WO2023165112A1 - 一种高透光率聚酯薄膜及其制造方法 - Google Patents

一种高透光率聚酯薄膜及其制造方法 Download PDF

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WO2023165112A1
WO2023165112A1 PCT/CN2022/119422 CN2022119422W WO2023165112A1 WO 2023165112 A1 WO2023165112 A1 WO 2023165112A1 CN 2022119422 W CN2022119422 W CN 2022119422W WO 2023165112 A1 WO2023165112 A1 WO 2023165112A1
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Prior art keywords
polyester film
light transmittance
high light
stretching
section
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PCT/CN2022/119422
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English (en)
French (fr)
Inventor
陈正坚
陆宇
楼涛
张军
范和强
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杭州和顺科技股份有限公司
浙江和顺新材料有限公司
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Publication of WO2023165112A1 publication Critical patent/WO2023165112A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/672—Dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C08K2003/3045—Sulfates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/346—Clay

Definitions

  • the invention belongs to the technical field of biaxially stretched polyester film (BOPET), and in particular relates to a method for improving the light transmittance of the BOPET film.
  • BOPET biaxially stretched polyester film
  • Biaxially oriented polyester film has excellent physical and chemical properties. Due to its excellent optical properties, mechanical properties and low cost, BOPET is widely used in the display field. Generally speaking, the light transmittance of transparent polyester film is in the range of 88-89%. The loss of light transmittance of optical resin in the visible region is mainly caused by the following three factors: reflection, scattering and absorption of light, BOPET light transmission The loss of efficiency is mainly caused by reflection and scattering. At present, most methods to increase the light transmittance of polyester film to about 92% are based on coating a layer of low refractive index material on the surface of polyester film to reduce the light transmittance caused by reflection. The light transmittance is lost, so as to achieve the purpose of improving the light transmittance, but there are few reports on improving the light transmittance of polyester films by reducing scattering.
  • Patent 202111445825.0 provides a preparation method of blended polyester resin and its application in high light transmittance polyester film. Under the condition of not adding solid powder particles, the BOPET film prepared by this method has high light transmittance, It has the advantages of good smoothness and good antistatic performance, but due to the low crystallinity of the obtained film, the thermal shrinkage rate is relatively large, and this polyester film will undergo large deformation due to high temperature during use, especially It is the plastic tensile deformation in the tension direction at high temperature that is easy to wrinkle, which will lead to a series of problems such as processing difficulties and unstable performance of the final product.
  • Patent 201110363014.6 provides a polyester film for electronic labels and its preparation method.
  • the raw materials for the preparation of polyester film for electronic labels include the following components in weight percentage: 0.1-35.6% functional slice A, 0.1-42.2% functional slice B , 20-68% regenerated particles of waste polyester materials, 40-90% ordinary polyester chips, 1-12% polyester chips containing IPA, 5-92% silicon-based chips; among them, the quality of shell powder in functional chip A
  • the percentage content is 0.1-13.5%
  • the mass percentage content of nano-montmorillonite in the functional slice B is 0.5-32.6%
  • the mass percentage content of IPA in the polyester chip containing IPA is 0.2-7.8%
  • the silicon-based slice is oxidized
  • the mass content of silicon is 200-18900PPM.
  • polyester chips are blended and extruded, and biaxially stretched; the polyester chip A contains shell micropowder, and the polyester chip B contains nano-montmorillonite, and its longitudinal thermal shrinkage rate is 0 at 180°C. -1% range; but the copolyester of this invention does not disclose the use of the third monomer, and the inorganic particles used are different from the present invention, and at the same time, the products prepared by this invention are only dedicated to improving the heat shrinkage of the film The transparency of the film cannot meet the application requirements.
  • the technical problem to be solved in the present invention is to overcome the deficiencies in the above-mentioned prior art, adopt the introduction of the third comonomer in the polyester, control the type, content and particle size of the crystallization nucleating agent, and use the inorganic opening agent and The stretching process improves the light transmittance of the polyester film while maintaining the good thermal stability, mechanical properties and processing properties of the polyester film.
  • a polyester film with high light transmittance which includes: 93%-98% of modified copolyester chips obtained by copolymerization of terephthalic acid, ethylene glycol and a third monomer, optical opening masterbatch 1%-5% and 1%-2% of crystallization nucleating agent, through melt extrusion and biaxial stretching to obtain a polyester film with a thickness of 12-75 ⁇ m and high light transmittance, wherein the third monomer is 1 , one or any combination of 4-cyclohexanediol, 1,3-cyclopentanediol, and isosorbide, the optical opening masterbatch is a mixture of barium sulfate and the modified copolyester, The crystallization nucleating agent is a mixture of nano kaolin and the modified copolyester.
  • the molar ratio of the third monomer to ethylene glycol is 0.1:10-0.8:10.
  • the third monomer is composed of 1,4-cyclohexanediol and isosorbide, and the ratio of 1,4-cyclohexanediol:isosorbide is 1:1-1:10.
  • the mass fraction of barium sulfate is 2%-5%, and the particle size is 1.2-1.6 ⁇ m.
  • the mass fraction of nano-kaolin is 1%-3%, and the particle size is 30-80nm.
  • the bidirectional stretching method includes synchronous stretching or asynchronous stretching, the stretching ratio is 3.3-3.6 times, and the stretching ratio in the MD direction is consistent with the stretching ratio in the TD direction.
  • the present invention also provides a corresponding manufacturing method, comprising the following steps:
  • the third monomer is mixed with ethylene glycol and a catalyst, it is then mixed with terephthalic acid, heated, and vacuumized for reaction. After the reaction is completed, the material is decompressed and discharged, cooled, and pelletized to make modified copolyester chips;
  • S4 Send the copolyester chip, the optical opening masterbatch and the crystallization nucleating agent into the extruder, melt extrude, and biaxially stretch to obtain a polyester film with a thickness of 12-75 ⁇ m and high light transmittance.
  • melt extrusion of the polyester film is segmented temperature control, which is divided into three sections, the temperature of the first section is 265-270°C, the temperature of the second section is 270-275°C, and the temperature of the third section is 265-270°C. °C.
  • the time ratio of the three stages is (2-2.5):(2-3):(1-1.5), preferably 2:3:1.
  • the longitudinal stretching is divided into a preheating section, a stretching section and a cooling and shaping section, the temperature of the preheating section is 65-85°C, the temperature of the stretching section is 90-110°C, and the temperature of the cooling and shaping section is 20-45°C. °C;
  • the transverse stretching is divided into a preheating section, a stretching section, a shaping section and a cooling section, the temperature of the preheating section is 80-95°C, the temperature of the stretching section is 100-120°C, and the temperature of the shaping section is 210-230°C.
  • the cooling section temperature is 40-60°C.
  • the crystallization of polymers is discharged into the crystal lattice through the coordinated movement of chain segments. Since the chain segment movement has a strong temperature and time dependence, the polymer crystallization also has a strong temperature and time dependence.
  • the melting temperature is low, the melting time is short, the crystallization speed is fast, and the crystal size is small and uniform, which is beneficial to improve the mechanical properties and heat distortion temperature.
  • the cooling rate during molding affects whether the product can crystallize, crystallization speed, crystallinity, crystal shape and size, etc. The faster the cooling rate, the smaller the crystallinity. Therefore, the present application uses a lower temperature for melting and stretching setting, and uses a faster time for cooling, which can reduce the crystal size and improve the thermal stability of the film.
  • the present invention also provides another kind of manufacture method of high light transmittance polyester film, comprises the following steps:
  • the third monomer is mixed with ethylene glycol and a catalyst, it is then mixed with terephthalic acid, heated, and vacuumized for reaction. After the reaction is completed, the material is decompressed and discharged, cooled, and pelletized to make modified copolyester chips;
  • the third monomer is mixed with ethylene glycol and catalyst, then mixed with terephthalic acid, barium sulfate and dispersant, heated, and vacuumized for reaction, after the reaction is completed, the material is discharged under reduced pressure, and granulated by twin-screw extrusion;
  • S4 Send the copolyester chip, the optical opening masterbatch and the crystallization nucleating agent into the extruder, melt extrude, and biaxially stretch to obtain a polyester film with a thickness of 12-75 ⁇ m and high light transmittance.
  • the above preparation method adopts the method of in-situ polymerization to prepare the optical opening masterbatch and the crystallization nucleating agent respectively.
  • the third monomer is mixed with ethylene glycol and catalyst, and then mixed with terephthalic acid, barium sulfate or nano-kaolin, and dispersed
  • the agent is fully mixed, and then the polymerization reaction, extrusion granulation and other processes are carried out.
  • the inorganic particles are added to the monomer with low viscosity in the early stage of polymerization, which is beneficial to the uniform dispersion of the inorganic particles, and along with the polymerization process, they are uniformly dispersed in the polymerization product.
  • the above-mentioned composite particles are also more likely to be uniformly dispersed and mixed in the copolyester matrix, so that the high light transmittance polyester film of the present invention fully and uniformly exhibits satisfactory transmittance. Light rate, thermal stability, mechanical properties and processing properties.
  • polyester film with high light transmittance can be applied in the field of electronic display and/or optical elements.
  • the present invention destroys the regularity of PET molecular chains through the introduction of the cyclic third monomer, prevents molecular chains from stacking to form large crystal regions, and reduces the scattering of visible light caused by large-sized crystal regions when passing through the film.
  • the refractive index is selected Barium sulfate, which is similar to PET, is used as an opening agent, which greatly reduces the influence of the film opening agent on the light transmittance.
  • the introduction of nano-crystal nucleating agents can make polyester films easier to form small-sized crystals during crystallization. While improving the temperature resistance of the ester film, it avoids the scattering effect of the crystal region on visible light. By using the method, the light transmittance of the polyester film can be improved under the condition of simple production process and low production cost.
  • the third monomer is one or any combination of 1,4-cyclohexanediol, 1,3-cyclopentanediol, and isosorbide, preferably the first
  • the three monomers are composed of 1,4-cyclohexanediol and isosorbide, and the molar ratio of 1,4-cyclohexanediol:isosorbide is 1:1-1:10.
  • copolyester chips into powder, mix copolyester chip powder with barium sulfate with a particle size of 1.2-1.6 ⁇ m, dispersant, and then extrude and granulate through twin-screw to prepare optical opening masterbatch, barium sulfate
  • the mass fraction is 2%-5%; the copolyester chips are ground into powder, the copolyester powder is mixed with nano-kaolin particles with a particle size of 30-80nm and a dispersant, and then granulated by twin-screw extrusion to prepare a crystalline compound
  • the core agent, the mass fraction of nano-kaolin particles is 1%-3%; in terms of mass percentage, 93%-98% of copolyester chips, 1%-5% of optical opening masterbatch and 1%-2% of
  • the crystallization nucleating agent is sent to the corresponding silo of the main extruder through the suction system, fed into the extruder, melted, vacuumed and filtered to remove
  • the temperature of the first section is 265-270°C
  • the second section is 270-275°C.
  • the third stage is 265-270°C.
  • the time ratio of the three stages is (2-2.5): (2-3): (1-1.5)
  • the melt extruded from the die is attached to the surface of the cold drum and cooled to obtain a cast sheet, and the obtained cast sheet is stretched , Shaping, longitudinal stretching is divided into preheating section, stretching section and cooling shaping section, the temperature of preheating section is 65-85°C, the temperature of stretching section is 90-110°C, and the temperature of cooling shaping section is 20-45°C.
  • Transverse stretching is divided into preheating section, stretching section, shaping section and cooling section.
  • the temperature is 40-60°C; the transverse and longitudinal stretch ratios are the same, and both are 3.3-3.6; after stretching and shaping, enter the traction system for thickness measurement feedback, ultrasonic cleaning, flattening, static removal and winding, and the obtained thickness is 12-75 ⁇ m high light transmittance polyester film.
  • the third monomer is one or any combination of 1,4-cyclohexanediol, 1,3-cyclopentanediol, and isosorbide, preferably the first
  • the three monomers are composed of 1,4-cyclohexanediol and isosorbide, and the molar ratio of 1,4-cyclohexanediol:isosorbide is 1:1-1:10.
  • the mass fraction of barium sulfate is 2%-5%; Yes, after mixing the 1,4 third monomer with a molar ratio of 0.1:10-0.8:10, ethylene glycol, and a catalyst, and then mixing it with terephthalic acid, nano-kaolin particles with a particle size of 30-80nm, and a dispersant , heating, and vacuuming to react, after the reaction is completed, the material is decompressed and discharged, and the crystallization nucleating agent is prepared through twin-screw extrusion and granulation.
  • the mass fraction of nano-kaolin particles is 1%-3%; in terms of mass percentage, the 93%-98% copolyester chips, 1%-5% optical opening masterbatch and 1%-2% crystallization nucleating agent are sent to the corresponding silo of the main extruder through the suction system, and fed to In the extruder, after melting, vacuuming and filtering, the moisture, oligomers and impurities in the raw material melt are removed as a melt; the resulting melt is extruded in a hanger-type die head, and the extrusion is segmented control
  • the temperature mode is divided into three sections, the first section temperature is 265-270°C, the second section is 270-275°C, and the third section is 265-270°C.
  • the time ratio of the three stages is (2-2.5): (2-3): (1-1.5), the melt extruded from the die is attached to the surface of the cold drum and cooled to obtain a cast sheet, and the obtained cast sheet is stretched , Shaping, longitudinal stretching is divided into preheating section, stretching section and cooling shaping section, the temperature of preheating section is 65-85°C, the temperature of stretching section is 90-110°C, and the temperature of cooling shaping section is 20-45°C. Transverse stretching is divided into preheating section, stretching section, shaping section and cooling section.
  • the temperature is 40-60°C; the transverse and longitudinal stretch ratios are the same, and both are 3.3-3.6; after stretching and shaping, enter the traction system for thickness measurement feedback, ultrasonic cleaning, flattening, static removal and winding, and the obtained thickness is 12-75 ⁇ m high light transmittance polyester film.
  • copolyester chips are ground into powder, and the particle size is 1.2 ⁇ m Barium sulfate and dispersant are mixed and granulated by twin-screw extrusion to prepare optical opening masterbatch; copolyester powder is mixed with nano-kaolin particles with a particle size of 50nm and dispersant and then granulated by twin-screw extrusion to prepare Obtain crystallization nucleating agent; In terms of mass percentage, 96% copolyester chips, 2% optical opening masterbatch and 2% crystallizing nucleating agent are sent to the corresponding feed bin of the main extruder through the suction system , fed into the extruder, melted, vacuumed, and filtered to remove moisture, oligomers and impurities in the raw material melt as a melt; the resulting melt is extruded in the die; extruded from the die The
  • 1,4 cyclohexanediol and isosorbide (the molar ratio of 1,4 cyclohexanediol and isosorbide is 1:1) with ethylene glycol and catalyst in a molar ratio of 0.2:10, and then Mix with terephthalic acid, heat and vacuumize to react.
  • copolyester chips are ground into powder, and the particle size is 1.2 ⁇ m Barium sulfate and dispersant are mixed and granulated by twin-screw extrusion to prepare optical opening masterbatch; copolyester powder is mixed with nano-kaolin particles with a particle size of 50nm and dispersant and then granulated by twin-screw extrusion to prepare Obtain crystallization nucleating agent; In terms of mass percentage, 96% copolyester chips, 2% optical opening masterbatch and 2% crystallizing nucleating agent are sent to the corresponding feed bin of the main extruder through the suction system , fed into the extruder, melted, vacuumed, and filtered to remove moisture, oligomers and impurities in the raw material melt as a melt; the resulting melt is extruded in the die; extruded from the die The
  • isosorbide After mixing isosorbide with a molar ratio of 0.4:10, ethylene glycol, and a catalyst, it is mixed with terephthalic acid, heated, and vacuumized to react. After the reaction is completed, the pressure is reduced, the material is discharged, cooled, and pelletized.
  • Copolyester chips grind the copolyester chips into powder, mix them with barium sulfate and dispersant with a particle size of 1.4 ⁇ m, and then extrude and granulate through twin-screws to prepare optical opening masterbatches; mix the copolyester powder with 30nm kaolin particles and dispersant are mixed and granulated by twin-screw extrusion to prepare a crystallization nucleating agent; in terms of mass percentage, 97% of copolyester chips, 2% of optical opening masterbatch and 1% of crystallization
  • the nucleating agent is sent to the corresponding silo of the main extruder through the suction system, fed into the extruder, melted, vacuumed and filtered to remove moisture, oligomers and impurities in the raw material melt as Melt; the resulting melt is extruded in the die; the melt extruded from the die is attached to the surface of the cold drum and cooled to obtain a cast sheet. Thick
  • the material is decompressed and discharged, and extruded and granulated by twin-screw to prepare optical opening masterbatch; 1,4 cyclohexanediol with a molar ratio of 0.2:10 and After mixing ethylene glycol and a catalyst, it is mixed with terephthalic acid, 40nm nano-kaolin particles and a dispersant, heated, and vacuumized for reaction.
  • the material is discharged under reduced pressure, and granulated by twin-screw extrusion to prepare crystallization Nucleating agent:
  • 96% of the copolyester chips, 3% of the optical opening masterbatch and 1% of the crystallization nucleating agent are sent to the corresponding feed bin of the main extruder through the suction system, and the feeding
  • the extruder after melting, vacuuming, and filtering, the moisture, oligomers and impurities in the raw material melt are removed as a melt; the resulting melt is extruded in a hanger-type die; extruded from the die
  • the melt is attached to the surface of the cold drum and cooled to obtain a cast sheet.
  • the obtained cast sheet is stretched and shaped at 3.4 ⁇ 3.4, and then enters the traction system for thickness measurement feedback, ultrasonic cleaning, flattening, static removal and winding, and the obtained thickness is 23 ⁇ m high light transmittance polyester film.
  • 1,4 cyclohexanediol, iso Sorbitol (the molar ratio of 1,4 cyclohexanediol to isosorbide is 1:10) is mixed with ethylene glycol and a catalyst, and then mixed with terephthalic acid, barium sulfate with a particle size of 1.2 ⁇ m and a dispersant Mixing, heating, and vacuuming for reaction, after the reaction is completed, the material is discharged under reduced pressure, extruded and granulated by twin-screw, and the optical opening masterbatch is prepared; 1,4 cyclohexanediol and isosorbide with a molar ratio of 0.2:10 (The molar ratio of 1,4 cyclohexanediol to isosorbide is 1:10) mixed with ethylene glycol and catalyst, then mixed with tere
  • the thickness of the film prepared by combining 98% copolyester chips with 2% optical opening masterbatch is 50 ⁇ m.
  • the film prepared by mass percent of 98% copolyester chip and 2% crystal nucleating agent has a thickness of 50 ⁇ m.
  • Light transmittance According to the ISO13468 standard, it is tested with BYK HAZE-gardi in Germany.
  • the light transmittance of Examples 1-6 is higher than that of Comparative Examples 1, 2 and 4 without using a crystal nucleating agent; although Comparative Example 3 has a higher light transmittance, it does not contain Anti-opening agent, the smoothness of the film is not enough to cause the mucous membrane, so it is difficult to produce normally and industrialize.
  • the polyester film prepared by the invention improves the light transmittance of the polyester film while maintaining the mechanical properties and thermal stability without significant changes, and is suitable for industrial production.
  • the third monomer in Examples 2 and 3 adopts the combination of 1,4 cyclohexanediol and isosorbide, which provides more asymmetric structures, further breaks the regularity of molecular chains, and reduces Crystallinity plays a positive role in improving light transmittance.
  • Example 5 is similar to Example 1 in the type and amount of the third monomer, the size and amount of the inorganic particles, etc.
  • Example 6 is similar to Example 2 in the case that the type and amount of the third monomer, the size and amount of inorganic particles, etc. are similar. It can be seen from comparison that in addition to better mechanical properties and thermal shrinkage, Examples 5 and 6 also have higher light transmittance than those obtained by the comparative examples and the products obtained by the common blending method. This also proves from the experimental data that the in-situ polymerization method is helpful in improving the dispersion of inorganic particles, especially nano-inorganic particles in the polymer matrix, and improving the performance of the final product.

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Abstract

本发明公开了一种高透光率聚酯薄膜及其制造方法，以质量百分比计，包括采用第三单体共聚改性的共聚酯切片93％-98％、光学开口母粒1％-5％以及结晶成核剂1％-2％，通过熔融挤出且双向拉伸以后获得厚度为12-75μm的高透光率的聚酯薄膜。本发明通过减少可见光在聚酯薄膜中散射损失来提高透光率，具有生产工艺简单、生产成本低且保留了普通聚酯薄膜的热稳定性的特点，可应用于在电子显示领域。

Description

一种高透光率聚酯薄膜及其制造方法 技术领域
本发明属于双向拉伸聚酯薄膜(BOPET)技术领域，具体涉及一种提高BOPET薄膜透光率的方法。
背景技术
双向拉伸聚酯薄膜(BOPET)有着优良的物理化学性能，由于其优异的光性能、力学性能以及低成本，BOPET在显示领域较为广泛的应用。一般而言，透明聚酯薄膜的透光率在88-89％范围内，光学树脂在可见光区的透光率的损失主要由以下三个因素造成：光的反射、散射和吸收，BOPET透光率的损失主要由反射和散射引起，目前绝大部分将聚酯薄膜透光率提高到92％左右的方法都是基于在聚酯薄膜表面涂布一层低折射率物质，减少因反射引起的透光率损失，从而实现提高透光率的目的，但对于通过减少散射来实现提高聚酯薄膜透光率的报道较少。
专利202111445825.0提供了一种共混聚酯树脂的制备方法及其在高透光聚酯薄膜中的应用，该方法在不添加固体粉末颗粒的条件下，制备出的BOPET薄膜具有高透光度、爽滑性好、抗静电性能好的优点，但由于其所得薄膜结晶度不高，导致其热收缩率较大，这种聚酯薄膜在使用过程中会因为高温而发生较大的变形，尤其是高温下在受张力方向上的塑性拉伸变形容易起皱，这会导致加工困难、最终产品性能不稳定等一系列问题。
专利201110363014.6提供了一种电子标签用聚酯薄膜及其制备方法，电子标签用聚酯薄膜的制备原料包括以下重量百分比的各组分：0.1-35.6％功能切片A，0.1-42.2％功能切片B，20-68％废旧聚酯料的再生粒子，40-90％普通聚酯切片，1-12％含IPA的聚酯切片，5-92％硅系切片；其中，功能切片A中贝壳微粉质量百分含量为0.1-13.5％，功能切片B中纳米蒙脱土质量百分含量为0.5-32.6％，含IPA的聚酯切片中IPA质量百分含量为0.2-7.8％，硅系切片中氧化硅质量含量为200-18900PPM。该种方法由多种聚酯切片共混挤出，双轴拉伸；聚酯切片A中含贝壳微粉，聚酯切片B中含纳米蒙脱土，180℃高温下其纵向热收缩率在0-1％范围内；但是该发明的共聚酯中未公开使用第三单体，且使用的无机粒子与本发明不同，同时，该发明所制备的产品仅致力于改良薄膜的热收缩率，薄膜的透明度不能满足应用需求。
因此，在提高薄膜透光率的同时使薄膜具有良好的热收缩率成为本领域技术人员亟待解决的问题。
发明内容
本发明要解决的技术问题是克服上述现有技术存在的不足，采用在聚酯中引入第三共聚单体、控制结晶成核剂的类型、含量和粒径大小，并配合使用无机开口剂及拉伸工艺从而提高聚酯薄膜的透光率，同时保持聚酯薄膜良好的热稳定性、力学性能及加工性能。
为实现上述发明目的，本发明具体采取以下技术方案：
提供一种高透光率聚酯薄膜，以质量百分比计包括：采用对苯二甲酸、乙二醇及第三单体共聚得到的改性共聚酯切片93％-98％、光学开口母粒1％-5％以及结晶成核剂1％-2％，通过熔融挤出且双向拉伸获得厚度为12-75μm的高透光率的聚酯薄膜，其中，所述第三单体为1,4-环己二醇、1,3-环戊二醇、异山梨醇中的一种或任意组合，所述光学开口母粒为硫酸钡与所述改性共聚酯的混炼物，所述结晶成核剂为纳米高岭土与所述改性共聚酯的混炼物。
进一步的，第三单体与乙二醇摩尔比为0.1:10-0.8:10。
进一步的，第三单体由1,4-环己二醇和异山梨醇组成，且1,4-环己二醇：异山梨醇为1:1-1:10。
进一步的，所述光学开口母粒中，硫酸钡的质量分数为2％-5％，粒径为1.2-1.6μm。
进一步的，所述结晶成核剂中，纳米高岭土的质量分数为1％-3％，粒径为30-80nm。
进一步的，所述双向拉伸方式包括同步拉伸或异步拉伸，拉伸倍率为3.3-3.6倍，且MD方向的拉伸倍率与TD方向的拉伸倍率一致。
为了制造上述高透光率聚酯薄膜，本发明还提供了相应的制造方法，包括以下步骤：
S1：改性共聚酯切片的制备：
将第三单体与乙二醇、催化剂混合后，再与对苯二甲酸混合、加热、抽真空进行反应，反应完毕降压出料，冷却，切粒制成改性共聚酯切片；
S2：光学开口母粒的制备：
将部分上述改性共聚酯切片磨成粉状，与硫酸钡、分散剂混合，经双螺杆挤出造粒；
S3：结晶成核剂的制备：
将部分上述改性共聚酯切片磨成粉状，与纳米高岭土、分散剂混合，经双螺杆挤出造粒；
S4：将共聚酯切片、光学开口母粒以及结晶成核剂送入挤出机，熔融挤出，双向拉伸获得厚度为12-75μm的高透光率的聚酯薄膜。
进一步的，所述聚酯薄膜的熔融挤出为分段控温，共分为三段，第一段温度为265-270℃，第二段为270-275℃，第三段为265-270℃。三段的时间比为(2-2.5)：(2-3)：(1-1.5)，优选为2：3：1。
进一步的，所述纵向拉伸分为预热段、拉伸段和冷却定型段，预热段温度为65-85℃，拉伸段温度为90-110℃，冷却定型段温度为20-45℃；
所述横向拉伸分为预热段、拉伸段、定型段和冷却段，预热段温度为80-95℃，拉伸段温度为100-120℃，定型段温度为210-230℃，冷却段温度为40-60℃。
高分子的结晶是通过链段的协同运动排入晶格的。由于链段运动有强烈的温度、时间依赖性，所以高分子结晶也具有很强的对温度、时间的依赖性。熔融温度低，熔融时间短，结晶速度快，结晶尺寸小而均匀，有利于提高机械性能和热变形温度。成型时的冷却速度影响制品能否结晶、结晶速度、结晶度、结晶形态和大小等，冷却速度越快，结晶度越小。因此，本申请用较低的温度进行熔融和拉伸定型，并且用较快的时间进行冷却，能够减小晶体尺寸，提高薄膜的热稳定性。
为了进一步提高聚酯薄膜的透光性，本发明还提供了另一种高透光率聚酯薄膜的制造方法，包括以下步骤：
S1：改性共聚酯切片的制备：
将第三单体与乙二醇、催化剂混合后，再与对苯二甲酸混合、加热、抽真空进行反应，反应完毕降压出料，冷却，切粒制成改性共聚酯切片；
S2：光学开口母粒的制备：
将第三单体与乙二醇、催化剂混合后，再与对苯二甲酸、硫酸钡及分散剂混合、加热、抽真空进行反应，反应完毕降压出料，经双螺杆挤出造粒；
S3：结晶成核剂的制备：
将第三单体与乙二醇、催化剂混合后，再与对苯二甲酸、纳米高岭土及分散剂混合、加热、抽真空进行反应，反应完毕降压出料，经双螺杆挤出造粒；
S4：将共聚酯切片、光学开口母粒以及结晶成核剂送入挤出机，熔融挤出，双向拉伸获得厚度为12-75μm的高透光率的聚酯薄膜。
上述制备方法采用原位聚合的方法分别制备光学开口母粒和结晶成核剂，首先把第三单体与乙二醇、催化剂混合，再与对苯二甲酸、硫酸钡或纳米高岭土、及分散剂充分混合，然后进行聚合反应、挤出造粒等工序。通过上述原位聚合的方法，无机粒子在聚合前期加入粘度较低的单体中，有利于无机粒子的均匀分散，并伴随聚合过程，均匀的分散于聚合产物中。此后的熔融挤出成膜过程中，上述复合粒子也更易均匀的分散并混熔于共聚酯基体中，使本发明的高透光率聚酯薄膜充分且均匀的展现出令人满意的透光率、热稳定性、力学性能及加工性能。
进一步的，上述高透光率聚酯薄膜能够在电子显示领域和/或光学元件中应用。
本发明具有如下有益效果：
1)本发明通过环状第三单体的引入来破坏PET分子链的规整性，阻止分子链堆砌形成大晶区，减少可见光在通过薄膜时由于大尺寸晶区引起的散射，同时选用折射率与PET相近的硫酸钡作为开口剂，大大减少薄膜开口剂对透光率的影响，此外，纳米结晶成核剂的引入可以使聚酯薄膜在结晶时更容易形成小尺寸的结晶，在保证聚酯薄膜耐温性的同时避免晶区对于可见光的散射作用。利用本方法可以在生产工艺简单、生产成本低的情况下实现聚酯薄膜透光率的提升。
2)采用原位聚合的方法分别制备光学开口母粒和结晶成核剂，有利于无机粒子的均匀稳定分散，特别有效地解决了纳米粒子易团聚难分散的问题，对产品透光率、热稳定性、力学性能及加工性能等均有明显提升促进作用。
具体实施方式
为了使本发明的目的、技术方案和优点更加清楚，下面将对本发明做进一步地详细描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
将摩尔比为0.1:10-0.8:10的1,4第三单体与乙二醇、以及催化剂混合以后，再与对苯二甲酸混合、加热、抽真空进行反应，反应完成后降压，出料，冷却，切粒制成共聚酯切片；第三单体为1,4-环己二醇、1,3-环戊二醇、异山梨醇中的一种或任意组合，优选第三单体由1,4-环己二醇和异山梨醇组成，且1,4-环己二醇：异山梨醇的摩尔比为1:1-1:10。将共聚酯切片磨成粉状，将共聚酯切片粉末与粒径为1.2-1.6μm的硫酸钡，分散剂混合后经双螺杆挤出造粒，制备得到光学开口母粒，硫酸钡的质量分数为2％-5％；将共聚酯切片磨成粉状，将共聚酯粉末与粒径30-80nm纳米高岭土颗粒、分散剂混合后经双螺杆挤出造粒，制备得到结晶成核剂，纳米高岭土颗粒的质量分数为1％-3％；以质量百分比计，将93％-98％的共聚酯切片、1％-5％的光学开口母粒与1％-2％的结晶成核剂通过吸料系统送至主挤出机相应的料仓内，加料至挤出机中，经熔融、抽真空、过滤处理，除去原料熔体中的水分、低聚物和杂质后作为熔体；所得熔体在衣架式模头中挤出，挤出为分段控温方式，共分为三段，第一段温度为265-270℃，第二段为270-275℃，第三段为265-270℃。三段的时间比为(2-2.5)：(2-3)：(1-1.5)，由模头挤出的熔体贴附到冷鼓表面经冷却得到铸片，所得铸片进行拉伸、定型，纵向拉伸分为预热段、拉伸段和冷却定型段，预热段温度为65-85℃，拉伸段温度为90-110℃，冷却定型段温度为20-45℃。横向拉伸分为预热段、拉伸段、定型段和冷却段，预热段温度为80-95℃，拉伸段温度为100-120℃，定型段温度为210-230℃，冷却段温度为40-60℃；横向和纵向拉伸倍率相同，且均为3.3-3.6；拉伸、定型后进入牵引系统进行测厚反馈、超声波清洗、展平、除静电和收卷，获得厚度为12-75μm的高透光率聚酯薄膜。
将摩尔比为0.1:10-0.8:10的1,4第三单体与乙二醇、以及催化剂混合以后，再与对苯二甲酸混合、加热、抽真空进行反应，反应完成后降压，出料，冷却，切粒制成共聚酯切片；第三单体为1,4-环己二醇、1,3-环戊二醇、异山梨醇中的一种或任意组合，优选第三单体由1,4-环己二醇和异山梨醇组成，且1,4-环己二醇：异山梨醇的摩尔比为1:1-1:10。将与上面原料相同的，摩尔比为0.1:10-0.8:10的1,4第三单体与乙二醇、以及催化剂混合以后，再与对苯二甲酸、粒径为1.2-1.6μm的硫酸钡及分散剂混合、加热、抽真空进行反应，反应完成后降压出料，经双螺杆挤出造粒，制备得到光学开口母粒，硫酸钡的质量分数为2％-5％；同样的，将摩尔比为0.1:10-0.8:10的1,4第三单体与乙二醇、以及催化剂混合以后，再与对苯二甲酸、粒径30-80nm纳米高岭土颗粒及分散剂混合、加热、抽真空进行反应，反应完成后降压出料，经双螺杆挤出造粒，制备得到结晶成核剂，纳米高岭土颗粒的质量分数为1％-3％；以质量百分比计，将93％-98％的共聚酯切片、1％-5％的光学开口母粒与1％-2％的结晶成核剂通过吸料系统送至主挤出机相应的料仓内，加料至挤出机中，经熔融、抽真空、过滤处理，除去原料熔体中的水分、低聚物和杂质后作为熔体；所得熔体在衣架式模头中挤出，挤出为分段控温方式，共分为三段，第一段温度为265-270℃，第二段为270-275℃，第三段为265-270℃。三段的时间比为(2-2.5)：(2-3)：(1-1.5)，由模头挤出的熔体贴附到冷鼓表面经冷却得到铸片，所得铸片进行拉伸、定型，纵向拉伸分为预热段、拉伸段和冷却定型段，预热段温度为65-85℃，拉伸段温度为90-110℃，冷却定型段温度为20-45℃。横向拉伸分为预热段、拉伸段、定型段和冷却段，预热段温度为80-95℃，拉伸段温度为100-120℃，定型段温度为210-230℃，冷却段温度为40-60℃；横向和纵向拉伸倍率相同，且均为3.3-3.6；拉伸、定型后进入牵引系统进行测厚反馈、超声波清洗、展平、除静电和收卷，获得厚度为12-75μm的高透光率聚酯薄膜。
实施例1
将摩尔比为0.2:10的1,4环己二醇与乙二醇、以及催化剂混合以后，再与对苯二甲酸混合、加热、抽真空进行反应，反应完成后降压，出料，冷却，切粒制成共聚酯切片；将共聚酯切片磨成粉状，与粒径为1.4μm的硫酸钡、分散剂混合后经双螺杆挤出造粒，制备得到光学开口母粒；将共聚酯粉末与40nm纳米高岭土颗粒、分散剂混合后经双螺杆挤出造粒，制备得到结晶成核剂；以质量百分比计，将96％的共聚酯切片、3％的光学开口母粒与1％的结晶成核剂通过吸料系统送至主挤出机相应的料仓内，加料至挤出机中，经熔融、抽真空、过滤处理，除去原料熔体中的水分、低聚物和杂质后作为熔体；所得熔体在衣架式模头中挤出；由模头挤出的熔体贴附到冷鼓表面经冷却得到铸片，所得铸片经3.4×3.4拉伸、定型后进入牵引系统进行测厚反馈、超声波清洗、展平、除静电和收卷，获得厚度为23μm的高透光率聚酯薄膜。
实施例2
将摩尔比为0.2:10的1,4环己二醇、异山梨醇(1，4环己二醇与异山梨醇的摩尔比为1：10)与乙二醇、以及催化剂混合以后，再与对苯二甲酸混合加热、抽真空进行反应，反应完成后降压，出料，冷却，切粒制成共聚酯切片；将共聚酯切片磨成粉状，与粒径为1.2μm的硫酸钡、分散剂混合后经双 螺杆挤出造粒，制备得到光学开口母粒；将共聚酯粉末与粒径为50nm的纳米高岭土颗粒、分散剂混合后经双螺杆挤出造粒，制备得到结晶成核剂；以质量百分比计，将96％的共聚酯切片、2％的光学开口母粒与2％的结晶成核剂通过吸料系统送至主挤出机相应的料仓内，加料至挤出机中，经熔融、抽真空、过滤处理，除去原料熔体中的水分、低聚物和杂质后作为熔体；所得熔体在模头中挤出；由模头挤出的熔体贴附到冷鼓表面经冷却得到铸片，所得铸片经3.5×3.5拉伸、定型后进入牵引系统进行测厚反馈、超声波清洗、展平、除静电和收卷，获得厚度为50μm的高透光率聚酯薄膜。
实施例3
将摩尔比为0.2:10的1,4环己二醇、异山梨醇(1，4环己二醇与异山梨醇的摩尔比为1：1)与乙二醇、以及催化剂混合以后，再与对苯二甲酸混合加热、抽真空进行反应，反应完成后降压，出料，冷却，切粒制成共聚酯切片；将共聚酯切片磨成粉状，与粒径为1.2μm的硫酸钡、分散剂混合后经双螺杆挤出造粒，制备得到光学开口母粒；将共聚酯粉末与粒径为50nm的纳米高岭土颗粒、分散剂混合后经双螺杆挤出造粒，制备得到结晶成核剂；以质量百分比计，将96％的共聚酯切片、2％的光学开口母粒与2％的结晶成核剂通过吸料系统送至主挤出机相应的料仓内，加料至挤出机中，经熔融、抽真空、过滤处理，除去原料熔体中的水分、低聚物和杂质后作为熔体；所得熔体在模头中挤出；由模头挤出的熔体贴附到冷鼓表面经冷却得到铸片，所得铸片经3.5×3.5拉伸、定型后进入牵引系统进行测厚反馈、超声波清洗、展平、除静电和收卷，获得厚度为50μm的高透光率聚酯薄膜。
实施例4
将摩尔比为0.4:10的异山梨醇与乙二醇、以及催化剂混合以后，再与对苯二甲酸混合加热、抽真空进行反应，反应完成后降压，出料，冷却，切粒制成共聚酯切片；将共聚酯切片磨成粉状，与粒径为1.4μm的硫酸钡、分散剂混合后经双螺杆挤出造粒，制备得到光学开口母粒；将共聚酯粉末与30nm的高岭土颗粒、分散剂混合后经双螺杆挤出造粒，制备得到结晶成核剂；以质量百分比计，将97％的共聚酯切片、2％的光学开口母粒与1％的结晶成核剂通过吸料系统送至主挤出机相应的料仓内，加料至挤出机中，经熔融、抽真空、过滤处理，除去原料熔体中的水分、低聚物和杂质后作为熔体；所得熔体在模头中挤出；由模头挤出的熔体贴附到冷鼓表面经冷却得到铸片，所得铸片经3.4×3.4拉伸、定型后进入牵引系统进行测厚反馈、超声波清洗、展平、除静电和收卷，获得厚度为36μm的高透光率聚酯薄膜。
实施例5
将摩尔比为0.2:10的1,4环己二醇与乙二醇、以及催化剂混合以后，再与对苯二甲酸混合、加热、抽真空进行反应，反应完成后降压，出料，冷却，切粒制成共聚酯切片；将摩尔比为0.2:10的1,4环己二醇与乙二醇、以及催化剂混合后，再与对苯二甲酸、粒径为1.4μm的硫酸钡及分散剂混合、加热、抽真空进行反应，反应完毕降压出料，经双螺杆挤出造粒，制备得到光学开口母粒；将摩尔比为0.2:10的1,4环己二醇与乙二醇、以及催化剂混合后，再与对苯二甲酸、40nm纳米高岭土颗粒及分散剂混合、加热、抽真空进行反应，反应完毕降压出料，经双螺杆挤出造粒，制备得到结晶成核剂；以质量百分比计，将96％的共聚酯切片、3％的光学开口母粒与1％的结晶成核剂通过吸料系统送至主挤出机相应的料仓内，加料至挤出机中，经熔融、抽真空、过滤处理，除去原料熔体中的水分、低聚物和杂质后作为熔体；所得熔体在衣架式模头中挤出；由模头挤出的熔体贴附到冷鼓表面经冷却得到铸片，所得铸片经3.4×3.4拉伸、定型后进入牵引系统进行测厚反馈、超声波清洗、展平、除静电和收卷，获得厚度为23μm的高透光率聚酯薄膜。
实施例6
将摩尔比为0.2:10的1,4环己二醇、异山梨醇(1，4环己二醇与异山梨醇的摩尔比为1：10)与乙二醇、以及催化剂混合以后，再与对苯二甲酸混合加热、抽真空进行反应，反应完成后降压，出料，冷却，切粒制成共聚酯切片；将摩尔比为0.2:10的1,4环己二醇、异山梨醇(1，4环己二醇与异山梨醇的摩尔比为1：10)与乙二醇、以及催化剂混合后，再与对苯二甲酸、粒径为1.2μm的硫酸钡及分散剂混合、加热、抽真空进行反应，反应完毕降压出料，经双螺杆挤出造粒，制备得到光学开口母粒；将摩尔比为0.2:10的1,4环己二醇、异山梨醇(1，4环己二醇与异山梨醇的摩尔比为1：10)与乙二醇、以及催化剂混合后，再与对苯二甲酸、50nm纳米高岭土颗粒及分散剂混合、加热、抽真空进行反应，反应完毕降压出料，经双螺杆挤出造粒，制备得到结晶成核剂；以质量百分比计，将96％的共聚酯切片、2％的光学开口母粒与2％的结晶成核剂通过吸料系统送至主挤出机相应的料仓内，加料至挤出机 中，经熔融、抽真空、过滤处理，除去原料熔体中的水分、低聚物和杂质后作为熔体；所得熔体在模头中挤出；由模头挤出的熔体贴附到冷鼓表面经冷却得到铸片，所得铸片经3.5×3.5拉伸、定型后进入牵引系统进行测厚反馈、超声波清洗、展平、除静电和收卷，获得厚度为50μm的高透光率聚酯薄膜。
对比例1
普通PET透明膜，厚度为50μm。
对比例2
质量百分比为98％的共聚酯切片与2％光学开口母粒组合所制备得到的薄膜，厚度为50μm。
对比例3
质量百分比为98％共聚酯切片与2％结晶成核剂所制备的薄膜，厚度为50μm。
对比例4
100％共聚酯切片所制备的薄膜，厚度为50μm。
聚酯薄膜性能测试方法：
1.透光率：按照ISO13468标准，用德国BYK HAZE-gard i测试。
2.力学性能：拉伸强度、断裂伸长率按照ASTM D882标准测试。
3.热收缩率：按照ASTM D1204标准测试。
各实施例与对比例的试验结果数据见下表：
Figure PCTCN2022119422-appb-000001
从实测数据可以看出，实施例1-6的透光率均高于未使用结晶成核剂的对比例1、2和4；对比例3虽然具有较高的透光率，但由于不含开口剂，薄膜爽滑性不够导致粘膜，难以正常生产以产业化。本发明所制备得到的聚酯薄膜在保持力学性能、热稳定性能不发生显著变化的情况下，提高了聚酯薄膜的透光率，并适于工业化生产。
优选的，实施例2和3中的第三单体采用了1，4环己二醇与异山梨醇组合的方式，提供了更多的不对称构造，进一步打破了分子链的规整性，降低结晶度，对透光率的提升起到积极作用。
更优选的，采用原位聚合法得到光学开口剂和结晶成核剂的实施例5和6中，实施例5与实施例1在第三单体种类和用量、无机粒子的尺寸及用量等相似，实施例6与实施例2在第三单体种类和用量、无机粒子的尺寸及用量等相似的情况下。比较可见，实施例5和6除了有较好的力学性能、热收缩性之外，其透光率相较于各对比例及采用普通共混法得到的产品也有所提高。这也从实验数据上，反向验证了原位聚合法对提高无机粒子，特别是纳米无机粒子在聚合物基质中的分散性，以及提高最终产品性能具有较好的帮助。
以上介绍了本发明的较佳实施方式，旨在使得本发明的精神更加清楚和便于理解，并不是为了限制本发明，凡在本发明的精神和原则之内，所做的修改、替换、改进，均应包含在本发明所附的权利要求概括的保护范围之内。

Claims (10)

  1. 一种高透光率聚酯薄膜，其特征在于，以质量百分比计包括：
    采用对苯二甲酸、乙二醇及第三单体共聚得到的改性共聚酯切片93％-98％、光学开口母粒1％-5％以及结晶成核剂1％-2％，通过熔融挤出且双向拉伸获得厚度为12-75μm的高透光率的聚酯薄膜，其中，所述第三单体为1,4-环己二醇、1,3-环戊二醇、异山梨醇中的一种或任意组合，所述光学开口母粒为硫酸钡与所述改性共聚酯的混炼物，所述结晶成核剂为纳米高岭土与所述改性共聚酯的混炼物。
  2. 根据权利1所述的高透光率聚酯薄膜，其特征在于，第三单体与乙二醇摩尔比为0.1:10-0.8:10。
  3. 根据权利1或2所述的高透光率聚酯薄膜，第三单体由1,4-环己二醇和异山梨醇组成，且1,4-环己二醇：异山梨醇摩尔比为1:1-1:10。
  4. 根据权利1所述的高透光率聚酯薄膜，其特征在于，所述光学开口母粒中，硫酸钡的质量分数为2％-5％，粒径为1.2-1.6μm。
  5. 根据权利1所述的高透光率聚酯薄膜，其特征在于，所述结晶成核剂中，纳米高岭土的质量分数为1％-3％，粒径为30-80nm。
  6. 根据权利1所述的高透光率聚酯薄膜，其特征在于，所述双向拉伸方式包括同步拉伸或异步拉伸，拉伸倍率为3.3-3.6倍，且MD方向的拉伸倍率与TD方向的拉伸倍率一致。
  7. 根据权利要求1至6任一项所述的高透光率聚酯薄膜的制造方法，包括以下步骤：
    S1：改性共聚酯切片的制备：
    将第三单体与乙二醇、催化剂混合后，再与对苯二甲酸混合、加热、抽真空进行反应，反应完毕降压出料，冷却，切粒制成改性共聚酯切片；
    S2：光学开口母粒的制备：
    将部分上述改性共聚酯切片磨成粉状，与硫酸钡、分散剂混合，经双螺杆挤出造粒；
    S3：结晶成核剂的制备：
    将部分上述改性共聚酯切片磨成粉状，与纳米高岭土、分散剂混合，经双螺杆挤出造粒；
    S4：将共聚酯切片、光学开口母粒以及结晶成核剂送入挤出机，熔融挤出，双向拉伸获得厚度为12-75μm的高透光率的聚酯薄膜。
  8. 根据权利要求1至6任一项所述的高透光率聚酯薄膜的制造方法，包括以下步骤：
    S1：改性共聚酯切片的制备：
    将第三单体与乙二醇、催化剂混合后，再与对苯二甲酸混合、加热、抽真空进行反应，反应完毕降压出料，冷却，切粒制成改性共聚酯切片；
    S2：光学开口母粒的制备：
    将第三单体与乙二醇、催化剂混合后，再与对苯二甲酸、硫酸钡及分散剂混合、加热、抽真空进行反应，反应完毕降压出料，经双螺杆挤出造粒；
    S3：结晶成核剂的制备：
    将第三单体与乙二醇、催化剂混合后，再与对苯二甲酸、纳米高岭土及分散剂混合、加热、抽真空进行反应，反应完毕降压出料，经双螺杆挤出造粒；
    S4：将共聚酯切片、光学开口母粒以及结晶成核剂送入挤出机，熔融挤出，双向拉伸获得厚度为12-75μm的高透光率的聚酯薄膜。
  9. 根据权利要求7或8所述的高透光率聚酯薄膜的制造方法，其特征在于，所述纵向拉伸分为预热段、拉伸段和冷却定型段，预热段温度为65-85℃，拉伸段温度为90-110℃，冷却定型段温度为20-45℃；
    所述横向拉伸分为预热段、拉伸段、定型段和冷却段，预热段温度为80-95℃，拉伸段温度为100-120℃，定型段温度为210-230℃，冷却段温度为40-60℃。
  10. 权利要求1至6任一项所述的高透光率聚酯薄膜在电子显示领域或光学元件中的应用。
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117510922A (zh) * 2023-11-21 2024-02-06 浙江中发薄膜有限公司 一种高透光聚酯薄膜及其制备方法
CN117736424A (zh) * 2024-02-20 2024-03-22 烟台舜康生物科技有限公司 异山梨醇改性pet共聚酯的合成方法

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114702789B (zh) * 2022-03-01 2023-12-19 杭州和顺科技股份有限公司 一种高透光率聚酯薄膜及其制造方法
CN115636982A (zh) * 2022-11-10 2023-01-24 江苏东材新材料有限责任公司 低取向高耐热的光学基膜用成核剂及光学基膜的制备方法

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102666681A (zh) * 2009-11-13 2012-09-12 Sk化学株式会社 共聚聚酯热收缩膜
CN103102474A (zh) * 2011-11-09 2013-05-15 中国石油化工股份有限公司 亚光聚酯薄膜的制备方法
CN103172990A (zh) * 2013-03-26 2013-06-26 江苏双星彩塑新材料股份有限公司 一种热收缩共聚酯薄膜的制备方法
CN103203934A (zh) * 2013-03-26 2013-07-17 江苏双星彩塑新材料股份有限公司 一种热收缩共聚酯薄膜及其制备方法
CN103753924A (zh) * 2013-12-30 2014-04-30 四川东方绝缘材料股份有限公司 一种高透明聚酯薄膜及其制备方法
WO2014112770A1 (ko) * 2013-01-15 2014-07-24 에스케이케미칼주식회사 폴리에스테르계 열수축 필름
CN114702789A (zh) * 2022-03-01 2022-07-05 杭州和顺科技股份有限公司 一种高透光率聚酯薄膜及其制造方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101458228B1 (ko) * 2008-11-03 2014-11-07 코오롱인더스트리 주식회사 폴리에스테르 필름 및 그의 제조방법
CN110920171A (zh) * 2018-09-19 2020-03-27 宝山钢铁股份有限公司 一种聚酯覆铁膜的制备方法以及覆膜金属容器
CN110626029A (zh) * 2019-10-25 2019-12-31 浙江和顺新材料有限公司 一种紫色双向拉伸聚酯薄膜及其制备方法
CN113956448A (zh) * 2021-10-26 2022-01-21 四川东材科技集团股份有限公司 一种光学膜用聚酯母粒及其制备方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102666681A (zh) * 2009-11-13 2012-09-12 Sk化学株式会社 共聚聚酯热收缩膜
CN103102474A (zh) * 2011-11-09 2013-05-15 中国石油化工股份有限公司 亚光聚酯薄膜的制备方法
WO2014112770A1 (ko) * 2013-01-15 2014-07-24 에스케이케미칼주식회사 폴리에스테르계 열수축 필름
CN103172990A (zh) * 2013-03-26 2013-06-26 江苏双星彩塑新材料股份有限公司 一种热收缩共聚酯薄膜的制备方法
CN103203934A (zh) * 2013-03-26 2013-07-17 江苏双星彩塑新材料股份有限公司 一种热收缩共聚酯薄膜及其制备方法
CN103753924A (zh) * 2013-12-30 2014-04-30 四川东方绝缘材料股份有限公司 一种高透明聚酯薄膜及其制备方法
CN114702789A (zh) * 2022-03-01 2022-07-05 杭州和顺科技股份有限公司 一种高透光率聚酯薄膜及其制造方法

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117510922A (zh) * 2023-11-21 2024-02-06 浙江中发薄膜有限公司 一种高透光聚酯薄膜及其制备方法
CN117736424A (zh) * 2024-02-20 2024-03-22 烟台舜康生物科技有限公司 异山梨醇改性pet共聚酯的合成方法
CN117736424B (zh) * 2024-02-20 2024-04-16 烟台舜康生物科技有限公司 异山梨醇改性pet共聚酯的合成方法

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