CN115625870A - Super-weather-resistant white polyester film and preparation method thereof - Google Patents
Super-weather-resistant white polyester film and preparation method thereof Download PDFInfo
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- CN115625870A CN115625870A CN202211517336.6A CN202211517336A CN115625870A CN 115625870 A CN115625870 A CN 115625870A CN 202211517336 A CN202211517336 A CN 202211517336A CN 115625870 A CN115625870 A CN 115625870A
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- Prior art keywords
- polyester film
- layer
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- resistant
- weather
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- 229920006267 polyester film Polymers 0.000 title claims abstract description 96
- 238000002360 preparation method Methods 0.000 title abstract description 18
- 229920000728 polyester Polymers 0.000 claims abstract description 81
- 239000002344 surface layer Substances 0.000 claims abstract description 73
- 239000012792 core layer Substances 0.000 claims abstract description 66
- 239000010410 layer Substances 0.000 claims abstract description 62
- 239000000155 melt Substances 0.000 claims abstract description 54
- 238000001125 extrusion Methods 0.000 claims abstract description 50
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 49
- 239000002994 raw material Substances 0.000 claims abstract description 45
- 238000002156 mixing Methods 0.000 claims abstract description 34
- 238000002834 transmittance Methods 0.000 claims abstract description 24
- 230000000655 anti-hydrolysis Effects 0.000 claims abstract description 18
- 238000005266 casting Methods 0.000 claims abstract 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 27
- 230000007062 hydrolysis Effects 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 20
- 239000003963 antioxidant agent Substances 0.000 claims description 16
- 239000002270 dispersing agent Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- 239000004611 light stabiliser Substances 0.000 claims description 15
- 230000003078 antioxidant effect Effects 0.000 claims description 14
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 10
- 238000009998 heat setting Methods 0.000 claims description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 9
- 150000001412 amines Chemical class 0.000 claims description 9
- 239000002131 composite material Substances 0.000 claims description 9
- 238000006068 polycondensation reaction Methods 0.000 claims description 9
- 238000010345 tape casting Methods 0.000 claims description 9
- 238000009826 distribution Methods 0.000 claims description 8
- 229940124543 ultraviolet light absorber Drugs 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 7
- 238000005096 rolling process Methods 0.000 claims description 7
- 239000007790 solid phase Substances 0.000 claims description 7
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 7
- 239000012964 benzotriazole Substances 0.000 claims description 6
- 230000009477 glass transition Effects 0.000 claims description 6
- 239000000049 pigment Substances 0.000 claims description 6
- UWSMKYBKUPAEJQ-UHFFFAOYSA-N 5-Chloro-2-(3,5-di-tert-butyl-2-hydroxyphenyl)-2H-benzotriazole Chemical group CC(C)(C)C1=CC(C(C)(C)C)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O UWSMKYBKUPAEJQ-UHFFFAOYSA-N 0.000 claims description 5
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical group CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 5
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 claims description 5
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 5
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 125000003354 benzotriazolyl group Chemical group N1N=NC2=C1C=CC=C2* 0.000 claims description 2
- VPKDCDLSJZCGKE-UHFFFAOYSA-N carbodiimide group Chemical group N=C=N VPKDCDLSJZCGKE-UHFFFAOYSA-N 0.000 claims description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical group [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 22
- 238000012360 testing method Methods 0.000 description 19
- 230000032683 aging Effects 0.000 description 16
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 12
- 229910052731 fluorine Inorganic materials 0.000 description 12
- 239000011737 fluorine Substances 0.000 description 12
- 230000003647 oxidation Effects 0.000 description 12
- 238000007254 oxidation reaction Methods 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 11
- 238000000576 coating method Methods 0.000 description 11
- 239000004408 titanium dioxide Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 230000005855 radiation Effects 0.000 description 7
- 150000003254 radicals Chemical class 0.000 description 7
- 229920006395 saturated elastomer Polymers 0.000 description 7
- 238000011045 prefiltration Methods 0.000 description 6
- 239000002250 absorbent Substances 0.000 description 5
- 230000002745 absorbent Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000006870 function Effects 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 150000001718 carbodiimides Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-M hydroperoxide group Chemical group [O-]O MHAJPDPJQMAIIY-UHFFFAOYSA-M 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000004383 yellowing Methods 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- 230000006750 UV protection Effects 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- -1 phenyl benzotriazol Chemical compound 0.000 description 2
- 238000007539 photo-oxidation reaction Methods 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 description 1
- XMIIGOLPHOKFCH-UHFFFAOYSA-N 3-phenylpropionic acid Chemical compound OC(=O)CCC1=CC=CC=C1 XMIIGOLPHOKFCH-UHFFFAOYSA-N 0.000 description 1
- UWDMKTDPDJCJOP-UHFFFAOYSA-N 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-ium-4-carboxylate Chemical compound CC1(C)CC(O)(C(O)=O)CC(C)(C)N1 UWDMKTDPDJCJOP-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 206010051246 Photodermatosis Diseases 0.000 description 1
- OCKWAZCWKSMKNC-UHFFFAOYSA-N [3-octadecanoyloxy-2,2-bis(octadecanoyloxymethyl)propyl] octadecanoate Chemical group CCCCCCCCCCCCCCCCCC(=O)OCC(COC(=O)CCCCCCCCCCCCCCCCC)(COC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC OCKWAZCWKSMKNC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-N hydroperoxyl Chemical compound O[O] OUUQCZGPVNCOIJ-UHFFFAOYSA-N 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QYVZEPLDLPYECM-XUTLUUPISA-N octadecyl (e)-3-(3,4-dihydroxyphenyl)prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)\C=C\C1=CC=C(O)C(O)=C1 QYVZEPLDLPYECM-XUTLUUPISA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000008845 photoaging Effects 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 125000003386 piperidinyl group Chemical group 0.000 description 1
- 238000006462 rearrangement reaction Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- 238000004804 winding Methods 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
- 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
- B29C48/001—Combinations of extrusion moulding with other shaping operations
- B29C48/0018—Combinations of extrusion moulding with other shaping operations combined with shaping by orienting, stretching or shrinking, e.g. film blowing
-
- 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
- B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
- B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/03—3 layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/24—All layers being polymeric
- B32B2250/244—All polymers belonging to those covered by group B32B27/36
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/71—Resistive to light or to UV
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/712—Weather resistant
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The invention relates to an ultra-weather-resistant white polyester film and a preparation method thereof, wherein the ultra-weather-resistant white polyester film consists of a core layer, an upper surface layer and a lower surface layer, wherein the core layer is prepared from a tackifying polyester slice, an anti-hydrolysis master batch and a white master batch according to the mass ratio of 82 to 95 to 2 to 8; the preparation method comprises the following steps: respectively and uniformly mixing the raw materials of the core layer and the raw materials of the surface layer, then carrying out melt extrusion, carrying out cast sheet casting after the melt is extruded by a three-layer co-extrusion die head, and then carrying out biaxial tension to obtain the super-weather-resistant white polyester film. The light transmittance of the super-weather-resistant white polyester film prepared by the invention is less than or equal to 30%, the transmittance at the ultraviolet wavelength of 380nm is less than or equal to 5%, the elongation at break is more than or equal to 40% after PCT 72 hours, and the delta b is less than or equal to 3 after ultraviolet irradiation of 200kWh, which is obviously superior to the prior art.
Description
Technical Field
The invention belongs to the technical field of polyester films, and relates to an ultra-weather-resistant white polyester film and a preparation method thereof.
Background
The back plate is used as a key part of the crystalline silicon solar module, plays a role in protecting and supporting the cell, and plays a vital role in the safety, the service life and the reduction of power attenuation of the module. The backsheet must have various balanced properties of good mechanical strength and toughness, weather resistance, insulation, moisture barrier, chemical resistance, and the like. The back sheet can be classified into a fluorine-containing back sheet and a non-fluorine back sheet according to the material category. Fluorine material recycling treatment can bring the influence to the environment, simultaneously along with the coming on day by day of the net footfall of photovoltaic flat price, in order to further reduce backplate cost, non-fluorine PET backplate becomes development trend. The PET back plate is of a three-layer structure and sequentially comprises a reinforced BOPET, a common BOPET and a PE film bonding layer. The reinforced BOPET replaces a fluorine film or a fluorine coating to be used as the outermost layer of the PET backboard, so that the cost of the fluorine film or the fluorine coating is saved, and the backboard is more convenient and environment-friendly to process.
BOPET is very easy to hydrolyze under the condition of high temperature and high humidity, and water molecules attack ester bonds to cause the ester bonds to be subjected to hydrolytic fracture to generate oligomers with carboxyl, and the carboxyl can promote the further progress of hydrolysis reaction. The ultraviolet aging reaction of BOPET is divided into photolysis reaction in which BOPET undergoes a radical rearrangement reaction to break a macromolecular main chain and generate CO and CO, and photooxidation reaction 2 Gas and other by-products, the mechanical properties of the BOPET change, such as tensile strength and elongation at break; in the photooxidation reaction, hydroperoxide groups are generated on the aromatic ring of BOPET, and further monophenol hydroxyl or diphenol hydroxyl derivatives are generated, and the yellowing of BOPET is mainly caused by the fluorescent products.
The Chinese patent application CN202010554043.X discloses a transparent anti-UV polyester film for a back plate, and compared with a common polyester film, the absorption peak of the film in an ultraviolet band is obviously improved; the transmittance is less than 10% at the ultraviolet 380nm position; after irradiation for 200kwh, the yellowing is less than or equal to 3; after PCT 48h, the elongation at break retention rate is more than or equal to 40 percent. The coating is a transparent product and has no covering performance, the ultraviolet resistant agent is dispersed in the aqueous coating liquid and is coated on the surface of the film in a coating mode, the ultraviolet resistant effect is common, and coating stripes are easy to generate to influence the appearance of the film surface. The anti-aging performance is poor, and the PCT 48 hours can be met only.
Chinese patent application CN200910184985.7 discloses a preparation method of a polyester film for a photovoltaic cell backboard, and the described performance indexes are that the product is forcedly aged for 100 hours at high temperature and high humidity, the strength retention rate is 120MPa, and the uvioresistant performance is not described. This application is also a transparent product, without hiding properties. And the master batch is prepared by blending, melting, extruding and granulating the polycarbodiimide, the ultraviolet absorbent, the antioxidant and the PET. The method blends various additives with different purposes with PET, which causes the dispersion of the additives to be uneven, and the prepared master batch has the defects of unstable performance and the like.
White polyester films in the prior art are common polyester films, and because master batches containing titanium dioxide are added, the titanium dioxide has strong active free radicals, and can catalyze the decomposition of hydroperoxide through electron transfer, so that the oxidation speed of PET is accelerated, the thermal oxidation resistance of the PET is reduced, and BOPET can be degraded through thermal oxidation in the preparation and long-term use processes, so that the ageing resistance of the PET is influenced.
Therefore, the research on the white polyester film with excellent ageing resistance and the preparation method thereof have very important significance.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides an ultra-weather-resistant white polyester film and a preparation method thereof.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
an ultra-weather-resistant white polyester film is a three-layer composite structure and consists of a core layer, an upper surface layer and a lower surface layer;
the core layer comprises the raw materials of a tackifying polyester slice, an anti-hydrolysis master batch and a white master batch, wherein the mass ratio of the tackifying polyester slice to the anti-hydrolysis master batch to the white master batch is 82 to 95;
the upper and lower surface layer raw materials are tackifying polyester chips, white master batches and ultraviolet-resistant master batches, and the mass ratio of the tackifying polyester chips to the white master batches to the ultraviolet-resistant master batches is 55 to 84;
the intrinsic viscosity of the tackifying polyester chip is 0.75 to 0.95dL/g, and the carboxyl end group content is 5 to 11mol/T;
the hydrolysis-resistant master batch is prepared by blending, extruding and granulating bottle-grade polyester chips (the bottle-grade polyester chips have higher viscosity and better thermal stability) and an hydrolysis-resistant agent; the molecular structure of the hydrolysis resistant agent contains carbodiimide groups or polycarbodiimide groups;
the white master batch is prepared by blending, extruding and granulating bottle-grade polyester chips, pigment and a dispersing agent; the pigment is nano titanium dioxide;
the uvioresistant master batch is prepared by blending, extruding and granulating polyester chips, ultraviolet light absorbers, light stabilizers, antioxidants and dispersing agents; the ultraviolet light absorber is a benzotriazole ultraviolet light absorber, the light stabilizer is a hindered amine light stabilizer, and the antioxidant is a hindered phenol antioxidant;
the light transmittance of the super-weather-resistant white polyester film is less than or equal to 30 percent, the transmittance at the ultraviolet wavelength of 380nm is less than or equal to 5 percent, the elongation at break is more than or equal to 40 percent after 72 hours of PCT (high-pressure accelerated aging test, the test conditions are that the saturated steam temperature is 121 ℃, and 2 standard atmospheric pressures), and the delta b is less than or equal to 3 after 200kWh of ultraviolet radiation (excellent yellowing resistance).
The content of the hydrolysis resistant agent added into the core layer in the prior art is 1.8 to 3 percent and is far higher than that of the core layer in the invention (0.3 to 1.2 percent), because the tackifying polyester chip in the core layer has high molecular weight and intrinsic viscosity and low carboxyl end group content, the thermal oxidation resistance is improved, and the hydrolysis resistance is greatly improved, so that the excellent ageing resistance can be still maintained under the condition that the content of the hydrolysis resistant agent added into the core layer is obviously lower than that in the prior art.
As a preferable technical scheme:
the thickness of the super-weather-resistant white polyester film is 36 to 50 micrometers, the thickness of the upper surface and the thickness of the lower surface of the super-weather-resistant white polyester film are respectively 3 to 10 percent of the thickness of the super-weather-resistant white polyester film, and the thickness of the core layer is 80 to 94 percent of the thickness of the super-weather-resistant white polyester film.
The super weather-resistant white polyester film is characterized in that the tackified polyester chip is prepared by heating the polyester chip to a temperature higher than the glass transition temperature and lower than the melting point, and performing solid phase polycondensation reaction in a vacuum or inert gas environment; ordinary polyester chip is heated to be higher than glass transition temperature (Tg) and lower than melting point (Tm), solid phase polycondensation reaction is carried out under vacuum or inert gas environment, the macromolecular chain is still in a fixed state at the moment, and terminal functional groups (terminal carboxyl and terminal hydroxyl) obtain enough activity, the terminal functional groups are mutually close to each other through diffusion and carry out polycondensation reaction, the molecular weight and the intrinsic viscosity of the tackified polyester chip are improved, the content of the terminal carboxyl is greatly reduced, and besides the thermal oxidation resistance is improved, the hydrolysis resistance is also greatly improved.
According to the super-weather-resistant white polyester film, the mass ratio of the bottle-grade polyester chip in the hydrolysis-resistant master batch to the hydrolysis resistant agent is 75 to 90;
the mass ratio of the white master batch medium bottle grade polyester chips to the pigment to the dispersant is 25 to 55, namely, the ratio is (1) to 2);
the mass ratio of the polyester chips, the ultraviolet light absorber, the light stabilizer, the antioxidant and the dispersant in the ultraviolet resistant master batch is 55 to 90.
According to the super-weather-resistant white polyester film, the benzotriazole ultraviolet absorbent is UV-327 [2- (2 ' -hydroxy-3 ', 5' -di-tert-butylphenyl) -5-chlorobenzotriazole ], UV-P [2- (2 ' -hydroxy-5 ' -methylphenyl) benzotriazol ] or UV-329 [2- (2 ' -hydroxy-5 ' -tert-octyl) phenyl benzotriazol ];
the hindered amine light stabilizer is UV-622 [ poly (4-hydroxy-2, 6-tetramethyl-1-piperidineethanol) succinate ] or UV-944 [ poly- { [6- [ (1, 3-tetramethylbutyl) ethyl ester-imino ] -1,3, 5-triazin-2, 4-diyl ] [2- (2, 6-tetramethylpiperidinyl) -amino ] -hexylene- [4- (2, 6-tetramethylpiperidinyl) -imino ] };
the hindered phenol antioxidant is antioxidant 1010 [ tetra [ (3, 5-di-tert-butyl-4-hydroxy) phenylpropionic acid ] pentaerythritol ester ] or antioxidant 1076 [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] n-octadecyl ester ].
The invention also provides a method for preparing the super-weather-resistant white polyester film, which comprises the steps of respectively uniformly mixing the raw materials for forming the core layer and the raw materials for forming the surface layers (all the raw materials for forming the upper and lower surface layers), carrying out melt extrusion, carrying out tape casting on the melt after the melt is extruded by a three-layer co-extrusion die head, and carrying out biaxial stretching to obtain the super-weather-resistant white polyester film.
As a preferable technical scheme:
the method comprises the following specific steps:
(1) Uniformly mixing the raw materials of the core layer, feeding the mixture into a main extruder for melt extrusion, uniformly mixing the raw materials of the surface layer, feeding the mixture into an auxiliary extruder for melt extrusion, feeding the melt into the same distribution block after passing through respective prefilters, metering pumps and fine filters of the main extruder and the auxiliary extruder respectively, distributing the melt of the main extruder in the core layer, and distributing the melt of the auxiliary extruder in the upper surface layer and the lower surface layer;
(2) The distributed melt enters a three-layer co-extrusion die head, the melt of a core layer is extruded from the middle layer of the three-layer co-extrusion die head, simultaneously, the melt of the upper and lower surface layers is respectively extruded from the upper and lower layers of the three-layer co-extrusion die head, and after the extruded melt is cooled, tape casting is carried out to obtain a polyester film sheet;
(3) Preheating the polyester film sheet to a temperature above the glass transition temperature, longitudinally stretching, transversely stretching, carrying out heat setting, cooling to room temperature, and finally drawing and rolling to obtain the super weather-resistant white polyester film.
In the above process, the temperature for melt extrusion in the step (1) is from 275 ℃ to 305 ℃ (the melt extrusion temperature of the main extruder is from 275 ℃ to 305 ℃, and the melt extrusion temperature of the auxiliary extruder is from 275 ℃ to 305 ℃).
In the above-mentioned method, the temperature for cooling in the step (2) is 18 to 40 ℃.
In the method, in the step (3), the temperature for longitudinal stretching is 80 to 110 ℃, the longitudinal stretching ratio is 2.8 to 4.5, the temperature for transverse stretching is 90 to 120 ℃, the transverse stretching ratio is 3.0 to 5.0, and the heat setting temperature is 200 to 240 ℃.
The principle of the invention is as follows:
the tackifying polyester chip is prepared by heating common polyester chips to a temperature higher than the glass transition temperature (Tg) and lower than the melting point (Tm) and carrying out solid-phase polycondensation reaction in a vacuum or inert gas environment, wherein the macromolecular chains are still in a fixed state, and the terminal functional groups (terminal carboxyl groups and terminal hydroxyl groups) obtain enough activity and are close to each other through diffusion and carry out polycondensation reaction. The molecular weight and the intrinsic viscosity of the tackified polyester chip are improved, the content of terminal carboxyl groups is greatly reduced, the thermal oxidation resistance is improved, the hydrolysis resistance is also greatly improved, and the anti-aging requirement that the elongation at break is more than or equal to 40% after a PCT (high-pressure accelerated aging test) is reached 72 hours under the condition that the content of the hydrolysis resistant agent added into the core layer is obviously lower than that in the prior art.
The nanometer titanium dioxide has high refractivity, can reflect and scatter ultraviolet rays and absorb ultraviolet rays, has certain blocking capability on the ultraviolet rays, and mainly blocks the ultraviolet rays in a long wave region and mainly blocks the ultraviolet rays in a medium wave region. In the prior art, a white polyester film is usually a common polyester film added with titanium dioxide master batches, and titanium dioxide has a free radical with high activity, and can catalyze the decomposition of hydroperoxide through electron transfer to accelerate the oxidation speed of PET, so that the thermal oxidation resistance of PET is reduced, and BOPET thermal oxidation degradation can be caused in the preparation and long-term use processes to influence the ageing resistance of PET. The solid-phase polycondensation tackifying polyester chip adopted in the invention ensures that the aging resistance of BOPET is not influenced by the addition of titanium dioxide. Meanwhile, the titanium dioxide has a covering function, and can reduce the light transmittance of the film, so that the titanium dioxide can replace a fluorine film or a fluorine coating.
For polyester materials, ester bonds in molecular chains of the polyester materials are easily corroded by water vapor and hydrolyzed under the humid and especially high humid and hot conditions, so that the comprehensive performance is reduced, and carboxylic acid generated by hydrolysis can further catalyze the hydrolysis reaction of polyester. The molecular structure of the hydrolysis resistant agent in the hydrolysis resistant master batch in the core layer (layer B) contains carbodiimide or polycarbodiimide groups, and the carbodiimide or polycarbodiimide groups and carboxyl have higher reaction activity and generate the carbamido compound with stable structure. By utilizing the characteristic of the carbodiimide or polycarbodiimide group, carboxyl which is easy to cause autocatalytic hydrolysis of the polyester material can be eliminated, and molecular chain breakage and reduction of comprehensive performance of the polyester material caused by hydrolysis are effectively inhibited.
The surface layer (layer A) uvioresistant master batch plays a role in enhancing uvioresistant effect. The benzotriazole ultraviolet absorbent in the ultraviolet resistant master batch has hydrogen bond chelating ring formed by hydroxyl oxygen and nitrogen on triazole group, and after absorbing ultraviolet light, the hydrogen bond is destroyed or changed into optical tautomer, so that harmful ultraviolet light energy is changed into harmless heat energy to be released. The hindered amine light stabilizer can effectively capture active free radicals generated by the polyester material under the action of ultraviolet rays, decompose hydroperoxide and transfer energy of excited molecules and the like, so that the polyester material can eliminate or slow down the possibility of degradation under the radiation of light, and the photoaging process is prevented or delayed, thereby prolonging the service life of the polyester material. The hindered phenol antioxidant is a compound with substituent groups on one side or two sides of hydroxyl on a benzene ring, atoms are easy to fall off from molecules due to the existence of a space barrier, and are combined with peroxide free radicals, alkoxy free radicals and hydroxyl free radicals to stop the reactive chain reaction, so that the aim of preventing oxidation is fulfilled. The combined use of benzotriazole ultraviolet absorbent, hindered amine light stabilizer and hindered phenol antioxidant in the anti-ultraviolet master batch is a stable system with light resistance, heat resistance and oxygen aging resistance. The ultraviolet absorbent can eliminate active products formed by the antioxidant in the illumination period, and simultaneously quinone generated after the hindered phenol antioxidant is oxidized and N-OH generated by the hindered amine light stabilizer are subjected to photochemical reaction to generate phenol, so that the stabilization efficiency is improved. Due to the regeneration of the hindered phenol antioxidant, the oxidation of piperidine ring in the hindered amine light stabilizer is inhibited, thereby prolonging the service life of the hindered amine light stabilizer and finally achieving the effects of ultraviolet light resistance, heat resistance and the like.
Has the beneficial effects that:
(1) The super-weather-resistant white polyester film prepared by adding the titanium dioxide master batch and other functional master batches has the functions of covering, ageing resistance, ultraviolet resistance and the like, is used as a reinforced BOPET layer on the outer layer of the PET backboard, can replace a fluorine film or a fluorine coating, and has the advantages of environmental friendliness, cost reduction, convenience in processing and the like;
(2) The ultraviolet resistance function of the super-weather-resistant white polyester film is realized by an internal addition mode, and the super-weather-resistant white polyester film has better coating effect than an online coating film and has no appearance defects such as coating lines;
(3) The preparation method of the super weather-resistant white polyester film has the advantages that the used master batches have single functions, the additive is uniformly dispersed, the performance is stable, and the processing is convenient;
(5) According to the preparation method of the super-weather-resistant white polyester film, solid-phase polycondensation tackifying polyester slices are used, the molecular weight and the intrinsic viscosity are improved, the content of terminal carboxyl groups is greatly reduced, the thermal oxidation resistance is improved, the hydrolysis resistance is also greatly improved, and the content of an hydrolysis resisting agent added into a core layer is obviously lower than that in the prior art.
Detailed Description
The present invention will be further described with reference to the following embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Some substances involved in the embodiments of the present invention are specifically as follows:
(1) Tackifying the polyester chip: heating polyester chips with the intrinsic viscosity of 0.68dL/g and the carboxyl end group content of 24mol/T to 200 ℃, and carrying out solid phase polycondensation reaction for 20 hours in a nitrogen environment to prepare tackifying polyester chips with the intrinsic viscosity of 0.82dL/g and the carboxyl end group content of 7 mol/T;
(2) Bottle grade polyester chip: from the instrumented chemical fiber company, the trade mark is FG720;
(3) Hydrolysis resistance agent: the specific name is polycarbodiimide which is sourced from Laian company and has the trade name of HYDROSTAB 2;
(4) And (3) hydrolysis-resistant master batch: the polyester resin is prepared by blending bottle-grade polyester chips and an anti-hydrolysis agent according to the mass ratio of 85 to 15 at 280 ℃ and extruding and granulating;
(5) Nano-scale titanium dioxide: is sourced from DuPont of America, and the trade mark is R-103;
(6) Dispersing agent: the specific name is pentaerythritol tetrastearate which is sourced from TCI company of Japan and has the trade mark of P0739;
(7) White master batch: the polyester resin is prepared by blending bottle-grade polyester chips, nano-scale titanium dioxide and the dispersing agent according to the mass ratio of 39;
(8) Polyester chip cutting: from the instrumented chemical fiber company, the trade mark is FG600;
(9) UV-622: the number average molecular weight is 3100;
(10) UV-944: the number average molecular weight is 2900;
the test method or test conditions of some performance indexes related by the invention are as follows:
(1) Light transmittance: testing the light transmittance of the super-weather-resistant white polyester film by adopting ASTM D-1003;
(2) Elongation at break: testing the elongation at break of the super-weather-resistant white polyester film by adopting ASTM D-882;
(3) Transmittance at ultraviolet wavelength of 380 nm: testing the transmittance of the ultra-weather-resistant white polyester film at the ultraviolet wavelength of 380nm by adopting ASTM D-1003;
(4) Δ b: the delta b of the super-weatherable white polyester film is tested by GB/T7921-2008.
Example 1
A preparation method of an ultra-weather-resistant white polyester film comprises the following specific steps:
(1) Preparing the raw materials of the core layer:
the core layer is prepared from tackifying polyester chips, anti-hydrolysis master batches and white master batches, wherein the mass ratio of the tackifying polyester chips to the anti-hydrolysis master batches to the white master batches is 94;
(2) Preparing raw materials for the composition of the surface layer:
the upper and lower surface layer raw materials are tackifying polyester slices, white master batches and uvioresistant master batches, and the mass ratio of the tackifying polyester slices, the white master batches and the uvioresistant master batches is 83;
wherein, the uvioresistant master batch is prepared by blending polyester chips, UV-327, UV-622, an antioxidant 1010 and a dispersing agent according to the mass ratio of 81.8;
(3) Uniformly mixing the raw materials of the core layer in the step (1), sending the mixture into a main extruder for melt extrusion at 275 ℃, uniformly mixing the raw materials of the surface layer in the step (2), sending the mixture into an auxiliary extruder for melt extrusion at 276 ℃, respectively passing the melt through a pre-filter, a metering pump and a fine filter of the main extruder and the auxiliary extruder, and then sending the melt into the same distribution block, wherein the melt of the main extruder is distributed in the core layer, and the melt of the auxiliary extruder is distributed on the upper surface layer and the lower surface layer;
(4) The distributed melt enters a three-layer co-extrusion die head, the melt of a core layer is extruded from the middle layer of the three-layer co-extrusion die head, meanwhile, the melt of the upper surface layer and the melt of the lower surface layer are respectively extruded from the upper layer and the lower layer of the three-layer co-extrusion die head, and the extruded melt is cooled at 32 ℃ and then subjected to tape casting to obtain a polyester film sheet;
(5) Preheating the polyester film sheet to 90 ℃, longitudinally stretching at 95 ℃ with the longitudinal stretching ratio of 2.8, transversely stretching at 115 ℃ with the transverse stretching ratio of 4, cooling to room temperature after heat setting at 215 ℃, and finally drawing and rolling to obtain the super-weather-resistant white polyester film.
The prepared super weather-proof white polyester film is of a three-layer composite structure and consists of a core layer, an upper surface layer and a lower surface layer; the thickness of the super weather-proof white polyester film is 50 micrometers, wherein the thickness of the upper surface is 4 micrometers, the thickness of the lower surface is 4 micrometers, and the thickness of the core layer is 42 micrometers;
the light transmittance of the super-weatherable white polyester film is 25.2 percent, the transmittance at the ultraviolet wavelength of 380nm is 4.9 percent, the elongation at break is 45 percent after 72 hours of PCT (high-pressure accelerated aging test, the test condition is that the saturated steam temperature is 121 ℃ and the 2 standard atmospheric pressure is adopted), and the Delta b is 2.9 after 200kWh of ultraviolet radiation.
Example 2
A preparation method of an ultra-weather-resistant white polyester film comprises the following specific steps:
(1) Preparing raw materials of a core layer:
the core layer is prepared from tackifying polyester chips, anti-hydrolysis master batches and white master batches, and the mass ratio of the tackifying polyester chips to the anti-hydrolysis master batches to the white master batches is 89;
(2) Preparing raw materials for the composition of the surface layer:
the upper and lower surface layer raw materials are tackifying polyester slices, white master batches and uvioresistant master batches, and the mass ratio of the tackifying polyester slices, the white master batches and the uvioresistant master batches is 65;
wherein, the uvioresistant master batch is prepared by blending polyester chips, UV-P, UV-622, an antioxidant 1076 and a dispersing agent according to the mass ratio of 75.5;
(3) Uniformly mixing the raw materials of the core layer in the step (1), sending the mixture into a main extruder for melt extrusion at 282 ℃, uniformly mixing the raw materials of the surface layer in the step (2), sending the mixture into an auxiliary extruder for melt extrusion at 282 ℃, enabling the melts to respectively pass through a pre-filter, a metering pump and a fine filter of the main extruder and the auxiliary extruder and then enter a same distribution block, distributing the melt of the main extruder in the core layer, and distributing the melt of the auxiliary extruder in the upper surface layer and the lower surface layer;
(4) The distributed melt enters a three-layer co-extrusion die head, the melt of a core layer is extruded from the middle layer of the three-layer co-extrusion die head, simultaneously, the melt of the upper and lower surface layers is respectively extruded from the upper and lower layers of the three-layer co-extrusion die head, and the extruded melt is cooled at 18 ℃ and then is subjected to tape casting to obtain a polyester film sheet;
(5) Preheating a polyester film sheet to 105 ℃, longitudinally stretching at 110 ℃ with the longitudinal stretching ratio of 3.3, transversely stretching at 105 ℃ with the transverse stretching ratio of 3.5, carrying out heat setting at 235 ℃, cooling to room temperature, and finally carrying out traction and winding to obtain the super-weather-resistant white polyester film.
The prepared super weather-proof white polyester film is of a three-layer composite structure and consists of a core layer, an upper surface layer and a lower surface layer; the thickness of the super weather-proof white polyester film is 36 micrometers, wherein the thickness of the upper surface is 1.5 micrometers, the thickness of the lower surface is 1.5 micrometers, and the thickness of the core layer is 33 micrometers;
the light transmittance of the super-weatherable white polyester film is 28.3 percent, the transmittance at the ultraviolet wavelength of 380nm is 4.5 percent, the elongation at break is 55 percent after 72 hours of PCT (high-pressure accelerated aging test, test conditions are that the saturated steam temperature is 121 ℃ and the pressure is 2 standard atmospheres), and the Delta b is 2.7 after 200kWh of ultraviolet radiation.
Example 3
A preparation method of an ultra-weather-resistant white polyester film comprises the following specific steps:
(1) Preparing raw materials of a core layer:
the core layer comprises the following raw materials of a tackifying polyester chip, an anti-hydrolysis master batch and a white master batch, wherein the mass ratio of the tackifying polyester chip to the anti-hydrolysis master batch to the white master batch is 85;
(2) Preparing raw materials for the composition of the surface layer:
the upper and lower surface layers are made of tackifying polyester chips, white master batches and uvioresistant master batches, and the mass ratio of the tackifying polyester chips to the white master batches to the uvioresistant master batches is 75;
the ultraviolet-resistant master batch is prepared by mixing polyester chips, UV-329, UV-622, an antioxidant 1010 and a dispersing agent according to the mass ratio of 71.2;
(3) Uniformly mixing the raw materials of the core layer in the step (1), sending the mixture into a main extruder for melt extrusion at 295 ℃, uniformly mixing the raw materials of the surface layer in the step (2), sending the mixture into an auxiliary extruder for melt extrusion at 290 ℃, respectively passing the melt through a pre-filter, a metering pump and a fine filter of the main extruder and the auxiliary extruder, and then sending the melt into the same distribution block, wherein the melt of the main extruder is distributed in the core layer, and the melt of the auxiliary extruder is distributed on the upper surface layer and the lower surface layer;
(4) The distributed melt enters a three-layer co-extrusion die head, the melt of a core layer is extruded from the middle layer of the three-layer co-extrusion die head, simultaneously, the melt of the upper and lower surface layers is respectively extruded from the upper and lower layers of the three-layer co-extrusion die head, and the extruded melt is cooled at 20 ℃ and then is subjected to tape casting to obtain a polyester film sheet;
(5) Preheating the polyester film sheet to 100 ℃, longitudinally stretching at 105 ℃, wherein the longitudinal stretching ratio is 3.2, transversely stretching at 110 ℃, the transverse stretching ratio is 4.2, carrying out heat setting at 220 ℃, cooling to room temperature, and finally carrying out traction rolling to obtain the super-weather-resistant white polyester film.
The prepared super weather-proof white polyester film is of a three-layer composite structure and consists of a core layer, an upper surface layer and a lower surface layer; the thickness of the super-weather-resistant white polyester film is 36 micrometers, wherein the thickness of the upper surface is 2 micrometers, the thickness of the lower surface is 2 micrometers, and the thickness of the core layer is 32 micrometers;
the ultra-weatherable white polyester film has a light transmittance of 27.8%, a transmittance of 4.3% at a wavelength of 380nm in ultraviolet, an elongation at break of 68% after 72 hours in PCT (high pressure accelerated aging test under test conditions of 121 ℃ for saturated steam and 2 standard atmospheric pressures), and a Δ b of 2.6 after 200kWh of ultraviolet irradiation.
Example 4
A preparation method of an ultra-weather-resistant white polyester film comprises the following specific steps:
(1) Preparing the raw materials of the core layer:
the core layer is prepared from tackifying polyester chips, anti-hydrolysis master batches and white master batches, and the mass ratio of the tackifying polyester chips to the anti-hydrolysis master batches to the white master batches is 89;
(2) Preparing raw materials of a surface layer:
the upper and lower surface layers are made of tackifying polyester chips, white master batches and uvioresistant master batches, and the mass ratio of the tackifying polyester chips to the white master batches to the uvioresistant master batches is 64;
the anti-ultraviolet master batch is prepared by mixing polyester chips, UV-327, UV-944, an antioxidant 1076 and a dispersing agent according to the mass ratio of (66);
(3) Uniformly mixing the raw materials of the core layer in the step (1), sending the mixture into a main extruder for melt extrusion at 280 ℃, uniformly mixing the raw materials of the surface layer in the step (2), sending the mixture into an auxiliary extruder for melt extrusion at 280 ℃, respectively passing the melt through a prefilter, a metering pump and a fine filter of the main extruder and the auxiliary extruder, and then sending the melt into the same distribution block, wherein the melt of the main extruder is distributed in the core layer, and the melt of the auxiliary extruder is distributed on the upper surface layer and the lower surface layer;
(4) The distributed melt enters a three-layer co-extrusion die head, the melt of a core layer is extruded from the middle layer of the three-layer co-extrusion die head, simultaneously, the melt of the upper and lower surface layers is respectively extruded from the upper and lower layers of the three-layer co-extrusion die head, and the extruded melt is cooled at 30 ℃ and then is subjected to tape casting to obtain a polyester film sheet;
(5) Preheating the polyester film sheet to 98 ℃, longitudinally stretching at 102 ℃ with the longitudinal stretching ratio of 3.1, transversely stretching at 95 ℃ with the transverse stretching ratio of 3.8, carrying out heat setting at 218 ℃, cooling to room temperature, and finally carrying out traction rolling to obtain the super-weather-resistant white polyester film.
The prepared super weather-proof white polyester film is of a three-layer composite structure and consists of a core layer, an upper surface layer and a lower surface layer; the thickness of the super weather-proof white polyester film is 38 micrometers, wherein the thickness of the upper surface is 3 micrometers, the thickness of the lower surface is 3 micrometers, and the thickness of the core layer is 32 micrometers;
the light transmittance of the super-weatherable white polyester film is 29 percent, the transmittance at the ultraviolet wavelength of 380nm is 4.0 percent, the elongation at break is 60 percent after 72 hours of PCT (high-pressure accelerated aging test, test conditions are that the saturated steam temperature is 121 ℃, and the 2 standard atmospheric pressure is adopted), and the delta b is 2.5 after 200kWh of ultraviolet radiation.
Example 5
A preparation method of an ultra-weather-resistant white polyester film comprises the following specific steps:
(1) Preparing the raw materials of the core layer:
the core layer comprises the following raw materials of a tackifying polyester chip, an anti-hydrolysis master batch and a white master batch, wherein the mass ratio of the tackifying polyester chip to the anti-hydrolysis master batch to the white master batch is 86;
(2) Preparing raw materials of a surface layer:
the upper and lower surface layer raw materials are tackifying polyester slices, white master batches and uvioresistant master batches, and the mass ratio of the tackifying polyester slices, the white master batches and the uvioresistant master batches is 67;
the ultraviolet-resistant master batch is prepared by blending polyester chips, UV-P, UV-944, an antioxidant 1010 and a dispersing agent according to the mass ratio of 66.5;
(3) Uniformly mixing the raw materials of the core layer in the step (1), feeding the mixture into a main extruder, performing melt extrusion at 290 ℃, uniformly mixing the raw materials of the surface layer in the step (2), feeding the mixture into an auxiliary extruder, performing melt extrusion at 288 ℃, feeding melt into the same distribution block after passing through a pre-filter, a metering pump and a fine filter of the main extruder and the auxiliary extruder respectively, distributing the melt of the main extruder in the core layer, and distributing the melt of the auxiliary extruder in the upper surface layer and the lower surface layer;
(4) The distributed melt enters a three-layer co-extrusion die head, the melt of a core layer is extruded from the middle layer of the three-layer co-extrusion die head, meanwhile, the melt of the upper surface layer and the melt of the lower surface layer are respectively extruded from the upper layer and the lower layer of the three-layer co-extrusion die head, and the extruded melt is cooled at 25 ℃ and then subjected to tape casting to obtain a polyester film sheet;
(5) Preheating the polyester film sheet to 96 ℃, longitudinally stretching at 100 ℃, wherein the longitudinal stretching ratio is 3, then transversely stretching at 100 ℃, the transverse stretching ratio is 3.9, cooling to room temperature after heat setting at 230 ℃, and finally drawing and rolling to obtain the super-weather-resistant white polyester film.
The prepared super weather-proof white polyester film is of a three-layer composite structure and consists of a core layer, an upper surface layer and a lower surface layer; the thickness of the super weather-proof white polyester film is 38 micrometers, wherein the thickness of the upper surface is 3.5 micrometers, the thickness of the lower surface is 3.5 micrometers, and the thickness of the core layer is 31 micrometers;
the light transmittance of the super-weatherable white polyester film is 25.1 percent, the transmittance at the ultraviolet wavelength of 380nm is 3.9 percent, the elongation at break is 55 percent after 72 hours of PCT (high-pressure accelerated aging test, the test condition is that the saturated steam temperature is 121 ℃ and the 2 standard atmospheric pressure is adopted), and the Delta b is 2.3 after 200kWh of ultraviolet radiation.
Example 6
A preparation method of an ultra-weather-resistant white polyester film comprises the following specific steps:
(1) Preparing the raw materials of the core layer:
the core layer comprises the following raw materials of a tackifying polyester chip, an anti-hydrolysis master batch and a white master batch, wherein the mass ratio of the tackifying polyester chip to the anti-hydrolysis master batch to the white master batch is 85;
(2) Preparing raw materials of a surface layer:
the upper and lower surface layers are made of tackifying polyester chips, white master batches and uvioresistant master batches, and the mass ratio of the tackifying polyester chips, the white master batches and the uvioresistant master batches is 62;
the anti-ultraviolet master batch is prepared by mixing polyester chips, UV-329, UV-944, an antioxidant 1076 and a dispersing agent according to the mass ratio of 75;
(3) Uniformly mixing the raw materials of the core layer in the step (1), sending the mixture into a main extruder for melt extrusion at 286 ℃, uniformly mixing the raw materials of the surface layer in the step (2), sending the mixture into an auxiliary extruder for melt extrusion at 285 ℃, respectively passing the melt through a pre-filter, a metering pump and a fine filter of the main extruder and the auxiliary extruder, and then sending the melt into the same distribution block, wherein the melt of the main extruder is distributed in the core layer, and the melt of the auxiliary extruder is distributed on the upper surface layer and the lower surface layer;
(4) The distributed melt enters a three-layer co-extrusion die head, the melt of a core layer is extruded from the middle layer of the three-layer co-extrusion die head, meanwhile, the melt of the upper surface layer and the melt of the lower surface layer are respectively extruded from the upper layer and the lower layer of the three-layer co-extrusion die head, and the extruded melt is cooled at 28 ℃ and then subjected to tape casting to obtain a polyester film sheet;
(5) Preheating the polyester film sheet to 95 ℃, longitudinally stretching at 99 ℃ with the longitudinal stretching ratio of 2.9, transversely stretching at 90 ℃ with the transverse stretching ratio of 3.7, carrying out heat setting at 225 ℃, cooling to room temperature, and finally carrying out traction rolling to obtain the super-weather-resistant white polyester film.
The prepared super weather-proof white polyester film is of a three-layer composite structure and consists of a core layer, an upper surface layer and a lower surface layer; the thickness of the super weather-proof white polyester film is 38 micrometers, wherein the thickness of the upper surface is 2 micrometers, the thickness of the lower surface is 2 micrometers, and the thickness of the core layer is 34 micrometers;
the light transmittance of the super-weatherable white polyester film is 26.5 percent, the transmittance at the ultraviolet wavelength of 380nm is 3.5 percent, the elongation at break is 62 percent after 72 hours of PCT (high-pressure accelerated aging test, test conditions are that the saturated steam temperature is 121 ℃ and the pressure is 2 standard atmospheres), and the Delta b is 2 after 200kWh of ultraviolet radiation.
Claims (10)
1. An ultra-weather-resistant white polyester film is characterized in that: the composite structure is a three-layer composite structure and consists of a core layer, an upper surface layer and a lower surface layer;
the core layer comprises the raw materials of a tackifying polyester slice, an anti-hydrolysis master batch and a white master batch, wherein the mass ratio of the tackifying polyester slice to the anti-hydrolysis master batch to the white master batch is 82 to 95;
the upper and lower surface layer raw materials are tackifying polyester chips, white master batches and ultraviolet-resistant master batches, and the mass ratio of the tackifying polyester chips to the white master batches to the ultraviolet-resistant master batches is 55 to 84;
the intrinsic viscosity of the tackifying polyester chip is 0.75-0.95dL/g, and the content of terminal carboxyl is 5-11mol/T;
the hydrolysis-resistant master batch is prepared by blending, extruding and granulating bottle-grade polyester chips and hydrolysis-resistant agents; the molecular structure of the hydrolysis-resistant agent contains carbodiimide groups or polycarbodiimide groups;
the white master batch is prepared by blending, extruding and granulating bottle-grade polyester chips, pigment and a dispersing agent; the pigment is nano titanium dioxide;
the uvioresistant master batch is prepared by blending, extruding and granulating polyester chips, ultraviolet light absorbers, light stabilizers, antioxidants and dispersing agents; the ultraviolet light absorber is a benzotriazole ultraviolet light absorber, the light stabilizer is a hindered amine light stabilizer, and the antioxidant is a hindered phenol antioxidant;
the light transmittance of the super-weather-resistant white polyester film is less than or equal to 30 percent, the transmittance at the ultraviolet wavelength of 380nm is less than or equal to 5 percent, the elongation at break is more than or equal to 40 percent after PCT 72 hours, and the delta b is less than or equal to 3 after ultraviolet irradiation of 200 kWh.
2. The super-weather-resistant white polyester film as claimed in claim 1, wherein the thickness of the super-weather-resistant white polyester film is 36 to 50 μm, the thickness of the upper surface and the thickness of the lower surface are respectively 3 to 10% of the thickness of the super-weather-resistant white polyester film, and the thickness of the core layer is 80 to 94% of the thickness of the super-weather-resistant white polyester film.
3. The white super weatherable polyester film as claimed in claim 1, wherein the polyester chips are prepared by heating polyester chips to a temperature above the glass transition temperature and below the melting point and performing solid phase polycondensation reaction in a vacuum or inert gas atmosphere.
4. The super-weather-resistant white polyester film as claimed in claim 1, wherein the mass ratio of the bottle-grade polyester chip in the hydrolysis-resistant master batch to the hydrolysis-resistant agent is 75 to 90;
the mass ratio of the white master batch medium bottle grade polyester chip to the pigment to the dispersant is 25 to 55;
the mass ratio of the polyester chips, the ultraviolet light absorber, the light stabilizer, the antioxidant and the dispersant in the ultraviolet resistant master batch is 55 to 90.
5. The super weatherable white polyester film according to claim 1, wherein the benzotriazole-based ultraviolet absorber is UV-327, UV-P or UV-329;
the hindered amine light stabilizer is UV-622 or UV-944;
the hindered phenol antioxidant is antioxidant 1010 or antioxidant 1076.
6. The method for preparing the super-weatherable white polyester film as claimed in any one of claims 1 to 5, wherein the method comprises the following steps: respectively and uniformly mixing the raw materials of the core layer and the raw materials of the surface layer, then carrying out melt extrusion, carrying out cast sheet casting after the melt is extruded by a three-layer co-extrusion die head, and then carrying out biaxial tension to obtain the super-weather-resistant white polyester film.
7. The method according to claim 6, characterized by the following specific steps:
(1) Uniformly mixing the raw materials of the core layer, feeding the mixture into a main extruder for melt extrusion, uniformly mixing the raw materials of the surface layer, feeding the mixture into an auxiliary extruder for melt extrusion, feeding the melt into the same distribution block after passing through respective prefilters, metering pumps and fine filters of the main extruder and the auxiliary extruder respectively, distributing the melt of the main extruder in the core layer, and distributing the melt of the auxiliary extruder in the upper surface layer and the lower surface layer;
(2) The distributed melt enters a three-layer co-extrusion die head, the melt of a core layer is extruded from the middle layer of the three-layer co-extrusion die head, meanwhile, the melt of the upper surface layer and the melt of the lower surface layer are respectively extruded from the upper layer and the lower layer of the three-layer co-extrusion die head, and after the extruded melt is cooled, tape casting is carried out to cast a sheet to obtain a polyester film sheet;
(3) Preheating the polyester film sheet to a temperature above the glass transition temperature, longitudinally stretching, transversely stretching, carrying out heat setting, cooling to room temperature, and finally drawing and rolling to obtain the super weather-resistant white polyester film.
8. The process according to claim 7, wherein the temperature of the melt extrusion in step (1) is 275 to 305 ℃.
9. The process according to claim 7, wherein the temperature for cooling in step (2) is 18 to 40 ℃.
10. The method according to claim 7, wherein the temperature of the longitudinal stretching in the step (3) is 80 to 110 ℃, the longitudinal stretching ratio is 2.8 to 4.5, the temperature of the transverse stretching is 90 to 120 ℃, the transverse stretching ratio is 3.0 to 5.0, and the heat setting temperature is 200 to 240 ℃.
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Application publication date: 20230120 |