阅读说明：本技术 硬质材料、其制造方法及使用该材料的覆盖板和显示装置 (Hard material, method for producing the same, and cover plate and display device using the same ) 是由 赵远 于 2019-08-30 设计创作，主要内容包括：本申请提供一种硬质材料,其具有由式<Image he="375" wi="700" file="DDA0002185540390000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>所表示的结构,其中,所述R<Sub>1</Sub>包括从由具有至少一个苯环的芳香基组成的群组中选择的至少一个,所述R<Sub>2</Sub>为甲基丙烯酰氧基丁基,m与n的比例在3:7～7:3的范围内。本申请还提供一种制造方法及使用所述材料的覆盖板和显示装置。(The present application provides a hard material having the formula The structure represented by (A) wherein R is 1 Including at least one selected from the group consisting of aromatic groups having at least one benzene ring, R 2 Is methacryloxybutyl, and the ratio of m to n is in the range of 3:7 to 7: 3. The present application also provides a method of manufacturing and a cover plate and display device using the material.)

1. A hard material characterized by having the formula

R₁including at least one selected from the group consisting of aromatic groups having at least one benzene ring, R₂Is methacryloxybutyl, and the ratio of m to n is in the range of 3:7 to 7: 3.

2. The hard material of claim 1, wherein the aromatic group is a benzene ring, a naphthalene ring, or a combination of one or two of a benzene ring and a naphthalene ring, wherein the hydrogen atoms on the benzene ring are substituted.

3. The hard material of claim 1, wherein the ratio of m to n is in the range of 5:5 to 7: 3.

4. A method of manufacturing a hard material, comprising the steps of:

a reaction step of adding a first reactant and a second reactant to water and an organic solvent, and heating and reacting in an argon atmosphere;

the structural formula of the first reactant is:

the R is₁Including at least one selected from the group consisting of aromatic groups having at least one benzene ring,

the structural formula of the second reactant is:

the R is₂Is a methacryloxybutyl group, and is,

the R is₁And said R₂The molar quantity ratio of (a) is in the range of 3:7 to 7: 3;

a separation step, wherein the mixture after the reaction is finished is separated and purified to obtain a target polymer;

the hard material is a germanium oxide polymer and has the formulaThe ratio of m to n is in the range of 3:7 to 7: 3.

5. The method of manufacturing a hard material according to claim 4, wherein the aromatic group is a benzene ring, a naphthalene ring, or a combination of one or two of a benzene ring and a naphthalene ring, in which a hydrogen atom on the benzene ring is substituted.

6. The method of making a hard material of claim 4, wherein R is₁And said R₂The molar number ratio of (a) is in the range of 5:5 to 7: 3.

7. The method for manufacturing a hard material according to claim 4, wherein the organic solvent is one or a combination of several of tetrahydrofuran methanol and acetone, and the catalyst is one or a combination of several of potassium carbonate, sodium carbonate and sodium bicarbonate.

8. The method for producing a hard material according to claim 4, wherein the reaction step is performed at 60 ℃ to 90 ℃ for 48 hours to 96 hours.

9. A cladding panel consisting of a stack of a hardened layer and a flexible substrate, the hardened layer being made of the hard material of claim 1.

10. A display device comprising a display panel, a case housing the display panel, and a cover plate covering the display panel, the cover plate being constituted by laminating a hardened layer made of the hard material according to claim 1 and a flexible substrate.

Technical Field

The present invention relates to a hard material, and more particularly, to a hard material having a high surface hardness, a method of manufacturing the same, and a cover plate and a display device using the same.

Background

A conventional display device is generally provided with a cover plate on a front side thereof for protecting a display module of the display device and providing a touch surface and the like. Cover plates for flexible, foldable display devices are typically constructed from a flexible substrate layer, typically made of a clear, colorless polyimide film, and a rigid laminate layer; the stiffening layer is used to provide mechanical properties and is typically made of a silicone polymer. However, the cured silicone polymer layer on the market has low surface hardness, so that it is difficult to meet the practical requirements.

Disclosure of Invention

In view of the above, the present application aims to provide a hard material having a high surface hardness, and a cover plate and a display device using the same.

A hard material characterized by having the formula

The structure is shown in a schematic representation,

the R is₁Including at least one selected from the group consisting of aromatic groups having at least one benzene ring, R₂Is methacryloxybutyl, and the ratio of m to n is in the range of 3:7 to 7: 3.

In the hard materials provided in the examples herein, the aromatic group is a benzene ring, a naphthalene ring, or a combination of one or both of a benzene ring and a naphthalene ring in which a hydrogen atom on the benzene ring is substituted.

In the hard material provided by the embodiment of the application, the ratio of m to n is within the range of 5: 5-7: 3.

A method of manufacturing a hard material, comprising the steps of:

a reaction step of adding a first reactant and a second reactant to water and an organic solvent, and heating and reacting in an argon atmosphere;

the structural formula of the first reactant is:

the R is₁Including at least one selected from the group consisting of aromatic groups having at least one benzene ring,

the structural formula of the second reactant is:

the R is₂Is a methacryloxybutyl group, and is,

the R is₁And said R₂In a molar quantity ratio of3: 7-7: 3;

a separation step, wherein the mixture after the reaction is finished is separated and purified to obtain a target polymer;

the hard material is a germanium oxide polymer and has the formula

The ratio of m to n is in the range of 3:7 to 7: 3.

In the method for manufacturing a hard material provided in the embodiments of the present application, the aromatic group is a benzene ring, a naphthalene ring, or a combination of one or two of the benzene ring and the naphthalene ring, in which a hydrogen atom on the benzene ring is substituted.

In the method for manufacturing hard material provided in the examples of the present application, R is₁And said R₂The molar number ratio of (a) is in the range of 5:5 to 7: 3.

In the method for manufacturing the hard material provided by the embodiment of the application, the organic solvent is selected from one or a combination of more of tetrahydrofuran methanol and acetone, and the catalyst is selected from one or a combination of more of potassium carbonate, sodium carbonate and sodium bicarbonate.

In the method for manufacturing a hard material according to the embodiment of the present application, the reaction step is performed at 60 to 90 ℃ for 48 to 96 hours.

A cladding sheet is formed by laminating a hardened layer and a flexible substrate, wherein the hardened layer is made of the hard material.

A display device includes a display panel, a case housing the display panel, and a cover plate covering the display panel, the cover plate being formed by laminating a hardened layer made of a hard material as described above and a flexible base material.

The hard material of the present application can improve the surface hardness of a polymer by introducing an aromatic ring structure such as a benzene ring or a naphthalene ring into the polymer of germanium oxide, and can improve the mechanical properties by introducing methacryloxybutyl to increase the degree of crosslinking of the polymer. In addition, in the present application, by using a material in which an aromatic ring structure such as a benzene ring or a naphthalene ring and methacryloxybutyl group are introduced into a germanium oxide polymer, a cover plate and a display device having higher surface hardness and better mechanical properties can be obtained.

Drawings

In order to more clearly illustrate the technical solutions in the present application, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.

Fig. 1 is a front view of an electronic device according to an embodiment of the present application.

Fig. 2 is a schematic cross-sectional view of the electronic device of fig. 1 along line a-a'.

FIG. 3 is a cross-sectional schematic view of a cover plate according to an embodiment of the present application.

Detailed Description

The technical solution in the present application will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present application. It should be apparent that the described embodiments are only some embodiments of the present application, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any inventive step based on the embodiments in the present application, are within the scope of protection of the present application.

The application provides a hard material which is a germanium oxide polymer having the formula

The structure represented by (A) wherein R is₁Including at least one selected from the group consisting of aromatic groups having at least one benzene ring, R₂Is methacryloyloxybutyl, and the ratio of m to n is in the range of 3:7 to 7: 3. The values of m and n can be, for example, 100 < m < 1000, 100 < n < 1000.

When the value of m is too small, i.e., m: when n is less than 3:7, the hardness of the polymer is reduced, the dispersion degree is too high, and the difficulty of processing and molding becomes large. When the value of m is too large, i.e. m: when n is more than 7:3, the weight average molecular weight of the polymer decreases, the mechanical strength and toughness decrease, and the stability also deteriorates. Therefore, the ratio of m to n is preferably in the range of 3:7 to 7:3, and further preferably m: n is in the range of 5:5 to 7: 3.

Specifically, R₁May include at least one selected from the group consisting of, for example, phenyl, naphthyl, anthryl, phenanthryl, benzanthryl, benzopyrene, biphenyl, triphenyl, etc., and at least one hydrogen atom on the benzene ring may be substituted with a substituent such as alkyl, alkoxy, halogen, carboxyl, etc.

Specifically, R₂Any of n-, sec-, iso-, and tert-butyl groups may be used.

The germanium oxide polymer can be prepared by respectively performing hydrolysis reaction on methoxyl germanium containing aromatic group and methoxyl germanium containing methacryloxybutyl to generate hydroxyl germanium containing aromatic group and trihydroxygermanium containing methacryloxybutyl, and performing intermolecular polycondensation reaction on the hydroxyl germanium containing aromatic group and the trihydroxygermanium containing methacryloxybutyl to generate the target polymer.

The surface hardness of the polymer can be improved by introducing an aromatic ring structure such as a benzene ring or a naphthalene ring into the germanium oxide polymer, and the degree of crosslinking of the polymer can be improved by introducing methacryloxybutyl, thereby improving the mechanical properties of the polymer.

In particular, the present application also provides a method of manufacturing a hard material comprising the steps of:

a reaction step of adding a first reactant and a second reactant to water and an organic solvent, and heating and reacting in an argon atmosphere;

the structural formula of the first reactant is:

wherein, R is₁Comprises a main body composed ofAt least one selected from the group consisting of aromatic groups of at least one benzene ring,

the structural formula of the second reactant is:

the R is₂Is a methacryloxybutyl group, and is,

the R is₁And said R₂The molar quantity ratio of (a) is in the range of 3:7 to 7: 3; further, in some embodiments of the present invention, the ratio may be in the range of 5:5 to 7: 3.

A separation step, wherein the mixture after the reaction is finished is separated and purified to obtain a target polymer;

the hard material is germanium oxide polymer and has the formula

In the structure shown, the ratio of m to n is in the range of 3:7 to 7:3, and further, in other embodiments of the present application, m: n can be in the range of 5:5 to 7: 3; the values of m and n can be, for example, 100 < m < 1000, 100 < n < 1000.

The equation for the above reaction is:

specifically, R₁May include at least one selected from the group consisting of, for example, phenyl, naphthyl, anthryl, phenanthryl, benzanthryl, benzopyrene, biphenyl, triphenyl, etc., and at least one hydrogen atom on the benzene ring may be substituted with a substituent such as alkyl, alkoxy, halogen, carboxyl, etc.

Specifically, R₂Any of n-, sec-, iso-, and tert-butyl groups may be used.

In some embodiments, the organic solvent may be one or a combination of tetrahydrofuran, methanol, and acetone. In some embodiments, the catalyst may be selected from one or a combination of potassium carbonate, sodium carbonate, and sodium bicarbonate.

The reaction step is carried out at 60-90 ℃, and the reaction time is 48-96 hours.

In addition, the step of separating and purifying the mixture after the reaction is finished to obtain the target polymer comprises the following steps: separating the mixture to obtain colorless liquid and viscous organic phase, dissolving the organic phase in organic solvent, extracting with water for several times, removing water, drying with desiccant, filtering, and removing organic solvent to obtain the target polymer.

The present application will be further described below based on examples. In addition, the present application is not limited to these examples in any way.

[ example 1-1]

Potassium carbonate (0.04g,0.29mmol), tetrahydrofuran (8g,0.110mmol) and deionized water (4.8g,0.267mmol) were placed in a reaction vessel, and phenyltrimethoxygermanium (0.08g, 0.3mmol) and methacryloyltrimethoxygermanium (0.1g,0.3mmol) were added, and the reaction was stirred at 60 ℃ to 90 ℃ for 48 hours to 96 hours under an argon atmosphere, the chemical reaction occurring being represented by the following chemical formula 1. The mixture was separated to give a colorless liquid and a viscous organic phase. After that, the organic phase was dissolved in dichloromethane and extracted three times with deionized water. Deionized water was removed, anhydrous magnesium sulfate was added for drying for 30 minutes, then filtration was performed, and the organic solvent was removed by a rotary evaporator to obtain m: n is 5: 5.

In the reaction, firstly, phenyltrimethoxygermanium and methacryloyl butyltrimethoxygermanium are subjected to hydrolysis reaction under the action of a catalyst to generate intermediate products of 4- (trihydroxymethyl) butyl methacrylate and phenyltrihydroxygermanium, and then intermolecular polycondensation reaction is performed to generate the target polymer.

Examples 1-2 to 1-5

The target polymers of examples 1-2 to 1-5, i.e., the target polymers having m: n of 3:7, 4:6, 6:4 and 7:3, respectively, were produced in the same manner as in example 1-1, except that the molar ratios of phenyl group to methacryloyl group butyl group were adjusted to 30:70, 40:60, 60:40 and 70:30, respectively, while keeping the total amount of phenyltrimethoxygermanium and methacryloyl butyl group trimethoxygermanium constant.

The relationship between the ratio of functional groups of the target polymer and the molecular weight and dispersity is shown in the following table by Gel Permeation Chromatography (GPC), and the temperature Td at which the corresponding polymer loses 5% weight is measured by the thermal weight loss method.

The pencil hardness of the hardened layer was tested with a flexible polyimide material as the substrate.

Table 1 shows the relationship between the molar weight percentage of phenyltrimethoxygermanium and methacryloyl butyltrimethoxygermanium in the reactant, the molecular weight and dispersion, Td and pencil hardness, wherein Rm is the molar weight percentage of phenyl functional groups in the reactant, and Rn is the molar weight percentage of methacryloyl butyl functional groups in the reactant.

[ Table 1]

As can be seen from table 1, as the content of phenyl groups in the reactants increases, the dispersity of the polymer gradually decreases, and the temperature Td at which the thermal weight loss method tests that the corresponding polymer loses 5% weight gradually decreases, but the pencil hardness gradually increases, when Rm: when Rn is in the range of 40:60 to 70:30, the weight average molecular weight of the polymer decreases as the content of the phenyl group increases.

It can also be seen from table 1 that when the phenyl content is too small and the methacryloyl butyl content is too large, i.e., Rm: when Rn is less than 3:7, the hardness of the polymer is reduced, the dispersion degree is too high, and the processing and forming difficulty is increased. When the phenyl content is too large and the methacryloyl butyl content is too small, Rm: when Rn is more than 7:3, the weight average molecular weight of the polymer decreases, the mechanical strength and toughness decrease, and the stability also deteriorates. Further, in order to compromise mechanical strength and processability of the polymer material, Rm: the ratio of Rn may be in the range of 5:5 to 7: 3.

[ example 2-1]

Potassium carbonate (0.04g,0.29mmol), tetrahydrofuran (8g,0.110mmol) and deionized water (4.8g,0.267mmol) were placed in a reaction vessel, and then naphthyltrimethoxygermanium (0.09g,0.3mmol) and methacryloyltrimethoxygermanium (0.1g,0.3mmol) were added, and the reaction was stirred at 60 ℃ to 90 ℃ for 48 hours to 96 hours under an argon atmosphere, and the chemical reaction occurred as represented by the following formula. The mixture was separated to give a colorless liquid and a viscous organic phase. Thereafter, the organic phase was dissolved in dichloromethane and extracted three times with deionized water. Deionized water was removed, anhydrous magnesium sulfate was added for drying for 30 minutes, then filtered, and the organic solvent was removed by a rotary evaporator to give m: n is 5:5 a target polymer.

In the reaction, firstly, naphthyl trimethoxy germanium and methacryloyl butyl trimethoxy germanium are subjected to hydrolysis reaction under the action of a catalyst to generate intermediate products of 4- (trihydroxy germanium) butyl methacrylate and naphthyl trihydroxy germanium, and then intermolecular polycondensation reaction is carried out to generate the target polymer.

[ examples 2-2 to 2-5]

The target polymers of examples 2-2 to 2-5, i.e., the target polymers having m: n of 3:7, 4:6, 6:4 and 7:3, respectively, were produced in the same manner as in example 2-1, except that the molar ratio of naphthyl group to methacryloyl group butyl group was adjusted to 30:70, 40:60, 60:40 and 70:30, respectively, while keeping the total amount of naphthyl trimethoxygermanium and methacryloyl butyl trimethoxygermanium constant.

The relationship between the ratio of functional groups of the target polymer and the molecular weight and the dispersity is shown in the following table through gel permeation chromatography, and the temperature Td when the corresponding polymer is subjected to 5% weight loss is tested through a thermal weight loss method.

The pencil hardness of the hardened layer was tested with a flexible polyimide material as the substrate.

Table 2 shows the relationship between the molar weight percentage of naphthyl trimethoxy germanium and methacryloyl butyl trimethoxy germanium in the reactant and the molecular weight and dispersity, Td and pencil hardness, wherein Rm 'is the molar weight percentage of naphthyl functional groups in the reactant and Rn' is the molar weight percentage of methacryloyl butyl functional groups in the reactant.

[ Table 2]

As can be seen from table 1, as the content of naphthyl trimethoxy germanium in the reactant increases, the degree of dispersion of the polymer gradually decreases, and the temperature Td at which the thermal weight loss method tests that the corresponding polymer loses 5% weight gradually decreases, but the pencil hardness gradually increases, when Rm: rn is in the range of 40:60 to 70:30, the weight average molecular weight of the polymer decreases as the content of naphthyl groups increases.

It can also be seen from table 2 that when the naphthyl content is too small and the methacryloyl butyl content is too large, i.e., Rm': rn' is less than 3:7, the hardness of the polymer is reduced, the dispersion degree is too high, and the processing and forming difficulty is increased. When the naphthyl content is too large and the methacryloylbutyl content is too small, Rm': when Rn' is more than 7:3, the weight average molecular weight of the polymer decreases, the mechanical strength and toughness decrease, and the stability also deteriorates. Further, in order to compromise the mechanical strength and processability of the polymeric material, Rm': the ratio of Rn' may be in the range of 5:5 to 7: 3.

In the above examples, although examples in which a benzene ring or a naphthalene ring is introduced into a polymer, respectively, are disclosed, in another embodiment of the present application, two or more groups such as a benzene ring and a naphthalene ring may be introduced at the same time.

Referring to fig. 3, the present application also provides a cover plate 100 for a display device, which is formed by stacking a hardened layer 110 and a flexible substrate 120, wherein the hardened layer 110 is made of a hard material, which is the hard material in the first embodiment of the present application and can be manufactured by the manufacturing method provided in the present application.

Referring to fig. 1 to 3, the present application further provides a display device 1, which includes a display panel 200, a housing 300 for accommodating the display panel 200, and a cover plate 100 for covering the display panel. The cover plate 100 employs the cover plate 100 provided herein.

By using a material in which an aromatic ring structure such as a benzene ring or a naphthalene ring and methacryloxybutyl group are introduced into a germanium oxide polymer, a cover plate and a display device having higher surface hardness and better mechanical properties can be obtained.

The foregoing provides a detailed description of embodiments of the present application, and the principles and embodiments of the present application have been described herein using specific examples, which are presented solely to aid in the understanding of the present application. Meanwhile, for those skilled in the art, according to the idea of the present application, there may be variations in the specific embodiments and the application scope, and in summary, the content of the present specification should not be construed as a limitation to the present application.