JP7174885B2 - Colorless and transparent polyimide composite film and its manufacturing method - Google Patents

Description

TECHNICAL FIELD The present invention relates to the technical field of polyimide films, and more particularly to a colorless and transparent polyimide composite film and a method for producing the same.

Polyimide film has excellent photoelectric properties, mechanical properties, water and gas barrier properties, etc. At present, it is widely used in electrical insulation materials, flexible copper clad laminates (FCCL) and flexible OLED displays, window films, new energy and other high-tech industries. Widely applied in various fields, colorless transparent polyimide (CPI) is mainly applied in flexible mobile phones, tablets, TVs and other smart display equipment in the future, and is an indispensable important material for future flexible electronic products. is. In the application of the flexible OLED display field, the transparency and flexibility of the CPI film basically meet the practical requirements, but the surface hardness and water and gas barrier properties of the CPI film cannot meet the practical requirements, Currently, there are two ways to solve the hardness defect, one is to apply an organic hard layer on top of the CPI film, which fundamentally reduces the high water and gas barrier requirements for the CPI film. The other is to apply an inorganic glass material on the CPI film to achieve high translucency, high water impermeability, and high hardness. Since the brittleness greatly affects the flexibility of CPI-glass composite membrane, the foldability and bendability of CPI-glass composite membrane cannot meet the practical requirements, and the thermal expansion coefficient of CPI and glass will be affected during manufacturing. The difference is large, and the manufacturing temperature of CPI and glass has a difference of at least 300°C, so when there is thermal stress, the CPI-glass composite film will experience delamination, so that the glass can be melted directly on the CPI film. It is impossible to apply.

Based on the above problems, it is highly necessary to improve the status quo of currently commercially available CPI films in flexible OLED displays and other field applications.

The present invention provides a novel colorless and transparent polyimide composite film and a method for producing the same in order to address the deficiencies of the prior art, such as the barrier properties and hardness of polyimide films not meeting practical requirements.

In order to solve the above technical problems, the present invention is achieved by the following technical solutions.
A colorless and transparent polyimide composite film comprising a polyimide base layer and a glass surface layer, wherein an intermediate structure is formed between the glass surface layer and the polyimide base layer.

In the colorless and transparent polyimide composite film, the intermediate structure is a buffer layer with a microstructure, which can effectively form a three-dimensional polyimide-glass composite structure, and the intermediate structure retains the characteristics of the glass material and is colorless. Excellent properties such as water barrier, oxygen barrier, bending resistance and high hardness can be imparted to the entire transparent polyimide composite film.

Preferably, in the above colorless and transparent polyimide composite film, the thickness T1 of the polyimide base layer is 5 μm≦T1≦200 μm, and the thickness T2 of the glass surface layer is 200 nm≦T2≦60 μm.

The thickness of the polyimide substrate layer and the glass surface layer can be controlled in a wide range, and based on satisfying the hardness requirements of the surface layer, it provides optimal flexibility, foldability and strength to the colorless and transparent polyimide composite film. In addition, by adjusting the thickness of the polyimide substrate layer and the glass surface layer, the overall performance of the colorless and transparent polyimide composite film can be adjusted, so as to meet the film thickness requirements of various application fields.

Preferably, in the colorless and transparent polyimide composite film, the intermediate structure is a diffusion structure formed by the penetration of the polyimide base layer and the glass surface layer, and the thickness of the intermediate structure is t, 100 nm≦ t≦50 μm.

The above-mentioned intermediate structure is a diffusion structure, which can give the colorless and transparent polyimide composite film a high interlayer bonding strength and is less likely to cause delamination, and the diffusion structure can increase the flexibility of the colorless and transparent polyimide composite film. . The thickness of the intermediate structure is obtained by measuring the distance between the polyimide substrate layer and the glass surface layer, and the thickness of the intermediate structure can be controlled in a wide range, and the optimization space of the membrane layer structure can be more Enlarge.

Preferably, in the colorless and transparent polyimide composite film, the intermediate structure is an entangled structure formed by entangling the polyimide base layer and the glass surface layer, and the thickness of the intermediate structure is t, 100 nm. ≦t≦50 μm.

Since the intermediate structure is an entangled structure, the colorless and transparent polyimide composite film is a three-dimensional polyimide-
A glass composite structure can be formed, thereby enhancing the composite properties, increasing the interlayer contact area, and improving the interfacial bonding strength, flexibility and bending resistance of the colorless and transparent polyimide composite film. The thickness of the intermediate structure is obtained by measuring the distance between the polyimide substrate layer and the glass surface layer, and the thickness of the intermediate structure can be controlled in a wide range, and the optimization space of the membrane layer structure can be more Enlarge.

Preferably, in the colorless and transparent polyimide composite film, the intermediate structure is a composite structure formed by mutually diffusing and entangling the polyimide base layer and the glass surface layer, and the thickness t of the intermediate structure is 100 nm≦t≦50 μm.

The intermediate structure is a composite structure formed by diffusion and entanglement with each other, giving the colorless and transparent polyimide composite film the composite characteristics of a diffusion structure and an entanglement structure, effectively increasing the interlayer contact area and interlayer bonding strength. At the same time, the composite structure can better buffer and absorb the surface stress of the colorless and transparent polyimide composite film, which makes the whole colorless and transparent polyimide composite film have better water barrier, oxygen barrier, bending resistance and high bending resistance. Excellent properties such as hardness can be imparted.

The thickness of the intermediate structure is obtained by measuring the distance between the polyimide substrate layer and the glass surface layer, and the thickness of the intermediate structure can be controlled in a wide range, and the optimization space of the membrane layer structure can be more Enlarge.

Preferably, in the above colorless and transparent polyimide composite film, the polyimide base layer is provided with a micropattern, and the shape of the upper surface of the glass surface layer matches or resembles the shape of the surface of the micropattern.

The micropattern defines the outline of the intermediate structure, and the upper surface of the glass surface layer has a shape that matches or resembles the micropattern, making the internal stress distribution of the colorless and transparent polyimide composite film structure more uniform. This can improve the ability of the colorless and transparent polyimide composite film to withstand deformation, and effectively improve the flexibility and foldability of the colorless and transparent polyimide composite film.

Preferably, in the colorless and transparent polyimide composite film, the ratio of the depth of the micropattern to the thickness of the polyimide base layer is 0.1 to 0.9.

The ratio of micro-pattern depth to polyimide substrate layer thickness is controlled in a wide range, based on meeting various application requirements, always maintaining the optimum structure and performance, and optimizing the space of the film layer structure to be larger.

Preferably, in the colorless and transparent polyimide composite film, the micropattern is wavy, and the distance L between adjacent peaks and troughs in the wavy micropattern is 20 nm to 100 μm.

The wavy micropattern includes at least one of a horizontal pattern and a vertical pattern, and by adopting the wavy pattern as the micropattern, the bending resistance in the horizontal direction and the vertical direction of the colorless transparent polyimide composite film can be improved. , which can not only increase the contact area of the membrane layers and improve the continuity of the membrane layers, but also reduce the overall thickness of the colorless and transparent polyimide composite membrane. By controlling the distance between adjacent peaks and troughs in a wavy micropattern over a wide range, the optimization space of the film layer structure is made larger.

Preferably, in the colorless and transparent polyimide composite film, the polyimide base layer, the glass surface layer, and the intermediate structure are bent and deformed by 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 relieve the internal stress caused by bending deformation, and the maximum deformation strength that the colorless and transparent polyimide composite film can withstand. , thereby effectively avoiding situations such as permanent deformation and cracks due to bending fatigue of the colorless and transparent polyimide composite film.

Preferably, the method for producing the colorless transparent polyimide composite film described above,
Step S1 of depositing a polyamic acid precursor on a rigid substrate and performing photocuring for 5s to 5min or thermal curing for 0.5 to 5h in an environment of 150 to 250°C to obtain a semi-cured polyimide base layer;
_On the surface of the semi-cured polyimide substrate layer, depositing a multi-component glass precursor including a _SiO2 precursor, an _Al2O3 precursor, a _Na2O precursor, and a _B2O3 precursor, forming a multi _- component glass precursor An intermediate structure is formed between the body and the semi-cured polyimide base layer, and photocuring for 5s to 5min or thermal curing for 0.5 to 5h is performed in an environment of 250 to 350°C to form a multicomponent glass precursor. A step S2 of semi-curing to obtain a semi-cured glass surface layer;
The rigid substrate is heated to 600 to 700° C. and photocured for 5 s to 5 min or thermally cured for 0.5 h to 5 h to completely cure the semi-cured polyimide base layer and the semi-cured glass surface layer to form a polyimide base. forming a layer and a glass surface layer and releasing from the mold to obtain a colorless and transparent polyimide composite film S3.

In the above step S1, by heating the polyamic acid precursor to form a semi-cured polyimide base material layer, physical processing such as precision pressing and photolithography can be performed better, and the structure of the film layer itself can be improved. It is advantageous for forming a stable processed shape without affecting
In step S2, the multi-component glass precursor is heated to form a semi-hardened glass surface layer, which is advantageous for forming a film layer with small particle diameters and a uniform distribution, and the denseness of the glass surface layer. improve uniformity,
In the above steps S1 to S3, the gradient heat curing step can sufficiently cure the colorless and transparent polyimide composite film, improve the film uniformity, reduce the surface defect rate, and increase the three-dimensional polyimide-glass composite structure. It is also more favorable for the formation of

The polyimide substrate layer is a cured polyamic acid precursor, and the glass surface layer is a cured multi-component glass precursor. and is advantageous for the production of a membrane layer structure with uniform components, improving the denseness and uniformity of the membrane layer, and the sol-gel molding process is simple, effectively reducing the cost of the production process. .

Here, the polyamic acid precursor can be formed by polymerizing a multicomponent dianhydride and a multicomponent diamine in a polar organic solvent. The multicomponent dianhydrides include benzophenone dianhydride, biphenyl dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, triphenyl diether dianhydride, hexafluoro dianhydride, diphenyl ether dianhydride, anhydride, diphenylene sulfide dianhydride, hydroquinone diether dianhydride, resorcin diether dianhydride, bisphenol A-type diether dianhydride, and pyromellitic dianhydride; is p-phenylenediamine, m-phenylenediamine, 2,2'-di(trifluoromethyl)diaminobiphenyl, 4,4'-diamino-2,2'-bistrifluoromethylbiphenyl, diphenylmethanediamine, hydroquinone dietherdiamine , 4,4′-diaminodiphenyl ether, bisphenol A-type diether diamine, and 1,3-bis(3-aminophenoxy)benzene, and the polar organic solvent includes tetrahydrofuran, dimethylformamide, N,N - dimethylacetamide, dimethanol dimethyl ether, and N-methylpyrrolidone.

The multicomponent glass precursor may comprise one or more of Si(OR) ₄ , Al(OR) ₃ , B(OR) ₃ and NaOR, where R is -CH ₃ , -C ₂ H ₅ , - _including one or _more of _C3H7 and _C4H9 .

Preferably, in the above method for producing a colorless and transparent polyimide composite film, the multicomponent glass precursor contains 20% to 80% glass or talc.

In multi-component glass precursors, the addition of glass or talc is advantageous for optimizing the shrinkage rate of the film layer during curing, and adjusting the content of glass or talc can be beneficial for colorless and transparent polyimide composites during curing. To avoid the occurrence of conditions such as film delamination, cracks and warping.

Preferably, in the method for producing a colorless and transparent polyimide composite film, in step S2, a micropattern is formed on the surface of the semi-cured polyimide base material layer using a precision press or a photolithography method.

By processing the micropattern using a precision press or photolithography method, the precision and depth of the micropattern can be ensured, which is advantageous for large-scale production and processing.

Compared with the prior art, the present invention has excellent beneficial effects. First, the colorless and transparent polyimide composite film prepared according to the present invention has excellent surface hardness and wear resistance similar to those of glass material, and can effectively reduce damage when impacted or worn by an external object. secondly, the colorless and transparent polyimide composite film has excellent water and gas barrier performance similar to that of glass material, which can extend the service life of the product; It retains flexibility and foldability, and has the potential to be used more widely.

FIG. 4 is a schematic diagram of a cross-sectional structure or a vertical cross-sectional structure when the intermediate structure of the present invention is a diffusion structure; FIG. 4 is a schematic diagram of a cross-sectional structure or a vertical cross-sectional structure when the intermediate structure of the present invention is an interlaced structure. FIG. 4 is a schematic diagram of a cross-sectional structure or a vertical cross-sectional structure when the intermediate structure of the present invention is a composite structure; FIG. 3 is a schematic diagram of a cross-sectional structure or a vertical cross-sectional structure when the intermediate structure of the present invention is an entangled structure and the shape of the upper surface of the glass surface layer is similar to the shape of the micropattern. FIG. 2 is a schematic diagram of a cross-sectional structure or a vertical cross-sectional structure when the intermediate structure of the present invention is a composite structure and the shape of the upper surface of the glass surface layer is similar to the shape of the micropattern.

The invention will now be described in more detail with reference to Figures 1 to 5 and specific embodiments, which are not intended to limit the invention.

As shown in FIGS. 1 to 5, a colorless and transparent polyimide substrate layer 1 and a glass surface layer 3, wherein an intermediate structure 2 is formed between the glass surface layer 3 and the polyimide substrate layer 1. It is a polyimide composite membrane.

Preferably, the thickness T1 of the polyimide base layer 1 is 200 μm, and the thickness T2 of the glass surface layer 3 is 60 μm.

Preferably, the intermediate structure 2 is a diffusion structure formed by the permeation of the polyimide base layer 1 and the glass surface layer 3, and the thickness t of the intermediate structure 2 is 50 μm.

Preferably, the intermediate structure 2 is an entangled structure formed by entangling the polyimide base layer 1 and the glass surface layer 3, and the thickness t of the intermediate structure 2 is 50 μm.

Preferably, the intermediate structure 2 is a composite structure formed by diffusing and entangling the polyimide base layer 1 and the glass surface layer 3, and the thickness t of the intermediate structure 2 is 50 μm. .

Preferably, the polyimide substrate layer 1 is provided with a micropattern, and the shape of the upper surface of the glass surface layer 3 matches or resembles the shape of the surface of the micropattern.

Preferably, the ratio of the depth of the micropattern to the thickness of the polyimide substrate layer 1 is 0.9.

Preferably, said micropattern is wavy and the distance L between adjacent peaks and troughs in said wavy micropattern is 100 μm.

Preferably, the polyimide base layer 1, the glass surface layer 3, and the intermediate structure 2 are bent and deformed by the action of an external force.

Preferably,
A step S1 of depositing a polyamic acid precursor on a rigid substrate and subjecting it to photocuring for 5 minutes or heat curing for 5 hours in an environment of 250° C. to obtain a semi-cured polyimide base layer 1;
_On the surface of the semi-cured polyimide substrate layer 1, a multi-component glass precursor containing a _SiO2 precursor, an _Al2O3 precursor _, a _Na2O precursor and a _B2O3 precursor is deposited to form a multi-component glass An intermediate structure 2 is formed between the precursor and the semi-cured polyimide base layer 1, and the multi-component glass precursor is semi-cured by photocuring for 5 minutes or heat curing for 5 hours in an environment of 350°C. , a step S2 of obtaining a semi-hardened glass surface layer 3;
The rigid substrate is heated to 700° C. and photocured for 5 minutes or thermally cured for 5 hours to completely cure the semi-cured polyimide base layer 1 and the semi-cured glass surface layer 3 to form the polyimide base layer 1 and the glass surface layer. forming 3 and releasing from the mold to obtain a colorless and transparent polyimide composite film S3.

Preferably, the multicomponent glass precursor contains 80% glass or talc.

Preferably, in step S2, a micropattern is formed on the surface of the semi-cured polyimide substrate 1 using precision press or photolithography.

As shown in FIGS. 1 to 5, a colorless and transparent polyimide substrate layer 1 and a glass surface layer 3, wherein an intermediate structure 2 is formed between the glass surface layer 3 and the polyimide substrate layer 1. It is a polyimide composite membrane.

Preferably, the thickness T1 of the polyimide base layer 1 is 5 μm, and the thickness T2 of the glass surface layer 3 is 200 nm.

Preferably, the intermediate structure 2 is a diffusion structure formed by interpenetrating the polyimide base layer 1 and the glass surface layer 3, and the thickness t of the intermediate structure 2 is 100 nm.

Preferably, the intermediate structure 2 is an entangled structure formed by entangling the polyimide base layer 1 and the glass surface layer 3, and the thickness t of the intermediate structure 2 is 100 nm.

Preferably, the intermediate structure 2 is a composite structure formed by diffusing and entangling the polyimide base layer 1 and the glass surface layer 3, and the thickness t of the intermediate structure 2 is 100 nm. .

Preferably, the polyimide substrate layer 1 is provided with a micropattern, and the shape of the upper surface of the glass surface layer 3 matches or resembles the shape of the surface of the micropattern.

Preferably, the ratio of the depth of the micropattern to the thickness of the polyimide substrate layer 1 is 0.1.

Preferably, said micropattern is wavy and the distance L between adjacent peaks and troughs in said wavy micropattern is 20 nm.

Preferably, the polyimide base layer 1, the glass surface layer 3, and the intermediate structure 2 are bent and deformed by the action of an external force.

Preferably,
Step S1 of depositing a polyamic acid precursor on a rigid substrate and subjecting it to photocuring for 5 s or heat curing for 0.5 h in an environment of 150° C. to obtain a semi-cured polyimide base layer 1;
_On the surface of the semi-cured polyimide substrate layer 1, a multi-component glass precursor containing a _SiO2 precursor, an _Al2O3 precursor _, a _Na2O precursor and a _B2O3 precursor is deposited to form a multi-component glass An intermediate structure 2 is formed between the precursor and the semi-cured polyimide base layer 1, and the multi-component glass precursor is semi-cured by photocuring for 5 s or heat curing for 0.5 h in an environment of 250°C. a step S2 of obtaining a semi-hardened glass surface layer 3;
The rigid substrate is heated to 600° C. and photocured for 5 s or thermally cured for 0.5 h to completely cure the semi-cured polyimide base layer 1 and the semi-cured glass surface layer 3 to form the polyimide base layer 1 and the glass. forming the surface layer 3 and releasing from the mold to obtain a colorless and transparent polyimide composite film S3.

Preferably, said multicomponent glass precursor contains 20% glass or talc.

Preferably, in step S2, a micropattern is formed on the surface of the semi-cured polyimide substrate 1 using precision press or photolithography.

As shown in FIGS. 1 to 5, a colorless and transparent polyimide substrate layer 1 and a glass surface layer 3, wherein an intermediate structure 2 is formed between the glass surface layer 3 and the polyimide substrate layer 1. It is a polyimide composite membrane.

Preferably, the thickness T1 of the polyimide base layer 1 is 50 μm, and the thickness T2 of the glass surface layer 3 is 2 μm.

Preferably, the intermediate structure 2 is a diffusion structure formed by the permeation of the polyimide base layer 1 and the glass surface layer 3, and the thickness t of the intermediate structure 2 is 5 μm.

Preferably, the intermediate structure 2 is an entangled structure formed by entangling the polyimide base layer 1 and the glass surface layer 3, and the thickness t of the intermediate structure 2 is 20 μm.

Preferably, the intermediate structure 2 is a composite structure formed by diffusing and entangling the polyimide base layer 1 and the glass surface layer 3, and the thickness t of the intermediate structure 2 is 20 μm. .

Preferably, the polyimide substrate layer 1 is provided with a micropattern, and the shape of the upper surface of the glass surface layer 3 matches or resembles the shape of the surface of the micropattern.

Preferably, the ratio of the depth of the micropatterns to the thickness of the polyimide substrate layer 1 is 0.5.

Preferably, said micropattern is wavy and the distance L between adjacent peaks and troughs in said wavy micropattern is 50 μm.

Preferably, the polyimide base layer 1, the glass surface layer 3, and the intermediate structure 2 are bent and deformed by the action of an external force.

Preferably,
Step S1 of depositing a polyamic acid precursor on a rigid substrate and performing photocuring for 2 minutes or heat curing for 3h in an environment of 200° C. to obtain a semi-cured polyimide base layer 1;
_On the surface of the semi-cured polyimide substrate layer 1, a multi-component glass precursor containing a _SiO2 precursor, an _Al2O3 precursor _, a _Na2O precursor and a _B2O3 precursor is deposited to form a multi-component glass An intermediate structure 2 is formed between the precursor and the semi-cured polyimide base layer 1, and the multi-component glass precursor is semi-cured by photocuring for 2 minutes or thermal curing for 3 hours in an environment of 300°C. , a step S2 of obtaining a semi-hardened glass surface layer 3;
The rigid substrate is heated to 650° C. and photocured for 2 minutes or thermally cured for 3 hours to completely cure the semi-cured polyimide base layer 1 and the semi-cured glass surface layer 3 to form the polyimide base layer 1 and the glass surface layer. forming 3 and releasing from the mold to obtain a colorless and transparent polyimide composite film S3.

Preferably, the multicomponent glass precursor contains 50% glass or talc.

Preferably, in step S2, a micropattern is formed on the surface of the semi-cured polyimide base material layer 1 using a precision press or a photolithography method.

Using the colorless and transparent polyimide composite film obtained in Example 3, an existing polyimide composite film manufactured by Yongjie Innovation Technology Co., Ltd. in Taiwan, a PI film manufactured by KOLON Industries Co., Ltd., and a flexible glass manufactured by Corning Inc. in the United States were used as comparative examples. , pencil hardness and bend resistance performance were tested as follows.
1. Pencil hardness test: Pencil hardness was tested according to GB/T 6739 "Measurement of coating film hardness by pencil method for paints and varnishes" using a pencil hardness tester.
2. Bending resistance test: Using a hinge bending tester, bend repeatedly at a bending radius of 5 mm, an angle of 0-180° and a speed of 20 rpm/min.

このうち、比較例１は台湾永捷創新科技有限公司製ポリイミド複合膜、比較例２はＫＯＬＯＮ工業株式会社製ＰＩフィルムである。 The performance parameters of the colorless and transparent polyimide composite films obtained in each example of the present invention and the comparative example are shown in Tables 1 and 2.

Among them, Comparative Example 1 is a polyimide composite film manufactured by Taiwan Yongjie Creative Technology Co., Ltd., and Comparative Example 2 is a PI film manufactured by KOLON Industry Co., Ltd.

このうち、比較例３は米国コーニング株式会社製フレキシブルガラスである。

Among them, Comparative Example 3 is a flexible glass manufactured by Corning Incorporated in the United States.

The above are only preferred embodiments of the present invention, and all equivalent changes and modifications made based on the scope of the patent application of the present invention should be included within the scope of the present invention.

Claims (11)

comprising a polyimide substrate layer (1) and a glass surface layer (3), with an intermediate structure (2) between said glass surface layer (3) and said polyimide substrate layer (1);
The intermediate structure (2) is a diffusion structure formed by permeating the polyimide base layer (1) and the glass surface layer (3), and the thickness t of the intermediate structure (2) is A colorless and transparent polyimide composite film, characterized in that 100 nm≦t≦50 μm. comprising a polyimide substrate layer (1) and a glass surface layer (3), with an intermediate structure (2) between said glass surface layer (3) and said polyimide substrate layer (1);
The intermediate structure (2) is an entangled structure formed by entangling the polyimide base layer (1) and the glass surface layer (3), and the thickness t of the intermediate structure (2) is A colorless and transparent polyimide composite film, characterized in that 100 nm≦t≦50 μm. comprising a polyimide substrate layer (1) and a glass surface layer (3), with an intermediate structure (2) between said glass surface layer (3) and said polyimide substrate layer (1);
The intermediate structure (2) is a composite structure formed by mutually diffusing and intertwining the polyimide base layer (1) and the glass surface layer (3), and the thickness of the intermediate structure (2) is t is 100 nm≦t≦50 μm. The thickness T1 of the polyimide base layer (1) is 5 μm≦T1≦200 μm, and the thickness T2 of the glass surface layer (3) is 200 nm≦T2≦60 μm. 4. The colorless and transparent polyimide composite film according to any one of 1 to 3 . Claim 1, characterized in that the polyimide substrate layer (1) is provided with a micro-pattern and the shape of the upper surface of the glass surface layer (3) is identical or similar to the shape of the surface of the micro-pattern. 4. The colorless and transparent polyimide composite film according to any one of items 1 to 3 . The colorless and transparent polyimide composite film according to claim 5 , characterized in that the ratio of the depth of the micropattern to the thickness of the polyimide base layer (1) is 0.1-0.9. 6. The colorless and transparent polyimide composite film according to claim 5 , wherein the micropattern is wavy, and the distance L between adjacent peaks and troughs in the wavy micropattern is 20 nm to 100 μm. 4. The polyimide substrate layer (1), the glass surface layer (3) and the intermediate structure (2) according to any one of claims 1 to 3 , characterized in that they bend and deform under the action of an external force. Colorless and transparent polyimide composite membrane. A method for producing a colorless transparent polyimide composite film according to any one of claims 1 to 3 ,
A step of depositing a polyamic acid precursor on a rigid substrate and performing photocuring for 5 s to 5 min or heat curing for 0.5 to 5 h in an environment of 150 to 250° C. to obtain a semi-cured polyimide base layer (1). S1 and
_On the surface of the semi-cured polyimide substrate layer (1), a multi-component glass precursor including _SiO2 precursor _{, Al2O3} precursor, _Na2O precursor, _B2O3 precursor is deposited, and multiple Forming an intermediate structure (2) between the component glass precursor and the semi-cured polyimide base layer (1), and photocuring for 5 s to 5 min in an environment of 250 to 350 ° C. or heat for 0.5 to 5 h a step S2 of curing and semi-curing the multi-component glass precursor to obtain a semi-cured glass surface layer (3);
The rigid substrate is heated to 600-700° C. and photo-cured for 5 s-5 min or heat-cured for 0.5 h-5 h to completely remove the semi-cured polyimide base layer (1) and the semi-cured glass surface layer (3). curing to form a polyimide substrate layer (1) and a glass surface layer (3) and releasing from the mold to obtain a colorless and transparent polyimide composite film (S3). The method for producing a colorless and transparent polyimide composite film according to claim 9 , wherein the multi-component glass precursor contains 20% to 80% glass or talc. 10. The production of a colorless and transparent polyimide composite film according to claim 9 , characterized in that in the step S2, a micropattern is formed on the surface of the semi-cured polyimide substrate layer (1) using a precision press or a photolithography method. Method.

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