CN101955576A - Polyester film - Google Patents
Polyester film Download PDFInfo
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- CN101955576A CN101955576A CN2009101823880A CN200910182388A CN101955576A CN 101955576 A CN101955576 A CN 101955576A CN 2009101823880 A CN2009101823880 A CN 2009101823880A CN 200910182388 A CN200910182388 A CN 200910182388A CN 101955576 A CN101955576 A CN 101955576A
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Abstract
The invention discloses a polyester film. The polyester film consists of structural units shown as I and II, wherein the structural unit number of I is 70 to 99.9 mole percent of a copolyester composition; and the structural unit number of II is 0.1 to 30 mole percent of the copolyester composition. The refractive index of the polyester film which is bi-directionally stretched is 1.7 to 1.80. The polyester film of invention has high refractive index and high heat resistance and can be applied to high-reflectivity films.
Description
Technical field:
The present invention relates to a kind of polyester film.The polyester film of high heat resistance, high refractive index particularly.
Background technology:
In recent years, increasing to optics with the demand of plastic material, the liquid-crystal display panel, the colour filter protective membrane, solar cell is very in vogue with the research of optics articles for use such as film.Because of plastic material easy-formation processing, characteristics such as light have purposes very widely.
Optical thin film need have performance requriementss such as high refractive index, low-gravity, plasticity, thermotolerance, photostabilization, shock-resistance usually according to its different purposes.In recent years, these performance demands are improved more, various monomer, oligopolymer and the polymkeric substance etc. that are used for optical applications are widely studied.
Polyester film, particularly pet film generally have characteristics such as mechanical Strong degree, dimensional stability, thermotolerance, optical characteristics, resistance to chemical reagents, therefore by a large amount of optical thin films that is used for.But the specific refractory power of pet film is not high, has limited its purposes, improves the specific refractory power of PET film, and is necessary.
Usually, when plastic material will be made high-index material, the general structure of pouring the πDian Zi conjugated system of lone-pair electron such as halogen atom, phosphorus atom and unsaturated group etc. according to the molecular configuration of material into.When importing many unsaturated groups in the molecular configuration, though the specific refractory power of material can improve, because the effect of light and heat, stability can variation.When importing halogen atom in the molecular configuration, the specific refractory power of material can improve, but since the sclerosis of halogen atom make optical material the proportion change greatly, transparent feel variation, deterioration of impact resistance.When importing phosphorus atom in the molecular configuration, the phosphorus atom import volume after a little while, specific refractory power can not get improving, the phosphorus atom import volume for a long time, material easily becomes fragile, and bad because of the albefaction transparency, because of water-absorbent water tolerance variation upwards.
Summary of the invention:
The object of the present invention is to provide have high refractive index, a kind of polyester film of high heat resistance.This polyester film is applicable to optical thin film.
Technical solution of the present invention:
A kind of polyester film, the polymer blend that the structural unit that this polyester film is represented by following I, II constitutes is formed:
The II structural formula
R1, R2, R3, R4 are fatty alkyl ester, aromatic alkyl ester of C1～C18 etc. in the formula.Concrete formic acid glycol ester, formic acid propylene glycol ester, formic acid butanediol ester, the formic acid biphenyl methyl esters etc. of can be, wherein, the structural unit number of I is 70～99.9mol% of polyester composition, the structural unit number of II is 0.1～30mol% of polyester composition.The structural unit number of II is many, and plastic material easily hardens and is not easy to be shaped, so because xanthochromia easily takes place the material that hardened, and easily crisp, it is big that the proportion of material becomes.The structural unit number of II has lacked, and the specific refractory power of polyester material can not get improving.The polyester film specific refractory power is 1.7～1.80.
Gained polyester film second-order transition temperature Tg80 of the present invention～120 ℃, limiting viscosity is 0.500～0.850.
Polyester film of the present invention can use existing apparatus and process, with a kind of polyester monocase of and/or more than one diprotic acid or its carboxylate and a kind of and/or more than one dibasic alcohol or its carboxylate, catalyzer proportioning routinely, after carrying out esterification or transesterification reaction, be prepared from through polycondensation.
Can use known catalyzer in esterification or the transesterify process, can enumerate by one or more mixture in manganese acetate, Cobaltous diacetate, magnesium acetate, the calcium acetate etc.It is 95% or 95% above the time that esterification or transesterification reaction reach reactivity, shifts and carries out polycondensation, and the used catalyzer of polycondensation is titanium compound, antimony compounds, germanium compound, magnesium compound.Can be used for inorganic antimony compounds of the present invention and be not particularly limited, and preferably compound comprises antimonous oxide that antimony peroxide etc. wherein preferably use antimonous oxide.
Titanium compound is a kind of metallic compound, and titanium and part form the chelating type structure, and its part is 1～30 ketone group, aldehyde radical, carboxyl or ester group.The example part can be Succinic Acid, hexanodioic acid, adjacent benzene dicarboxylic acid, terephthalic acid, vinyl-acetic ester, methyl-formiate, dimethyl malonate, pentyl acetate, methyl phenyl ketone, 2-phenylpropionaldehyde, salicylaldhyde, crotonic aldehyde, 3-phenylacrolein etc.
In the amount of polymer blend, the antimony element addition was that 50～300ppm or titanium elements addition are 3～20ppm when polyester was synthetic.
In the amount of polymer blend, the mol ratio of phosphoric (P) is that the mol ratio of phosphoric (P) in titanium elements in 0.05≤Sb/P≤15.5 or the titanium compound (Ti) and the phosphorus compound is 0.008≤Ti/P≤2.6 in antimony element in the antimony compounds (Sb) and the phosphorus compound.
Magnesium compound is organic acid magnesium or mineral acid magnesium.Organic acid magnesium is magnesium oxalate, propionic acid magnesium, propanedioic acid magnesium, Succinic Acid magnesium, magnesium acetate or Magnesium Stearate; Mineral acid magnesium is magnesium hydroxide, sal epsom or magnesium chloride.The preferred magnesium compound of the present invention is a magnesium acetate.
Used stablizer phosphorus compound among the present invention, can be trivalent or phosphoric organic or inorganic compound, that can simply enumerate has phosphoric acid, trimethyl phosphite 99, a triphenylphosphate, can be the trivalent of commercially available phosphorus system and the antioxidant of pentavalent, as commercially available PEP36, AP1500, AX-71.Do not enumerate more specifically at this.
Advantage of the present invention is apparent in view, and the gained polyester film has high refractive index, high heat resistance.Polyester film second-order transition temperature Tg80～120 ℃, specific refractory power is 1.7～1.8.This polyester film is applicable to optical thin film, can be applicable to the highly reflective film.
The following describes the measuring method and the evaluation method of the every index of the present invention.
(1) limiting viscosity (IV) (dL/g)
The polymer blend of 1.6 grams is dissolved in the ortho chloro phenol solution of 20ml, measures its limiting viscosity (IV) down at 25 ℃.
(2) detecting refractive index
The polyester thin-film process comprises that chip drying enters screw extrusion press and extrudes, casts sheet, electrostatic adhesion, stretching, typing after handling, and draws rolling at last.Extrusion temperature is 250 ℃～290 ℃, and the drawing zone temperature is 60 ℃～120 ℃, and setting temperature is 195 ℃～235 ℃.
Then above-mentioned film is placed on abbe flexion Meter (ATAGO Co., Ltd.) and goes up mensuration, draw refractive index value
(3) tone L, b value
Measure by GB GB/T 14190-1993.
(4) DSC test
Differential scanning calorimeter DSC (TA, Q100) be warmed up to 280 ℃ from 40 ℃ with 16 ℃/min after constant temperature 3 minutes, eliminate thermal history; Rapid cool to room temperature then, be warmed up to 280 ℃ from 40 ℃ with 16 ℃/min again after constant temperature 3 minutes, cool to 40 ℃ with 16 ℃/min again, finish.Obtain second-order transition temperature in heating up for the second time and be designated as T
g, cold crystallization temperature T
CcWith melt temperature be fusing point T
m
Embodiment:
Embodiment 1
In the transesterify process, add acetate as catalyzer, finish the back in transesterification reaction (EI reaction) and add the phosphorus stabilizer agent, in polycondensation process, add antimony compounds, carry out polycondensation and obtain polymer blend as catalyzer.
Wherein polymer blend is to carry out the resulting multipolymer of transesterify by dimethyl terephthalate (DMT) (DMT) and biphenyl dicarboxylic acid dimethyl ester and ethylene glycol (EG).
The acetate catalyst that uses is a magnesium acetate.The antimony compounds catalyzer is an antimonous oxide.
Concrete reaction process is as follows:
Under 150 ℃ temperature, make 175 parts of (weight) DMT (BASF AG) and 21.4 parts of (weight) biphenyl dicarboxylic acid dimethyl esters (the rich chemical industry of riel company limited) and 119 parts of (weight) EG (sub-petrochemical industry is raised by China) carry out transesterify reaction (EI reaction), be placed in the polymerization flask of being furnished with rectifying tower, and will be as the magnesium acetate (AR of catalyzer in the transesterify, Shanghai leads to inferior Fine Chemical Works) (addition with respect to weight polyester Mg is 55ppm), under normal pressure, react, temperature is 235 ℃ in flask, when the rectifying tower tower top temperature drops to 50 ℃, above-mentioned reaction is finished, and obtains micromolecular polymkeric substance.Add phosphorus stabilizer agent triethyl phosphine acyl acetic acid ester TEPA (Xiamen Hai Chuan reaches industry and trade company limited) this moment, is 70ppm with respect to the addition of weight polyester P.
As polymeric The catalytic antimony trioxide compound S b
2O
3Middle Sb (AR, Shishewei Chemical Co., Ltd., Shanghai) addition 200ppm, add in the above-mentioned small molecules polymkeric substance, under atmospheric pressure be decompressed to about 300Pa through 1.5 hours, temperature was warming up to 290 ℃ through 1.5 hours, and when described reaction was finished, the temperature in the flask was 290 ℃, resulting pressure is about 200Pa, obtains polymer blend of the present invention.
Polyester thin-film process: the section that makes through after the drying treatment, is entered screw extrusion press and extrudes, casts sheet, electrostatic adhesion, stretching, typing, draw rolling at last.Extrusion temperature is 250 ℃～290 ℃, and the drawing zone temperature is 60 ℃～120 ℃, and setting temperature is 195 ℃～235 ℃.Make polyester film of the present invention at last.
Embodiment 2
Polymer blend is the multipolymer that is obtained by terephthalic acid, ethylene glycol, biphenyl dimethanol esterification.
Concrete reaction process is as follows:
Under 250 ℃ temperature, make 332 parts of (weight) terephthalic acids and 128.3 parts of (weight) ethylene glycol and 49.2 parts of (weight) biphenyl dimethanols (sea, Shanghai Qu Huagong company limited) carry out the direct esterification reaction, above-mentioned reaction is finished, and obtains micromolecular polymkeric substance.
Add The catalytic antimony trioxide compound S b in the above-mentioned small molecules polymkeric substance
2O
3Middle Sb addition 200ppm, the magnesium acetate addition is 55ppm (with respect to the weight of polyester), phosphorus stabilizer agent triethyl phosphine acyl acetic acid ester TEPA70ppm (with respect to the weight of polyester).Under atmospheric pressure be decompressed to about 300Pa through 1 hour, temperature was warming up to 290 ℃ through 1.5 hours, and when described reaction was finished, the temperature in the flask was 290 ℃, and resulting pressure is about 200Pa, obtains polymer blend of the present invention.Carry out the polyester film with embodiment 1 one quadrat methods then.
Embodiment 3
Make 163 (weight) DMT and 32.1 parts of (weight) biphenyl dicarboxylic acid dimethyl esters and 117 parts of (weight) EG carry out transesterify reaction (EI reaction).
All the other are the same with embodiment 1.
Embodiment 4
Make 153.6 parts of (weight) DMT (BASF AG) and 42.8 parts of (weight) biphenyl dicarboxylic acid dimethyl esters (weight) and 119 parts of EG carry out transesterify reaction (EI reaction).
All the other are the same with embodiment 1.
Comparative example
Under 250 ℃ temperature, make 166 parts of (weight) terephthalic acids and 75 parts of (weight) ethylene glycol carry out the direct esterification reaction, above-mentioned reaction is finished, and obtains micromolecular polymkeric substance.
As polymeric The catalytic antimony trioxide compound S b
2O
3Middle Sb addition 70ppm, add in the above-mentioned small molecules polymkeric substance, under atmospheric pressure be decompressed to about 300Pa through 1 hour, temperature was warming up to 290 ℃ through 1.5 hours, when described reaction is finished, temperature in the flask is 290 ℃, and resulting pressure is about 200Pa, obtains polymer blend of the present invention.Carry out the polyester film with embodiment 1 one quadrat methods then.
Claims (3)
1. polyester film is characterized in that:
(1) polymer blend that constitutes of the structural unit represented by following I, II of this polyester film is formed:
R1, R2 are the fatty alkyl ester of C1～C18 in the formula, and R3, R4 are fatty alkyl ester or the aromatic alkyl ester of C1～C18;
Wherein, the structural unit number of I is 70～99.9mol% of polymer blend, and the structural unit number of II is 0.1～30mol% of polymer blend.
(2) this polyester film specific refractory power is 1.70～1.80.
2. polyester film according to claim 1 is characterized in that: 80～120 ℃ of the second-order transition temperature Tg of this polyester film, limiting viscosity is 0.500～0.850.
3. the application of the described polyester film of claim 1 in preparation highly reflective film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101823880A CN101955576A (en) | 2009-07-13 | 2009-07-13 | Polyester film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101823880A CN101955576A (en) | 2009-07-13 | 2009-07-13 | Polyester film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101955576A true CN101955576A (en) | 2011-01-26 |
Family
ID=43483187
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009101823880A Pending CN101955576A (en) | 2009-07-13 | 2009-07-13 | Polyester film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101955576A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104136487A (en) * | 2012-02-24 | 2014-11-05 | 东洋纺株式会社 | Polyester resin for surface-mounted led reflective plate |
| CN113292708A (en) * | 2021-05-25 | 2021-08-24 | 吉林建筑大学 | Bio-based copolyester and preparation method and application thereof |
-
2009
- 2009-07-13 CN CN2009101823880A patent/CN101955576A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104136487A (en) * | 2012-02-24 | 2014-11-05 | 东洋纺株式会社 | Polyester resin for surface-mounted led reflective plate |
| CN104136487B (en) * | 2012-02-24 | 2016-03-02 | 东洋纺株式会社 | Surface mounting LED reflector vibrin |
| CN113292708A (en) * | 2021-05-25 | 2021-08-24 | 吉林建筑大学 | Bio-based copolyester and preparation method and application thereof |
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Application publication date: 20110126 |