CN103818070A - White polyester film and preparation method thereof - Google Patents
White polyester film and preparation method thereof Download PDFInfo
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- CN103818070A CN103818070A CN201310683821.5A CN201310683821A CN103818070A CN 103818070 A CN103818070 A CN 103818070A CN 201310683821 A CN201310683821 A CN 201310683821A CN 103818070 A CN103818070 A CN 103818070A
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- Prior art keywords
- white
- polyester film
- antistatic
- master batch
- white polyester
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- 229920006267 polyester film Polymers 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title abstract description 24
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 36
- 229920000728 polyester Polymers 0.000 claims abstract description 36
- 238000001125 extrusion Methods 0.000 claims abstract description 17
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 46
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 40
- 239000000463 material Substances 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 28
- 238000006068 polycondensation reaction Methods 0.000 claims description 23
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 18
- 230000032050 esterification Effects 0.000 claims description 17
- 238000005886 esterification reaction Methods 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 239000000654 additive Substances 0.000 claims description 15
- 230000000996 additive effect Effects 0.000 claims description 15
- 229910052787 antimony Inorganic materials 0.000 claims description 14
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 14
- -1 amine salt Chemical class 0.000 claims description 13
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 12
- 238000005266 casting Methods 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 12
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 10
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 10
- 150000001298 alcohols Chemical class 0.000 claims description 10
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 10
- 238000005096 rolling process Methods 0.000 claims description 9
- 239000004408 titanium dioxide Substances 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 238000005520 cutting process Methods 0.000 claims description 8
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000005453 pelletization Methods 0.000 claims description 8
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 8
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 5
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 5
- 239000011787 zinc oxide Substances 0.000 claims description 5
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 4
- MMEDJBFVJUFIDD-UHFFFAOYSA-N 2-[2-(carboxymethyl)phenyl]acetic acid Chemical compound OC(=O)CC1=CC=CC=C1CC(O)=O MMEDJBFVJUFIDD-UHFFFAOYSA-N 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- XVZBIIBOLKHMNP-UHFFFAOYSA-N OC(=O)C(O)=O.c1ccc2ccccc2c1 Chemical compound OC(=O)C(O)=O.c1ccc2ccccc2c1 XVZBIIBOLKHMNP-UHFFFAOYSA-N 0.000 claims description 4
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical class CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 claims description 3
- 235000011037 adipic acid Nutrition 0.000 claims description 3
- 239000001361 adipic acid Substances 0.000 claims description 3
- 150000007942 carboxylates Chemical class 0.000 claims description 3
- 150000002290 germanium Chemical class 0.000 claims description 3
- 238000005469 granulation Methods 0.000 claims description 3
- 230000003179 granulation Effects 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 3
- 150000005846 sugar alcohols Polymers 0.000 claims description 3
- 150000003871 sulfonates Chemical class 0.000 claims description 3
- 150000003608 titanium Chemical class 0.000 claims description 3
- 238000009998 heat setting Methods 0.000 claims description 2
- 238000004513 sizing Methods 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 abstract description 4
- 230000002045 lasting effect Effects 0.000 abstract description 3
- 239000012792 core layer Substances 0.000 abstract 3
- 239000002344 surface layer Substances 0.000 abstract 3
- 239000010410 layer Substances 0.000 abstract 2
- 239000004973 liquid crystal related substance Substances 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 16
- 229920000139 polyethylene terephthalate Polymers 0.000 description 10
- 239000005020 polyethylene terephthalate Substances 0.000 description 10
- 230000032683 aging Effects 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 230000003287 optical effect Effects 0.000 description 6
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 238000007766 curtain coating Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 229920006254 polymer film Polymers 0.000 description 5
- 238000004781 supercooling Methods 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- 230000009193 crawling Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 1
- 229920001634 Copolyester Polymers 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920005644 polyethylene terephthalate glycol copolymer Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
Landscapes
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
- Laminated Bodies (AREA)
Abstract
The invention relates to a white polyester film and a preparation method thereof. The white polyester film comprises a core layer and at least one surface layer, wherein the core layer and the surface layers are obtained by a coextrusion die head extrusion and two-way stretch technology; the core layer is a white polyester layer; each surface layer comprises 70-99.9wt% of pure polyester, 0-30wt% of white master batch and 0.1-10wt% of antistatic master batch. The white polyester film has a lasting antistatic property. The preparation method is simple in technology; an antistatic layer of an obtained product does not fall off; the surface of a film still has the good antistatic property under the conditions of high temperature and humidity; the product is applicable to industries of liquid crystal display, printing and the like.
Description
Technical field
The present invention relates to a kind of white polyester film, particularly there is white polyester film of antistatic property and preparation method thereof.
Background technology
Polyester film (PET film) is the more comprehensive film of a kind of Performance Ratio, the advantage such as compared with other thermoplastic plastics, it has, and light transmittance is good, glossy, mechanical performance is excellent, obdurability and impact strength, and dimensionally stable.White polyester film is because high brightness, reflection characteristic and excellent disguise show and there is unique application the aspect such as printing at advertisement tag, image, particularly in FPD industry, as the reflectance coating of backlight module and indispensable.
In the production process of white polyester film, because making film, the reasons such as friction produce static, while being applied to backlight module with the film of static easily because static discharge makes backlight module impaired, integrated circuit, light emitting diode or the CCFL of infringement backlight module, therefore, in order to prevent the generation of these problems, for white polyester film, require it to there is anlistatig performance.
Conventionally, for giving white polyester film antistatic property, the method conventionally adopting is at white polyester film surface-coated antistatic layer, but the method for this coating exists following shortcoming: (1) technique is comparatively complicated, increases production cost; (2), because antistatic layer sticks to reflectance coating surface by adhesive, in some specific environment (as extreme conditions such as hot and humid, low temperature and low humidities), antistatic layer easily comes off, and does not have anlistatig effect; (3) in coating process process, can make film apparently occur that crawling is even, produce bar road, the disadvantage such as grow dim.
Summary of the invention
The technical problem to be solved in the present invention is for the deficiencies in the prior art, and a kind of white polyester film is provided, and it has lasting antistatic property.
Another technical problem that the present invention will solve is to provide a kind of preparation method of white polyester film.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows:
A kind of white polyester film, comprise sandwich layer and one deck top layer at least, it is characterized in that, described sandwich layer and top layer are extruded with stretch processes and are obtained through mutual aid die head, sandwich layer is white polyester layer, pure polyester, the white master material of 0wt% ~ 30wt% and the antistatic master batch of 0.1wt% ~ 10wt% that 70wt% ~ 99.9wt% is contained on top layer.
Above-mentioned white polyester film, the pure polyester that described sandwich layer contains 20wt% ~ 75wt% and the white master material of 25wt% ~ 80wt%.
Above-mentioned white polyester film, described white master material is made up of pure polyester, the titanium dioxide of 15 wt % ~ 60 wt % and calcium carbonate, barium sulfate, zinc oxide or the zirconia of 0 wt % ~ 10 wt % of 30wt% ~ 70 wt %, is obtained by double-screw extruding pelletizing.
Above-mentioned white polyester film, described antistatic master batch is prepared by following method:
(1) esterification process:
In consersion unit, add binary acid, dihydroxylic alcohols and catalyst, pass into nitrogen protection, esterification 3 ~ 4 hours under the condition of 220 ℃ ~ 270 ℃;
(2) polycondensation process:
After esterification, in esterification system, add antistatic additive, after consersion unit vacuumizes, under the condition of 265 ℃ ~ 290 ℃, carry out polycondensation reaction 3-5 hour, obtain polycondensation products;
(3) granulation process:
Polycondensation product, through making silk, cooling, cutting, makes biaxially oriented polyester film antistatic master batch.
Above-mentioned white polyester film, described binary acid is selected from terephthalic acid (TPA), to phenylenediacetic Acid, naphthalenedicarboxylic acid, to naphthalene oxalic acid, adipic acid, SA, M-phthalic acid, phthalic acid.
Above-mentioned white polyester film, described dihydroxylic alcohols is that carbon number is 2 ~ 4 aliphatic diol.
Above-mentioned white polyester film, described dihydroxylic alcohols is selected from ethylene glycol, propane diols, butanediol, 1,3-PD, BDO, cyclohexanedimethanol.
Above-mentioned white polyester film, described catalyst is selected from one or both in antimony-based catalyst, germanium series catalysts and Titanium series catalyst.
Above-mentioned white polyester film, described catalyst is antimony glycol, wherein, the content of antimony in antistatic master batch is 0.001wt% ~ 0.05wt%.
Above-mentioned white polyester film, described antistatic additive is selected from one or both of amine salt class, quaternary ammonium salt, metal carboxylate, Sulfonates, phosphate type, polyalcohol type;
The addition of described antistatic additive is the 1wt% ~ 20wt% of antistatic master batch gross weight.
Above-mentioned white polyester film, the inherent viscosity of described antistatic master batch is 0.50dL/g ~ 0.80dL/g.
A preparation method for white polyester film, it comprises the steps:
(1) melt extrude: pure polyester and white master material are mixed in proportion and send into melting in single screw extrusion machine, antistatic master batch, white master material, pure polyester are mixed in proportion and send into melting in double screw extruder, and melt is extruded by co-extrusion die head;
(2) cooling slab: melt forms unformed polyester casting sheet on the chill roll rotating;
(3) biaxial tension: by after sheet preheating, 3.0 ~ 4.4 times of longitudinal stretchings, then carry out 2.5 ~ 4.5 times of cross directional stretch;
(4) sizing rolling: the film after biaxial tension is carried out to thermal finalization, more cooling rolling, obtain white anti-static polyester film.
Above-mentioned preparation method, described melt temperature is 260 ℃ ~ 300 ℃; Described heat setting temperature is 200 ℃ ~ 240 ℃.
Compared with prior art, tool of the present invention has the following advantages:
The present invention extrudes and stretch processes by the co-extrusion die head that adopts sandwich layer and top layer, and by controlling the content of each component in top layer, make antistatic additive being evenly distributed in film, antistatic property is lasting, solved simultaneously coating process even to the apparent crawling causing of film, produce bar road, the quality drawback such as grow dim, improve the quality of product.Preparation method's technique provided by the invention is simple, and the antistatic layer of the product obtaining does not come off, and under hot and humid condition, film surface still has good antistatic property.
The specific embodiment
In the present invention, the pure polyester on described sandwich layer, top layer is the polymer that binary acid and dihydroxylic alcohols obtain by polycondensation, wherein binary acid comprise terephthalic acid (TPA), to phenylenediacetic Acid, to naphthalene oxalic acid, M-phthalic acid, phthalic acid etc., preferably terephthalic acid (TPA), also can add a small amount of M-phthalic acid class modified copolyester; Dihydroxylic alcohols is that carbon number is 2 ~ 4 aliphatic diol, comprises ethylene glycol, propane diols, butanediol, 1,3-PD etc., preferably ethylene glycol.Being applicable to pure polyester of the present invention is PETG, and its inherent viscosity is 0.55dL/g ~ 0.95dL/g, preferably 0.60dL/g ~ 0.75dL/g.
In the present invention, in described sandwich layer, top layer, white master material is made up of pure polyester and inorganic particulate, make by double-screw extruding pelletizing, wherein inorganic particulate can be selected from one or more in titanium dioxide, barium sulfate, zinc oxide, zirconia, aluminium oxide, calcium carbonate, consider the requirements such as whiteness, photostability and the reflectivity of polyester film, preferable particle size is the titanium dioxide of 0.1 ~ 10 μ m, can mix a little calcium carbonate, barium sulfate, zinc oxide or zirconia.
In the present invention, the antistatic master batch in top layer is prepared by following method:
(1) esterification process:
In consersion unit, add binary acid, dihydroxylic alcohols and catalyst, pass into nitrogen protection, esterification 3 ~ 4 hours under the condition of 220 ℃ ~ 270 ℃; Wherein, what binary acid can be with pure polyester is identical, can be selected from terephthalic acid (TPA), to phenylenediacetic Acid, naphthalenedicarboxylic acid, to naphthalene oxalic acid, adipic acid, SA, M-phthalic acid, phthalic acid; Dihydroxylic alcohols is that carbon number is 2 ~ 4 aliphatic diol, and what it can be with pure polyester is identical, as ethylene glycol, propane diols, butanediol, 1,3-PD, BDO, cyclohexanedimethanol; Catalyst can be selected from one or both in antimony-based catalyst, germanium series catalysts and Titanium series catalyst, and when preferred catalyst is antimony glycol, the content of antimony in antistatic master batch is 0.001wt% ~ 0.05wt%.
(2) polycondensation process:
After esterification, in esterification system, add antistatic additive, after consersion unit vacuumizes, under the condition of 265 ℃ ~ 290 ℃, carry out polycondensation reaction 3-5 hour, obtain polycondensation products; Antistatic additive can be selected from one or both of amine salt class, quaternary ammonium salt, metal carboxylate, Sulfonates, phosphate type, polyalcohol type, and the addition of antistatic additive is the 1wt% ~ 20wt% of antistatic master batch gross weight.
(3) granulation process:
Polycondensation product, through making silk, cooling, cutting, makes biaxially oriented polyester film antistatic master batch.The inherent viscosity of described antistatic master batch is 0.50dL/g ~ 0.80dL/g.
Below in conjunction with specific embodiment, the present invention is specifically described, but the present invention is not limited thereto.
Embodiment 1
1. the preparation of antistatic master batch
In reactor, add 15kg terephthalic acid (TPA), 7.85kg ethylene glycol and 0.21g antimony glycol, nitrogen protection, under 265 ℃ of conditions, carry out esterification after 3 hours, in reactor, add 1.2kg hexadecyltrimethylammonium chloride, reactor is vacuumized, and to keep temperature in the kettle be to carry out polycondensation reaction 3h under the condition of 280 ℃; Stop polycondensation reaction, through making silk, cooling, cutting, obtaining inherent viscosity is the antistatic master batch that 0.55dL/g, weight are 18.54kg, and wherein the content of antistatic additive is 6.9wt%, for subsequent use.
2. the preparation of white master material
By the pure polyester drying and crushing of 30g, then mix with the calcium carbonate of the zirconia 5g of the titanium dioxide of 60g, 5g, through double screw extruder extruding pelletization, make white master material, for subsequent use.
3. the preparation of white polyester film
The polyethylene terephthalate polyester that is 0.65dL/g by inherent viscosity section and above-mentioned white master material, mix according to the weight ratio of 75%:25%, sends into single screw extrusion machine, under 270 ℃ of conditions, melt extrudes.
The polyethylene terephthalate polyester that is 0.60dL/g by inherent viscosity section, above-mentioned white master material and antistatic master batch, mix according to the weight ratio of 83%:10%:7%, sends into double screw extruder, under 275 ℃ of conditions, melt extrudes.
Above-mentioned two kinds of fused materials, by a co-extrusion die head, to the chill roll of a rotation, are become to the casting sheet of unformed A/B/A three-decker by melt curtain coating.
By after this casting sheet preheating, carry out longitudinal stretching multiple with 4.0 multiplying power successively and carry out longitudinal stretching, multiplying power with 3.0 is carried out cross directional stretch, by polymer film thermal finalization under the temperature conditions of approximately 220 ℃ of biaxial tension orientation, finally through the process such as supercooling, rolling, obtain white polyester film, test optical property, the antistatic property of its hydrothermal aging front and back.
Embodiment 2
1. the preparation of antistatic master batch
In reactor, add 10kg terephthalic acid (TPA), 5.21kg ethylene glycol and 3.83g antimony glycol, nitrogen protection, under 250 ℃ of conditions, carry out esterification after 3.5 hours, to the hexadecyltrimethylammonium chloride that adds 1.12kg in reactor, reactor is vacuumized, and to keep temperature in the kettle be to carry out polycondensation reaction 3.5h under the condition of 285 ℃; Stop polycondensation reaction, through making silk, cooling, cutting, making inherent viscosity is 0.60dL/g, the antistatic master batch that weight is 12.68kg, and wherein the content of antistatic additive is 9.7wt%, for subsequent use.
2. the preparation of white master material
By the pure polyester drying and crushing of 78g, then mix with the titanium dioxide of 15g and the zinc oxide of 7g, through double screw extruder extruding pelletization, make white master material, for subsequent use.
3. the preparation of white polyester film
The polyethylene terephthalate polyester that is 0.80dL/g by inherent viscosity section and above-mentioned white master material, mix and send into single screw extrusion machine according to the weight ratio of 20%:70%, under 275 ℃ of conditions, melt extrudes.
The polyethylene terephthalate polyester that is 0.55dL/g by inherent viscosity section, above-mentioned white master material and antistatic master batch, mix according to the weight ratio of 70%:28%:2%, sends into double screw extruder, under 285 ℃ of conditions, melt extrudes.
Above-mentioned two kinds of fused materials, by a co-extrusion die head, to the chill roll of a rotation, are become to the casting sheet of unformed A/B/A three-decker by melt curtain coating.
By after this casting sheet preheating, carry out longitudinal stretching multiple with 3.0 multiplying power successively and carry out longitudinal stretching, multiplying power with 4.5 is carried out cross directional stretch, by polymer film thermal finalization under the temperature conditions of approximately 225 ℃ of biaxial tension orientation, finally through the process such as supercooling, rolling, obtain white polyester film, test optical property, the antistatic property of its hydrothermal aging front and back.
Embodiment 3
1. the preparation of antistatic master batch
In reactor, add 8kg terephthalic acid (TPA), 4.17kg ethylene glycol and 3.22g antimony glycol, nitrogen protection, under 266 ℃ of conditions, carry out esterification after 3 hours, to the hexadecyltrimethylammonium chloride that adds 1.80kg in reactor, reactor is vacuumized, and to keep temperature in the kettle be to carry out polycondensation reaction 3.5h under the condition of 283 ℃; Stop polycondensation reaction, through making silk, cooling, cutting, making inherent viscosity is 0.66dL/g, the antistatic master batch that weight is 11.05kg, and wherein the content of antistatic additive is 19.5wt%, for subsequent use.
2. the preparation of white master material
By the pure polyester drying and crushing of 60g, then mix with the titanium dioxide of 40g, through double screw extruder extruding pelletization, make white master material, for subsequent use.
3. the preparation of white polyester film
The polyethylene terephthalate polyester that is 0.55dL/g by inherent viscosity section and above-mentioned white master material, mix and send into single screw extrusion machine according to the weight ratio of 60%:40%, under 285 ℃ of conditions, melt extrudes.
The polyethylene terephthalate polyester that is 0.80dL/g by inherent viscosity section, above-mentioned white master material and antistatic master batch, mix according to the weight ratio of 99.9%:0.1%, sends into double screw extruder, under 290 ℃ of conditions, melt extrudes.
Above-mentioned two kinds of fused materials, by a co-extrusion die head, to the chill roll of a rotation, are become to the casting sheet of unformed A/B/A three-decker by melt curtain coating.
By after this casting sheet preheating, carry out longitudinal stretching multiple with 3.3 multiplying power successively and carry out longitudinal stretching, multiplying power with 3.5 is carried out cross directional stretch, by polymer film thermal finalization under the temperature conditions of approximately 230 ℃ of biaxial tension orientation, finally through the process such as supercooling, rolling, obtain white polyester film, test optical property, the antistatic property of its hydrothermal aging front and back.
Embodiment 4
1. the preparation of antistatic master batch
In reactor, add 5kg terephthalic acid (TPA), 2.60kg ethylene glycol and 2.88g antimony glycol, nitrogen protection, under 255 ℃ of conditions, carry out esterification after 4 hours, to the hexadecyltrimethylammonium chloride that adds 0.86kg in reactor, reactor is vacuumized, and to keep temperature in the kettle be to carry out polycondensation reaction 4h under the condition of 288 ℃; Stop polycondensation reaction, through making silk, cooling, cutting, making inherent viscosity is 0.70dL/g, the antistatic master batch that weight is 6.64kg, and wherein the content of antistatic additive is 14.9wt%, for subsequent use.
2. the preparation of white master material
By the pure polyester drying and crushing of 45g, then mix with the titanium dioxide of 50g and the barium sulfate of 5g, through double screw extruder extruding pelletization, make white master material, for subsequent use.
3. the preparation of white polyester film
The polyethylene terephthalate polyester that is 0.65dL/g by inherent viscosity section and above-mentioned white master material, mix and send into single screw extrusion machine according to the weight ratio of 75%:35%, under 280 ℃ of conditions, melt extrudes.
The polyethylene terephthalate polyester that is 0.65dL/g by inherent viscosity section, above-mentioned white master material and antistatic master batch, mix according to the weight ratio of 80%:17%:3%, sends into double screw extruder, under 290 ℃ of conditions, melt extrudes.
Above-mentioned two kinds of fused materials, by a co-extrusion die head, to the chill roll of a rotation, are become to the casting sheet of unformed A/B/A three-decker by melt curtain coating.
By after this casting sheet preheating, carry out longitudinal stretching multiple with 3.1 multiplying power successively and carry out longitudinal stretching, multiplying power with 3.0 is carried out cross directional stretch, by polymer film thermal finalization under the temperature conditions of approximately 235 ℃ of biaxial tension orientation, finally through the process such as supercooling, rolling, obtain white polyester film, test optical property, the antistatic property of its hydrothermal aging front and back.
Embodiment 5
1. the preparation of antistatic master batch
In reactor, add 20kg terephthalic acid (TPA), 10.42kg ethylene glycol and 7.26g antimony glycol, nitrogen protection, under 270 ℃ of conditions, carry out esterification after 3 hours, to the hexadecyltrimethylammonium chloride that adds 0.24kg in reactor, reactor is vacuumized, and to keep temperature in the kettle be to carry out polycondensation reaction 4.5h under the condition of 278 ℃; Stop polycondensation reaction, through making silk, cooling, cutting, making inherent viscosity is 0.75dL/g, the antistatic master batch that weight is 23.36kg, and wherein the content of antistatic additive is 1wt%.
2. the preparation of white master material
By the pure polyester drying and crushing of 40g, then mix with the titanium dioxide of 30g and the zirconia of 6g, through double screw extruder extruding pelletization, make white master material, for subsequent use.
3. the preparation of white polyester film
The polyethylene terephthalate polyester that is 0.67dL/g by inherent viscosity section and above-mentioned white master material, mix and send into single screw extrusion machine according to the weight ratio of 50%:50%, under 265 ℃ of conditions, melt extrudes.
The polyethylene terephthalate polyester that is 0.67dL/g by inherent viscosity section, above-mentioned white master material and antistatic master batch, mix according to the weight ratio of 60%:30%:10%, sends into double screw extruder, under 280 ℃ of conditions, melt extrudes.
Above-mentioned two kinds of fused materials, by a co-extrusion die head, to the chill roll of a rotation, are become to the casting sheet of unformed A/B/A three-decker by melt curtain coating.
By after this casting sheet preheating, carry out longitudinal stretching multiple with 3.5 multiplying power successively and carry out longitudinal stretching, multiplying power with 3.8 is carried out cross directional stretch, by polymer film thermal finalization under the temperature conditions of approximately 225 ℃ of biaxial tension orientation, finally through the process such as supercooling, rolling, obtain white polyester film, test optical property, the antistatic property of its hydrothermal aging front and back.
Table one: optical property and antistatic property contrast before and after hydrothermal aging
In table, the method for testing of properties is as follows:
1, light transmittance, mist degree: test according to ASTM D1003;
2, surface resistivity: according to ASTM D257 standard testing;
3, hydrothermal aging performance: with reference to ASTM D257 standard, wherein print is 65 ℃ of temperature, constant temperature and humidity 500h under humidity 90% condition.
Data from table 1 can find out, the white polyester film surface resistivity that adopts technical solution of the present invention to obtain is less than 1E+10 Ω; After hydrothermal aging, its antistatic property is still better.
Claims (10)
1. a white polyester film, comprise sandwich layer and one deck top layer at least, it is characterized in that, described sandwich layer and top layer are extruded with stretch processes and are obtained through co-extrusion die head, sandwich layer is white polyester layer, pure polyester, the white master material of 0wt% ~ 30wt% and the antistatic master batch of 0.1wt% ~ 10wt% that 70wt% ~ 99.9wt% is contained on top layer.
2. white polyester film according to claim 1, is characterized in that, the pure polyester that described sandwich layer contains 20wt% ~ 75wt% and the white master material of 25wt% ~ 80wt%.
3. white polyester film according to claim 2, it is characterized in that, described white master material is made up of pure polyester, the titanium dioxide of 15wt % ~ 60wt % and calcium carbonate, barium sulfate, zinc oxide or the zirconia of 0wt % ~ 10wt % of 30wt% ~ 85wt %, is obtained by double-screw extruding pelletizing.
4. white polyester film according to claim 3, is characterized in that, described antistatic master batch is prepared by following method:
(1) esterification process:
In consersion unit, add binary acid, dihydroxylic alcohols and catalyst, pass into nitrogen protection, esterification 3 ~ 4 hours under the condition of 220 ℃ ~ 270 ℃;
(2) polycondensation process:
After esterification, in esterification system, add antistatic additive, after consersion unit vacuumizes, under the condition of 265 ℃ ~ 290 ℃, carry out polycondensation reaction 3-5 hour, obtain polycondensation products;
(3) granulation process:
Polycondensation product, through making silk, cooling, cutting, makes biaxially oriented polyester film antistatic master batch.
5. white polyester film according to claim 4, is characterized in that, described binary acid is selected from terephthalic acid (TPA), to phenylenediacetic Acid, naphthalenedicarboxylic acid, to naphthalene oxalic acid, adipic acid, SA, M-phthalic acid, phthalic acid;
Described dihydroxylic alcohols is that carbon number is 2 ~ 4 aliphatic diol;
Described dihydroxylic alcohols is selected from ethylene glycol, propane diols, butanediol, 1,3-PD, BDO, cyclohexanedimethanol.
6. white polyester film according to claim 5, is characterized in that, described catalyst is selected from one or both in antimony-based catalyst, germanium series catalysts and Titanium series catalyst;
Described catalyst is antimony glycol, and wherein, the content of antimony in antistatic master batch is 0.001wt% ~ 0.05wt%.
7. white polyester film according to claim 6, is characterized in that, described antistatic additive is selected from one or both of amine salt class, quaternary ammonium salt, metal carboxylate, Sulfonates, phosphate type, polyalcohol type;
The addition of described antistatic additive is the 1wt% ~ 20wt% of antistatic master batch gross weight.
8. white polyester film according to claim 7, is characterized in that, the inherent viscosity of described antistatic master batch is 0.50dL/g ~ 0.80dL/g.
9. a method of preparing white polyester film as described in claim 1～8, is characterized in that, it comprises the steps:
(1) melt extrude: pure polyester and white master material are mixed in proportion and send into melting in single screw extrusion machine, antistatic master batch, white master material, pure polyester are mixed in proportion and send into melting in double screw extruder, and melt is extruded by co-extrusion die head;
(2) cooling slab: melt forms unformed polyester casting sheet on the chill roll rotating;
(3) biaxial tension: by after sheet preheating, 3.0 ~ 4.4 times of longitudinal stretchings, then carry out 2.5 ~ 4.5 times of cross directional stretch;
(4) sizing rolling: the film after biaxial tension is carried out to thermal finalization, more cooling rolling, obtain white anti-static polyester film.
10. method according to claim 9, is characterized in that, described melt temperature is 260 ℃ ~ 300 ℃;
Described heat setting temperature is 200 ℃ ~ 240 ℃.
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| CN111703167A (en) * | 2020-06-28 | 2020-09-25 | 广东裕泰实业有限公司 | High-antistatic modified polymer insulating material and preparation method thereof |
| CN117004064A (en) * | 2023-08-14 | 2023-11-07 | 广东宝佳利新材料股份有限公司 | Special polyester film for shallow screen printing and preparation process thereof |
| CN117004064B (en) * | 2023-08-14 | 2024-02-20 | 广东宝佳利新材料股份有限公司 | Special polyester film for shallow screen printing and preparation process thereof |
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