CN103694459A - Preparation method of antistatic masterbatches for biaxially oriented polyester film - Google Patents
Preparation method of antistatic masterbatches for biaxially oriented polyester film Download PDFInfo
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- CN103694459A CN103694459A CN201310683844.6A CN201310683844A CN103694459A CN 103694459 A CN103694459 A CN 103694459A CN 201310683844 A CN201310683844 A CN 201310683844A CN 103694459 A CN103694459 A CN 103694459A
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Abstract
A preparation method of antistatic masterbatches for a biaxially oriented polyester film comprises the following steps: (1) esterification process: adding binary acid, diol and a catalyst into a reaction device, introducing nitrogen for protection, and performing esterification reaction at 220-270 DEG C for 3-4 hours; (2) polycondensation process: after esterification reaction, adding an antistatic agent into the esterification reaction system, vacuumizing the reaction device, and performing polycondensation reaction at 265-290 DEG C for 3-5 hours, so as to form polycondensate; (3) granulation process: processing the polycondensate by silk forming, cooling and cutting, so as to form the antistatic masterbatches for the biaxially oriented polyester film. The antistatic agent is directly added into the synthesis process, the disperse uniformity of the antistatic agent in the masterbatches is improved and the optical performance of the thin film product is not affected; the final viscosity of the synthesized masterbatches is relatively conveniently controlled and the masterbatches are conveniently granulated; the secondary fusion of the resin is not needed; moreover, the process is simple and energy-saving, and the production cost is low.
Description
Technical field
The present invention relates to a kind of antistatic master batch, particularly the preparation method of antistatic master batch for a kind of biaxially oriented polyester film.
Background technology
The performances such as the physical strength of biaxially oriented polyester film (BOPET), dimensional stability, flatness, thermotolerance, optical characteristics are all comparatively excellent, so, be used as base material use take in the plate-making various uses that is representative with film, film for packaging, optical film.But because polyester insulated property is good, volume resistance is high, in production, carrying and the course of processing, be easy to produce and accumulate static, the following process that affects polyester film is used.
For eliminating the static of polyester film, the scheme conventionally adopting is to add static inhibitor in the course of processing of polyester film, by reducing the surface resistivity of polyester film, and then reduces the accumulation of static, eliminates and produces electrostatic interaction.
For static inhibitor can be dispersed in thin film layer in BOPET film production process, static inhibitor generally adds with the form of masterbatch.At present, the preparation of antistatic master batch adopts twin screw to melt extrude the method preparation of granulation conventionally, there is following shortcoming in this preparation method: (1) static inhibitor can only be dispersed in vector resin surface, because the viscosity of vector resin is higher, after vector resin melting, the dispersion of static inhibitor in vector resin there will be non-uniform phenomenon, causes the streaking of antistatic master batch even, and then affects the homogeneity of film antistatic property; (2) need to, to vector resin melting again, cause the viscosity degradation of vector resin, thereby cannot prepare the antistatic master batch higher than the viscosity of vector resin own, thereby can not meet Production requirement; (3) lack of homogeneity of the dispersion of static inhibitor in vector resin, affects the optical properties such as transmittance of film.
Summary of the invention
Technical problem to be solved by this invention is for the deficiencies in the prior art, and the preparation method of a kind of biaxially oriented polyester film with antistatic master batch is provided.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows:
A preparation method for antistatic master batch for biaxially oriented polyester film, it comprises following operation:
(1) esterification process:
In conversion unit, add diprotic acid, dibasic alcohol and catalyzer, pass into nitrogen protection, under the condition of 220 ℃ ~ 270 ℃, esterification is 3 ~ 4 hours;
(2) polycondensation process:
After esterification, in esterification system, add static inhibitor, after conversion unit vacuumizes, under the condition of 265 ℃ ~ 290 ℃, carry out polycondensation 3-5 hour, obtain polycondensation products;
(3) granulation process:
Polycondensation product, through making silk, cooling, cutting, makes biaxially oriented polyester film antistatic master batch.
In above-mentioned preparation method, described diprotic acid comprises terephthalic acid, to phenylene-diacetic acid, naphthalic acid, to naphthalene oxalic acid, hexanodioic acid, SA, m-phthalic acid, phthalic acid etc., preferred terephthalic acid.
In above-mentioned preparation method, described dibasic alcohol is that carbonatoms is 2 ~ 4 aliphatic diol, comprises ethylene glycol, propylene glycol, butyleneglycol, 1,3-PD, BDO, cyclohexanedimethanol etc., preferably ethylene glycol.During preferably synthetic polyethylene terephthalate masterbatch, the weight ratio of terephthalic acid and ethylene glycol is 1.92:1.
In above-mentioned preparation method, described catalyzer can be selected from one or both in antimony-based catalyst, germanium series catalysts, Titanium series catalyst, preferred antimony glycol, and the content of antimony in antistatic master batch is 0.001wt% ~ 0.05wt%.
In above-mentioned preparation method, described static inhibitor is ionic anti-static agent, non-ionic antistatic agent, zwitter-ion static inhibitor, can be selected from one or both of amine salt class, quaternary ammonium salt, metal carboxylate, Sulfonates, phosphate type, polyvalent alcohol type, preferably Sulfonates.
In above-mentioned preparation method, the addition of described static inhibitor is the 1wt% ~ 20wt% of antistatic master batch gross weight.
In above-mentioned preparation method, the limiting viscosity of the antistatic master batch making can be controlled within the scope of 0.50dL/g ~ 0.80dL/g.
Compared with prior art, the present invention, by directly add static inhibitor in the building-up process of masterbatch, has improved the dispersing uniformity of static inhibitor in masterbatch on the one hand, does not affect the optical property of following film product; Can control comparatively expediently on the other hand the final viscosity of synthetic masterbatch, be convenient to the granulation of masterbatch; The third aspect is not need resin to carry out second melting, and technique is simple, energy-conservation, production cost is low.
Embodiment
Below in conjunction with specific embodiment, the present invention is specifically described, but the present invention is not limited thereto.
Embodiment 1
In reactor, add 15kg terephthalic acid, 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 palmityl trimethyl ammonium chloride, reactor is vacuumized, and to keep temperature in the kettle be to carry out polycondensation 3h under the condition of 280 ℃; Stop polycondensation, through making silk, cooling, cutting, obtaining limiting viscosity is the antistatic master batch that 0.55dL/g, weight are 18.54kg, and wherein the content of static inhibitor is 6.9wt%.
Embodiment 2
In reactor, add 10kg terephthalic acid, 5.21kg ethylene glycol and 3.83g antimony glycol, nitrogen protection, under 250 ℃ of conditions, carry out esterification after 3.5 hours, to the palmityl trimethyl ammonium chloride that adds 1.12kg in reactor, reactor is vacuumized, and to keep temperature in the kettle be to carry out polycondensation 3.5h under the condition of 285 ℃; Stop polycondensation, through making silk, cooling, cutting, making limiting viscosity is 0.60dL/g, the antistatic master batch that weight is 12.68kg, and wherein the content of static inhibitor is 9.7wt%.
Embodiment 3
In reactor, add 8kg terephthalic acid, 4.17kg ethylene glycol and 3.22g antimony glycol, nitrogen protection, under 266 ℃ of conditions, carry out esterification after 3 hours, to the palmityl trimethyl ammonium chloride that adds 1.80kg in reactor, reactor is vacuumized, and to keep temperature in the kettle be to carry out polycondensation 3.5h under the condition of 283 ℃; Stop polycondensation, through making silk, cooling, cutting, making limiting viscosity is 0.66dL/g, the antistatic master batch that weight is 11.05kg, and wherein the content of static inhibitor is 19.5wt%.
Embodiment 4
In reactor, add 5kg terephthalic acid, 2.60kg ethylene glycol and 2.88g antimony glycol, nitrogen protection, under 255 ℃ of conditions, carry out esterification after 4 hours, to the palmityl trimethyl ammonium chloride that adds 0.86kg in reactor, reactor is vacuumized, and to keep temperature in the kettle be to carry out polycondensation 4h under the condition of 288 ℃; Stop polycondensation, through making silk, cooling, cutting, making limiting viscosity is 0.70dL/g, the antistatic master batch that weight is 6.64kg, and wherein the content of static inhibitor is 14.9wt%.
Embodiment 5
In reactor, add 20kg terephthalic acid, 10.42kg ethylene glycol and 7.26g antimony glycol, nitrogen protection, under 270 ℃ of conditions, carry out esterification after 3 hours, to the palmityl trimethyl ammonium chloride that adds 0.24kg in reactor, reactor is vacuumized, and to keep temperature in the kettle be to carry out polycondensation 4.5h under the condition of 278 ℃; Stop polycondensation, through making silk, cooling, cutting, making limiting viscosity is 0.75dL/g, the antistatic master batch that weight is 23.36kg, and wherein the content of static inhibitor is 1wt%.
In order to check the antistatic property of the masterbatch that the dispersing uniformity of static inhibitor in masterbatch and the inventive method obtain, the masterbatch that the present invention is obtained mixes with PET polyester slice, then through melting, slab, two-way stretch, obtain polyester film, the antistatic property of testing film.
Table 1: film antistatic property contrast before and after hydrothermal aging
In table, the testing method of properties is as follows:
1, surface resistivity: according to ASTM D257 standard testing.
2, hydrothermal aging performance: with reference to ASTM D257 standard, wherein print respectively hot and humid (85 ℃, 90%RH) and normal temperature low humidity (25 ℃, 35%RH) fixed temperature and humidity 500h under condition.
Claims (8)
1. a preparation method for antistatic master batch for biaxially oriented polyester film, is characterized in that, it comprises following operation:
(1) esterification process:
In conversion unit, add diprotic acid, dibasic alcohol and catalyzer, pass into nitrogen protection, under the condition of 220 ℃ ~ 270 ℃, esterification is 3 ~ 4 hours;
(2) polycondensation process:
After esterification, in esterification system, add static inhibitor, after conversion unit vacuumizes, under the condition of 265 ℃ ~ 290 ℃, carry out polycondensation 3-5 hour, obtain polycondensation products;
(3) granulation process:
Polycondensation product, through making silk, cooling, cutting, makes biaxially oriented polyester film antistatic master batch.
2. preparation method according to claim 1, is characterized in that, described diprotic acid is selected from terephthalic acid, to phenylene-diacetic acid, naphthalic acid, to naphthalene oxalic acid, hexanodioic acid, SA, m-phthalic acid, phthalic acid.
3. preparation method according to claim 2, is characterized in that, described dibasic alcohol is that carbonatoms is 2 ~ 4 aliphatic diol.
4. preparation method according to claim 3, is characterized in that, described dibasic alcohol is selected from ethylene glycol, propylene glycol, butyleneglycol, 1,3-PD, BDO, cyclohexanedimethanol.
5. preparation method according to claim 1, is characterized in that, described catalyzer is selected from antimony-based catalyst, germanium series catalysts and Titanium series catalyst.
6. preparation method according to claim 5, is characterized in that, described catalyzer is antimony glycol, and wherein, the content of antimony in antistatic master batch is 0.001wt% ~ 0.05wt%.
7. preparation method according to claim 6, is characterized in that, described static inhibitor is selected from one or both of amine salt class, quaternary ammonium salt, metal carboxylate, Sulfonates, phosphate type, polyvalent alcohol type.
8. preparation method according to claim 7, is characterized in that, the addition of described static inhibitor is the 1wt% ~ 20wt% of antistatic master batch gross weight; The limiting viscosity of described antistatic master batch is 0.50dL/g ~ 0.80dL/g.
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| CN201310683844.6A CN103694459A (en) | 2013-12-13 | 2013-12-13 | Preparation method of antistatic masterbatches for biaxially oriented polyester film |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104629029A (en) * | 2015-02-12 | 2015-05-20 | 广东轻工职业技术学院 | PET-based transparent permanent static dissipative polymer material and preparation method thereof |
| CN117700799A (en) * | 2023-11-29 | 2024-03-15 | 广东诚和信新材料有限公司 | Production and preparation method of antistatic PET release film |
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| CN101362821A (en) * | 2008-09-26 | 2009-02-11 | 江苏中鲈科技发展股份有限公司 | Preparation method of PTT polyester chip and antistatic PTT polyester fiber |
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| JP2010037533A (en) * | 2008-08-07 | 2010-02-18 | Toray Saehan Inc | Method of manufacturing antistatic polyester film, antistatic polyester film manufactured by the method and use thereof |
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2013
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| CN1763276A (en) * | 2004-10-21 | 2006-04-26 | 天津石油化工公司化纤厂 | Method for manufacturing far infrared-antistatic polyester fiber |
| CN101555636A (en) * | 2008-04-09 | 2009-10-14 | 东丽纤维研究所（中国）有限公司 | Antistatic polyester fiber |
| JP2010037533A (en) * | 2008-08-07 | 2010-02-18 | Toray Saehan Inc | Method of manufacturing antistatic polyester film, antistatic polyester film manufactured by the method and use thereof |
| CN101362821A (en) * | 2008-09-26 | 2009-02-11 | 江苏中鲈科技发展股份有限公司 | Preparation method of PTT polyester chip and antistatic PTT polyester fiber |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104629029A (en) * | 2015-02-12 | 2015-05-20 | 广东轻工职业技术学院 | PET-based transparent permanent static dissipative polymer material and preparation method thereof |
| CN117700799A (en) * | 2023-11-29 | 2024-03-15 | 广东诚和信新材料有限公司 | Production and preparation method of antistatic PET release film |
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Application publication date: 20140402 |