CN110570765B - Flexible cover plate and manufacturing method thereof - Google Patents

Flexible cover plate and manufacturing method thereof Download PDF

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CN110570765B
CN110570765B CN201910806276.1A CN201910806276A CN110570765B CN 110570765 B CN110570765 B CN 110570765B CN 201910806276 A CN201910806276 A CN 201910806276A CN 110570765 B CN110570765 B CN 110570765B
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polymer
group
hardened layer
flexible cover
flexible
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CN110570765A (en
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赵远
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Wuhan China Star Optoelectronics Semiconductor Display Technology Co Ltd
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Wuhan China Star Optoelectronics Semiconductor Display Technology Co Ltd
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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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C08G18/341—Dicarboxylic acids, esters of polycarboxylic acids containing two carboxylic acid groups
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/778—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur silicon
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • 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 invention provides a flexible cover plate and a manufacturing method thereof, wherein the flexible cover plate comprises: flexible substrate and locate the last sclerosis layer of flexible substrate, wherein the material of sclerosis layer includes the polymer of benzene ring and ester group, side chain including siloxy group or germanium oxygen group for the main chain. The flexible cover plate and the manufacturing method thereof adjust the hardness of the polymer, improve the friction resistance of the polymer and further improve the mechanical property of the hardened layer.

Description

Flexible cover plate and manufacturing method thereof
Technical Field
The invention relates to the technical field of display, in particular to a flexible cover plate and a manufacturing method thereof.
Background
Currently, flexible display devices are an important research hotspot, and a cover plate for a flexible display device is generally composed of a flexible substrate and a hardened layer. Wherein, the flexible substrate can ensure that the cover plate has good flexibility, and the hardened layer has high hardness and good friction resistance to resist the damage of the screen.
The existing hardening layer is mainly an acrylic hardening layer, the hardness of the acrylic hardening layer is enhanced by generally adjusting the proportion of a flexible group and a rigid group in a main chain, but the friction resistance of the hardening layer is often influenced, so that the friction resistance of the hardening layer cannot meet the requirement of a flexible display device.
Therefore, a new flexible cover plate is needed to solve the above problems.
Disclosure of Invention
The invention provides a flexible cover plate and a manufacturing method thereof, which can improve the mechanical property of a hardening layer by adjusting the hardness of the hardening layer and increasing the friction resistance of the hardening layer so as to solve the technical problem that the friction resistance of the conventional hardening layer can not meet the requirement of display equipment.
In order to solve the above problems, the technical scheme provided by the invention is as follows:
the present invention provides a flexible cover plate comprising:
a flexible substrate;
a hardening layer disposed on the flexible substrate;
the hardened layer is made of a polymer, wherein the main chain of the polymer comprises a benzene ring and an ester group, and the side chain of the polymer comprises a silicon oxygen group or a germanium oxygen group.
According to a preferred embodiment of the present invention, the general formula of the polymer is as follows:
Figure GDA0002983062000000021
wherein R is1Comprising a germoxyl or siloxy group, R2Is an amide group, R3Including ester groups.
According to a preferred embodiment of the invention, R1Is represented by the following formula:
Figure GDA0002983062000000022
or, R1Is represented by the following formula:
Figure GDA0002983062000000023
according to a preferred embodiment of the invention, R2Is represented by the following formula:
Figure GDA0002983062000000024
according to a preferred embodiment of the present invention, R is3Is represented by the following formula:
Figure GDA0002983062000000025
according to the above technical object, the present invention further provides a method for manufacturing a flexible cover plate, comprising the steps of:
providing a flexible substrate;
forming a hardened layer on the flexible substrate;
the hardened layer is made of a polymer, wherein the main chain of the polymer comprises a benzene ring and an ester group, and the side chain of the polymer comprises a silicon oxygen group or a germanium oxygen group.
According to a preferred embodiment of the present invention, a hardened layer is formed on the flexible substrate, specifically:
carrying out chemical combination reaction on a silicon-oxygen halide or a germanium-oxygen halide and a halogenated isocyanide under the argon atmosphere to form an alkoxy isocyanide;
carrying out a polymerization reaction on the alkoxy isocyanide and an acid reagent under an argon atmosphere to form the polymer;
coating the polymer on the surface of the flexible substrate to form the hardened layer.
According to a preferred embodiment of the present invention, the general formula of the polymer is as follows:
Figure GDA0002983062000000031
wherein R is1Is a group comprising germanium oxygen or silicon oxygen, R2Comprising an amide group, R3Including ester groups.
According to a preferred embodiment of the invention, R1Is represented by the following formula:
Figure GDA0002983062000000032
or, R1Is represented by the following formula:
Figure GDA0002983062000000033
according to a preferred embodiment of the present invention, the reaction equation of the alkoxy isocyanide to form the polymer is shown as the following formula:
Figure GDA0002983062000000041
the invention has the beneficial effects that: the invention provides a flexible cover plate comprising: the flexible substrate and the hardening layer arranged on the flexible substrate are made of polymers, wherein the main chain of each hardening layer comprises a benzene ring and an ester group, and the side chain of each hardening layer comprises a silicon-oxygen group or a germanium-oxygen group; the hardness of the polymer is adjusted by introducing the side chain containing silicon oxygen or germanium oxygen, and the friction resistance of the polymer is improved by changing the length of the side chain, so that the mechanical property of the hardened layer is improved, and the requirement of flexible equipment is met; the manufacturing method of the flexible cover plate provided by the invention is simple, the process of preparing the hardened layer material is simple and easy to control, and the manufactured flexible cover plate has good friction resistance and can meet the requirements of flexible display equipment.
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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 embodiments of the invention, and it is obvious for a person skilled in the art that other drawings can be obtained according to these drawings without creative efforts.
Fig. 1 is a schematic structural diagram of a flexible cover plate according to an embodiment of the present invention;
fig. 2 is a schematic flow chart of a manufacturing method of a flexible cover plate according to an embodiment of the present invention.
Detailed Description
The following description of the various embodiments refers to the accompanying drawings that illustrate specific embodiments in which the invention may be practiced. The directional terms mentioned in the present invention, such as [ upper ], [ lower ], [ front ], [ rear ], [ left ], [ right ], [ inner ], [ outer ], [ side ], are only referring to the directions of the attached drawings. Accordingly, the directional terms used are used for explanation and understanding of the present invention, and are not used for limiting the present invention. In the drawings, elements having similar structures are denoted by the same reference numerals.
The invention aims at the technical problem that the display is influenced because the friction resistance of the hardened layer of the conventional flexible cover plate cannot meet the requirement, and the embodiment can solve the defect.
Referring to fig. 1, a flexible cover according to an embodiment of the present invention may be used as a cover for covering a flexible display device, where the flexible cover includes: a flexible substrate 101 and a hardened layer 102, where the flexible substrate 101 may be flexible or may be a light-transmitting substrate, for example, the flexible substrate 101 is a transparent polyimide substrate, and the flexible substrate 101 is a carrier for carrying other components, for example, the flexible substrate 101 may carry the hardened layer 102.
In the embodiment of the present invention, the hardened layer 102 of the flexible cover plate is disposed on the flexible substrate 101, and the hardened layer 102 is made of a polymer whose main chain includes a benzene ring and an ester group and whose side chain includes a silicon-oxygen group or a germanium-oxygen group.
The existing hardening layer is made of acrylic polymer, the acrylic is polymethyl methacrylate (PMMA), the transparent thermoplastic plastic has the advantages of good optical performance, low density, good toughness, easy coloring, easy processing and forming and the like, but the acrylic has the defect of no wear resistance, the acrylic polymer is polymer comprising phenyl and ester groups, the characteristic of the acrylic polymer is similar to that of the acrylic, and when the acrylic polymer is used for the hardening layer, the friction resistance can not meet the requirement of flexible equipment; in the embodiment of the invention, the side chain is introduced into the original acrylic polymer, the side chain is a long chain comprising a germanium oxygen group or a silicon oxygen group, the advantages of the alkoxy polymer and the acrylic polymer are combined to adjust the hardness of the hardened layer 102 and improve the friction resistance, and the mechanical property of the hardened layer 102 is improved by adjusting the length of the side chain so as to be suitable for the flexible cover plate.
The general formula of the polymer applied to the hardened layer 102 in the embodiment of the present invention is as follows:
Figure GDA0002983062000000061
in the formula (1), R1Comprising siloxy or germoxy groups, R2Is an amide group, R3Including ester groups.
R in the formula (1)1IncludedIn the case of a siloxy group, the R1Is shown as follows:
Figure GDA0002983062000000062
in the formula (2), one bond of silicon atom at long-chain side is bonded with one carbon atom of phenyl in main chain of the polymer to form chemical bond, and R1May be 6 to 10, said R1Must not be too small or too large, the number of carbon atoms being from 6 to 10, it is possible to adjust the flexibility of the polymer, thus increasing the mechanical properties of the polymer, and if the side chains are too long, it will increase the rigidity of the polymer, reducing the mechanical properties of the polymer.
R in the formula (1)1When including a germyloxy group, the R1Is shown as follows:
Figure GDA0002983062000000063
in the formula (3), one bond of the germanium atom positioned on the long-chain side is bonded with one carbon atom of the phenyl in the main chain of the polymer to form a chemical bond, and the R1May be 6 to 10, said R1Must not be too small or too large, the number of carbon atoms being from 6 to 10, it is possible to adjust the flexibility of the polymer, thus increasing the mechanical properties of the polymer, and if the side chains are too long, it will increase the rigidity of the polymer, reducing the mechanical properties of the polymer.
R in the formula (1)2Is shown as follows:
Figure GDA0002983062000000071
the R is2Is an amide group, since the main chain contains a phenyl group, the polymer is an aromatic amide polymer having an amide group therein, and the amide group can be raisedElasticity and surface hardness of the polymer, but the abrasion resistance of the polymer cannot be improved.
R in the formula (1)3Is shown as follows:
Figure GDA0002983062000000072
in the formula (5), R is3The polymer comprises an ester group and an amine group, wherein the ester group is a flexible group, the polarity of the ester group is high, and the ester group and the amine group can adjust the hardness and the elasticity of the polymer but cannot improve the friction resistance of the polymer.
The flexibility refers to the characteristic that a high molecular long chain can be curled in different degrees and is the special attribute of a polymer, the flexible source of the high molecular chain is the structure of the long chain and the free rotation of each chain on the long chain, and the main chain of the high molecular chain consists of thousands of covalent bonds; because the rotation of the bond never stops, the conformation of the adjacent bond of the polymer chain is continuously changed, and the appearance of the polymer chain is bent and curved to be like a disordered clew, which is called a random clew; wherein the internal rotation frequency of the single bond is very high, and the form of the random coil is continuously changed; the flexibility of the polymer chain depends mainly on the structure of the polymer main chain and substituents, and is also influenced by intermolecular interactions.
The introduction of polar substituents into the polymer will increase the intramolecular interactions and thus affect the flexibility of the polymer chain, depending on the polarity of the substituents, the distance along the chain and the symmetry, as for non-polar substituents, the effect is mainly determined by the size of the substituent volume.
For example, a side chain group is introduced into a high molecular polymer, and when the introduced group is a polar group, the stronger the polarity is, the higher the distribution density of the polar group is, the poorer the flexibility of the high molecular chain is, and when the structure of the polar group is symmetrical, the good flexibility of the high molecular chain is obtained; when the introduced groups are nonpolar groups, the space between molecular chains is increased, and the flexibility of the high molecular chains can be increased.
According to the flexible cover plate provided by the embodiment of the invention, a side chain is introduced into the material of the hardened layer 102, the side chain includes a germanium oxygen group or a silicon oxygen group, germanium and silicon are elements of the same group, the germanium oxygen group and the silicon oxygen group are both polar groups, the polarity is not strong, and the structures of the germanium oxygen group and the silicon oxygen group are symmetrical, so that the introduction of the germanium oxygen group or the silicon oxygen group can increase the flexibility of a polymer chain of a polymer in the hardened layer 102, and the flexibility and toughness of the polymer chain are directly influenced, so that the flexibility of the polymer is increased, and the toughness of the polymer is also increased; the germanium oxygen group or the silicon oxygen group can also adjust the elastic modulus of the polymer, so that the deformation capacity of the polymer is enhanced, and when the hardened layer 102 is damaged by external force, the self-recovery capacity is enhanced.
According to the flexible cover plate provided by the embodiment of the invention, the hardened layer is made of the polymer of which the main chain comprises the benzene ring and the ester group and the side chain comprises the silicon-oxygen group or the germanium-oxygen group, the hardness of the polymer is adjusted by introducing the side chain containing silicon oxygen or germanium oxygen, and the friction resistance of the polymer is improved by changing the length of the side chain, so that the mechanical property of the hardened layer is improved, and the requirement of flexible equipment is met.
Referring to fig. 2, an embodiment of the present invention further provides a method for manufacturing a flexible cover plate, which specifically includes the following steps:
s201, providing a flexible substrate.
In this step, the flexible substrate may be flexible or may be a light-transmitting substrate, for example, the flexible substrate is a transparent polyimide substrate, and the flexible substrate is a carrier for carrying other components, for example, the flexible substrate may carry the hardened layer.
S202, forming a hardening layer on the flexible substrate; the hardened layer is made of a polymer, wherein the main chain of the polymer comprises a benzene ring and an ester group, and the side chain of the polymer comprises a silicon oxygen group or a germanium oxygen group.
The existing hardening layer is made of acrylic polymer, the acrylic is polymethyl methacrylate (PMMA), the transparent thermoplastic plastic has the advantages of good optical performance, low density, good toughness, easy coloring, easy processing and forming and the like, but the acrylic has the defect of no wear resistance, the acrylic polymer is polymer comprising phenyl and ester groups, the characteristic of the acrylic polymer is similar to that of the acrylic, and when the acrylic polymer is used for the hardening layer, the friction resistance can not meet the requirement of flexible equipment; in the embodiment of the invention, the side chain is introduced into the original acrylic polymer, the side chain is a long chain comprising a germanium oxygen group or a silicon oxygen group, the advantages of the alkoxy polymer and the acrylic polymer are combined to adjust the hardness of the hardened layer 102 and improve the friction resistance, and the mechanical property of the hardened layer 102 is improved by adjusting the length of the side chain so as to be suitable for the flexible cover plate.
Step S202 specifically includes:
step 1, carrying out a chemical combination reaction on a silicon-oxygen halide or a germanium-oxygen halide and a halogenated isocyanide in an argon atmosphere to form an alkoxy isocyanide.
When the alkoxy isocyanide is a siloxy isocyanide, the step 1 is as follows: carrying out chemical combination reaction on a silicon-oxygen halide or a halogenated isocyanide in an argon atmosphere to form a silicon-oxygen isocyanide; the silicon-oxygen halide can be 1- (6-bromohexyl) -1,1,3,3, 3-pentamethyl disiloxane, the halogenated isocyanide can be bis (3-bromo-4-isocyanatophenyl) methane, the combination reaction needs to be carried out under an argon atmosphere, N-methyl pyrrolidone (NMP) needs to be added to remove oxygen generated in the reaction, the reaction temperature is kept at 60 ℃, the reaction time is 24 hours, extraction needs to be carried out after the reaction is finished, and column chromatography separation is carried out to obtain the white solid silicon-oxygen isocyanide.
For example, bis (3-bromo-4-isocyanatophenyl) methane (10mmol),1- (6-bromohexyl) -1,1,3,3, 3-pentamethyldisiloxane (20mmol) was charged into a 100mL two-necked flask, followed by three-times evacuation, purging with argon, addition of 50mL of deoxygenated N-methylpyrrolidone (NMP) and a small amount of hydrochloric acid, and reaction at 60 ℃ for 24 hours. The reaction was then cooled to room temperature, the mixture was poured into 100ml of ice water, extracted three times with dichloromethane, the organic phases were combined, silica gel was added, the solvent was removed and the siloxyisocyanide was isolated by column chromatography (dichloromethane: n-hexane v/v ═ 1:1) to give the siloxyisocyanide, in this case bis (4-isocyanato-3- (6- (1,1,3,3, 3-pentamethyldisiloxane) hexyl) phenyl) methane as a white solid with a mass of 4.2g and a yield of 60%.
When the alkoxy isocyanide is germano-oxy isocyanide, the step 1 is as follows: carrying out chemical combination reaction on germanium oxide halide or halogenated isocyanide under the argon atmosphere to form germanium oxide isocyanide; the germanium oxyhalide can be 1- (6-bromohexyl) -1,1,3,3, 3-pentamethyl digermoxane, the halogenated isocyanide can be bis (3-bromo-4-isocyanatophenyl) methane, the combination reaction needs to be carried out under an argon atmosphere, N-methylpyrrolidone (NMP) needs to be added to remove oxygen generated in the reaction, the reaction temperature is kept at 60 ℃, the reaction time is 24 hours, extraction needs to be carried out after the reaction is finished, and column chromatography separation is carried out to obtain the white solid germanium oxyisocyanide.
For example, bis (3-bromo-4-isocyanatophenyl) methane (10mmol),1- (6-bromohexyl) -1,1,3,3, 3-pentamethyldigermanoxane (20mmol) was charged into a 100mL two-necked flask, followed by three-pass evacuation, argon gas charge, addition of 50mL of deoxygenated N-methylpyrrolidone (NMP) and a small amount of hydrochloric acid, and reaction at 60 ℃ for 24 hours. The reaction is then cooled to room temperature, the mixture is poured into 100ml of ice water, extracted three times with dichloromethane, the organic phases are combined, silica gel is added, the solvent is removed and the product is isolated by column chromatography (dichloromethane: n-hexane v/v ═ 1:1) to give the germanooxyisocyanide, in this case bis (4-isocyanato-3- (6- (1,1,3,3, 3-pentamethyldigermanoxane) hexyl) phenyl) methane as a white solid in 40% yield.
And 2, carrying out polymerization reaction on the alkoxy isocyanide and an acid reagent under the argon atmosphere to form the polymer.
The method comprises the following steps: and mixing the alkoxy isocyanide with the acid reagent, introducing argon to remove oxygen, carrying out polymerization reaction at 80 ℃ for 12 hours, carrying out methanol precipitation on the mixture, and extracting in normal hexane and acetone to obtain the polymer.
One reaction formula for the alkoxyisocyanide to form the polymer is as follows:
Figure GDA0002983062000000111
when the alkoxy isocyanide is a siloxy isocyanide, the specific steps of formula (6) may be: bis (4-isocyanato-3- (6- (1,1,3,3, 3-pentamethyldisiloxane) hexyl) phenyl) methane (6mmol) and oxalic acid (0.558g,6.2mmol) were placed in a 25ml round bottom flask, argon was bubbled through to remove oxygen, 10ml of dilute hydrochloric acid was then added, and the mixture was allowed to react at 80 ℃ for 12 hours and then stopped. The polymer was obtained by settling with 50ml of methanol and extracting the resulting white solid in n-hexane and acetone in this order for two days, at which time the polymer was a colorless solid with a mass of 2.51g and a yield of 53%. The weight-average molecular weight of the polymer was 3567kg/mol, the number-average molecular weight was 2985kg/mol, and the dispersity was 1.83.
When the alkoxyisocyanide is a germanooxyisocyanide, the specific steps of formula (6) may be: bis (4-isocyanato-3- (6- (1,1,3,3, 3-pentamethyldigermoxane) hexyl) phenyl) methane (6mmol) and oxalic acid (0.558g,6.2mmol) were placed in a 25ml round bottom flask, argon was passed through to remove oxygen, 10ml of dilute hydrochloric acid was then added, and the mixture was allowed to react at 80 ℃ for 12 hours and then stopped. The polymer was obtained by settling with 50ml of methanol and extracting the resulting white solid in n-hexane and acetone in this order for two days, at which time the polymer was a colorless solid with a yield of 37%. The weight-average molecular weight of the polymer was 4897kg/mol, the number-average molecular weight was 3298kg/mol, and the dispersity was 1.96.
And 3, coating the polymer on the surface of the flexible substrate to form the hardened layer.
The method comprises the following steps: mixing the polymer with an organic solvent containing a photoinitiator, processing to obtain a polymer solution, and coating the polymer solution on the flexible substrate to form the hardened layer; wherein the organic solvent containing the photoinitiator may be tetrahydrofuran (50wt. -%) containing the photoinitiator (Irgacure 2503 wt.%)) For example, the obtained polymer solid is dissolved in tetrahydrofuran (50 wt.%) containing a photoinitiator (Irgacure 2503 wt.%), and shaken or sonicated for one hour to give a colorless viscous solution of the polymer; the polymer should be formed in a film form to serve as the hardened layer, for example, the polymer solution is uniformly coated on a glass or PET surface, dried overnight at room temperature, then vacuum-dried at 40 ℃ for two hours, and then dried with a light density of 100mW cm-2Total UV output energy of 3J cm2The HITACHI UV lamp of (1) irradiates a film on the surface of PET or glass to obtain a polymer film.
The general formula of the polymer of the hardened layer in the embodiment of the present invention is as follows:
Figure GDA0002983062000000121
in the formula (1), R1Comprising siloxy or germoxy groups, R2Is an amide group, R3Including ester groups.
R in the formula (1)1When including a siloxy group, said R1Is shown as follows:
Figure GDA0002983062000000122
in the formula (2), one bond of silicon atom at long-chain side is bonded with one carbon atom of phenyl in main chain of the polymer to form chemical bond, and R1May be 6 to 10, said R1Must not be too small or too large, the number of carbon atoms being from 6 to 10, it is possible to adjust the flexibility of the polymer, thus increasing the mechanical properties of the polymer, and if the side chains are too long, it will increase the rigidity of the polymer, reducing the mechanical properties of the polymer.
R in the formula (1)1When including a germyloxy group, the R1Is shown as follows:
Figure GDA0002983062000000131
in the formula (3), one bond of the germanium atom positioned on the long-chain side is bonded with one carbon atom of the phenyl in the main chain of the polymer to form a chemical bond, and the R1May be 6 to 10, said R1Must not be too small or too large, the number of carbon atoms being from 6 to 10, it is possible to adjust the flexibility of the polymer, thus increasing the mechanical properties of the polymer, and if the side chains are too long, it will increase the rigidity of the polymer, reducing the mechanical properties of the polymer.
R in the formula (1)2Is shown as follows:
Figure GDA0002983062000000132
the R is2The amide group in the polymer can improve the elasticity and surface hardness of the polymer, but cannot improve the friction resistance of the polymer.
R in the formula (1)3Is shown as follows:
Figure GDA0002983062000000133
in the formula (5), R is3The polymer comprises an ester group and an amine group, wherein the ester group is a flexible group, the polarity of the ester group is high, and the ester group and the amine group can adjust the hardness and the elasticity of the polymer but cannot improve the friction resistance of the polymer.
The manufacturing method of the flexible cover plate provided by the invention is simple, the process of preparing the hardened layer material is simple and easy to control, and the manufactured flexible cover plate has good friction resistance and can meet the requirements of flexible display equipment.
The invention has the beneficial effects that: the invention provides a flexible cover plate comprising: the flexible substrate and the hardening layer arranged on the flexible substrate are made of polymers, wherein the main chain of each hardening layer comprises a benzene ring and an ester group, and the side chain of each hardening layer comprises a silicon-oxygen group or a germanium-oxygen group; the hardness of the polymer is adjusted by introducing the side chain containing silicon oxygen or germanium oxygen, and the friction resistance of the polymer is improved by changing the length of the side chain, so that the mechanical property of the hardened layer is improved, and the requirement of flexible equipment is met; the manufacturing method of the flexible cover plate provided by the invention is simple, the process of preparing the hardened layer material is simple and easy to control, and the manufactured flexible cover plate has good friction resistance and can meet the requirements of flexible display equipment.
In summary, although the present invention has been described with reference to the preferred embodiments, the above-described preferred embodiments are not intended to limit the present invention, and those skilled in the art can make various changes and modifications without departing from the spirit and scope of the present invention, therefore, the scope of the present invention shall be determined by the appended claims.

Claims (8)

1. A flexible cover sheet, comprising:
a flexible substrate;
a hardening layer disposed on the flexible substrate;
the hardened layer is made of a polymer, wherein the main chain of the hardened layer comprises a benzene ring and an ester group, and the side chain of the hardened layer comprises a siloxy group or a germoxy group, and the general formula of the polymer is shown as the following formula:
Figure FDA0002983061990000011
wherein R is1Comprising a germoxyl or siloxy group, R2Is an amide group, R3Including ester groups.
2. The flexible cover sheet of claim 1, wherein R1Is represented by the following formula:
Figure FDA0002983061990000012
or, R1Is represented by the following formula:
Figure FDA0002983061990000013
3. the flexible cover sheet of claim 1, wherein R2Is represented by the following formula:
Figure FDA0002983061990000014
4. the flexible cover sheet of claim 1, wherein R is3Is represented by the following formula:
Figure FDA0002983061990000021
5. a manufacturing method of a flexible cover plate is characterized by comprising the following steps:
providing a flexible substrate;
forming a hardened layer on the flexible substrate;
the hardened layer is made of a polymer, wherein the main chain of the hardened layer comprises a benzene ring and an ester group, and the side chain of the hardened layer comprises a siloxy group or a germoxy group, and the general formula of the polymer is shown as the following formula:
Figure FDA0002983061990000022
wherein R is1Is a group comprising germanium oxygen or silicon oxygen, R2Comprising an amide group, R3Comprising an ester group。
6. The method for manufacturing a flexible cover plate according to claim 5, wherein a hardened layer is formed on the flexible substrate, specifically:
carrying out chemical combination reaction on a silicon-oxygen halide or a germanium-oxygen halide and a halogenated isocyanide under the argon atmosphere to form an alkoxy isocyanide;
carrying out a polymerization reaction on the alkoxy isocyanide and an acid reagent under an argon atmosphere to form the polymer;
coating the polymer on the surface of the flexible substrate to form the hardened layer.
7. Method for making a flexible cover according to claim 6, wherein R is1Is represented by the following formula:
Figure FDA0002983061990000031
or, R1Is represented by the following formula:
Figure FDA0002983061990000032
8. the method of claim 7, wherein the reaction equation for forming the polymer from the alkoxyisocyanide is as follows:
Figure FDA0002983061990000033
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