WO2021120496A1 - 一种无色透明聚酰亚胺复合膜及其制备方法 - Google Patents

一种无色透明聚酰亚胺复合膜及其制备方法 Download PDF

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WO2021120496A1
WO2021120496A1 PCT/CN2020/088406 CN2020088406W WO2021120496A1 WO 2021120496 A1 WO2021120496 A1 WO 2021120496A1 CN 2020088406 W CN2020088406 W CN 2020088406W WO 2021120496 A1 WO2021120496 A1 WO 2021120496A1
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colorless
composite film
base layer
transparent polyimide
glass
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PCT/CN2020/088406
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English (en)
French (fr)
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陈图强
徐鸿
李祥涛
王宏
蓝庆东
胡浩亨
胡锋
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浙江道明光电科技有限公司
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Priority to JP2022519345A priority Critical patent/JP7174885B2/ja
Priority to KR1020227014359A priority patent/KR20220078632A/ko
Publication of WO2021120496A1 publication Critical patent/WO2021120496A1/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
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/06—Coating with compositions not containing macromolecular substances
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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  • the invention relates to the technical field of polyimide films, in particular to a colorless and transparent polyimide composite film and a preparation method thereof.
  • Polyimide film has good photoelectric properties, mechanical properties, water vapor barrier properties, etc., and has been widely used in electrical insulation materials, flexible copper clad laminates (FCCL), flexible OLED displays, window films, new energy and other high-tech high-tech
  • CPI colorless and transparent polyimide
  • the transparency and flexibility of CPI films basically meet the requirements of practical applications, but the surface hardness and water vapor barrier properties of CPI films do not meet the requirements of practical applications.
  • the first is to coat an organic hard layer on the CPI film.
  • This method cannot fundamentally solve the requirement for high water vapor barrier of the CPI film; the second is to coat an inorganic glass material on the CPI film to obtain high The performance of light transmission, high water resistance and high hardness, but because the brittleness of the glass layer greatly affects the flexibility of the CPI-glass composite film, the foldability and bendability of the CPI-glass composite film are far from reaching the practical use.
  • Requirement due to the large difference between the thermal expansion coefficient of CPI and glass during the preparation process, and the difference between the preparation temperature of CPI and glass at least 300 °C, in the case of thermal stress, the CPI-glass composite film will produce delamination, so in the CPI It is impossible to melt-coat glass directly on the film.
  • the present invention provides a new colorless and transparent polyimide composite film and a preparation method thereof.
  • a colorless and transparent polyimide composite film includes a polyimide base layer and a glass surface layer, and an intermediate structure is formed between the glass surface layer and the polyimide base layer.
  • the intermediate structure is a buffer layer with a fine structure, which can effectively form a three-dimensional polyimide-glass composite structure, and the intermediate structure can maintain the characteristics of the glass material and make it colorless
  • the transparent polyimide composite film as a whole has excellent characteristics such as water blocking, oxygen blocking, bending resistance and high hardness.
  • the thickness of the polyimide base layer is T1, 5 ⁇ m ⁇ T1 ⁇ 200 ⁇ m, and the thickness of the glass surface layer is T2, 200nm ⁇ T2 ⁇ 60 ⁇ m.
  • the thickness of the polyimide base layer and the glass surface layer can be controlled in a wide range, and the colorless and transparent polyimide composite film can be given the best flexibility and foldability on the basis of meeting the hardness of the surface layer.
  • the overall performance of the colorless and transparent polyimide composite film can be adjusted by adjusting the thickness of the polyimide base layer and the glass surface layer, so as to meet the film thickness requirements of different application fields.
  • the intermediate structure is a diffusion structure formed by mutual penetration between the polyimide base layer and the glass surface layer, and the intermediate The thickness of the structure is t, 100nm ⁇ t ⁇ 50 ⁇ m.
  • the above-mentioned intermediate structure is a diffusion structure, which can make the colorless and transparent polyimide composite film have strong interlayer bonding and is not prone to delamination.
  • the diffusion structure can enhance the flexibility of the colorless and transparent polyimide composite film.
  • the thickness of the above-mentioned intermediate structure is obtained by measuring the distance between the polyimide base layer and the glass surface layer, and the thickness of the intermediate structure is controlled in a wider range, so that the film structure has a larger optimization space.
  • the intermediate structure is a staggered structure formed by staggering the polyimide base layer and the glass surface layer.
  • the thickness of the structure is t, 100nm ⁇ t ⁇ 50 ⁇ m.
  • the above-mentioned intermediate structure is a staggered structure, which can make the colorless and transparent polyimide composite film form a three-dimensional polyimide-glass composite structure, thereby enhancing the composite characteristics, increasing the contact area between layers, and improving the colorless and transparent polyimide
  • the interface bonding force, flexibility and flexural resistance of the composite film is obtained by measuring the distance between the polyimide base layer and the glass surface layer, and the thickness of the intermediate structure is controlled in a wider range, so that the film structure has a larger optimization space.
  • the intermediate structure is a composite structure formed by mutual diffusion and interleaving between the polyimide base layer and the glass surface layer, so The thickness of the intermediate structure is t, 100nm ⁇ t ⁇ 50 ⁇ m.
  • the above-mentioned intermediate structure is a composite structure formed by mutual diffusion and staggering, so that the colorless and transparent polyimide composite film has the composite characteristics of a diffusion structure and a staggered structure, which can effectively increase the contact area and the bonding force between the layers, and simultaneously composite
  • the structure can better buffer and absorb the stress on the surface of the colorless and transparent polyimide composite film, so that the colorless and transparent polyimide composite film has better water resistance, oxygen resistance, bending resistance and high hardness. Excellent characteristics.
  • the thickness of the above-mentioned intermediate structure is obtained by measuring the distance between the polyimide base layer and the glass surface layer, and the thickness of the intermediate structure is controlled in a wider range, so that the film structure has a larger optimization space.
  • the polyimide base layer is provided with a micro pattern, and the upper surface of the glass surface layer has the same shape or shape as the surface of the micro pattern. similar.
  • the above micro pattern defines the outline of the intermediate structure.
  • the upper surface of the above glass surface layer has a shape consistent or similar to the micro pattern, which can make the internal stress distribution of the colorless and transparent polyimide composite film structure more uniform, thereby improving the The color and transparent polyimide composite film's ability to withstand deformation effectively enhances the flexibility and foldability of the colorless and transparent polyimide composite film.
  • the ratio of the depth of the micro pattern to the thickness of the polyimide base layer is 0.1 to 0.9.
  • the ratio of the depth of the micro pattern to the thickness of the polyimide base layer is controlled in a wide range, and the best structure and performance are always maintained on the basis of meeting different application requirements, so that the film structure has more room for optimization .
  • the microscopic pattern is wavy, and the distance L between adjacent peaks and troughs in the wavy microscopic pattern is 20 nm-100 ⁇ m.
  • the wave-shaped micro pattern includes at least one of a horizontal pattern and a vertical pattern.
  • the use of a wave-shaped pattern in the micro pattern can improve the bending resistance of the colorless transparent polyimide composite film in the horizontal and vertical directions, and not only increase the film
  • the contact area of the layer makes the film layer have better continuity and at the same time reduces the overall thickness of the colorless and transparent polyimide composite film.
  • the distance between adjacent wave peaks and wave troughs in the wave-shaped micro pattern is controlled in a wide range, so that the film structure has a larger optimization space.
  • the polyimide base layer, the glass surface layer, and the intermediate structure are bent and deformed under the action of an external force.
  • the polyimide base layer, the glass surface layer and the intermediate structure together form a three-dimensional polyimide-glass composite structure, which can effectively release the internal stress caused by bending deformation and improve the ability of the colorless and transparent polyimide composite film to withstand
  • the maximum deformation strength of the colorless transparent polyimide composite film can effectively avoid permanent deformation and cracking caused by bending fatigue of the colorless transparent polyimide composite film.
  • the method for preparing a colorless and transparent polyimide composite film described above includes the following preparation steps:
  • S1 Deposit a polyamic acid precursor on a rigid substrate, and light-curing for 5s-5min or thermal curing for 0.5-5h under an environment of 150-250°C to obtain a semi-cured polyimide base layer;
  • the multi-component glass precursor includes SiO 2 precursor, Al 2 O 3 precursor, Na 2 O precursor, and B 2 O 3 Precursor, an intermediate structure is formed between the multi-component glass precursor and the semi-cured polyimide base layer. At the same time, it is light-cured for 5s-5min or thermally cured for 0.5-5h at 250-350°C to make multi-component glass After the precursor is semi-cured, a semi-cured glass surface layer is obtained;
  • the polyamic acid precursor is heated to form a semi-cured polyimide base layer, which can better perform physical processing such as precision pressing or photolithography, which is conducive to forming a stable processing shape without affecting the film itself Structure;
  • step S2 heating the multi-component glass precursor to form a semi-cured glass surface layer is conducive to forming a film with a smaller particle size and a uniform distribution, and improving the density and uniformity of the glass surface layer;
  • the polyimide base layer is formed by curing a polyamic acid precursor, and the glass surface layer is formed by curing a multi-component glass precursor, which is conducive to preparing a film structure with a small particle size, a uniform distribution and a uniform composition, and improves the film
  • the density and uniformity of the layer, and the sol-gel method is simple and convenient, which effectively reduces the cost of the preparation process.
  • the polyamic acid precursor can be polymerized by a multi-component dianhydride and a multi-component diamine in a polar organic solvent.
  • the above-mentioned multi-component dianhydrides include benzophenone dianhydride, biphenyl dianhydride, 1,2,4,5-cyclohexane tetracarboxylic dianhydride, triphenyl diether dianhydride, hexafluoro dianhydride, diphenyl ether two One or more of anhydride, diphenyl sulfide dianhydride, hydroquinone diether dianhydride, resorcinol diether dianhydride, bisphenol A type diether dianhydride and pyromellitic dianhydride;
  • the above-mentioned multi-component diamines include p-phenylenediamine, m-phenylenediamine, 2,2'-bis(trifluoromethyl)diaminobiphenyl;
  • the multi-component glass precursor may include one or more of Si(OR) 4 , Al(OR) 3 , B(OR) 3 and NaOR, where R includes -CH 3 , -C 2 H 5 , -One or more of C 3 H 7 and C 4 H 9.
  • the multi-component glass precursor contains 20% to 80% of glass or talc.
  • glass or talc powder to the multi-component glass precursor is beneficial to optimize the shrinkage rate during the curing process of the film.
  • the content of glass or talc powder By adjusting the content of glass or talc powder, the colorless and transparent polyimide composite film can be prevented from delamination during the curing process. Cracking and warping.
  • the surface of the semi-cured polyimide base layer is formed with microscopic patterns by precision pressing or photolithography.
  • Using precision pressing or photoetching methods to process microscopic patterns can ensure the precision and depth of the microscopic patterns, which is conducive to mass production and processing.
  • the present invention has outstanding beneficial effects: firstly, the colorless and transparent polyimide composite film prepared by the present invention has excellent surface hardness and wear resistance similar to that of glass material, and suffers from external It can effectively reduce the damage after the collision and abrasion of the object; secondly, the colorless and transparent polyimide composite film has excellent water vapor barrier properties similar to the glass material, which can prolong the service life of the product; finally, the colorless and transparent polyimide The amine composite film still maintains the excellent flexibility and foldability of the PI film, and has a broader application prospect.
  • FIG. 1 is a schematic diagram of the transverse or longitudinal cross-sectional structure of the intermediate structure of the present invention as a diffusion structure;
  • FIG. 2 is a schematic diagram of a transverse or longitudinal cross-sectional structure of the intermediate structure of the present invention as a staggered structure
  • Fig. 3 is a schematic diagram of the transverse or longitudinal cross-sectional structure of the intermediate structure of the present invention as a composite structure
  • FIG. 4 is a schematic diagram of a transverse or longitudinal cross-sectional structure in which the intermediate structure of the present invention is a staggered structure and the upper surface of the glass surface layer is similar to the micro pattern shape;
  • FIG. 5 is a schematic diagram of the transverse or longitudinal cross-sectional structure of the intermediate structure of the present invention is a composite structure and the upper surface of the glass surface layer is similar to the micro pattern shape.
  • a colorless and transparent polyimide composite film comprising a polyimide base layer 1, a glass surface layer 3, the glass surface layer 3 and the polyimide base layer
  • An intermediate structure 2 is formed between 1.
  • the thickness T1 of the polyimide base layer 1 is 200 ⁇ m, and the thickness T2 of the glass surface layer 3 is 60 ⁇ m.
  • the intermediate structure 2 is a diffusion structure formed by mutual penetration between the polyimide base layer 1 and the glass surface layer 3, and the thickness t of the intermediate structure 2 is 50 ⁇ m.
  • the intermediate structure 2 is a staggered structure formed by staggering the polyimide base layer 1 and the glass surface layer 3, and the thickness t of the intermediate structure 2 is 50 ⁇ m.
  • the intermediate structure 2 is a composite structure formed by mutual diffusion and interleaving between the polyimide base layer 1 and the glass surface layer 3, and the thickness t of the intermediate structure 2 is 50 ⁇ m.
  • the polyimide base layer 1 is provided with a micro pattern, and the upper surface of the glass surface layer 3 has the same or similar shape to the surface of the micro pattern.
  • the ratio of the depth of the micro pattern to the thickness of the polyimide base layer 1 is 0.9.
  • the microscopic pattern is wave-shaped, and the distance L between adjacent wave peaks and wave troughs in the wave-shaped microscopic pattern is 100 ⁇ m.
  • the polyimide base layer 1, the glass surface layer 3, and the intermediate structure 2 are bent and deformed under the action of an external force.
  • S2 Deposit a multi-component glass precursor on the surface of the semi-cured polyimide base layer 1.
  • the multi-component glass precursor includes SiO 2 precursor, Al 2 O 3 precursor, Na 2 O precursor, and B 2 O 3 Precursor, an intermediate structure 2 is formed between the multi-component glass precursor and the semi-cured polyimide base layer 1.
  • the multi-component glass precursor is semi-cured by light curing for 5 minutes or thermal curing for 5 hours at 350°C.
  • a semi-cured glass surface layer 3 is obtained after curing;
  • the multi-component glass precursor contains 80% glass or talc.
  • the surface of the semi-cured polyimide base layer 1 is formed with a microscopic pattern by precision pressing or photolithography.
  • a colorless and transparent polyimide composite film comprising a polyimide base layer 1, a glass surface layer 3, the glass surface layer 3 and the polyimide base layer
  • An intermediate structure 2 is formed between 1.
  • the thickness T1 of the polyimide base layer 1 is 5 ⁇ m, and the thickness T2 of the glass surface layer 3 is 200 nm.
  • the intermediate structure 2 is a diffusion structure formed by mutual penetration between the polyimide base layer 1 and the glass surface layer 3, and the thickness t of the intermediate structure 2 is 100 nm.
  • the intermediate structure 2 is a staggered structure formed by staggering the polyimide base layer 1 and the glass surface layer 3, and the thickness t of the intermediate structure 2 is 100 nm.
  • the intermediate structure 2 is a composite structure formed by mutual diffusion and interleaving between the polyimide base layer 1 and the glass surface layer 3, and the thickness t of the intermediate structure 2 is 100 nm.
  • the polyimide base layer 1 is provided with a micro pattern, and the upper surface of the glass surface layer 3 has the same or similar shape to the surface of the micro pattern.
  • the ratio of the depth of the micro pattern to the thickness of the polyimide base layer 1 is 0.1.
  • the microscopic pattern is wave-shaped, and the distance L between adjacent peaks and troughs in the wave-shaped microscopic pattern is 20 nm.
  • the polyimide base layer 1, the glass surface layer 3, and the intermediate structure 2 are bent and deformed under the action of an external force.
  • S2 Deposit a multi-component glass precursor on the surface of the semi-cured polyimide base layer 1.
  • the multi-component glass precursor includes SiO 2 precursor, Al 2 O 3 precursor, Na 2 O precursor, and B 2 O 3 Precursor, an intermediate structure 2 is formed between the multi-component glass precursor and the semi-cured polyimide base layer 1. At the same time, it is light-cured for 5s or thermally cured for 0.5h at 250°C to make the multi-component glass precursor After semi-curing, a semi-cured glass surface layer 3 is obtained;
  • the multi-component glass precursor contains 20% glass or talc.
  • the surface of the semi-cured polyimide base layer 1 is formed with a microscopic pattern by precision pressing or photolithography.
  • a colorless and transparent polyimide composite film comprising a polyimide base layer 1, a glass surface layer 3, the glass surface layer 3 and the polyimide base layer
  • An intermediate structure 2 is formed between 1.
  • the thickness T1 of the polyimide base layer 1 is 50 ⁇ m, and the thickness T2 of the glass surface layer 3 is 2 ⁇ m.
  • the intermediate structure 2 is a diffusion structure formed by mutual penetration between the polyimide base layer 1 and the glass surface layer 3, and the thickness t of the intermediate structure 2 is 5 ⁇ m.
  • the intermediate structure 2 is a staggered structure formed by staggering the polyimide base layer 1 and the glass surface layer 3, and the thickness t of the intermediate structure 2 is 20 ⁇ m.
  • the intermediate structure 2 is a composite structure formed by mutual diffusion and interleaving between the polyimide base layer 1 and the glass surface layer 3, and the thickness t of the intermediate structure 2 is 20 ⁇ m.
  • the polyimide base layer 1 is provided with a micro pattern, and the upper surface of the glass surface layer 3 has the same or similar shape to the surface of the micro pattern.
  • the ratio of the depth of the micro pattern to the thickness of the polyimide base layer 1 is 0.5.
  • the microscopic pattern is wave-shaped, and the distance L between adjacent peaks and troughs in the wave-shaped microscopic pattern is 50 ⁇ m.
  • the polyimide base layer 1, the glass surface layer 3, and the intermediate structure 2 are bent and deformed under the action of an external force.
  • S1 Deposit a polyamic acid precursor on a rigid substrate, and light-curing for 2 minutes or thermally curing for 3 hours at 200°C to obtain a semi-cured polyimide base layer 1;
  • S2 Deposit a multi-component glass precursor on the surface of the semi-cured polyimide base layer 1.
  • the multi-component glass precursor includes SiO 2 precursor, Al 2 O 3 precursor, Na 2 O precursor, and B 2 O 3 Precursor, the intermediate structure 2 is formed between the multi-component glass precursor and the semi-cured polyimide base layer 1. At the same time, it is cured by light for 2 minutes or thermally cured for 3 hours at 300 °C to make the multi-component glass precursor half A semi-cured glass surface layer 3 is obtained after curing;
  • the multi-component glass precursor contains 50% glass or talc.
  • the surface of the semi-cured polyimide base layer 1 is formed with a microscopic pattern by precision pressing or photolithography.
  • Pencil hardness test Use a pencil hardness tester to test the hardness of the pencil according to the method of GB/T 6739 "Pencil Method for Paints and Varnishes to Determine the Hardness of Paint Films";
  • Bending resistance test a hinge type bending test machine is used for reciprocating bending at a bending radius of 5mm, an angle of 0-180° and a speed of 20rpm/min;
  • Comparative Example 1 is a polyimide composite film produced by Taiwan Yongjie Innovation Technology Co., Ltd.
  • Comparative Example 2 is a PI film produced by KOLON Industrial Co., Ltd.
  • Comparative Example 3 is flexible glass produced by Corning Incorporated of the United States.

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Abstract

本发明公开一种无色透明聚酰亚胺复合膜及其制备方法，包括聚酰亚胺基底层、玻璃表面层，所述玻璃表面层与所述聚酰亚胺基底层之间形成中间结构。与现有技术相比，本发明具有突出的有益效果：首先，通过本发明所制得的无色透明聚酰亚胺复合膜具有与玻璃材质相近的优异表面硬度和抗磨损性能，在遭受外物的碰撞和磨损后能够有效降低损伤；其次，无色透明聚酰亚胺复合膜具有与玻璃材质相近的优异抗水气阻隔性能，能够延长产品的使用寿命；最后，无色透明聚酰亚胺复合膜仍保持PI薄膜的优异的柔性、可折叠性，具有更加广阔的应用前景。

Description

一种无色透明聚酰亚胺复合膜及其制备方法 技术领域
本发明涉及聚酰亚胺薄膜技术领域，尤其涉及一种无色透明聚酰亚胺复合膜及其制备方法。
背景技术
聚酰亚胺薄膜具有良好的光电性质、机械性能、水气阻隔性等特性，现已广泛应用于电工绝缘材料、挠性覆铜板(FCCL)以及柔性OLED显示器、窗膜、新能源等高新技术产业领域，无色透明聚酰亚胺(CPI)主要应用于柔性手机、平板、电视及未来其他智能显示设备，是未来柔性电子不可或缺的关键材料。在柔性OLED显示器领域的应用中，CPI薄膜的透明度和柔性基本达到实际应用的要求，但CPI薄膜的表面硬度和水气阻隔性能不满足实际应用的要求，目前解决硬度缺陷的方法有两种，第一种是在CPI膜上涂敷有机加硬层，这种方法无法从根本上解决对CPI膜高水气阻隔的要求；第二种是在CPI膜上涂敷无机玻璃材料，以获得高透光、高阻水和高硬度的性能，但由于玻璃层的脆性极大地影响了CPI-玻璃复合膜的柔性，使CPI-玻璃复合膜的可折叠性和可弯曲性远不能达到实际使用的要求，在制备过程中由于CPI和玻璃的热膨胀系数相差较大，且CPI和玻璃的制备温度相差至少300℃，在有热应力的情况下，CPI-玻璃复合膜会产生层离，所以在CPI膜上直接熔融涂敷玻璃是不可能的。
基于上述问题，在柔性OLED显示以及其它领域的应用上，极需对目前市场上的CPI薄膜现状进行改善。
发明内容
本发明针对现有技术中存在的聚酰亚胺薄膜的阻隔性和硬度不满足实际使用要求等缺陷，提供了一种新的无色透明聚酰亚胺复合膜及其制备方法。
为了解决上述技术问题，本发明通过以下技术方案实现：
一种无色透明聚酰亚胺复合膜，包括聚酰亚胺基底层、玻璃表面层，所述玻璃表面层与所述聚酰亚胺基底层之间形成中间结构。
上述无色透明聚酰亚胺复合膜中，中间结构为具有微细结构的缓冲层，能有效地形成三维聚酰亚胺-玻璃复合结构，且中间结构能保持玻璃材质的特性，能使无色透明聚酰亚胺复合膜整体具有阻水、阻氧、耐弯折及高硬度等优异特性。
作为优选，上述所述的一种无色透明聚酰亚胺复合膜，所述聚酰亚胺基底层的厚度为T1，5μm≤T1≤200μm，所述玻璃表面层厚度为T2，200nm≤T2≤60μm。
聚酰亚胺基底层和玻璃表面层的厚度能够在较宽的范围内进行控制，在满足表层硬度需求的基础上能赋予无色透明聚酰亚胺复合膜最佳的柔韧性、可折叠性和强度，同时通过调整聚酰亚胺基底层和玻璃表面层的厚度能够调整无色透明聚酰亚胺复合膜的综合性能，从而满足不同应用领域对膜厚的需求。
作为优选，上述所述的一种无色透明聚酰亚胺复合膜，所述中间结构为所述聚酰亚胺基底层与所述玻璃表面层之间相互渗透形成的扩散结构，所述中间结构厚度为t，100nm≤t≤50μm。
上述的中间结构为扩散结构，能使无色透明聚酰亚胺复合膜具有较强的层间结合力且不易产生层裂，扩散结构能够增强无色透明聚酰亚胺复合膜的柔韧性。上述中间结构的厚度是通过测量聚酰亚胺基底层和玻璃表面层之间的间距而得，将中间结构的厚度控制在较宽的范围，使膜层结构具有更大的优化空间。
作为优选，上述所述的一种无色透明聚酰亚胺复合膜，所述中间结构为所述聚酰亚胺基底层与所述玻璃表面层之间相互交错形成的交错结构，所述中间结构厚度为t，100nm≤t≤50μm。
上述的中间结构为交错结构，能使无色透明聚酰亚胺复合膜形成三维聚酰亚胺-玻璃复合结构，从而增强复合特性，增大层间接触面积，提高无色透明聚酰亚胺复合膜的界面结合力、柔韧性及抗折性。上述中间结构的厚度是通过测量聚酰亚胺基底层和玻璃表面层之间的间距而得，将中间结构的厚度控制在较宽的范围，使膜层结构具有更大的优化空间。
作为优选，上述所述的一种无色透明聚酰亚胺复合膜，所述中间结构为所述聚酰亚胺基底层与所述玻璃表面层之间相互扩散和交错形成的复合结构，所述中间结构厚度为t，100nm≤t≤50μm。
上述的中间结构为相互扩散和交错形成的复合结构，使无色透明聚酰亚胺复合膜具有扩散结构和交错结构的复合特性，能有效增大层间接触面积和层间结合力，同时复合结构能更好地缓冲和吸收无色透明聚酰亚胺复合膜表面的应力，能使无色透明聚酰亚胺复合膜整体具有更好的阻水、阻氧、耐弯折及高硬度等优异特性。
上述中间结构的厚度是通过测量聚酰亚胺基底层和玻璃表面层之间的间距而得，将中间结构的厚度控制在较宽的范围，使膜层结构具有更大的优化空间。
作为优选，上述所述的一种无色透明聚酰亚胺复合膜，所述聚酰亚胺基底层上设有微观图案，所述玻璃表面层的上表面与所述微观图案表面形状一致或相似。
上述微观图案定义了中间结构的轮廓，上述的玻璃表面层的上表面具有与微观图案一致或相似的形状，能够使无色透明聚酰亚胺复合膜结构的内应力分布更均匀，从而提高无 色透明聚酰亚胺复合膜承受形变的能力，有效增强无色透明聚酰亚胺复合膜的柔性和可折叠性。
作为优选，上述所述的一种无色透明聚酰亚胺复合膜，所述微观图案的深度与所述聚酰亚胺基底层厚度之比为0.1～0.9。
微观图案的深度与聚酰亚胺基底层厚度之比在较宽的范围内进行控制，在满足不同应用需求的基础上始终保持最佳的结构及性能，使膜层结构具有更大的优化空间。
作为优选，上述所述的一种无色透明聚酰亚胺复合膜，所述微观图案为波浪形，所述波浪形微观图案中相邻波峰与波谷距离L为20nm～100μm。
上述波浪形微观图案包括横向型图案和纵向型图案中的至少一种，微观图案采用波浪形图案能提高无色透明聚酰亚胺复合膜在横向和纵向上的耐弯折性，不仅增加膜层的接触面积，使膜层具有更好的连续性，同时也减少无色透明聚酰亚胺复合膜的整体厚度。波浪形微观图案中相邻波峰与波谷距离在较宽的范围内进行控制，使膜层结构具有更大的优化空间。
作为优选，上述所述的一种无色透明聚酰亚胺复合膜，所述聚酰亚胺基底层、所述玻璃表面层、所述中间结构在外力的作用下弯曲变形。
聚酰亚胺基底层、玻璃表面层以及中间结构共同形成三维聚酰亚胺-玻璃复合结构，能够有效地释放弯曲形变所产生的内应力，提高无色透明聚酰亚胺复合膜所能承受的最大形变强度，从而有效避免无色透明聚酰亚胺复合膜因弯曲疲劳造成的永久性形变、开裂等情况。
作为优选，上述所述的一种无色透明聚酰亚胺复合膜的制备方法，包括以下制备步骤：
S1：在刚性基板上沉积聚酰胺酸前驱体，在150～250℃的环境下光固化5s～5min或热固化0.5～5h，得到半固化聚酰亚胺基底层；
S2：在半固化聚酰亚胺基底层表面上沉积多组份玻璃前驱体，多组份玻璃前驱体包含SiO 2前驱体、Al 2O 3前驱体、Na 2O前驱体、B 2O 3前驱体，多组份玻璃前驱体与半固化聚酰亚胺基底层之间形成中间结构，同时在250～350℃的环境下光固化5s～5min或热固化0.5～5h，使多组份玻璃前驱体半固化后得到半固化的玻璃表面层；
S3：加热刚性基板至600～700℃，光固化5s～5min或热固化0.5h～5h，将半固化的聚酰亚胺基底层和半固化的玻璃表面层完全固化形成聚酰亚胺基底层和玻璃表面层，脱模后即得到无色透明聚酰亚胺复合膜。
在上述的步骤S1中，加热聚酰胺酸前驱体形成半固化聚酰亚胺基底层，能够更好进 行物理加工如精密压制或光刻等，有利于形成稳定的加工形状且不影响膜层本身的结构；
在上述的步骤S2中，加热多组份玻璃前驱体形成半固化的玻璃表面层，有利于形成粒径较小、分布均匀的膜层，提高玻璃表面层的致密度和均匀性；
在上述的步骤S1～S3中，经过梯度的加热固化工序，能确保无色透明聚酰亚胺复合膜充分固化，提高成膜均匀性，降低表面缺陷率，也更有利于形成三维聚酰亚胺-玻璃复合结构。
上述聚酰亚胺基底层由聚酰胺酸前驱体固化形成，上述玻璃表面层由多组份玻璃前驱体固化形成，有利于制备粒度较小、分布均匀且组份均匀的膜层结构，提高膜层的致密度和均匀性，且溶胶凝胶法成型工艺简便，有效地降低了制备工艺的成本。
其中，聚酰胺酸前驱体可以由多组分二酐和多组分二胺在极性有机溶剂里聚合而成。上述多组分二酐包括二苯酮二酐、联苯二酐，1,2,4,5-环己烷四甲酸二酐、三苯二醚二酐、六氟二酐、二苯醚二酐、二苯硫醚二酐、对苯二酚二醚二酐、间苯二酚二醚二酐、双酚A型二醚二酐和均苯四甲酸二酐中的一种或多种；上述多组分二胺包括对苯二胺、间苯二胺、2,2’-二(三氟甲基)二氨基联苯；4,4’-二氨基-2,2’-双三氟甲基联苯、二苯甲烷二胺、对苯二酚二醚二胺、4,4’-二氨基二苯醚、双酚A型二醚二胺和1,3-双(3-氨基苯氧基)苯中的一种或多种；上述极性有机溶剂包括四氢呋喃、二甲基甲酰胺、N,N-二甲基乙酰胺、二甲醇二甲醚和N-甲基吡咯烷酮中的一种或多种。
其中，多组份玻璃前驱体可以包括Si(OR) 4、Al(OR) 3、B(OR) 3和NaOR中的一种或多种，其中R包括-CH 3、-C 2H 5、-C 3H 7和C 4H 9中的一种或多种。
作为优选，上述所述的一种无色透明聚酰亚胺复合膜的制备方法，所述多组份玻璃前驱体含有20％～80％的玻璃或滑石粉。
多组份玻璃前驱体加入玻璃或滑石粉，有利于优化膜层固化过程中收缩率，通过调整玻璃或滑石粉的含量从而避免无色透明聚酰亚胺复合膜在固化过程中出现分层、开裂和翘曲等情况。
作为优选，上述所述的一种无色透明聚酰亚胺复合膜的制备方法，所述步骤S2中半固化聚酰亚胺基底层表面采用精密压制或光刻方法制出微观图案。
采用精密压制或光刻方法加工微观图案，能够保证微观图案的精度和深度，有利于进行批量化生产和加工。
与现有技术相比，本发明具有突出的有益效果：首先，通过本发明所制得的无色透明聚酰亚胺复合膜具有与玻璃材质相近的优异表面硬度和抗磨损性能，在遭受外物的碰撞和磨损后能够有效降低损伤；其次，无色透明聚酰亚胺复合膜具有与玻璃材质相近的优异抗水气阻隔性能，能够延长产品的使用寿命；最后，无色透明聚酰亚胺复合膜仍保持PI薄膜的 优异的柔性、可折叠性，具有更加广阔的应用前景。
附图说明
图1为本发明的中间结构为扩散结构的横向或纵向截面结构示意图；
图2为本发明的中间结构为交错结构的横向或纵向截面结构示意图；
图3为本发明的中间结构为复合结构的横向或纵向截面结构示意图；
图4为本发明的中间结构为交错结构且玻璃表面层上表面与微观图案形状相似的横向或纵向截面结构示意图；
图5为本发明的中间结构为复合结构且玻璃表面层上表面与微观图案形状相似的横向或纵向截面结构示意图。
具体实施方式
下面结合附图1～5和具体实施方式对本发明作进一步详细描述，但它们不是对本发明的限制：
实施例1
如图1至图5所示，一种无色透明聚酰亚胺复合膜，包括聚酰亚胺基底层1、玻璃表面层3，所述玻璃表面层3与所述聚酰亚胺基底层1之间形成中间结构2。
作为优选，所述聚酰亚胺基底层1的厚度T1为200μm，所述玻璃表面层3厚度T2为60μm。
作为优选，所述中间结构2为所述聚酰亚胺基底层1与所述玻璃表面层3之间相互渗透形成的扩散结构，所述中间结构2厚度t为50μm。
作为优选，所述中间结构2为所述聚酰亚胺基底层1与所述玻璃表面层3之间相互交错形成的交错结构，所述中间结构2厚度t为50μm。
作为优选，所述中间结构2为所述聚酰亚胺基底层1与所述玻璃表面层3之间相互扩散和交错形成的复合结构，所述中间结构2厚度t为50μm。
作为优选，所述聚酰亚胺基底层1上设有微观图案，所述玻璃表面层3的上表面与所述微观图案表面形状一致或相似。
作为优选，所述微观图案的深度与所述聚酰亚胺基底层1厚度之比为0.9。
作为优选，所述微观图案为波浪形，所述波浪形微观图案中相邻波峰与波谷距离L为100μm。
作为优选，所述聚酰亚胺基底层1、所述玻璃表面层3、所述中间结构2在外力的作用下弯曲变形。
作为优选，包括以下制备步骤：
S1：在刚性基板上沉积聚酰胺酸前驱体，在250℃的环境下光固化5min或热固化5h，得到半固化聚酰亚胺基底层1；
S2：在半固化聚酰亚胺基底层1表面上沉积多组份玻璃前驱体，多组份玻璃前驱体包含SiO 2前驱体、Al 2O 3前驱体、Na 2O前驱体、B 2O 3前驱体，多组份玻璃前驱体与半固化聚酰亚胺基底层1之间形成中间结构2，同时在350℃的环境下光固化5min或热固化5h，使多组份玻璃前驱体半固化后得到半固化的玻璃表面层3；
S3：加热刚性基板至700℃，光固化5min或热固化5h，将半固化的聚酰亚胺基底层1和半固化的玻璃表面层3完全固化形成聚酰亚胺基底层1和玻璃表面层3，脱模后即得到无色透明聚酰亚胺复合膜。
作为优选，所述多组份玻璃前驱体含有80％的玻璃或滑石粉。
作为优选，所述步骤S2中半固化聚酰亚胺基底层1表面采用精密压制或光刻方法制出微观图案。
实施例2
如图1至图5所示，一种无色透明聚酰亚胺复合膜，包括聚酰亚胺基底层1、玻璃表面层3，所述玻璃表面层3与所述聚酰亚胺基底层1之间形成中间结构2。
作为优选，所述聚酰亚胺基底层1的厚度T1为5μm，所述玻璃表面层3厚度T2为200nm。
作为优选，所述中间结构2为所述聚酰亚胺基底层1与所述玻璃表面层3之间相互渗透形成的扩散结构，所述中间结构2厚度t为100nm。
作为优选，所述中间结构2为所述聚酰亚胺基底层1与所述玻璃表面层3之间相互交错形成的交错结构，所述中间结构2厚度t为100nm。
作为优选，所述中间结构2为所述聚酰亚胺基底层1与所述玻璃表面层3之间相互扩散和交错形成的复合结构，所述中间结构2厚度t为100nm。
作为优选，所述聚酰亚胺基底层1上设有微观图案，所述玻璃表面层3的上表面与所述微观图案表面形状一致或相似。
作为优选，所述微观图案的深度与所述聚酰亚胺基底层1厚度之比为0.1。
作为优选，所述微观图案为波浪形，所述波浪形微观图案中相邻波峰与波谷距离L为20nm。
作为优选，所述聚酰亚胺基底层1、所述玻璃表面层3、所述中间结构2在外力的作用下弯曲变形。
作为优选，包括以下制备步骤：
S1：在刚性基板上沉积聚酰胺酸前驱体，在150℃的环境下光固化5s或热固化0.5h，得到半固化聚酰亚胺基底层1；
S2：在半固化聚酰亚胺基底层1表面上沉积多组份玻璃前驱体，多组份玻璃前驱体包含SiO 2前驱体、Al 2O 3前驱体、Na 2O前驱体、B 2O 3前驱体，多组份玻璃前驱体与半固化聚酰亚胺基底层1之间形成中间结构2，同时在250℃的环境下光固化5s或热固化0.5h，使多组份玻璃前驱体半固化后得到半固化的玻璃表面层3；
S3：加热刚性基板至600℃，光固化5s或热固化0.5h，将半固化的聚酰亚胺基底层1和半固化的玻璃表面层3完全固化形成聚酰亚胺基底层1和玻璃表面层3，脱模后即得到无色透明聚酰亚胺复合膜。
作为优选，所述多组份玻璃前驱体含有20％的玻璃或滑石粉。
作为优选，所述步骤S2中半固化聚酰亚胺基底层1表面采用精密压制或光刻方法制出微观图案。
实施例3
如图1至图5所示，一种无色透明聚酰亚胺复合膜，包括聚酰亚胺基底层1、玻璃表面层3，所述玻璃表面层3与所述聚酰亚胺基底层1之间形成中间结构2。
作为优选，所述聚酰亚胺基底层1的厚度T1为50μm，所述玻璃表面层3厚度T2为2μm。
作为优选，所述中间结构2为所述聚酰亚胺基底层1与所述玻璃表面层3之间相互渗透形成的扩散结构，所述中间结构2厚度t为5μm。
作为优选，所述中间结构2为所述聚酰亚胺基底层1与所述玻璃表面层3之间相互交错形成的交错结构，所述中间结构2厚度t为20μm。
作为优选，所述中间结构2为所述聚酰亚胺基底层1与所述玻璃表面层3之间相互扩散和交错形成的复合结构，所述中间结构2厚度t为20μm。
作为优选，所述聚酰亚胺基底层1上设有微观图案，所述玻璃表面层3的上表面与所述微观图案表面形状一致或相似。
作为优选，所述微观图案的深度与所述聚酰亚胺基底层1厚度之比为0.5。
作为优选，所述微观图案为波浪形，所述波浪形微观图案中相邻波峰与波谷距离L为50μm。
作为优选，所述聚酰亚胺基底层1、所述玻璃表面层3、所述中间结构2在外力的作用下弯曲变形。
作为优选，包括以下制备步骤：
S1：在刚性基板上沉积聚酰胺酸前驱体，在200℃的环境下光固化2min或热固化3h，得到半固化聚酰亚胺基底层1；
S2：在半固化聚酰亚胺基底层1表面上沉积多组份玻璃前驱体，多组份玻璃前驱体包含SiO 2前驱体、Al 2O 3前驱体、Na 2O前驱体、B 2O 3前驱体，多组份玻璃前驱体与半固化聚酰亚胺基底层1之间形成中间结构2，同时在300℃的环境下光固化2min或热固化3h，使多组份玻璃前驱体半固化后得到半固化的玻璃表面层3；
S3：加热刚性基板至650℃，光固化2min或热固化3h，将半固化的聚酰亚胺基底层1和半固化的玻璃表面层3完全固化形成聚酰亚胺基底层1和玻璃表面层3，脱模后即得到无色透明聚酰亚胺复合膜。
作为优选，所述多组份玻璃前驱体含有50％的玻璃或滑石粉。
作为优选，所述步骤S2中半固化聚酰亚胺基底层1表面采用精密压制或光刻方法制出微观图案。
实施例4
取上述实施例3得到的无色透明聚酰亚胺复合膜，取现有的台湾永捷创新科技有限公司生产的聚酰亚胺复合膜、KOLON工业株式会社生产的PI膜、美国康宁股份有限公司生产的柔性玻璃为对比例，进行铅笔硬度、抗弯折两项性能的测试，测试方法如下：
一、铅笔硬度测试：采用铅笔硬度计按照GB/T 6739《色漆和清漆铅笔法测定漆膜硬度》的方法测试铅笔硬度；
二、耐弯折测试：采用合页式弯折试验机以5mm的弯折半径、0～180°的角度及20rpm/min的速度下进行往复弯折；
本发明各实施例得到的无色透明聚酰亚胺复合膜和对比例性能参数参见表1、表2：
表1
样品 铅笔硬度
实施例3 9H
对比例1 8H
对比例2 2H
其中，对比例1为台湾永捷创新科技有限公司生产的聚酰亚胺复合膜，对比例2为KOLON工业株式会社生产的PI膜。
表2
样品 耐弯折
实施例3 ≥20万次
对比例3 不可弯折
其中，对比例3为美国康宁股份有限公司生产的柔性玻璃。
总之，以上所述仅为本发明的较佳实施例，凡依本发明申请专利的范围所作的均等变化与修饰，皆应属本发明的涵盖范围。

Claims (12)

  1. 一种无色透明聚酰亚胺复合膜，其特征在于：包括聚酰亚胺基底层(1)、玻璃表面层(3)，所述玻璃表面层(3)与所述聚酰亚胺基底层(1)之间形成中间结构(2)。
  2. 根据权利要求1所述的一种无色透明聚酰亚胺复合膜，其特征在于：所述聚酰亚胺基底层(1)的厚度为T1，5μm≤T1≤200μm，所述玻璃表面层(3)厚度为T2，200nm≤T2≤60μm。
  3. 根据权利要求1所述的一种无色透明聚酰亚胺复合膜，其特征在于：所述中间结构(2)为所述聚酰亚胺基底层(1)与所述玻璃表面层(3)之间相互渗透形成的扩散结构，所述中间结构(2)厚度为t，100nm≤t≤50μm。
  4. 根据权利要求1所述的一种无色透明聚酰亚胺复合膜，其特征在于：所述中间结构(2)为所述聚酰亚胺基底层(1)与所述玻璃表面层(3)之间相互交错形成的交错结构，所述中间结构(2)厚度为t，100nm≤t≤50μm。
  5. 根据权利要求1所述的一种无色透明聚酰亚胺复合膜，其特征在于：所述中间结构(2)为所述聚酰亚胺基底层(1)与所述玻璃表面层(3)之间相互扩散和交错形成的复合结构，所述中间结构(2)厚度为t，100nm≤t≤50μm。
  6. 根据权利要求1所述的一种无色透明聚酰亚胺复合膜，其特征在于：所述聚酰亚胺基底层(1)上设有微观图案，所述玻璃表面层(3)的上表面与所述微观图案表面形状一致或相似。
  7. 根据权利要求6所述的一种无色透明聚酰亚胺复合膜，其特征在于：所述微观图案的深度与所述聚酰亚胺基底层(1)厚度之比为0.1～0.9。
  8. 根据权利要求6所述的一种无色透明聚酰亚胺复合膜，其特征在于：所述微观图案为波浪形，所述波浪形微观图案中相邻波峰与波谷距离L为20nm～100μm。
  9. 根据权利要求1所述的一种无色透明聚酰亚胺复合膜，其特征在于：所述聚酰亚胺基底层(1)、所述玻璃表面层(3)、所述中间结构(2)在外力的作用下弯曲变形。
  10. 根据权利要求1所述的一种无色透明聚酰亚胺复合膜的制备方法，其特征在于：包括以下制备步骤：
    S1：在刚性基板上沉积聚酰胺酸前驱体，在150～250℃的环境下光固化5s～5min或热固化0.5～5h，得到半固化聚酰亚胺基底层(1)；
    S2：在半固化聚酰亚胺基底层(1)表面上沉积多组份玻璃前驱体，多组份玻璃前驱体包含SiO 2前驱体、Al 2O 3前驱体、Na 2O前驱体、B 2O 3前驱体，多组份玻璃前驱体与半固化聚酰亚胺基底层(1)之间形成中间结构(2)，同时在250～350℃的环境下光固化5s～5min或热固化0.5～5h，使多组份玻璃前驱体半固化后得到半固化的玻璃表面层(3)；
    S3：加热刚性基板至600～700℃，光固化5s～5min或热固化0.5h～5h，将半固化的聚酰亚胺基底层(1)和半固化的玻璃表面层(3)完全固化形成聚酰亚胺基底层(1)和玻璃表面层(3)，脱模后即得到无色透明聚酰亚胺复合膜。
  11. 根据权利要求10所述的一种无色透明聚酰亚胺复合膜的制备方法，其特征在于：所述多组份玻璃前驱体含有20％～80％的玻璃或滑石粉。
  12. 根据权利要求10所述的一种无色透明聚酰亚胺复合膜的制备方法，其特征在于：所述步骤S2中半固化聚酰亚胺基底层(1)表面采用精密压制或光刻方法制出微观图案。
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