CN110349508B - Manufacturing method of cover plate, display panel and display device - Google Patents
Manufacturing method of cover plate, display panel and display device Download PDFInfo
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- CN110349508B CN110349508B CN201910526414.0A CN201910526414A CN110349508B CN 110349508 B CN110349508 B CN 110349508B CN 201910526414 A CN201910526414 A CN 201910526414A CN 110349508 B CN110349508 B CN 110349508B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
- C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxyl groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
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- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
- G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
- G09F9/301—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements flexible foldable or roll-able electronic displays, e.g. thin LCD, OLED
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Abstract
The disclosure provides a manufacturing method of a cover plate, a display panel and a display device. The method comprises the following steps: step S10: dissolving a polymer in a solvent containing a photoinitiator to obtain a solution; step S20: providing a flexible substrate, and coating the solution on the flexible substrate; and step S30: sequentially performing a drying process and an illumination process on the solution coated on the flexible substrate to form a hardened layer; wherein the polymer contains a silicon hydroxyl group and a germanium hydroxyl group. The hardened layer containing germanium hydroxyl groups and silicon hydroxyl groups is modified, so that the hydrophobicity of the surface of the hardened layer is improved, and the hardness and the optical performance of the surface of the hardened layer are improved.
Description
Technical Field
The invention relates to the technical field of display, in particular to a manufacturing method of a cover plate, a display panel and a display device.
Background
The cover sheet for the flexible and foldable display device needs to have good hydrophobic properties in addition to good mechanical properties because it is located on the uppermost layer of the module structure. The hydrophobic properties of the hardened layer surface are generally determined by the surface free energy and surface roughness of the material. Compounds containing alkyl or fluoroalkyl functional groups generally have a low surface free energy and are therefore used for producing hydrophobic hardened layers, but fluorine-containing compounds are not environmentally friendly and also do not have good hardness and abrasion resistance.
In conclusion, the existing flexible foldable display device has the problems that the hardened layer material is not environment-friendly, and the hydrophobicity, hardness and abrasion resistance are not good. Therefore, it is desirable to provide a method for manufacturing a display panel, a display panel and a display device to improve the defect.
Disclosure of Invention
The embodiment of the disclosure provides a manufacturing method of a cover plate, a display panel and a display device, which are used for solving the problems that a hardened layer of an existing flexible foldable display device is not environment-friendly in material and poor in hydrophobicity, hardness and abrasion resistance.
The embodiment of the disclosure provides a manufacturing method of a cover plate, which includes:
step S10: dissolving a polymer in a solvent containing a photoinitiator to obtain a solution;
step S20: providing a flexible substrate, and coating the solution on the flexible substrate; and
step S30: sequentially performing a drying process and an illumination process on the solution coated on the flexible substrate to form a hardened layer;
wherein the polymer contains a silicon hydroxyl group and a germanium hydroxyl group.
According to an embodiment of the present disclosure, a method of forming the polymer comprises:
step S101: dissolving ethyl n-germanate in isophthalic acid, adding dilute hydrochloric acid to initiate sol-gel reaction, and stirring to generate sol;
step S102: adding a mixed solution of 3- (trimethoxysilylene) propyl methacrylate and dilute hydrochloric acid into the sol, and then sequentially carrying out stirring and aging processes to obtain a first reaction solution; and
step S103: and dissolving hexamethyldisilazane in 2-propanol, stirring and keeping the temperature constant, adding the first reaction solution, and aging after the reaction is finished to obtain the polymer.
According to one embodiment of the present disclosure, the structural formula of the polymer is described in formula (1) below:
according to an embodiment of the present disclosure, in the step S101, the molar ratio of the ethyl n-germanate to the isophthalic acid is 2.25: 1.
According to an embodiment of the present disclosure, in the step S102, the molar ratio of ethyl n-germanate, water and 3- (trimethoxysilyl) propyl methacrylate is 4.5:3: 1.
According to an embodiment of the present disclosure, in the step S30, the drying process includes drying at room temperature, and then performing vacuum drying at 40 ℃.
The disclosed embodiment provides a display panel, including:
a substrate base plate;
a light emitting layer disposed on the substrate base plate; and
the cover plate is arranged on one side, away from the substrate base plate, of the light emitting layer and comprises a flexible substrate and a hardening layer arranged on the flexible substrate;
the material of the hardening layer comprises a polymer containing germanium hydroxyl groups and silicon hydroxyl groups.
According to one embodiment of the present disclosure, the structural formula of the polymer is shown in formula (1) below:
according to an embodiment of the present disclosure, the material of the flexible substrate includes polyimide or polyethylene terephthalate.
The embodiment of the disclosure also provides a display device, which includes the display panel.
The beneficial effects of the disclosed embodiment are as follows: in the manufacturing method of the cover plate, the display panel and the display device provided by the embodiment of the disclosure, the material of the existing hardened layer containing the silicon nanoparticles is replaced by the polymer containing the germanium hydroxyl group and the silicon hydroxyl group, and the hardened layer containing the germanium hydroxyl group and the silicon hydroxyl group is modified, so that the hydrophobicity of the surface of the hardened layer is improved, and the hardness and the optical performance of the surface of the hardened layer are improved.
Drawings
In order to illustrate the embodiments or the technical solutions in the prior art more clearly, the drawings needed to be used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some of the disclosed embodiments, and that other drawings can be obtained by those skilled in the art without inventive effort.
Fig. 1 is a schematic flow chart illustrating a method for manufacturing a cover plate according to an embodiment of the disclosure;
fig. 2 is a schematic cross-sectional structure diagram of a display panel according to an embodiment of the disclosure;
FIG. 3 is a schematic flow chart of a polymer synthesis method according to an embodiment of the present disclosure;
FIG. 4A is a schematic diagram illustrating a chemical reaction of a polymer according to an embodiment of the present disclosure;
FIG. 4B is a schematic diagram illustrating a chemical reaction of a polymer according to an embodiment of the present disclosure;
FIG. 4C is a schematic diagram of a chemical reaction of a polymer according to one embodiment of the present disclosure;
fig. 5 is a schematic cross-sectional structure diagram of a display panel according to a second embodiment of the disclosure.
Detailed Description
The following description of the various embodiments refers to the accompanying drawings, which illustrate specific embodiments in which the disclosure may be practiced. Directional phrases used in this disclosure, such as [ upper ], [ lower ], [ front ], [ back ], [ left ], [ right ], [ inner ], [ outer ], [ side ], etc., refer only to the directions of the attached drawings. Accordingly, the directional terms used are used for the purpose of illustration and understanding of the present disclosure, and are not used to limit the present disclosure. In the drawings, elements having similar structures are denoted by the same reference numerals.
The disclosure is further described with reference to the following drawings and specific embodiments:
the first embodiment is as follows:
the embodiment of the present disclosure provides a method for manufacturing a cover plate, which is described in detail below with reference to fig. 1 to 4C. Fig. 1 is a schematic flow chart of a manufacturing method of a cover plate according to an embodiment of the disclosure, fig. 2 is a schematic cross-sectional structure of a display panel according to an embodiment of the disclosure, fig. 3 is a schematic flow chart of a polymer synthesis method according to an embodiment of the disclosure, and fig. 4A, 4B, and 4C are chemical structural formulas of polymers according to an embodiment of the disclosure.
As shown in fig. 1, the method includes:
step S10: the polymer is dissolved in a solvent containing a photoinitiator to obtain a solution. The solvent is tetrahydrofuran, the photoinitiator can be Irgacure 250 iodonium salt cation photoinitiator, the polymer is dissolved in tetrahydrofuran containing the photoinitiator, and the solution can be obtained by shaking or ultrasonic vibration for 1 hour, and is colorless and viscous.
Step S20: providing a flexible substrate 111, and coating the solution on the flexible substrate 111.
Step S30: the solution coated on the flexible substrate 111 is subjected to a drying process and a light irradiation process to form a hardened layer 112. Wherein, the drying process comprises the following steps: drying was first carried out at room temperature and overnight, followed by vacuum drying at 40 ℃. The light density adopted in the illumination process is 100mW/cm2The total ultraviolet output energy is 3J/cm2The solution applied on the flexible substrate 111 is irradiated with the ultraviolet lamp to form a hardened layer 112. The hardened layer 112 and the flexible substrate 111 together constitute a cover plate of the display panel 100.
The chemical structural formula of the polymer is shown as a formula (1), and the polymer comprises germanium hydroxyl groups and silicon hydroxyl groups. As shown in formula (1), the germanium hydroxyl group further includes two oxytrimethylsilane groups connected with the germanium nanoparticles, and a hydroxyl group connected with the germanium nanoparticles, and the silicon hydroxyl group further includes two hydroxyl groups connected with the silicon nanoparticles and a methacrylate group.
The formula (1) only shows the structure of the polymer, and since the polymer is a spherical structure, the complete spherical structure of the polymer cannot be shown by the structural formula of the formula (1), the polymer can be shown as a spherical structure only by a chain-like structure on the surface of a germanium atom, and meanwhile, the surface of the germania sol contains a plurality of hydroxyl groups, and the formula (1) only shows 4 of the polymer, and other hydroxyl groups are not shown.
As shown in fig. 3, the method of synthesizing the polymer includes:
step S101: dissolving ethyl n-germanate in isophthalic acid, adding dilute hydrochloric acid to initiate sol-gel reaction, and stirring to generate sol.
Wherein the molar ratio of the ethyl n-germanate to the isophthalic acid is 2.25:1, and stirring is required after the addition of the isophthalic acid to the ethyl n-germanate so as to dissolve the ethyl n-germanate. After adding dilute hydrochloric acid, the sol-gel reaction is initiated, and the sol is generated after stirring for 6 hours at room temperature. The specific process is shown in fig. 4A, wherein n-germanic acid ethyl ester undergoes hydrolysis reaction to generate monogermanic acid.
Step S102: adding a mixed solution of 3- (trimethoxysilylpropyl) propyl methacrylate (MSMA) and dilute hydrochloric acid into the sol, and then sequentially carrying out stirring and aging processes to obtain a first reaction solution. The specific process is shown in fig. 4B, and germanic acid in the sol generated in step S101 undergoes a condensation reaction with MSMA and n-ethyl germanate.
Wherein the stirring is continued for 3 hours, and the time required for the aging process after the stirring is 3 days. In the step S102, the molar ratio of the ethyl n-germanate to the water to the 3- (trimethoxysilylpropyl) propyl methacrylate is 4.5:3: 1. Nuclear magnetic hydrogen spectroscopy characterization was performed on a 400mhz nmr instrument with CDCl3 as the solvent.
Measuring characteristic structure parameters: (1) elemental analysis: c16.59%, H3.32%; (2) mass spectrum: MS (EI) M/z [ M + ] 286.54; (3) nuclear magnetic resonance Hydrogen Spectroscopy 1H NMR (400MHZ, CDCl3, Δ) 6.48-6.43(m,2H),6.40(s,1H),2.01(s,3H),1.2(s,5H), in substantial agreement with the structural data of C4H10GeO8 Si.
Step S103: and dissolving hexamethyldisilazane in 2-propanol, stirring and keeping the temperature constant, adding the first reaction solution, and aging after the reaction is finished to obtain the polymer.
Wherein the constant temperature is kept at 15 ℃, the reaction time is 3 hours after the first reaction solution is added, and the polymer can be obtained after the aging process after the reaction is finished is aged for 6 days at room temperature. The specific process is shown in fig. 4C, and the oligomer in the first reaction solution further undergoes a polymerization reaction to form a long-chain skeleton structure extending to a three-dimensional space.
Measuring characteristic structure parameters: (1) elemental analysis; 27.69% of C, 6.12% of H, 16.38% of GeC and 20.73% of Si; (2) mass spectrum: MS (EI) M/z [ M + ] 431.38; (3) nuclear magnetic resonance hydrogen spectrum 1H NMR (400MHZ, CDCl3, δ): 6.46-6.41(m,2H),6.38(s,1H),2.05(s,3H),1.2(s,5H),0.21(s,18H), in substantial agreement with the structural data of C10H26GeO8Si 3.
In the manufacturing method of the cover plate provided by the embodiment of the present disclosure, the material of the hardened layer 112 containing silicon nanoparticles is replaced by the polymer containing germanium hydroxyl groups and silicon hydroxyl groups, and the hardened layer 112 containing germanium hydroxyl groups and silicon hydroxyl groups is modified, so that the hydrophobicity of the surface of the hardened layer 112 is improved, and the hardness and the optical performance of the hardened layer 112 are improved.
Example two:
the present disclosure provides a display panel, which is described in detail with reference to fig. 5.
As shown in fig. 5, fig. 5 is a schematic cross-sectional structure diagram of a display panel according to an embodiment of the disclosure. The display panel 200 includes a substrate 210, a light emitting layer 220, and a cover plate 230, the light emitting layer 220 is disposed on the substrate 210, the cover plate 230 is disposed on a side of the light emitting layer 220 away from the substrate 210, and the cover plate 230 includes a flexible substrate 231 and a hardened layer 232 disposed on the flexible substrate 231. The material of the hardened layer 232 includes a polymer containing germanium hydroxyl groups and silicon hydroxyl groups.
In this embodiment, the structural formula of the polymer is shown in formula (1), the germanium hydroxyl group further includes two oxytrimethylsilane groups connected with the germanium nanoparticles, and a hydroxyl group connected with the germanium nanoparticles, and the silicon hydroxyl group further includes two hydroxyl groups connected with the silicon nanoparticles and a methacrylate group.
Preferably, the material of the flexible substrate includes polyimide or polyethylene terephthalate.
In the display panel 200 provided by the embodiment of the present disclosure, the material of the conventional hardened layer 232 including the silicon nanoparticles is replaced by the polymer including the germyl group and the silicon hydroxyl group, and the hardened layer 232 including the germyl group and the silicon hydroxyl group is modified, so that the hydrophobicity of the surface of the hardened layer 232 is improved, and the hardness and the optical performance of the hardened layer 232 are improved.
The embodiment of the present disclosure further provides a display device, which includes the display panel 200, and the display device can achieve the same technical effects as the display panel 200, and the details are not repeated herein.
In summary, although the present disclosure has been described with reference to the preferred embodiments, the above-described preferred embodiments are not intended to limit the present disclosure, and those skilled in the art can make various changes and modifications without departing from the spirit and scope of the present disclosure, so that the scope of the present disclosure is defined by the appended claims.
Claims (7)
1. A method for manufacturing a cover plate is characterized by comprising the following steps:
step S10: dissolving a polymer in a solvent containing a photoinitiator to obtain a solution;
step S20: providing a flexible substrate, and coating the solution on the flexible substrate; and
step S30: sequentially performing a drying process and an illumination process on the solution coated on the flexible substrate to form a hardened layer;
wherein the polymer contains silicon hydroxyl groups and germanium hydroxyl groups, and a method of forming the polymer comprising:
step S101: dissolving ethyl n-germanate in isophthalic acid, adding dilute hydrochloric acid to initiate sol-gel reaction, and stirring to generate sol;
step S102: adding a mixed solution of 3- (trimethoxysilyl) propyl methacrylate and dilute hydrochloric acid into the sol, and then sequentially carrying out stirring and aging processes to obtain a first reaction solution; and
step S103: and dissolving hexamethyldisilazane in 2-propanol, stirring and keeping the hexamethyldisilazane at a constant temperature, adding the first reaction solution, and after the reaction is finished, carrying out an aging process to obtain the polymer.
2. The method according to claim 1, wherein in step S101, the molar ratio of the n-ethyl germanate to the isophthalic acid is 2.25: 1.
3. The method according to claim 2, wherein in step S102, the mixed solution of 3- (trimethoxysilyl) propyl methacrylate and dilute hydrochloric acid contains water, and the molar ratio of the ethyl n-germanate to the water to the 3- (trimethoxysilyl) propyl methacrylate is 4.5:3: 1.
4. The method of claim 1, wherein in step S30, the drying process includes drying at room temperature and then vacuum drying at 40 ℃.
5. A display panel, comprising:
a substrate base plate;
a light emitting layer disposed on the substrate base plate; and
a cover plate disposed on a side of the light emitting layer away from the substrate base plate, the cover plate being prepared by the manufacturing method of any one of claims 1 to 4.
6. The display panel according to claim 5, wherein a material of the flexible substrate includes polyimide or polyethylene terephthalate.
7. A display device characterized in that it comprises a display panel as claimed in claim 5 or 6.
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| CN111128017B (en) * | 2019-12-03 | 2021-09-24 | 武汉华星光电半导体显示技术有限公司 | Flexible cover plate, manufacturing method of flexible cover plate and display device |
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| CN106782094A (en) * | 2017-01-12 | 2017-05-31 | 京东方科技集团股份有限公司 | A kind of motherboard and preparation method thereof, cover plate and preparation method thereof, display device |
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