CN111056746A - High hardness and high transparency polyimide flexible cover sheet and preparation method thereof - Google Patents

High hardness and high transparency polyimide flexible cover sheet and preparation method thereof Download PDF

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CN111056746A
CN111056746A CN201911422857.1A CN201911422857A CN111056746A CN 111056746 A CN111056746 A CN 111056746A CN 201911422857 A CN201911422857 A CN 201911422857A CN 111056746 A CN111056746 A CN 111056746A
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polyimide
glass substrate
hardness
cover plate
flexible cover
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CN111056746B (en
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刘继延
尤庆亮
刘志宏
刘学清
邹立勇
刘翠
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Jianghan University
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/3405—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of organic materials
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
    • C03C17/32—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with synthetic or natural resins
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract

The invention relates to a polyimide flexible cover plate with high hardness and high transparency and a preparation method thereof, wherein the cover plate comprises: the polyimide film comprises a glass substrate, a first polyimide film layer adhered to the glass substrate and a second polyimide film layer adhered to the first polyimide film layer. The method comprises the following steps: coating a first polyimide slurry of 2-10 um on a glass substrate in a flowing manner to obtain a first polyimide glass substrate; coating 30-40um second polyimide slurry on the first polyimide glass substrate in a flowing manner to obtain a second polyimide glass substrate; and thinning the second polyimide glass substrate to the thickness of 1-100 um by using a hydrofluoric acid-containing mixed acid thinning process. The outer surface hardness of the high-hardness and high-transparency polyimide flexible cover plate reaches 6H, the bending radius is less than or equal to 3mm, and the requirement of a flexible display cover plate can be met.

Description

High-hardness and high-transparency polyimide flexible cover plate and preparation method thereof
Technical Field
The invention relates to the technical field of display screens, in particular to a high-hardness and high-transparency polyimide flexible cover plate and a preparation method thereof.
Background
The flexible foldable AMOLED display screen is used as a next generation display terminal device, related products are successively released in recent years along with important manufacturers of the display screen, and rapid development of related technologies is initiated. The flexible display has the characteristics of flexibility, high definition and high color gamut saturation, but the substrate of the flexible screen has the defects of low hardness and poor external force damage resistance, so that the service life and the comfort level of the flexible screen are determined by the stable and reliable cover plate material. In the field of smart phones and pads dominated by touch screens, how to exert the advantages of flexible screens and realize reliable touch screen operation is an important link.
Disclosure of Invention
The invention provides a high-hardness high-transparency polyimide flexible cover plate and a preparation method thereof, solves the technical problems of low hardness and poor external force damage resistance of a flexible screen substrate in the prior art, and achieves the technical effects of effectively improving the hardness of the substrate and improving the external force damage resistance.
The invention provides a high-hardness and high-transparency polyimide flexible cover plate, which comprises: a glass substrate, a first polyimide film layer adhered on the glass substrate, and a second polyimide film layer adhered on the first polyimide film layer,
the structural formula of the first polyimide film layer is as follows:
Figure BDA0002352776680000021
wherein m, n and y are integers, m is greater than 0, n is greater than or equal to 0, and y is greater than or equal to 0; m: n: y is 1: (0-10): (0-10).
Preferably, the second polyimide of the second polyimide film layer has a structural formula:
Figure BDA0002352776680000022
Figure BDA0002352776680000031
wherein m and n are integers, m is greater than 0, and n is greater than or equal to 0; m: n is 1: (0-10).
Preferably, the first polyimide film layer is prepared by a first polyimide slurry; the second polyimide film layer is made from a second polyimide slurry.
Preferably, the preparation method of the first polyimide slurry comprises the following steps:
using N, N' -dimethylacrylamide as solvent, N2Adding diamine into the solvent for protecting gas, heating to 30-50 ℃, gradually dissolving the diamine into the solvent, adding a dianhydride solution once after the temperature is reduced to room temperature, and mechanically stirring for reaction for 4-7 hours to obtain the first polyimide slurry.
Preferably, the preparation method of the first polyimide slurry comprises the following steps:
using N, N' -dimethylacrylamide as solvent, N2Adding diamine into the solvent for protecting gas, heating to 40 ℃, gradually dissolving the diamine into the solvent, adding a dianhydride solution once after the temperature is reduced to room temperature, and mechanically stirring for reaction for 6 hours to obtain the first polyimide slurry.
The invention also provides a polyimide flexible cover plate with high hardness and high transparency, which comprises: a glass substrate and a polyimide film layer adhered on the glass substrate, wherein,
the structural formula of the polyimide film layer is as follows:
Figure BDA0002352776680000041
wherein m, n and y are integers, m is greater than 0, n is greater than or equal to 0, and y is greater than or equal to 0; m: n: y is 1: (0-10): (0-10).
Based on the same inventive concept, the application also provides a preparation method for the polyimide flexible cover plate with high hardness and high transparency, which comprises the following steps:
coating the first polyimide slurry with the thickness of 2-10 um on the glass substrate in a flowing manner to obtain a first polyimide glass substrate;
coating 30-40um of the second polyimide slurry on the first polyimide glass substrate in a flowing manner to obtain a second polyimide glass substrate;
through the mixed acid thinning process containing hydrofluoric acid, the second polyimide glass substrate is thinned to the thickness of 1-100 um, and the high-hardness and high-transparency polyimide flexible cover plate is obtained.
Preferably, after the first polyimide slurry of 2-10 um is flow-coated on the glass substrate, the pressure is reduced to 10Pa in a vacuum oven, the temperature is raised to 60 ℃, and the drying is carried out for 15min, so as to prepare the first polyimide glass substrate with the thickness of 2-5 um.
Preferably, the second polyimide slurry of 30-40um is flow-coated on the first polyimide glass substrate, the pressure is reduced to 10Pa in a vacuum oven, the temperature is raised to 60 ℃, the baking is carried out for 15min, the pressure is further reduced to 0.5Pa in the vacuum oven, the temperature is raised to 120 ℃, the baking is carried out for 30min, and the baking is further carried out in N2And carrying out temperature programming thermal imidization under protection to obtain the second polyimide glass substrate.
Preferably, the second polyimide glass substrate is placed in a polytetrafluoroethylene groove, mixed acid containing hydrofluoric acid is poured into the polytetrafluoroethylene groove, the second polyimide glass substrate is immersed, ultrasonic oscillation treatment is carried out for 30min, the interval is 30min, ultrasonic oscillation treatment is carried out for 30min again, the second polyimide glass substrate is repeatedly treated for 10-25 h until the second polyimide glass substrate is thinned to be 1-100 um thick, the second polyimide glass substrate is taken out and washed by pure water, and air is blown to dry, so that the high-hardness and high-transparency polyimide flexible cover plate is obtained.
One or more technical solutions provided in the embodiments of the present application have at least the following technical effects or advantages:
the application provides a high transparency polyimide flexible cover plate's of high rigidity surface hardness has reached 6H, and radius less than or equal to 3mm buckles can satisfy the demand that flexible demonstration was lapped.
Drawings
Fig. 1 is a schematic flow chart of a method for preparing a high-hardness and high-transparency polyimide flexible cover plate according to an embodiment of the present application.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention will be described in detail with reference to the accompanying drawings.
The invention provides a high-hardness and high-transparency polyimide flexible cover plate, which comprises: a glass substrate, a first polyimide film layer adhered on the glass substrate and a second polyimide film layer adhered on the first polyimide film layer, wherein,
the structural formula of the first polyimide film layer is as follows:
Figure BDA0002352776680000061
wherein m, n and y are integers, m is more than 0, n is more than or equal to 0, and y is more than or equal to 0; m: n: y is 1: (0-10): (0-10).
Further, the structural formula of the second polyimide film layer is as follows:
Figure BDA0002352776680000062
Figure BDA0002352776680000071
wherein m and n are integers, m is more than 0, and n is more than or equal to 0; m: n is 1: (0-10).
Further, the first polyimide film layer is prepared by first polyimide slurry; the second polyimide film layer is made from a second polyimide slurry.
The preparation method of the first polyimide slurry comprises the following steps: using N, N' -dimethylacrylamide as solvent, N2Adding diamine into the solvent as protective gas, heating to 30-50 ℃,and gradually dissolving diamine in a solvent, cooling to room temperature, adding a dianhydride solution at one time, and mechanically stirring for reaction for 4-7 hours to obtain a first polyimide slurry. As a preferred example, the first polyimide slurry is prepared by the following method: using N, N' -dimethylacrylamide as solvent, N2Adding diamine into the solvent for protecting gas, heating to 40 ℃, gradually dissolving the diamine into the solvent, adding the dianhydride solution once after the temperature is reduced to room temperature, and mechanically stirring for reaction for 6 hours to obtain first polyimide slurry.
The prepared first polyimide slurry has high transparency and high adhesiveness, the concentration is 5-25% (wt), the viscosity is 3000-6000 centipoises, the light transmittance of the 15-micrometer film UV-Vis is 89%, the cut-off wavelength is 380nm, and the adhesion force on the glass substrate is 1 grade by adopting a 3M adhesive tape cross-cut method test.
Based on the same inventive concept, the present application further provides a preparation method for the above polyimide flexible cover plate with high hardness and high transparency, referring to fig. 1, comprising the following steps:
s1: coating a first polyimide slurry of 2-10 um on a glass substrate in a flowing manner to obtain a first polyimide glass substrate; the glass substrate can be a gorilla glass substrate;
s2: coating 30-40um second polyimide slurry on the first polyimide glass substrate in a flowing manner to obtain a second polyimide glass substrate;
s3: and thinning the second polyimide glass substrate to the thickness of 30 +/-5 um by using a hydrofluoric acid-containing mixed acid thinning process to obtain the high-hardness and high-transparency polyimide flexible cover plate.
Further, in step S3, after the second polyimide glass substrate is thinned to a thickness of 30 ± 5um, the thinned second polyimide glass substrate may be polished, and the specific process is as follows: and immersing the thinned second polyimide glass substrate into a NaOH mixed aqueous solution of a polytetrafluoroethylene groove, carrying out ultrasonic oscillation treatment for 30min, carrying out intermittent 5min, taking out, washing for 3 times by using purified water until the aqueous solution is neutral, and finally blowing by using air to dry so as to obtain the high-hardness and high-transparency polyimide flexible cover plate.
Further, after the first polyimide slurry of 2-10 um is flow-coated on the glass substrate, the pressure is reduced to 10Pa in a vacuum oven, the temperature is raised to 60 ℃, and the drying is carried out for 15min, so as to prepare the first polyimide glass substrate with the thickness of 2-5 um.
Further, coating a second polyimide slurry of 30-40um on the first polyimide glass substrate in a flowing manner, reducing the pressure to 10Pa in a vacuum oven, heating to 60 ℃, baking for 15min, further reducing the pressure to 0.5Pa in the vacuum oven, heating to 120 ℃, baking for 30min, and further performing N-coating on the second polyimide slurry2And carrying out temperature programming thermal imidization under protection to obtain a second polyimide glass substrate.
Further, placing a second polyimide glass substrate into a polytetrafluoroethylene groove, pouring mixed acid containing hydrofluoric acid, immersing the second polyimide glass substrate, treating for 30min by ultrasonic oscillation, stopping for 30min, treating for 30min by ultrasonic oscillation again, repeatedly treating for 10-25 h until the second polyimide glass substrate is thinned to 30 +/-5 um, taking out, washing with purified water, and drying with air to obtain the high-hardness and high-transparency polyimide flexible cover plate.
Further, the prepared high-hardness and high-transparency polyimide flexible cover plate is subjected to UV-Vis transmittance detection, glass layer surface hardness detection, glass layer and polyimide layer peeling force detection and 2-5 mm bending property detection, so that the optical and mechanical properties of the cover plate can be obtained.
The following describes in detail the preparation method of the polyimide flexible cover plate according to the present application by specific examples:
example 1
S1: and (3) coating 2um of first polyimide slurry on the glass substrate in a flowing manner, reducing the pressure to 10Pa in a vacuum oven, heating to 60 ℃, and baking for 15min to obtain a first polyimide glass substrate with the thickness of 2 um.
S2: coating 30um second polyimide slurry on the first polyimide glass substrate, reducing pressure to 10Pa in a vacuum oven, heating to 60 ℃, baking for 15min, further reducing pressure to 0.5Pa in the vacuum oven, heating to 120 ℃, baking for 30min, and further baking in N2Carrying out temperature programming thermal imidization under protection,a second polyimide glass substrate was prepared.
S3: and (3) putting the second polyimide glass substrate into a polytetrafluoroethylene groove, pouring mixed acid containing hydrofluoric acid, treating the second polyimide glass substrate for 30min by ultrasonic oscillation, pausing for 30min, treating the second polyimide glass substrate for 30min by ultrasonic oscillation again, repeatedly treating the second polyimide glass substrate for 10h in such a way until the second polyimide glass substrate is thinned to the thickness of 25um, taking out the second polyimide glass substrate, washing the second polyimide glass substrate by using purified water, and drying the second polyimide glass substrate by air.
S4: and immersing the thinned second polyimide glass substrate into a NaOH mixed aqueous solution of a polytetrafluoroethylene groove, carrying out ultrasonic oscillation treatment for 30min, carrying out intermittent 5min, taking out, washing for 3 times by using purified water until the aqueous solution is neutral, and finally blowing by using air to dry so as to obtain the high-hardness and high-transparency polyimide flexible cover plate.
For the prepared high-hardness and high-transparency polyimide flexible cover plate, a 3M adhesive tape grid cutting method is adopted to test that the adhesion force between the PI (polyimide) and the glass substrate is 1 grade, the ultraviolet visible spectrum (UV-Vis) test light transmittance is 89%, the cut-off wavelength is 380nm, the hardness of the glass surface is 6H, the hardness of the PI surface is 2H, and the minimum inner and outer bending radius can be restored to be 3 mm.
Example 2
S1: and (3) coating the first polyimide slurry with the thickness of 4um on the glass substrate in a flowing manner, reducing the pressure to 10Pa in a vacuum oven, heating to 60 ℃, and baking for 15min to obtain the first polyimide glass substrate with the thickness of 3 um.
S2: coating 32um second polyimide slurry on the first polyimide glass substrate, reducing pressure to 10Pa in a vacuum oven, heating to 60 ℃, baking for 15min, further reducing pressure to 0.5Pa in the vacuum oven, heating to 120 ℃, baking for 30min, and further baking in N2And carrying out temperature programming thermal imidization under protection to obtain a second polyimide glass substrate.
S3: and (3) putting the second polyimide glass substrate into a polytetrafluoroethylene groove, pouring mixed acid containing hydrofluoric acid, treating the second polyimide glass substrate for 30min by ultrasonic oscillation, pausing for 30min, treating the second polyimide glass substrate for 30min by ultrasonic oscillation again, repeatedly treating the second polyimide glass substrate for 12h in the way until the second polyimide glass substrate is thinned to 26um, washing the second polyimide glass substrate by using purified water after being taken out, and drying the second polyimide glass substrate by air.
S4: and immersing the thinned second polyimide glass substrate into a NaOH mixed aqueous solution of a polytetrafluoroethylene groove, carrying out ultrasonic oscillation treatment for 30min, carrying out intermittent 5min, taking out, washing for 3 times by using purified water until the aqueous solution is neutral, and finally blowing by using air to dry so as to obtain the high-hardness and high-transparency polyimide flexible cover plate.
For the prepared high-hardness and high-transparency polyimide flexible cover plate, a 3M adhesive tape grid cutting method is adopted to test that the adhesion force between the PI (polyimide) and the glass substrate is 1 grade, the ultraviolet visible spectrum (UV-Vis) test light transmittance is 89%, the cut-off wavelength is 380nm, the hardness of the glass surface is 6H, the hardness of the PI surface is 2H, and the minimum inner and outer bending radius can be restored to be 3 mm.
Example 3
S1: and (3) flow-coating 6um of first polyimide slurry on the glass substrate, reducing the pressure to 10Pa in a vacuum oven, heating to 60 ℃, and baking for 15min to obtain a first polyimide glass substrate with the thickness of 3 um.
S2: coating 34um second polyimide slurry on the first polyimide glass substrate, reducing pressure to 10Pa in a vacuum oven, heating to 60 ℃, baking for 15min, further reducing pressure to 0.5Pa in the vacuum oven, heating to 120 ℃, baking for 30min, and further baking in N2And carrying out temperature programming thermal imidization under protection to obtain a second polyimide glass substrate.
S3: and (3) putting the second polyimide glass substrate into a polytetrafluoroethylene groove, pouring mixed acid containing hydrofluoric acid, treating the second polyimide glass substrate for 30min by ultrasonic oscillation without the second polyimide glass substrate, performing intermittent treatment for 30min, treating the second polyimide glass substrate for 30min by ultrasonic oscillation again, repeatedly treating the second polyimide glass substrate for 14h in such a way until the second polyimide glass substrate is thinned to 28um, taking out the second polyimide glass substrate, washing the second polyimide glass substrate by using purified water, and drying the second polyimide glass substrate by air blowing.
S4: and immersing the thinned second polyimide glass substrate into a NaOH mixed aqueous solution of a polytetrafluoroethylene groove, carrying out ultrasonic oscillation treatment for 30min, carrying out intermittent 5min, taking out, washing for 3 times by using purified water until the aqueous solution is neutral, and finally blowing by using air to dry so as to obtain the high-hardness and high-transparency polyimide flexible cover plate.
For the prepared high-hardness and high-transparency polyimide flexible cover plate, a 3M adhesive tape grid cutting method is adopted to test that the adhesion force between the PI (polyimide) and the glass substrate is 1 grade, the ultraviolet visible spectrum (UV-Vis) test light transmittance is 89%, the cut-off wavelength is 380nm, the hardness of the glass surface is 6H, the hardness of the PI surface is 2H, and the minimum inner and outer bending radius can be restored to be 3 mm.
Example 4
S1: and (3) coating the first polyimide slurry of 8um on the glass substrate in a flowing manner, reducing the pressure to 10Pa in a vacuum oven, heating to 60 ℃, and baking for 15min to obtain the first polyimide glass substrate with the thickness of 4 um.
S2: coating 38um second polyimide slurry on the first polyimide glass substrate, reducing pressure to 10Pa in a vacuum oven, heating to 60 deg.C, baking for 15min, further reducing pressure to 0.5Pa in the vacuum oven, heating to 120 deg.C, baking for 30min, and further baking in N2And carrying out temperature programming thermal imidization under protection to obtain a second polyimide glass substrate.
S3: and (3) putting the second polyimide glass substrate into a polytetrafluoroethylene groove, pouring mixed acid containing hydrofluoric acid, treating the second polyimide glass substrate for 30min by ultrasonic oscillation, pausing for 30min, treating the second polyimide glass substrate for 30min by ultrasonic oscillation again, repeatedly treating the second polyimide glass substrate for 16h in such a way until the second polyimide glass substrate is thinned to 30um, taking out the second polyimide glass substrate, washing the second polyimide glass substrate by using purified water, and drying the second polyimide glass substrate by air blowing.
S4: and immersing the thinned second polyimide glass substrate into a NaOH mixed aqueous solution of a polytetrafluoroethylene groove, carrying out ultrasonic oscillation treatment for 30min, carrying out intermittent 5min, taking out, washing for 3 times by using purified water until the aqueous solution is neutral, and finally blowing by using air to dry so as to obtain the high-hardness and high-transparency polyimide flexible cover plate.
For the prepared high-hardness and high-transparency polyimide flexible cover plate, a 3M adhesive tape grid cutting method is adopted to test that the adhesion force between the PI (polyimide) and the glass substrate is 1 grade, the ultraviolet visible spectrum (UV-Vis) test light transmittance is 89%, the cut-off wavelength is 380nm, the hardness of the glass surface is 6H, the hardness of the PI surface is 2H, and the minimum inner and outer bending radius can be restored to be 3 mm.
Example 5
S1: and (3) coating the first polyimide slurry of 8um on the glass substrate in a flowing manner, reducing the pressure to 10Pa in a vacuum oven, heating to 60 ℃, and baking for 15min to obtain the first polyimide glass substrate with the thickness of 4 um.
S2: coating 38um second polyimide slurry on the first polyimide glass substrate, reducing pressure to 10Pa in a vacuum oven, heating to 60 deg.C, baking for 15min, further reducing pressure to 0.5Pa in the vacuum oven, heating to 120 deg.C, baking for 30min, and further baking in N2And carrying out temperature programming thermal imidization under protection to obtain a second polyimide glass substrate.
S3: and (3) putting the second polyimide glass substrate into a polytetrafluoroethylene groove, pouring mixed acid containing hydrofluoric acid, treating the second polyimide glass substrate for 30min by ultrasonic oscillation, pausing for 30min, treating the second polyimide glass substrate for 30min by ultrasonic oscillation again, repeatedly treating the second polyimide glass substrate for 18h in such a way until the second polyimide glass substrate is thinned to the thickness of 32um, taking out the second polyimide glass substrate, washing the second polyimide glass substrate by using purified water, and drying the second polyimide glass substrate by air.
S4: and immersing the thinned second polyimide glass substrate into a NaOH mixed aqueous solution of a polytetrafluoroethylene groove, carrying out ultrasonic oscillation treatment for 30min, carrying out intermittent 5min, taking out, washing for 3 times by using purified water until the aqueous solution is neutral, and finally blowing by using air to dry so as to obtain the high-hardness and high-transparency polyimide flexible cover plate.
For the prepared high-hardness and high-transparency polyimide flexible cover plate, a 3M adhesive tape grid cutting method is adopted to test that the adhesion force between the PI (polyimide) and the glass substrate is 1 grade, the ultraviolet visible spectrum (UV-Vis) test light transmittance is 89%, the cut-off wavelength is 380nm, the hardness of the glass surface is 6H, the hardness of the PI surface is 2H, and the minimum inner and outer bending radius can be restored to be 3 mm.
Example 6
S1: and (3) coating 9um of first polyimide slurry on the glass substrate in a flowing manner, reducing the pressure to 10Pa in a vacuum oven, heating to 60 ℃, and baking for 15min to obtain a first polyimide glass substrate with the thickness of 4 um.
S2: a second polyimide slurry of 39um was flow-coated on the first polyimide glass substrate, in a vacuum ovenReducing pressure to 10Pa, heating to 60 deg.C, baking for 15min, further reducing pressure to 0.5Pa in vacuum oven, heating to 120 deg.C, baking for 30min, and further baking in N2And carrying out temperature programming thermal imidization under protection to obtain a second polyimide glass substrate.
S3: and (3) putting the second polyimide glass substrate into a polytetrafluoroethylene groove, pouring mixed acid containing hydrofluoric acid, treating the second polyimide glass substrate for 30min by ultrasonic oscillation, pausing for 30min, treating the second polyimide glass substrate for 30min by ultrasonic oscillation again, repeatedly treating the second polyimide glass substrate for 20h in such a way until the second polyimide glass substrate is thinned to 33um, taking out the second polyimide glass substrate, washing the second polyimide glass substrate by using purified water, and drying the second polyimide glass substrate by air blowing.
S4: and immersing the thinned second polyimide glass substrate into a NaOH mixed aqueous solution of a polytetrafluoroethylene groove, carrying out ultrasonic oscillation treatment for 30min, carrying out intermittent 5min, taking out, washing for 3 times by using purified water until the aqueous solution is neutral, and finally blowing by using air to dry so as to obtain the high-hardness and high-transparency polyimide flexible cover plate.
For the prepared high-hardness and high-transparency polyimide flexible cover plate, a 3M adhesive tape grid cutting method is adopted to test that the adhesion force between the PI (polyimide) and the glass substrate is 1 grade, the ultraviolet visible spectrum (UV-Vis) test light transmittance is 89%, the cut-off wavelength is 380nm, the hardness of the glass surface is 6H, the hardness of the PI surface is 2H, and the minimum inner and outer bending radius can be restored to be 3 mm.
Example 7
S1: and (3) coating 10um of first polyimide slurry on the glass substrate in a flowing manner, reducing the pressure to 10Pa in a vacuum oven, heating to 60 ℃, and baking for 15min to obtain a first polyimide glass substrate with the thickness of 5 um.
S2: coating 40um second polyimide slurry on the first polyimide glass substrate, reducing pressure to 10Pa in a vacuum oven, heating to 60 ℃, baking for 15min, further reducing pressure to 0.5Pa in the vacuum oven, heating to 120 ℃, baking for 30min, and further baking in N2And carrying out temperature programming thermal imidization under protection to obtain a second polyimide glass substrate.
S3: and (3) putting the second polyimide glass substrate into a polytetrafluoroethylene groove, pouring mixed acid containing hydrofluoric acid, treating the second polyimide glass substrate for 30min by ultrasonic oscillation, pausing for 30min, treating the second polyimide glass substrate for 30min by ultrasonic oscillation again, repeatedly treating the second polyimide glass substrate for 23h in such a way until the second polyimide glass substrate is thinned to 35um, taking out the second polyimide glass substrate, washing the second polyimide glass substrate by using purified water, and drying the second polyimide glass substrate by air blowing.
S4: and immersing the thinned second polyimide glass substrate into a NaOH mixed aqueous solution of a polytetrafluoroethylene groove, carrying out ultrasonic oscillation treatment for 30min, carrying out intermittent 5min, taking out, washing for 3 times by using purified water until the aqueous solution is neutral, and finally blowing by using air to dry so as to obtain the high-hardness and high-transparency polyimide flexible cover plate.
For the prepared high-hardness and high-transparency polyimide flexible cover plate, a 3M adhesive tape grid cutting method is adopted to test that the adhesion force between the PI (polyimide) and the glass substrate is 1 grade, the ultraviolet visible spectrum (UV-Vis) test light transmittance is 89%, the cut-off wavelength is 380nm, the hardness of the glass surface is 6H, the hardness of the PI surface is 2H, and the minimum inner and outer bending radius can be restored to be 3 mm.
The invention also provides a second high-hardness high-transparency polyimide flexible cover plate, which comprises: a glass substrate and a polyimide film layer adhered on the glass substrate, wherein,
the structural formula of the polyimide film layer is as follows:
Figure BDA0002352776680000151
wherein m, n and y are integers, m is more than 0, n is more than or equal to 0, and y is more than or equal to 0; m: n: y is 1: (0-10): (0-10).
Further, the polyimide film layer is made of a polyimide slurry, which is the same as the above-mentioned first polyimide slurry.
Compared with the first cover plate in the prior art, the cover plate is formed by directly and thickly coating a gorilla glass plate with first polyimide slurry, wherein the thickness of the slurry is 30-40 um; reducing the pressure to 10Pa in a vacuum oven, heating to 60 ℃, baking for 15min, further reducing the pressure to 0.5Pa in the vacuum oven,heating to 120 deg.C, baking for 30min, and further baking in N2Carrying out temperature programming thermal imidization under protection, then adopting the thinning and polishing process used by the first cover plate, finally obtaining a second polyimide flexible cover plate, and testing the cover plate to obtain the following relevant properties:
the adhesion between the PI and the glass substrate is 1 grade by adopting a 3M adhesive tape grid cutting method, the light transmittance is 89 percent by adopting an ultraviolet-visible spectrum (UV-Vis) test, the cut-off wavelength is 390nm, the hardness of the glass surface is 6H, the hardness of the PI surface is 2H, and the minimum inner and outer bending radius can be restored to be 2 mm.
The invention also provides a third high-hardness high-transparency polyimide flexible cover plate, which comprises: a glass substrate and a polyimide film layer adhered on the glass substrate, wherein,
the structural formula of the polyimide film layer is as follows:
Figure BDA0002352776680000161
wherein m and n are integers, m is more than 0, and n is more than or equal to 0; m: n is 1: (0-10).
Further, the polyimide film layer is prepared from a polyimide slurry, which is prepared in the same manner as the second polyimide slurry described above.
The polyimide flexible cover plate is another two-layer composite plate formed by combining a glass substrate and a polyimide film layer, and compared with the first cover plate, the cover plate is formed by directly coating a second polyimide slurry on a gorilla glass plate, wherein the thickness of the slurry is 30-40 mu m; reducing pressure to 10Pa in a vacuum oven, heating to 60 deg.C, baking for 15min, further reducing pressure to 0.5Pa in the vacuum oven, heating to 120 deg.C, baking for 30min, and further baking in N2Carrying out temperature programming thermal imidization under protection, then adopting the thinning and polishing process used by the first cover plate, finally obtaining a third polyimide flexible cover plate, and testing the cover plate to obtain the following relevant properties:
the adhesion between the PI and the glass substrate is 3-4 grade by using a 3M adhesive tape grid cutting method, the light transmittance is 90% by using an ultraviolet-visible spectrum (UV-Vis) test, the cut-off wavelength is 380nm, the hardness of the glass surface is 6H, the hardness of the PI surface is 2H, and the minimum inner and outer bending radius can be restored to 5mm (delamination can occur after the PI surface is continuously bent to 3 mm).
The series of experiments and tests prove that: the high-transparency high-adhesiveness PI slurry prepared by the application adopts a sandwich three-layer method, which is excessively beneficial to improving the adhesive force between a transparent PI layer and a glass plate; the outer surface hardness of the high-flexibility PI cover plate reaches 6H through a series of processes, the bending radius is less than or equal to 3mm, and the requirement of the flexible display cover plate can be met; the prepared high-transparency high-adhesiveness PI slurry can be coated in one step, and the double layer method achieves the same good effect as the three-layer method.
The above-mentioned embodiments, objects, technical solutions and advantages of the present invention are further described in detail, it should be understood that the above-mentioned embodiments are only illustrative of the present invention and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1.一种高硬度高透明性聚酰亚胺柔性盖板，其特征在于，包括：玻璃基板、粘附在所述玻璃基板上的第一聚酰亚胺膜层及粘附在所述第一聚酰亚胺膜层上的第二聚酰亚胺膜层，其中，1. A high-hardness and high-transparency polyimide flexible cover plate, characterized in that it comprises: a glass substrate, a first polyimide film layer adhered on the glass substrate, and a first polyimide film layer adhered on the glass substrate. A second polyimide film layer on a polyimide film layer, wherein, 所述第一聚酰亚胺膜层的第一聚酰亚胺的结构式为：The structural formula of the first polyimide of the first polyimide film layer is:
Figure FDA0002352776670000011
Figure FDA0002352776670000011
 A:
Figure FDA0002352776670000012
A:
Figure FDA0002352776670000012
 B:
Figure FDA0002352776670000013
B:
Figure FDA0002352776670000013
 C:
Figure FDA0002352776670000014
C:
Figure FDA0002352776670000014
 其中，所述m，n，y为整数，且所述m＞0，n≥0，y≥0；m：n：y＝1：(0～10)：(0～10)。Wherein, the m, n, and y are integers, and m>0, n≥0, y≥0; m:n:y=1:(0-10):(0-10). 2.如权利要求1所述的高硬度高透明性聚酰亚胺柔性盖板，其特征在于，2. The high-hardness and high-transparency polyimide flexible cover plate according to claim 1, wherein, 所述第二聚酰亚胺膜层的第二聚酰亚胺的结构式为：The structural formula of the second polyimide of the second polyimide film layer is:
Figure FDA0002352776670000021
Figure FDA0002352776670000021
 A：
Figure FDA0002352776670000022
A:
Figure FDA0002352776670000022
 B：
Figure FDA0002352776670000023
B:
Figure FDA0002352776670000023
 其中，所述m，n为整数，且所述m＞0，n≥0；m：n＝1：(0～10)。Wherein, the m and n are integers, and m>0, n≥0; m: n=1: (0-10). 3.如权利要求1所述的高硬度高透明性聚酰亚胺柔性盖板，其特征在于，所述第一聚酰亚胺膜层通过第一聚酰亚胺浆液制得；所述第二聚酰亚胺膜层通过第二聚酰亚胺浆液制得。3 . The high-hardness and high-transparency polyimide flexible cover plate according to claim 1 , wherein the first polyimide film layer is obtained by a first polyimide slurry; The bispolyimide film layer is made from a second polyimide slurry. 4.如权利要求3所述的高硬度高透明性聚酰亚胺柔性盖板，其特征在于，所述第一聚酰亚胺浆液的制备方法为：4. The high-hardness and high-transparency polyimide flexible cover plate according to claim 3, wherein the preparation method of the first polyimide slurry is: 将N,N’-二甲基丙烯酰胺作为溶剂，N2为保护气体，向所述溶剂中加入二胺，升温至30～50℃，使所述二胺逐步溶解在所述溶剂中，待温度降至室温后，一次性加入二酐溶液，机械搅拌反应4～7h，得到所述第一聚酰亚胺浆液。Using N,N'-dimethylacrylamide as a solvent and N2 as a protective gas, diamine is added to the solvent, and the temperature is raised to 30-50° C. to gradually dissolve the diamine in the solvent. After the temperature is lowered to room temperature, the dianhydride solution is added at one time, and the reaction is mechanically stirred for 4-7 hours to obtain the first polyimide slurry. 5.如权利要求4所述的高硬度高透明性聚酰亚胺柔性盖板，其特征在于，所述第一聚酰亚胺浆液的制备方法为：5. The high-hardness and high-transparency polyimide flexible cover plate according to claim 4, wherein the preparation method of the first polyimide slurry is: 将N,N’-二甲基丙烯酰胺作为溶剂，N2为保护气体，向所述溶剂中加入二胺，升温至40℃，使所述二胺逐步溶解在所述溶剂中，待温度降至室温后，一次性加入二酐溶液，机械搅拌反应6h，得到所述第一聚酰亚胺浆液。Using N,N'-dimethylacrylamide as a solvent and N2 as a protective gas, add diamine to the solvent, raise the temperature to 40°C, and gradually dissolve the diamine in the solvent, wait until the temperature drops After reaching room temperature, the dianhydride solution was added at one time, and the reaction was mechanically stirred for 6 hours to obtain the first polyimide slurry. 6.一种高硬度高透明性聚酰亚胺柔性盖板，其特征在于，包括：玻璃基板及粘附在所述玻璃基板上的聚酰亚胺膜层，其中，6. A high-hardness and high-transparency polyimide flexible cover plate, characterized by comprising: a glass substrate and a polyimide film layer adhered on the glass substrate, wherein, 所述聚酰亚胺膜层的聚酰亚胺的结构式为：The structural formula of the polyimide of the polyimide film layer is:
Figure FDA0002352776670000031
Figure FDA0002352776670000031
 A:
Figure FDA0002352776670000032
A:
Figure FDA0002352776670000032
 B:
Figure FDA0002352776670000033
B:
Figure FDA0002352776670000033
 C:
Figure FDA0002352776670000034
C:
Figure FDA0002352776670000034
 其中，所述m，n，y为整数，且所述m＞0，n≥0，y≥0；m：n：y＝1：(0～10)：(0～10)。Wherein, the m, n, and y are integers, and m>0, n≥0, y≥0; m:n:y=1:(0-10):(0-10). 7.一种用于权利要求1～5任一项所述的高硬度高透明性聚酰亚胺柔性盖板的制备方法，其特征在于，包括以下步骤：7. A preparation method for the high-hardness and high-transparency polyimide flexible cover sheet according to any one of claims 1 to 5, characterized in that, comprising the following steps: 在所述玻璃基板上流涂2～10um的所述第一聚酰亚胺浆液，制得第一聚酰亚胺玻璃基板；Flow coating 2-10um of the first polyimide slurry on the glass substrate to prepare a first polyimide glass substrate; 在所述第一聚酰亚胺玻璃基板上流涂30～40um的所述第二聚酰亚胺浆液，制得第二聚酰亚胺玻璃基板；Flow coating 30-40um of the second polyimide slurry on the first polyimide glass substrate to prepare a second polyimide glass substrate; 通过含氢氟酸的混酸减薄工艺，将所述第二聚酰亚胺玻璃基板减薄至1～100um厚度，即获得所述高硬度高透明性聚酰亚胺柔性盖板。Through the mixed acid thinning process containing hydrofluoric acid, the second polyimide glass substrate is thinned to a thickness of 1-100 um, so as to obtain the high-hardness and high-transparency polyimide flexible cover plate. 8.如权利要求7所述的高硬度高透明性聚酰亚胺柔性盖板的制备方法，其特征在于，8. The method for preparing a high-hardness and high-transparency polyimide flexible cover plate according to claim 7, wherein, 在所述玻璃基板上流涂2～10um的所述第一聚酰亚胺浆液后，在真空烘箱中减压至10Pa，升温到60℃，烘15min，制得厚度为2-5um的第一聚酰亚胺玻璃基板。After the first polyimide slurry of 2-10um is flow-coated on the glass substrate, the pressure is reduced to 10Pa in a vacuum oven, the temperature is raised to 60°C, and baked for 15min to prepare a first polyimide with a thickness of 2-5um. Imide glass substrate. 9.如权利要求7所述的高硬度高透明性聚酰亚胺柔性盖板的制备方法，其特征在于，9. The method for preparing a high-hardness and high-transparency polyimide flexible cover plate according to claim 7, wherein, 在所述第一聚酰亚胺玻璃基板上流涂30～40um的所述第二聚酰亚胺浆液，在真空烘箱中减压至10Pa，升温到60℃，烘15min，进一步在真空烘箱中减压至0.5Pa，升温到120℃，烘30min，再进一步在N2保护下进行程序升温热亚胺化，制得所述第二聚酰亚胺玻璃基板。Flow-coat 30-40um of the second polyimide slurry on the first polyimide glass substrate, reduce the pressure to 10Pa in a vacuum oven, raise the temperature to 60°C, bake for 15min, and further reduce the pressure in a vacuum oven Press to 0.5 Pa, heat up to 120° C., bake for 30 min, and further perform temperature-programmed thermal imidization under the protection of N 2 to prepare the second polyimide glass substrate. 10.如权利要求7所述的高硬度高透明性聚酰亚胺柔性盖板的制备方法，其特征在于，10. The method for preparing a high-hardness and high-transparency polyimide flexible cover plate according to claim 7, wherein, 将所述第二聚酰亚胺玻璃基板放入聚四氟乙烯槽中，倒入含氢氟酸的混酸，没过所述第二聚酰亚胺玻璃基板，通过超声波震荡处理30min，间歇30min，再次用超声波震荡处理30min，如此反复处理10～25h，直至将所述第二聚酰亚胺玻璃基板减薄至1～100um厚度，取出后采用纯净水冲洗，空气吹干，获得所述高硬度高透明性聚酰亚胺柔性盖板。Put the second polyimide glass substrate into a polytetrafluoroethylene tank, pour in the mixed acid containing hydrofluoric acid, cover the second polyimide glass substrate, and perform ultrasonic vibration treatment for 30 minutes, with an interval of 30 minutes. , and ultrasonically vibrated again for 30 minutes, and repeated the treatment for 10 to 25 hours until the second polyimide glass substrate was thinned to a thickness of 1 to 100um. High hardness and transparency polyimide flexible cover.
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