurement angle 20~) 2nd side : 195 - light transmission : 91.1%
- clarity : 100%
- haze : 1.6%
- overall discoloration AE : 0.22 - dark discoloration ~L : -0.18 - red-green discoloration ~A : -0.08 - blue-yellow discoloration ~B : 0.10 - surface defects (cracks, embrittlement) : none - yellow value G : 4 - Charpy impact strength an : no fracture - Izod notched impact strength ak : 4.1 kJ/m2 - cold formability : good Example 2:
A transparent, amorphous sheet is produced analogously to Example 1, with the W stabilizer 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-(hexyl)-oxyphenol (~Tinuvin 1577) being metered in in the form of a masterbatch. The masterbatch consists of 5% by weight of ~Tinuvin 1577 as active ingredient and 95% by weight of the polyethylene tere-CA 0222~173 1997-12-18 phthalate from Example 1.
Before extrusion, 80% by weight of the polyethylene terephthalate from Example 1 are dried at 170~C for 5 hours with 20% by weight of the masterbatch. The extru-sion and sheet production are carried out analogously toExample 1.
The transparent, amorphous PET sheet produced has the following property profile:
- thickness : 3 mm - surface gloss, 1st side : 194 (measurement angle 20~) 2nd side : 193 - light transmission : 91.3%
- clarity : 100%
- haze : 1.4%
- surface defects : none (fisheyes, orange peel, bubbles, etc) - Charpy impact strength an : no fracture - Izod notched impact strength ak : 4-0 kJ/m2 - cold formability : good - crystallinity : 0%
- density : 1.33 g/cm3 After weathering for 1000 hours per side using the Atlas Ci 65 Weather-O-Meter, the PET sheet exhibits the following properties:
- thickness : 3 mm - surface gloss, 1st side : 192 (measurement angle 20~) 2nd side : 190 - light transmission : 91.1%
CA 0222~173 1997-12-18 - clarity : 100%
- haze : 1. 5%
- overall discoloration ~E : 0. 24 - dark discoloration AL : -0.19 - red-green discoloration ~A : -O.08 - blue-yellow discoloration ~B : 0.12 - surface defects (cracks, embrittlement) : none - yellow value G : 5 - Charpy impact strength an : no fracture - Izod notched impact strength ak : 4-0 kJ/m2 - cold formability : good Example 3 A transparent amorphous sheet is produced analogously to Example 1 using a polyethylene terephthalate with the following properties:
- SV (DCA) : 1100 - IV (DCA) : 0.85 dl/g - Density : 1.3 8 g/cm3 - Crystallinity : 44%
- Crystalline melting point Tm : 245~C
- Crystallization temperature range Tc : 82~C to 245~C
- After- or cold-crystallization temperature TCN : 152~C
- Polydispersity M~,/Mn : 2.02 - Glass transition temperature : 82~C
A transparent, amorphous sheet with a thickness of 6 mm CA 0222~173 1997-12-18 i8 produced which contains, as principal constituents, the polyethylene terephthalate described and 0.6% by weight of the W Rtabilizer 2,2'-methylene-bis-(6-(2H-benzotriazole-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol (~Tinuvin 360 from Ciba-Geigy), ba~ed on the weight of the polymer.
Tinuvin 360 has a melting point of 195~C and is thermally stable up to about 250~C.
As in Example 1, 0.6% by weight of W stabilizer are incorporated into the polyethylene terephthalate directly by the producer of the raw material.
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 take-off rate and the speed of the calender rolls are 2.9 m/min.
The transparent, amorphous PET sheet produced has the following property profile:
- thickness : 6 mm - surface gloss, 1st side -: 175 (measurement angle 20~) 2nd side : 173 - light transmission : 88.6%
- clarity : 99.6%
- haze : 2.5%
- surface defects per m2 : none (fisheyes, orange peel, bubbles, etc) - Charpy impact strength an : no fracture - Izod notched impact strength ak : 4.8 kJ/m2 - cold formability : good, no defects - crystallinity : 0%
CA 0222~173 1997-12-18 - density : 1.33 g/cm3 After weathering for 1000 hours per side using the Atlas Ci 65 Weather-O-Meter, the PET sheet exhibits the follow-ing properties:
- thickness : 6 mm - surface glos~, 1st side : 171 (measurement angle 20~) 2nd side : 169 - light transmi~sion : 88.3%
- clarity 99.5%
- haze : 2.7%
- overall discoloration ~E : 0.56 - dark discoloration ~ : -0.21 - red-green discoloration ~A : -0.11 - blue-yellow discoloration ~B : l0.51 - surface defects (cracks, embrittlement) : none - yellow value G : 6 - Charpy impact strength an : no fracture - Izod notched impact strength ak : 4.6 kJ/m2 - cold formability : good, no defects Example 4:
A transparent amorphous sheet is produced analogously to Example 3. The extrusion temperature is 275~C. The first calender roll has a temperature of 57~C and the sub-sequent rolls have a temperature of 50~C. The take-off rate and the calender roll speed are 1.7 m/min. The sheet is stabilized as described in Example 3.
The PET sheet produced has the following property profile:
CA 0222~173 1997-12-18 - thickness : 10 mm - surface gloss, 1st side : 163 (measurement angle 20~) 2nd side : 161 - light transmission : 86.5%
- clarity : 99.2%
- haze : 4-95%
- surface defects per m2 : none (fisheye B, orange peel, bubbles, etc) - Charpy impact strength an : no fracture - Izod notched impact strength ak : 5.1 kJ/m2 - cold formability : good, no defects - crystallinity : 0.1%
- density : 1.33 g/cm3 After weathering for 1000 hours per side using the Atlas ~i 65 Weather-O-Meter, the PET sheet exhibits the follow-ing properties:
- thickness : 10 mm - surface gloss, 1st side : 160 (measurement angle 20~) 2nd side : 159 - light transmission : 86.2%
- clarity : 99.1%
- haze : 5.0%
- overall discoloration AE : 0.47 - dark discoloration ~L : -0.18 - red-green discoloration ~A : -0.09 - blue-yellow discoloration AB : +0.42 CA 0222~173 1997-12-18 - surface defects (cracks, embrittlement) : none - yellow value G : 5 - Charpy impact strength an : no fracture - Izod notched impact strength ak : 4. 5 kJ/m2 - cold formability : good, no defects Comparative Example 1:
A transparent, amorphous sheet i8 produced analogously to Example 1. In contrast to Example 1, the sheet contains no W stabilizer. The polyethylene terephthalate em-ployed, the extrusion parameters, the process parameters and the temperatures are selected as in Example 1.
The transparent PET sheet produced has the following property profile:
- thickness : 3 mm - surface gloss, 1st side : 200 (measurement angle 20~) 2nd side : 198 - light transmission : 91. 4%
- clarity : 100%
- haze : 1.3%
- surface defects per m2 : none (fisheyes, orange peel, bubbles, etc) - Charpy impact strength an : no fracture - Izod notched impact strength ak : 4.3 kJ/m2 - cold formability : good, no defects - crystallinity : 0%
- density : 1.33 g/cm3 After weathering for 1000 hours per side using the Atlas CA 0222~173 1997-12-18 Ci 65 Weather-O-Meter, the PET sheet exhibits the follow-ing properties:
- thickness : 3 mm - surface gloss, 1st side : 98 (measurement angle 20~) 2nd side : 95 - light transmission : 79.5%
- clarity : 81.2%
- haze : 7.8%
- overall discoloration ~E : 3.41 - dark discoloration ~L : -0.29 - red-green di~coloration ~A : -0.87 - blue-yellow discoloration ~B : +3.29 - surface defects (cracks, embrittlement) : embrittlement - yellow value G : 17 - Charpy impact strength an : complete frac-ture at 34.8 kJ/m2 - Izod notched impact strength ak : 1.3 kJ/m2 - cold formability : cracking The sheet exhibits a clearly visible "yellow" discolor-ation. The surfaces are matt and embrittled.
Comparative Example 2 A tran~parent, amorphous sheet is produced analogously to Example 3. In contrast to Example 3, the sheet contains no W stabilizer. The polyethylene terephthalate em-ployed, the extrusion parameters, the process parametersand the temperatures are selected as in Example 3.
The transparent PET sheet produced has the following property profile:
CA 0222~173 1997-12-18 - thickness : 6 mm - surface gloss, 1st side : 180 (measurement angle 20~) 2nd side : 178 - light transmis~ion : 88.9%
- clarity : 99.6%
- haze : 2.3%
- surface defects per m2 : none (fisheyes, orange peel, bubbles, etc) - Charpy impact strength an : no fracture - Izod notched impact strength ak : 4.8 kJ/m2 - cold formability : good, no defects - crystallinity : 0%
- density : 1.33 g/cm3 After weathering for 1000 hours per side using the Atlas Ci 65 Weather-O-Meter, the PET sheet exhibits the follow-ing properties:
- thickness : 6 mm - surface gloss, 1st side : 91 -(measurement angle 20~) 2nd side : 87 - light transmission : 72.5%
- clarity : 78.3%
- haze : 12.9%
- overall discoloration ~E : 3.61 - dark discoloration AL : -0.26 - red-green discoloration ~A : -0.91 - blue-yellow discoloration ~B : +3.48 CA 0222~173 1997-12-18 - surface defects (cracks, embrittlement) : embrittlement, cracks - yellow value G : 18 - Charpy impact strength an : complete frac-ture at 46.2 kJ/m2 - Izod notched impact strength ak : 1.6 kJ/m2 - cold formability : cracking The sheet exhibits a clearly visible "yellow" discolor-ation. The surfaces have been strongly attacked (matt, embrittled, cracking).
Comparative Example 3:
A W-stabilized, transparent, translucent sheet is produced analogously to Example 3, likewise using the polyethylene terephthalate, the W stabilizer and the masterbatch from Example 3. The first calender roll has a temperature of 83~C and the subsequent rolls each have a temperature of 77~C.
The sheet produced is extremely hazy and virtually opaque. The light transmission, the clarity and the gloss are significantly reduced. The sheet exhibits surface defects and structures. The optical properties are unacceptable for a transparent application.
The sheet produced has the following property profile:
- thickness : 6 mm - surface gloss, 1st side : 86 (measurement angle 20~) 2nd side 88 - light transmission : 8%
- clarity : not measurable CA 0222~173 1997-12-18 - haze : not measurable - surface defects per m2 : bubbles, orange (fisheyes, orange peel, bubbles, peel etc) - Charpy impact strength an : no fracture - Izod notched impact strength ak: 5-0 kJ/m2 - cold formability : good - crystallinity : approx. 8%
- density : 1.34 g/cm3 Owing to the unacceptable optical properties, the 6 mm sheet was not subjected to a weathering test.
WO 97/00284 ~ PCT/~P96/02514 Amorphous, transparent, W-stabilized sheet of a crys-tallizable thermoplastic The invention relates to an amorphous, transparent, W-stabilized sheet of a crystallizable thermoplastic whose thickness is in the range from 1 to 20 mm. The sheet contains at least one W light stabilizer and is distin-guished by very good optical and mechanical properties.
The invention furthermore relates to a process for the production of this sheet, and to the use of the sheet.
Amorphous, transparent sheets having a thickness of from 1 to 20 mm are well known. These two-dimensional struc-tures comprise amorphous, non-crystallizable thermoplastics. Typical examples of such thermoplastics which can be converted into sheets are, for example, polyvinyl chloride (PVC), polycarbonate (PC) and poly-methyl methacrylate (PMMA). These semifinished products are produced on so-called extrusion lines (cf. Polymer Werkstoffe, Volume II, Technologie 1, p. 136, Georg Thieme Verlag, Stuttgart, 1984). The pulverulent or granular raw material is melted in an extruder. After extrusion, the amorphous thermoplastics can easily be shaped via polishing stacks or other shaping tools as a consequence of their viscosity, which continuously increases with decreasing temperature. After shaping, amorphous thermoplastics then have adequate stability, i.e. a high viscosity, in order to be self-supporting in the calibration die. However, they are still sufficiently soft to be shaped by the die. The melt viscosity and inherent rigidity of amorphous thermoplastics is 80 high in the calibration die that the semifinished product does not collapse in the calibration die before cooling. In the case of easily decomposed materials, for example PVC, special processing aids, for example processing stabi-lizers against decomposition and lubricants against excessive internal friction and thus uncontrollable warming, are necessary during extrusion. External lubricants are necessary to prevent sticking to walls and CA 0222~173 1997-12-18 rolls.
The processing of PMMA is carried out using, for example, a vented extruder to enable removal of moisture.
The production of transparent sheets from amorphous thermoplastics sometimes requires expensive additives, which can migrate and can cause production problems owing to evaporations and surface coatings on the semifinished product. PVC sheets can be recycled only with difficulty or using special neutralization or electrolysis process-es. PC and PMMA sheets can likewise only be recycled withdifficulty and only with 1088 or extreme impairment of the mechanical properties.
In addition to these disadvantages, PMMA sheets also have extremely poor impact strength and splinter on fracture or mechanical loading. Furthermore, PMMA sheets are readily combustible, which means that they cannot be employed, for example, for internal applications and in exhibitions.
PMMA and PC sheets furthermore cannot be shaped when cold; PMMA sheets disintegrate to form dangerous splin-ters, while PC sheets undergo hairline cracking and stress whitening.
DE-A-3 531 878 describes plastic films made from thermo-plastic polyesters and cont~;n;ng a W stabilizer and having a thickness of 0.5 - 0.03 mm.
These films are obtained by extrusion blow molding and are thus partially crystalline. Consequently, the process described in this specification cannot give an amorphous film having a thickness of 1 mm or greater.
JP-A-5 320 528 describes a thermoplastic resin composi-tion cont~;n;ng an epoxidized polyester. According to a preferred embodiment, this composition contains PVC as CA 0222~173 1997-12-18 principal constituent. The sheets obtained therefrom by compo~n~;~g are transparent and have a thickness of 1 mm.
EP-A-0 471 528 describes a process for shaping an article from a polyethylene terephthalate (PET) sheet. The PET
sheet is heat-treated on both sides in the thermofilming mold in a temperature range between the glass transition temperature and the melting point. The shaped PET sheet is removed from the mold when the degree of crystalliza-tion of the shaped PET sheet is in the region of 25 to 50%. The PET sheets disclosed in EP-A-0 471 528 have a thickness of from 1 to 10 mm. Since the thermoformed molding produced from the PET sheet is partially crystal-line and thus no longer transparent and the surface properties of the molding are determined by the thermo-forming process and by the thermoforming temperature and mold, it is unimportant what optical properties (for example gloss, haze and light transmission) the PET
sheets employed have. In general, the optical properties of these sheets are poor and in need of optimization.
In addition, these sheets contain no W light stabiliz-ers, 80 that neither the sheets nor the moldings produced therefrom are suitable for external applications. If used externally, these sheets or moldings exhibit, after only a short time, yellowing and an impairment in the mechani-cal properties as a consequence of photooxidative degra-dation by sunlight.
US-A-3,496,143 describes the vacuum thermoforming of a 3 mm thick PET sheet whose degree of crystallization is said to be in the range from 5 to 25%. However, the crystallinity of the thermoformed molding is greater than 25%. Again, no requirements regarding optical properties are made of these PET sheets. Since the crystallinity of the sheets employed is already between 5 and 25%, these sheets are hazy and non-transparent. These sheets again contain no light stabilizer and consequently are unsuit-able for external applications.
CA 0222~173 1997-12-18 The processes known hitherto do not allow the production of amorphous sheets contA; n; ng a crystallizable thermo-plastic as principal constituent in a thickness of 1 mm or greater in adequate quality.
The object of the present invention was to provide an amorphous, transparent sheet having a thickness of from 1 to 20 mm which, in addition to good mechanical and optical properties, also has, in particular, high W
stability.
High W stability means that the sheets experience extremely little damage, or none at all, due to sunlight or other W radiation, 80 that the sheets are suitable for outdoor applications and/or critical indoor applica-tions. In particular, after several years of use outside, lS the sheets do not yellow or exhibit embrittlement or cracking of the surface or impairment of the mechanical properties.
The good optical properties include, for example, high light transmission, high surface gloss, extremely low haze and high clarity.
The good mechanical properties include, inter alia, high impact strength and high bre~k; ng strength.
In addition, the novel sheet should be recyclable, in particular without 1088 of the mechanical properties, and have low combustibility 80 that it can also be employed, for example, for indoor applicat~ons and in exhibitions.
This object is achieved by a transparent, amorphous sheet having a thickness in the range from 1 to 20 mm which contains, as principal constituent, a crystallizable thermoplastic, wherein the sheet contains at least one W
light stabilizer.
The transparent, amorphous sheet contains, as principal CA 0222~173 1997-12-18 constituent, a crystallizable thermoplastic. Suitable crystallizable or partially crystalline thermoplastics are, for example, polyethylene terephthalate, polybuty-lene terephthalate, cycloolefin polymers and cycloolefin copolymers, preference being given to polyethylene terephthalate.
For the purposes of the invention, the term crystal-lizable thermoplastics is taken to mean - crystallizable homopolymers, - crystallizable copolymers, - crystallizable compounds, - crystallizable recyclate and - other variations of crystallizable thermoplastics.
For the purposes of the present invention, the term amorphous sheet is taken to mean a sheet which is non-crystalline, although the crystallizable thermoplastic employed preferably has a crystallinity of from 5 to 65%, particularly preferably from 25 to 65%. Non-crystalline or amorphous means that the degree of crystallinity is generally less than 5%, preferably less than 2%, particu-larly preferably 0%. The novel amorphous sheet is essentially unoriented.
The transparent, amorphous sheet furthermore contains at least one W light stabilizer, of which the concentration is preferably from 0.01 to 5% by weight, based on the weight of the crystallizable thermoplastic.
Light, in particular the ultra-violet part of sunlight, i.e. having a wavelength in the range of 280 to 400 nm, initiates degradation processes in thermoplastics, resulting not only in a change in the visual appearance as a consequence of color change or yellowing, but also adversely affecting the mechanical-physical properties.
The inhibition of these photooxidative degradation processes is of considerable industrial and economic CA 0222~173 1997-12-18 importance, since otherwise the potential uses of numer-ous thermoplastics are drastically limited.
Polyethylene terephthalates begin to absorb W light, for example, even at below 360 nm, their absorption increases considerably below 320 nm and is very pronounced at below 300 nm. The maximum absorption is between 280 and 300 nm.
In the presence of oxygen, principally chain cleavage, but no crossl;nk;ng is observed. Carbon monoxide, carbon dioxide and carboxylic acids represent the predominant photooxidation products in terms of amount. Besides direct photolysis of the ester groups, consideration must also be given to oxidation reactions, which likewise result in the formation of carbon dioxide via peroxide free radicals.
The photooxidation of polyethylene terephthalates can also result, by elimination of hydrogen in the ~-position of the ester groups, in hydroperoxides and decomposition products thereof, and associated chain cleavage (H. Day, D. M. Wiles: J. Appl. Polym. Sci 16, 1972, page 203).
W stabilizers and W absorbers as light stabilizers are chemical compounds which can engage in the physical and chemical processes of photoinduced degradation. Carbon black and other pigments can provide partial protection from light. However, the substances are unsuitable for transparent sheets since they result is discoloration or a color change. For transparent, amorphous sheets, the only suitable compounds are organic and organometallic compounds which impart only an extremely weak color or color change, or none at all, in the thermoplastics to be stabilized.
Examples of suitable W light stabilizers are 2-hydroxy-benzophenones, 2-hydroxybenzotriazoles, organonickel compounds, salicylic esters, c;nnA~;c ester derivatives, resorcinol monobenzoates, oxanilides, hydroxybenzoic CA 0222~173 1997-12-18 esters, sterically hindered amines and triazines, prefer-ence being given to 2-hydroxybenzotriazoles and tri-azines .
In a particularly preferred embodiment, the novel trans-parent, amorphous sheet contains, as principle constitu-ents, a crystallizable polyethylene terephthalate and from 0.01 to 5.0% by weight of 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-(hexyl)oxyphenol (structure in Fig. la) or from 0.01 to 5.0% by weight of 2,2'-methylene-bis(6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol (structure in Fig. lb). In a preferred ~mhodiment, it is also possible to employ mixtures of these two W stabi-lizers or mixtures of at least one of these two W
stabilizers with other W stabilizers, with a total concentration of light stabilizers, preferably from 0.01 to 5.0% by weight, based on the weight of crystallizable polyethylene terephthalate.
The surface gloss, measured in accordance with DIN 67530 (measurement angle 20~), is greater than 120, preferably greater than 140, the light transmission, measured in accordance with ASTM D 1003, being greater than 84%, preferably greater than 86%, and the haze of the sheet, measured in accordance with ASTM D 1003, being less than 15%, preferably less than 11%.
The clarity of the sheet measured at an angle of less than 2.5~ (ASTM D 1003) is preferably greater than 96%, particularly preferably greater than 97~.
In the case of polyethylene terephthalate, measurement of the Charpy impact strength an (measured in accordance with ISO 179/lD) of the sheet is preferably not accompa-nied by a fracture. In addition, the Izod notched impact strength ak (measured in accordance with ISO 180/lA) of the sheet is in the range from 2.0 to 8.0 kJ/m2, prefer-ably from 3.0 to 8.0 kJ/m2, particularly preferably in the range from 4.0 to 6.0 kJ/m2.
CA 0222~173 1997-12-18 Polyethylene terephthalate polymers having a crystalline melting point Tm~ as measured by DSC (differential sc~nn;ng calorimetry) at a heating rate of 10~C/min, of from 220~ to 280~C, preferably from 250~C to 270~C, a crystallization temperature range Tc from 75~C to 280~C, preferably from 75~C to 260~C, a glass transition temper-ature Tg of from 65~C to 90~C and a density, measured in accordance with DIN 53479, of from 1.30 to 1.45 g/cm3 and a crystallinity of from 5 to 65%, preferably from 25% to 65%, are preferred polymers as starting materials for production of the novel sheet.
The st~n~rd viscosity SV (DCA) of the polyethylene terephthalate, measured in dichloroacetic acid in accordance with DIN 53728, is from 800 to 1800, prefera-bly from 950 to 1250, particularly preferably from 1000 to 1200.
The intrinsic viscosity IV (DCA) is calculated from the st~n~rd viscosity SV (DCA) as follows:
IV (DCA) = 6.67 ~ 10-4 SV (DCA) + 0.118 The bulk density, measured in accordance with DIN 53466, is preferably from 0.75 to 1.0 kg/dm3, particularly preferably from 0.80 to 0.90 kg/dm3.
The polydispersity of the polyethylene terephthalate MW/Mn, measured by gel permeation chromatography, is preferably from 1.5 to 6.0, particularly preferably from 2.0 to 3.5.
Weathering tests have shown that the novel W -stabilized sheets exhibit no yellowing, no ~brittlement, no 1088 in gloss on the surface, no cracking on the surface and no impairment of the mechanical properties even after use outside for from five to seven years.
Besides excellent W stability, entirely unexpectedly, CA 0222~173 1997-12-18 good cold formability without fracture, hairline cracking and/or stress whitening was observed, me~n; ng that the novel sheet can be shaped and bent without the action of heat.
In addition, measurements showed that the novel PET sheet has low combustibility and low flammability, 80 that it is suitable, for example, for internal applications and in exhibitions.
Furthermore, the novel sheet can easily be recycled without environmental pollution and without 1088 of the mechanical properties, me~ning that it is suitable, for example, for use as short-term advertising hoardings or other advertising articles.
The novel transparent, amorphous, W-stabilized sheet can be produced, for example, by extrusion in an extrusion line.
An extrusion line of this type is shown diagrammatically in Fig. 2. It essentially comprises - an extruder (1) as plastication unit, - a sheet die (2) as shaping tool, - a polishing stack/calender (3) as calibration die, - a cooling bed (4) and/or a roller conveyor (5) for aftercooling, - a take-off roll (6), - a separating saw (7), - an edge trimming device (9), and, if desired, - a stacking unit (8).
The process for the production of the novel sheet is described in detail below using the example of polyethy-lene terephthalate as thermoplastic.
The process comprises drying the crystallizable thermo-plastic (e.g. polyethylene terephthalate) if necessary, then melting the dry polymer in the extruder, preferably CA 0222~173 1997-12-18 together with the W stabilizer, extruding the melt through a die, calibrating, smoothing and cooling the sheet in the polishing stack and then cutting the sheet to size.
It is essential in the novel process that the first roll of the polishing stack has a temperature in the range from 50~C to 80~C, since it is otherwise difficult to obtain an amorphous transparent sheet contA; n; ng a crystallizable thermoplastic in a thickness of 1 mm or greater.
In accordance with the invention, it is possible for the light stabilizer already to have been added by the producer of the thermoplastic raw material or to be metered into the extruder during production of the sheet.
The light stabilizer is particularly preferably added via masterbatch technology, where the light stabilizer is fully dispersed in a solid carrier material. Suitable carrier materials are certain resins, the thermoplastic itself, such as for example, polyethylene terephthalate, or alternatively other polymers which are sufficiently compatible with the thermoplastic.
It is important that the particle size and bulk density of the masterbatch are similar to the particle size and bulk density of the thermoplastic, 80 that a homogeneous distribution and thus homogeneous W stabilization can take place.
The polyethylene terephthalate is preferably dried at from 160 to 180~C for from 4 to 6 hours before extrusion.
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, it being possible for the temperature of the melt to be adjusted essentially both through the temperature of the extruder and through the CA 0222~173 1997-12-18 residence time of the melt in the extruder.
The melt then leaves the extruder through a die. This die is preferably a sheet die.
The PET melted by the extruder and shaped by a sheet die is calibrated, i.e. intensively cooled and smoothed, by smoothing calender rolls. The calender rolls can be arranged, for example, in an I-, F-, L- or S-shape (see Fig. 3).
The PET material can then be cooled on a roller conveyor, cut to size in width, cut into appropriate lengths and finally stacked.
The thickness of the PET sheet is determined essentially by the take-off unit, which is arranged at the end of the cooling zone, the chill (smoothing) rolls, which are coupled to the take-off unit with respect to speed, and the conveying rate of the extruder on the one hand and the separation between the rolls on the other hand.
The extruders employed can be either single-screw or twin-screw extruders.
The sheet die preferably comprises a collapsible die body, the lips and the restrictor bar for flow regulation over the width. To this end, the restrictor bar can be bent by means of tension and pressure screws. The thick-ness is set by adjusting the lips. It i8 important to ensure a uniform temperature of the PET and of the lip, since otherwise the PET melt flows out through the various flow channels in different thicknesses.
The calibration tool, ie. the smoothing calender, gives the PET melt shape and dimensions. This is achieved by freezing at below the glass transition temperature by cooling and smoothing. Shaping should not be carried out in this state, since otherwise surface defects would form CA 0222~l73 l997-l2-l8 in this cooled state. For this reason, the calender rolls are preferably driven jointly. The temperature of the calender rolls must be lower than the crystalline melting point in order to avoid sticking of the PFT melt. The PET
melt leaves the sheet die at a temperature of from 240 to 300~C. The first smoothing/chill roll is at a temperature of from 50~C to 80~C, dep~n~;ng on the output rate and sheet thickness. The second, somewhat colder roll cools the second or other surface.
While the calibration unit freezes the PET surfaces as smoothly as possible and cools the profile until it is rigid in shape, the aftercooling device lowers the temperature of the PET sheet virtually to room tempera-ture. The aftercooling can be carried out on a roller board. The take-off rate should be matched accurately to the calender roll speed in order to prevent defects and thickness variations.
As additional equipment, the extrusion line for the production of PET sheets can also include a separating saw for cutting the sheet to length, a side trimmer, a stacking unit and a monitoring station. The side or edge trimmer is advantageous since the thickness in the edge region may under certain circumstances not be uniform. At the monitoring station, the thickness and optical proper-ties of the sheet are measured.
The surprising multiplicity of excellent properties makesthe novel, transparent, amorphous sheet highly suitable for a multiplicity of different uses, for example for interior room panels, for exhibitions and exhibition articles, as displays, for signs, for protective glazing of machines and vehicles, in the lighting sector, in shop fitting and shelf construction, as advertizing articles, as menu holders, as basketball backboards, as room divid-ers, for aquaria, as information panels and as brochure and newspaper stands.
- CA 0222~173 1997-12-18 Owing to the good W stability, the novel transparent, amorphous sheet is likewise suitable for external appli-cations, such as, for example, for greenhouse~, roofing systems, glazing systems, safety glass, external clad-ding, covers, applications in the construction sector,illuminated advertising profiles, balcony clA~;ng, roof exit doors and caravan windows.
The invention is described in greater detail below with reference to working examples without this representing a limitation.
The individual properties are measured in accordance with the following stAn~Ands or by the following processes.
Measurement methods Surface gloss:
The surface gloss is measured at a measurement angle of 20~ in accordance with DIN 67530.
Light transmission:
The light transmission is taken to mean the ratio between the total amount of transmitted light and the amount of incident light.
The light transmission is measured using a "Hazegard plus" instrument in accordance with ASTM D 1003.
Eaze and clarity:
Haze is the percentage of transmitted light deflected from the incident ray bundle by an average of more than 2.5~. The clarity is measured at an angle of less than 2.5~.
The haze and clarity are measured using a "Hazegard plus"
instrument in accordance with ASTM D 1003.
CA 0222~173 1997-12-18 Surface defects:
The surface defects are determined visually.
Charpy impact strength an:
This parameter is determined in accordance with IS0 179/lD.
Izod notched impact strength ak:
The Izod notched impact strength ak i8 measured in accordance with IS0 180/lA.
Density:
The density is determined in accordance with DIN 53479.
SV (DCA) and IV (DCA):
The stAn~Ard viscosity SV (DCA) is measured in accordance with DIN 53726 in dichloroacetic acid.
The intrinsic viscosity (IV) is calculated as follows from the stAn~Ard viscosity (SV):
IV (DCA) = 6.67 x 10-4 SV (DCA) + 0.118.
Thermal properties:
The thermal properties, such as crystalline melting point Tm~ crystallization temperature range Tc, after- or cold-crystallization temperature TCN and glass transitiontemperature Tg are measured by differential 8cAnn;ng calorimetry (DSC) at a heating rate of 10~C/min.
Molecular weight and polydispersity:
The molecular weights Mw and Mn and the resultant poly-dispersity MW/Mn are measured by gel permeation chroma-tography (GPC).
Weathering (on both sides), W stability:
The W stability is tested as follows in accordance with IS0 4892 test ~pecification:
CA 0222~173 1997-12-18 Test instrument : Atlas Ci 65 Weather-O-meter Test conditions : ISO 4892, i.e. artificial weathering Exposure time : 1000 hours, (per side) Exposure : 0.5 W/m2, 340 nm Temperature : 63~C
Relative atmospheric humidity : 50%
Xenon lamp : inner and outer filters made of borosilicate Exposure cycles : 102 minutes W light, then 18 minutes W light with water spraying of the samples, then a further 102 minutes W light, etc.
Color change:
The color change of the samples after artificial weather-ing is measured in accordance with DIN 5033 using a spectrophotometer.
The following symbols are used:
~L: Difference in brightness +~L: The sample is brighter than the stAn~Ard -AL: The sample is darker than the stAn~Ard ~A: Difference in the red-green region +~A: The sample is redder than the stAn~Ard -~A: The sample is greener than the stAn~Ard ~B: Difference in the blue-yellow region +~B: The sample i6 yellower than the stAn~lArd -~B: The sample is bluer than the stAn~Ard ~E: Overall color change ~E = ~L2 + AA2 + ~B2 The larger the numerical deviation from the stAn~Ard, the greater the color difference.
CA 0222~173 1997-12-18 Numerical values of 5 0.3 can be neglected and mean that there is no significant color change.
Yellow value:
The yellow value G is a deviation from colorlessness toward "yellow" and is measured in accordance with DIN
6167. Yellow values of 5 5 are invisible.
The examples and comparative example~ below each relate to single-layer transparent sheets of various thicknesses produced on the extrusion line described.
All sheets were weathered in accordance with IS0 4892 test specification on both sides for 1000 hours per side using the Atlas Ci 65 Weather-0-meter and subsequently tested for their mechanical properties discoloration, surface defects, haze and gloss.
Example 1:
A transparent, amorphous sheet with a thickness of 3 mm is produced which contains, as principal constituents, polyethylene terephthalate and 1.0% by weight o$ W
stabilizer 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-(hexyl)-oxyphenol (~Tinuvin 1577 from Ciba-Geigy).
Tinuvin 1577 has a melting point of 149~C and is thermal-ly stable up to about 330~C.
In order to ensure homogeneous distribution, 1.0% by weight of the W stabilizer are incorporated into the polyethylene terephthalate directly by the raw material producer. The polyethylene terephthalate from which the transparent sheet is produced has a st~n~rd viscosity SV
(DCA) of 1010, which corresponds to an intrinsic visco-~ity IV (DCA) of 0.79 dl/g. The moisture content is c 0.2% and the density (DIN 53479) is 1.41 g/cm3. The crystallinity is 59%, and the crystalline melting point, according to DSC measurements, is 258~C. The crystal-CA 0222~173 1997-12-18 lization temperature range Tc i8 between 83~C and 258~C, and the after- crystallization temperature (also known as cold-crystallization temperature) TCN i8 144~C. The polydispersity MW/Mn of the polyethylene terephthalate is 2.14. The glass transition temperature is 83~C.
Before extrusion, the polyethylene terephthalate with a crystallinity of 59% is dried in a drier for 5 hours at 170~C and then extruded in a single-screw extruder at an extrusion temperature of 286~C through a sheet die onto a smoothing calender whose rolls are arranged in an S-shape, and smoothed to give a sheet with a thickness of 3 mm. The first calender roll has a temperature of 73~C
and the subsequent rolls each ha~e a temperature of 67~C.
The take-off rate and the calender roll speed are 6.5 m/min.
Following aftercooling, the transparent PET sheet with a thickness of 3 mm is trimmed at the edges using separating saws, cut to length and stacked.
The transparent, amorphous PET sheet produced has the following property profile:
- thickness : 3 mm - surface gloss, 1st side : 198 (measurement angle 20~) 2nd side : 196 - light transmission : 91%
- clarity : 100%
- haze : 1.5%
- surface defects per m2 : none (fisheyes, orange peel, bubbles, etc) - Charpy impact strength an : no fracture - Izod notched impact strength ak : 4.2 kJ/m2 CA 0222~l73 l997-l2-l8 - cold formability : good, no defects - crystallinity : 0%
- density : 1.33 g/cm3 After weathering for 1000 hours per side using the Atlas Ci 65 Weather-O-meter, the PET sheet exhibits the follow-ing properties:
- thickness : 3 mm - surface gloss, 1st side : 196 (measurement angle 20~) 2nd side : 195 - light transmission : 91.1%
- clarity : 100%
- haze : 1.6%
- overall discoloration AE : 0.22 - dark discoloration ~L : -0.18 - red-green discoloration ~A : -0.08 - blue-yellow discoloration ~B : 0.10 - surface defects (cracks, embrittlement) : none - yellow value G : 4 - Charpy impact strength an : no fracture - Izod notched impact strength ak : 4.1 kJ/m2 - cold formability : good Example 2:
A transparent, amorphous sheet is produced analogously to Example 1, with the W stabilizer 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-(hexyl)-oxyphenol (~Tinuvin 1577) being metered in in the form of a masterbatch. The masterbatch consists of 5% by weight of ~Tinuvin 1577 as active ingredient and 95% by weight of the polyethylene tere-CA 0222~173 1997-12-18 phthalate from Example 1.
Before extrusion, 80% by weight of the polyethylene terephthalate from Example 1 are dried at 170~C for 5 hours with 20% by weight of the masterbatch. The extru-sion and sheet production are carried out analogously toExample 1.
The transparent, amorphous PET sheet produced has the following property profile:
- thickness : 3 mm - surface gloss, 1st side : 194 (measurement angle 20~) 2nd side : 193 - light transmission : 91.3%
- clarity : 100%
- haze : 1.4%
- surface defects : none (fisheyes, orange peel, bubbles, etc) - Charpy impact strength an : no fracture - Izod notched impact strength ak : 4-0 kJ/m2 - cold formability : good - crystallinity : 0%
- density : 1.33 g/cm3 After weathering for 1000 hours per side using the Atlas Ci 65 Weather-O-Meter, the PET sheet exhibits the following properties:
- thickness : 3 mm - surface gloss, 1st side : 192 (measurement angle 20~) 2nd side : 190 - light transmission : 91.1%
CA 0222~173 1997-12-18 - clarity : 100%
- haze : 1. 5%
- overall discoloration ~E : 0. 24 - dark discoloration AL : -0.19 - red-green discoloration ~A : -O.08 - blue-yellow discoloration ~B : 0.12 - surface defects (cracks, embrittlement) : none - yellow value G : 5 - Charpy impact strength an : no fracture - Izod notched impact strength ak : 4-0 kJ/m2 - cold formability : good Example 3 A transparent amorphous sheet is produced analogously to Example 1 using a polyethylene terephthalate with the following properties:
- SV (DCA) : 1100 - IV (DCA) : 0.85 dl/g - Density : 1.3 8 g/cm3 - Crystallinity : 44%
- Crystalline melting point Tm : 245~C
- Crystallization temperature range Tc : 82~C to 245~C
- After- or cold-crystallization temperature TCN : 152~C
- Polydispersity M~,/Mn : 2.02 - Glass transition temperature : 82~C
A transparent, amorphous sheet with a thickness of 6 mm CA 0222~173 1997-12-18 i8 produced which contains, as principal constituents, the polyethylene terephthalate described and 0.6% by weight of the W Rtabilizer 2,2'-methylene-bis-(6-(2H-benzotriazole-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol (~Tinuvin 360 from Ciba-Geigy), ba~ed on the weight of the polymer.
Tinuvin 360 has a melting point of 195~C and is thermally stable up to about 250~C.
As in Example 1, 0.6% by weight of W stabilizer are incorporated into the polyethylene terephthalate directly by the producer of the raw material.
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 take-off rate and the speed of the calender rolls are 2.9 m/min.
The transparent, amorphous PET sheet produced has the following property profile:
- thickness : 6 mm - surface gloss, 1st side -: 175 (measurement angle 20~) 2nd side : 173 - light transmission : 88.6%
- clarity : 99.6%
- haze : 2.5%
- surface defects per m2 : none (fisheyes, orange peel, bubbles, etc) - Charpy impact strength an : no fracture - Izod notched impact strength ak : 4.8 kJ/m2 - cold formability : good, no defects - crystallinity : 0%
CA 0222~173 1997-12-18 - density : 1.33 g/cm3 After weathering for 1000 hours per side using the Atlas Ci 65 Weather-O-Meter, the PET sheet exhibits the follow-ing properties:
- thickness : 6 mm - surface glos~, 1st side : 171 (measurement angle 20~) 2nd side : 169 - light transmi~sion : 88.3%
- clarity 99.5%
- haze : 2.7%
- overall discoloration ~E : 0.56 - dark discoloration ~ : -0.21 - red-green discoloration ~A : -0.11 - blue-yellow discoloration ~B : l0.51 - surface defects (cracks, embrittlement) : none - yellow value G : 6 - Charpy impact strength an : no fracture - Izod notched impact strength ak : 4.6 kJ/m2 - cold formability : good, no defects Example 4:
A transparent amorphous sheet is produced analogously to Example 3. The extrusion temperature is 275~C. The first calender roll has a temperature of 57~C and the sub-sequent rolls have a temperature of 50~C. The take-off rate and the calender roll speed are 1.7 m/min. The sheet is stabilized as described in Example 3.
The PET sheet produced has the following property profile:
CA 0222~173 1997-12-18 - thickness : 10 mm - surface gloss, 1st side : 163 (measurement angle 20~) 2nd side : 161 - light transmission : 86.5%
- clarity : 99.2%
- haze : 4-95%
- surface defects per m2 : none (fisheye B, orange peel, bubbles, etc) - Charpy impact strength an : no fracture - Izod notched impact strength ak : 5.1 kJ/m2 - cold formability : good, no defects - crystallinity : 0.1%
- density : 1.33 g/cm3 After weathering for 1000 hours per side using the Atlas ~i 65 Weather-O-Meter, the PET sheet exhibits the follow-ing properties:
- thickness : 10 mm - surface gloss, 1st side : 160 (measurement angle 20~) 2nd side : 159 - light transmission : 86.2%
- clarity : 99.1%
- haze : 5.0%
- overall discoloration AE : 0.47 - dark discoloration ~L : -0.18 - red-green discoloration ~A : -0.09 - blue-yellow discoloration AB : +0.42 CA 0222~173 1997-12-18 - surface defects (cracks, embrittlement) : none - yellow value G : 5 - Charpy impact strength an : no fracture - Izod notched impact strength ak : 4. 5 kJ/m2 - cold formability : good, no defects Comparative Example 1:
A transparent, amorphous sheet i8 produced analogously to Example 1. In contrast to Example 1, the sheet contains no W stabilizer. The polyethylene terephthalate em-ployed, the extrusion parameters, the process parameters and the temperatures are selected as in Example 1.
The transparent PET sheet produced has the following property profile:
- thickness : 3 mm - surface gloss, 1st side : 200 (measurement angle 20~) 2nd side : 198 - light transmission : 91. 4%
- clarity : 100%
- haze : 1.3%
- surface defects per m2 : none (fisheyes, orange peel, bubbles, etc) - Charpy impact strength an : no fracture - Izod notched impact strength ak : 4.3 kJ/m2 - cold formability : good, no defects - crystallinity : 0%
- density : 1.33 g/cm3 After weathering for 1000 hours per side using the Atlas CA 0222~173 1997-12-18 Ci 65 Weather-O-Meter, the PET sheet exhibits the follow-ing properties:
- thickness : 3 mm - surface gloss, 1st side : 98 (measurement angle 20~) 2nd side : 95 - light transmission : 79.5%
- clarity : 81.2%
- haze : 7.8%
- overall discoloration ~E : 3.41 - dark discoloration ~L : -0.29 - red-green di~coloration ~A : -0.87 - blue-yellow discoloration ~B : +3.29 - surface defects (cracks, embrittlement) : embrittlement - yellow value G : 17 - Charpy impact strength an : complete frac-ture at 34.8 kJ/m2 - Izod notched impact strength ak : 1.3 kJ/m2 - cold formability : cracking The sheet exhibits a clearly visible "yellow" discolor-ation. The surfaces are matt and embrittled.
Comparative Example 2 A tran~parent, amorphous sheet is produced analogously to Example 3. In contrast to Example 3, the sheet contains no W stabilizer. The polyethylene terephthalate em-ployed, the extrusion parameters, the process parametersand the temperatures are selected as in Example 3.
The transparent PET sheet produced has the following property profile:
CA 0222~173 1997-12-18 - thickness : 6 mm - surface gloss, 1st side : 180 (measurement angle 20~) 2nd side : 178 - light transmis~ion : 88.9%
- clarity : 99.6%
- haze : 2.3%
- surface defects per m2 : none (fisheyes, orange peel, bubbles, etc) - Charpy impact strength an : no fracture - Izod notched impact strength ak : 4.8 kJ/m2 - cold formability : good, no defects - crystallinity : 0%
- density : 1.33 g/cm3 After weathering for 1000 hours per side using the Atlas Ci 65 Weather-O-Meter, the PET sheet exhibits the follow-ing properties:
- thickness : 6 mm - surface gloss, 1st side : 91 -(measurement angle 20~) 2nd side : 87 - light transmission : 72.5%
- clarity : 78.3%
- haze : 12.9%
- overall discoloration ~E : 3.61 - dark discoloration AL : -0.26 - red-green discoloration ~A : -0.91 - blue-yellow discoloration ~B : +3.48 CA 0222~173 1997-12-18 - surface defects (cracks, embrittlement) : embrittlement, cracks - yellow value G : 18 - Charpy impact strength an : complete frac-ture at 46.2 kJ/m2 - Izod notched impact strength ak : 1.6 kJ/m2 - cold formability : cracking The sheet exhibits a clearly visible "yellow" discolor-ation. The surfaces have been strongly attacked (matt, embrittled, cracking).
Comparative Example 3:
A W-stabilized, transparent, translucent sheet is produced analogously to Example 3, likewise using the polyethylene terephthalate, the W stabilizer and the masterbatch from Example 3. The first calender roll has a temperature of 83~C and the subsequent rolls each have a temperature of 77~C.
The sheet produced is extremely hazy and virtually opaque. The light transmission, the clarity and the gloss are significantly reduced. The sheet exhibits surface defects and structures. The optical properties are unacceptable for a transparent application.
The sheet produced has the following property profile:
- thickness : 6 mm - surface gloss, 1st side : 86 (measurement angle 20~) 2nd side 88 - light transmission : 8%
- clarity : not measurable CA 0222~173 1997-12-18 - haze : not measurable - surface defects per m2 : bubbles, orange (fisheyes, orange peel, bubbles, peel etc) - Charpy impact strength an : no fracture - Izod notched impact strength ak: 5-0 kJ/m2 - cold formability : good - crystallinity : approx. 8%
- density : 1.34 g/cm3 Owing to the unacceptable optical properties, the 6 mm sheet was not subjected to a weathering test.
Claims (23)
1. A transparent, amorphous sheet having a thickness in the range from 1 to 20 mm which contains, as principal constituent, a crystallizable thermoplastic, and contains at least one UV light stabilizer.
2. A sheet as claimed in claim 1, wherein the concentration of the UV stabilizer is in the range from 0.01 to 5% by weight, based on the weight of the crystallizable thermoplastic.
3. A sheet as claimed in claim 1 or 2, wherein the UV
stabilizer is selected from 2-hydroxybenzotriazoles and triazines.
stabilizer is selected from 2-hydroxybenzotriazoles and triazines.
4. A sheet as claimed in claim 3, wherein the UV stabilizer used is at least one compound selected from 2- (4,6-diphenyl-1,3,5-triazin-2-yl)-5-(hexyl)oxyphenol and 2,2'-methylene-bis(6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol.
5. A sheet as claimed in any one of the preceding claims, wherein the surface gloss, measured in accordance with DIN 67530 (measurement angle 20°), is greater than 120.
6. A sheet as claimed in any one of the preceding claims, wherein the light transmission, measured in accordance with ASTM D 1003, is greater than 84%.
7. A sheet as claimed in any one of the preceding claims, wherein the haze, measured in accordance with ASTM D 1003, is less than 15%.
8. A sheet as claimed in any one of the preceding claims, wherein the crystallizable thermoplastic has a crystallinity in the range from 5 to 65%.
9. A sheet as claimed in one of the preceding claims, wherein the crystallizable thermoplastic used is selected from polyethylene terephthalate, polybutylene terephthalate, a cycloolefin polymer and a cycloolefin copolymer.
10. A sheet as claimed in claim 9, wherein the crystallizable thermoplastic used is polyethylene terephthalate.
11. A sheet as claimed in claim 10, wherein the polyethylene terephthalate contains recycled polyethylene terephthalate.
12. A sheet as claimed in claim 10 or 11, wherein the measurement of the Charpy impact strength an, measured in accordance with ISO 179/1D, is not accompanied by a fracture.
13. A sheet as claimed in any one of claims 10 to 12, wherein the Izod notched impact strength ak, measured in accordance with ISO 180/1A, is in the range from 2.0 to 8.0 kJ/m2.
14. A sheet as claimed in any one of claims 10 to 13, wherein the clarity, measured in accordance with ASTM D 1003 at an angle of less than 2.5°, is greater than 96%.
15. A sheet as claimed in any one of claims 10 to 14, wherein the polyethylene terephthalate has a crystalline melting point, measured by DSC at a heating rate of 10°C/min, in the range from 220° to 280°C.
16. A sheet as claimed in any one of claims 10 to 15, wherein the polyethylene terephthalate has a crystallization temperature, measured by DSC at a heating rate of 10°C/min, in the range from 75° to 280°C
17. A sheet as claimed in any one of claims 10 to 16, wherein the polyethylene terephthalate employed has a standard viscosity SV (DCA), measured in dichloroacetic acid in accordance with DIN 53728, in the range from 800 to 1800.
18. A process for the production of a transparent, amorphous sheet as claimed in any one of claims 1 to 17, which comprises melting the crystallizable thermoplastic in the extruder together with the UV
stabilizer, extruding the melt through a die, calibrating, smoothing and cooling the extrudate in a polishing stack with at least two rolls, and cutting of the sheet to size, where the first roll of the polishing stack has a temperature in the range from 50 to 80°C.
stabilizer, extruding the melt through a die, calibrating, smoothing and cooling the extrudate in a polishing stack with at least two rolls, and cutting of the sheet to size, where the first roll of the polishing stack has a temperature in the range from 50 to 80°C.
19. The process as claimed in claim 18, wherein the crystallizable thermoplastic is dried before melting in the extruder.
20. The process as claimed in claim 18 or 19, wherein the crystallizable thermoplastic is polyethylene terephthalate.
21. The process as claimed in claim 20, wherein the polyethylene terephthalate is dried at from 160 to 180°C for from 4 to 6 hours before extrusion.
22. The process as claimed in claim 20 or 21, where the temperature of the PET melt is in the range from 250 to 320°C.
23. The process as claimed in any one of claims 20 to 22, wherein the UV stabilizer is added by masterbatch technology.
23. The process as claimed in any one of claims 20 to 22, wherein the UV stabilizer is added by masterbatch technology.
23. The use of a transparent, amorphous sheet as claimed in any one of claims 1 to 17 for external applications .
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19522118A DE19522118C1 (en) | 1995-06-19 | 1995-06-19 | Amorphous, transparent, UV-stabilized plate made of a crystallizable thermoplastic, process for its production and its use |
| DE19522118.4 | 1995-06-19 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2225173A1 true CA2225173A1 (en) | 1997-01-03 |
Family
ID=7764642
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002225173A Abandoned CA2225173A1 (en) | 1995-06-19 | 1996-06-10 | Amorphous, transparent, uv-stabilized sheet of a crystallizable thermoplastic |
Country Status (16)
| Country | Link |
|---|---|
| EP (1) | EP0833858A1 (en) |
| JP (1) | JPH11507965A (en) |
| KR (1) | KR19990028207A (en) |
| AU (1) | AU6125896A (en) |
| BG (1) | BG102073A (en) |
| BR (1) | BR9609412A (en) |
| CA (1) | CA2225173A1 (en) |
| CZ (1) | CZ414297A3 (en) |
| DE (1) | DE19522118C1 (en) |
| HU (1) | HUP9803029A2 (en) |
| NO (1) | NO975870L (en) |
| OA (1) | OA10552A (en) |
| PL (1) | PL324207A1 (en) |
| RU (1) | RU2169158C2 (en) |
| TW (1) | TW355717B (en) |
| WO (1) | WO1997000284A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8088847B2 (en) | 2005-12-23 | 2012-01-03 | Evonik Roehm Gmbh | PMMA film featuring particularly great weather resistance and great UV protection |
Families Citing this family (26)
| 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 |
| 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 |
| US5958581A (en) * | 1998-04-23 | 1999-09-28 | Hna Holdings, Inc. | Polyester film 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 |
| US6063464A (en) * | 1998-04-23 | 2000-05-16 | Hna Holdings, Inc. | Isosorbide containing polyesters and methods for making same |
| US9786194B2 (en) | 1999-06-11 | 2017-10-10 | Sydney Hyman | Image making medium compositions and images |
| US8669325B1 (en) | 1999-06-11 | 2014-03-11 | Sydney Hyman | Compositions image making mediums and images |
| AU5871500A (en) | 1999-06-11 | 2001-01-02 | Sydney Hyman | Image making medium |
| US9744800B2 (en) | 1999-06-11 | 2017-08-29 | Sydney Hyman | Compositions and image making mediums |
| DE10002171A1 (en) * | 2000-01-20 | 2001-07-26 | Mitsubishi Polyester Film Gmbh | Transparent, flame-retardant, UV-stable film made of a crystallizable thermoplastic, process for its production and its use |
| DE10009246A1 (en) * | 2000-02-28 | 2001-08-30 | Mitsubishi Polyester Film Gmbh | White, biaxially-oriented, UV-stabilized polyester film, used e.g. for packaging light- or air-sensitive food, has at least one layer containing a cyclo-olefin copolymer and a UV stabilizer |
| US7888405B2 (en) | 2004-01-30 | 2011-02-15 | E. I. Du Pont De Nemours And Company | Aliphatic-aromatic polyesters, and articles made therefrom |
| US7452927B2 (en) | 2004-01-30 | 2008-11-18 | E. I. Du Pont De Nemours And Company | Aliphatic-aromatic polyesters, and articles made therefrom |
| US11355027B2 (en) | 2004-04-30 | 2022-06-07 | Sydney Hyman | Image making medium compositions and images |
| DE202005006412U1 (en) * | 2004-05-27 | 2005-06-30 | Battenfeld Extrusionstechnik Gmbh | cooler |
| 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 (en) | 2005-06-10 | 2008-10-02 | Soitec Silicon On Insulator | Calibration method for thermal treatment equipment |
| JP5292958B2 (en) * | 2007-07-18 | 2013-09-18 | 東レ株式会社 | Polishing pad |
| WO2013149157A1 (en) | 2012-03-30 | 2013-10-03 | E. I. Du Pont De Nemours And Company | Polyesters and fibers made therefrom |
| JP6709076B2 (en) * | 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 | Method for producing polycarbonate resin composition |
| WO2017189552A1 (en) | 2016-04-25 | 2017-11-02 | E I Du Pont De Nemours And Company | Process for producing polyester article |
| KR102357178B1 (en) | 2020-01-08 | 2022-01-28 | 한세진 | Plastic duplex plate |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 (en) * | 1986-05-28 | 1987-12-03 | Bayer Ag | BRANCHED THERMOPLASTIC POLYCARBONATE WITH IMPROVED PROTECTION AGAINST UV LIGHT |
| JPH02500033A (en) * | 1986-08-22 | 1990-01-11 | イーストマン・コダック・カンパニー | thermoformed polyester articles |
| US4983653A (en) * | 1986-11-12 | 1991-01-08 | Diafoil Company, Ltd. | Polyester shrinkable film containing benzotriazole |
| JPH01284543A (en) * | 1988-05-11 | 1989-11-15 | Mitsubishi Rayon Co Ltd | Thermoplastic resin composition |
| BE1008335A3 (en) * | 1994-04-18 | 1996-04-02 | Axxis Nv | PLASTIC PLATE CONTAINING A COPOLYESTER, A METHOD FOR MANUFACTURING THE PLASTIC PLATE AND FORMULAS MADE FROM THE PLASTIC PLATE. |
-
1995
- 1995-06-19 DE DE19522118A patent/DE19522118C1/en not_active Expired - Fee Related
-
1996
- 1996-06-10 AU AU61258/96A patent/AU6125896A/en not_active Abandoned
- 1996-06-10 BR BR9609412A patent/BR9609412A/en not_active Application Discontinuation
- 1996-06-10 HU HU9803029A patent/HUP9803029A2/en unknown
- 1996-06-10 KR KR1019970709518A patent/KR19990028207A/en not_active Application Discontinuation
- 1996-06-10 CA CA002225173A patent/CA2225173A1/en not_active Abandoned
- 1996-06-10 RU RU98101098/04A patent/RU2169158C2/en active
- 1996-06-10 PL PL96324207A patent/PL324207A1/en unknown
- 1996-06-10 CZ CZ974142A patent/CZ414297A3/en unknown
- 1996-06-10 JP JP9502619A patent/JPH11507965A/en not_active Ceased
- 1996-06-10 WO PCT/EP1996/002514 patent/WO1997000284A1/en not_active Application Discontinuation
- 1996-06-10 EP EP96918681A patent/EP0833858A1/en not_active Withdrawn
- 1996-06-17 TW TW085107307A patent/TW355717B/en active
-
1997
- 1997-11-27 BG BG102073A patent/BG102073A/en unknown
- 1997-12-12 NO NO975870A patent/NO975870L/en unknown
- 1997-12-19 OA OA70167A patent/OA10552A/en unknown
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8088847B2 (en) | 2005-12-23 | 2012-01-03 | Evonik Roehm Gmbh | PMMA film featuring particularly great weather resistance and great UV protection |
Also Published As
| Publication number | Publication date |
|---|---|
| BR9609412A (en) | 1999-05-18 |
| PL324207A1 (en) | 1998-05-11 |
| CZ414297A3 (en) | 1998-03-18 |
| BG102073A (en) | 1998-08-31 |
| KR19990028207A (en) | 1999-04-15 |
| TW355717B (en) | 1999-04-11 |
| HUP9803029A2 (en) | 1999-04-28 |
| MX9710294A (en) | 1998-03-29 |
| JPH11507965A (en) | 1999-07-13 |
| RU2169158C2 (en) | 2001-06-20 |
| AU6125896A (en) | 1997-01-15 |
| NO975870D0 (en) | 1997-12-12 |
| DE19522118C1 (en) | 1997-03-13 |
| NO975870L (en) | 1997-12-12 |
| EP0833858A1 (en) | 1998-04-08 |
| WO1997000284A1 (en) | 1997-01-03 |
| OA10552A (en) | 2002-05-29 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |