阅读说明：本技术 一种柔性复合玻璃及其制备方法 (Flexible composite glass and preparation method thereof ) 是由 李青 李赫然 崔海舰 陈兵哲 集建昌 闫冬成 胡恒广 于 2021-03-17 设计创作，主要内容包括：本公开涉及一种制备柔性复合玻璃的方法,该方法包括以下步骤：S1使柔性玻璃基体在涂布机上进行柔性膜浆料涂布,形成第一前体；S2使所述第一前体在预固化炉中进行第一预固化,然后在固化炉中进行第一固化,形成覆有柔性膜层的第二前体；S3使所述第二前体在所述涂布机上进行硬化膜浆料涂布,形成第三前体；S4使所述第三前体在所述预固化炉中进行第二预固化,然后在所述固化炉中进行第二固化,形成依次覆有柔性膜层和硬化膜层的柔性复合玻璃。本公开的方法在柔性玻璃基体上直接依次涂布和固化柔性膜浆料和硬化膜浆料,省去增加粘合剂的步骤,简化工艺,降低生成成本；采用自动化设备完成玻璃抓取、传送、搬运等,实现批量生产,有效提高产量。(The present disclosure relates to a method of making a flexible composite glass, the method comprising the steps of: s1, coating the flexible glass substrate with the flexible film slurry on a coating machine to form a first precursor; s2, performing first precuring on the first precursor in a precuring furnace, and then performing first curing in a curing furnace to form a second precursor coated with a flexible film layer; s3 coating the second precursor with a hardened film slurry on the coater to form a third precursor; s4 allowing the third precursor to undergo a second pre-curing in the pre-curing oven, and then undergoing a second curing in the curing oven, to form a flexible composite glass coated with a flexible film layer and a hardened film layer in this order. According to the method, the flexible film slurry and the hardened film slurry are directly and sequentially coated and cured on the flexible glass substrate, so that the step of adding an adhesive is omitted, the process is simplified, and the generation cost is reduced; adopt automation equipment to accomplish glass snatchs, conveys, transport etc. and realize batch production, effectively improve output.)

1. A method of making a flexible composite glass, comprising the steps of:

s1 coating a flexible glass substrate with a flexible film slurry on a first coater to form a first precursor;

s2, performing first precuring on the first precursor in a first precuring furnace, and then performing first curing in the first curing furnace to form a second precursor coated with a flexible film layer;

s3 coating the second precursor with a hardening film slurry on a second coating machine to form a third precursor;

s4, carrying out second precuring on the third precursor in a second precuring furnace, and then carrying out second curing in the second curing furnace to form the flexible composite glass coated with the flexible film layer and the hardening film layer in sequence;

the viscosity of the flexible film slurry at 24 ℃ is 200-.

2. The method according to claim 1, wherein the flexible glass substrate has a thickness of 15-110 μm, preferably 25-70 μm.

3. The method of claim 1, wherein the flexible film slurry comprises: one or more of polyimide, polyethylene terephthalate and polypropylene film, wherein the flexible film slurry contains a solvent which is dimethylacetamide; the hardened film paste includes: polyethylene terephthalate and/or polyurethane, and the hardened film slurry comprises a solvent which is dimethylacetamide.

4. The method of claim 1 or 3, wherein the flexible film slurry has a viscosity of 3000-8000cps at 24 ℃; the viscosity of the hardened film slurry at 24 ℃ is 3000-8000 cps.

5. The method according to claim 1 or 3, wherein the flexible film slurry has a number of bending times of 20 ten thousand or more after film formation, a minimum bending radius of 1-5mm, and a surface pencil hardness of 0-1 HB;

the hardening film slurry has the bending times of more than 20 ten thousand times after film forming, the minimum bending radius of 1-5mm and the surface pencil hardness of more than 3 HB.

6. The method of claim 1, wherein in steps S1 and S3, the flexible film paste and the hardened film paste are formed on the same side of the flexible glass substrate, and the flexible film layer is formed between the flexible glass substrate and the hardened film layer.

7. The method of claim 1, wherein the first pre-cure, second pre-cure, first cure, and second cure are each independently thermal and/or photo-curing.

8. The method of claim 1, wherein the coating forms of the first coater and the second coater are each independently selected from one or more of blade coating, slot coating, and wire bar coating.

9. The method of claim 1, wherein the method further comprises:

prior to step S1, transferring the flexible glass substrate to the first coater using a first pick and transfer device;

before step S2, transferring the first precursor to the first pre-curing oven and the first curing oven in sequence by using a second grasping and transferring device;

prior to step S3, transferring the second precursor to the second coater using a third pick and transfer device;

before step S4, transferring the third precursor to the second pre-curing oven and the second curing oven in sequence by using a fourth grabbing and transferring device;

after step S4, removing the flexible composite glass using a fifth pick and transfer device;

wherein the first, second, third, fourth and fifth grabbing and conveying devices are the same or different and are each independently a three-axis robot and/or a robotic arm.

10. A flexible composite glass produced by the method of any one of claims 1-9;

optionally, the thickness of the flexible composite glass is 25-150 μm, preferably 30-80 μm;

optionally, the minimum bend radius of the flexible composite glass is 1-5 mm.

Technical Field

The disclosure relates to the field of composite glass production, in particular to flexible composite glass and a preparation method thereof.

Background

As the folding screen is more and more exploded, the flexible cover plate becomes a key factor restricting the development of the folding screen. At present, two technical schemes of the flexible cover plate are provided, one is a manufacturing process of transparent polyimide (CPI) and a Hardened Coating (HC), and the flexible cover plate is mature at present. Another type directly uses foldable flexible glass (abbreviated as UTG). The two materials have different advantages and disadvantages, the CPI is inferior to that of the UTG in the aspects of hardness, ageing resistance, scratch resistance, transparency and the like, the UTG has better rigidity and dimensional stability when being repeatedly bent, and the crease of a folding area can be effectively reduced. The CPI has good bending performance and high yield.

However, after the UTG flexible cover is applied to the folding screen, the use performance and the human experience demand of the flexible display are synthesized, UTG will be the mainstream of the flexible display cover material in the future, and the development of the flexible display technology will be led. In the prior art, a process mode of UTG + binder (OCA) + flexible coating (PET) + OCA + HC is adopted to realize the manufacturing and application of the flexible cover plate, but the manual participation is more, and because the process is complex, the PET is connected with UTG, the PET is connected with HC through OCA, the yield is low, automatic production cannot be realized, the production cost is high, mass production cannot be realized, and the key factor that the price of the folding screen is high and the folding screen cannot be popularized is also restricted.

Disclosure of Invention

The purpose of the present disclosure is to provide a flexible composite glass and a method for preparing the same.

In order to achieve the above object, a first aspect of the present disclosure provides a method of manufacturing a flexible composite glass, the method comprising the steps of:

s1 coating a flexible glass substrate with a flexible film slurry on a first coater to form a first precursor;

s2, performing first precuring on the first precursor in a first precuring furnace, and then performing first curing in the first curing furnace to form a second precursor coated with a flexible film layer;

s3 coating the second precursor with a hardening film slurry on a second coating machine to form a third precursor;

s4, carrying out second precuring on the third precursor in a second precuring furnace, and then carrying out second curing in the second curing furnace to form the flexible composite glass coated with the flexible film layer and the hardening film layer in sequence;

the viscosity of the flexible film slurry at 24 ℃ is 200-.

Optionally, the flexible glass substrate has a thickness of 15-110 μm, preferably 25-70 μm.

Optionally, the flexible film paste comprises: one or more of polyimide, polyethylene terephthalate and polypropylene film, wherein the flexible film slurry contains a solvent which is dimethylacetamide; the hardened film paste includes: polyethylene terephthalate and/or polyurethane, and the hardened film slurry comprises a solvent which is dimethylacetamide.

Optionally, the flexible film slurry has a viscosity of 3000-; the viscosity of the hardened film slurry at 24 ℃ is 3000-8000 cps.

Optionally, the flexible film slurry is bent for more than 20 ten thousand times after being formed into a film, the minimum bending radius is 1-5mm, and the surface pencil hardness is 0-1 HB;

the hardening film slurry has the bending times of more than 20 ten thousand times after film forming, the minimum bending radius of 1-5mm and the surface pencil hardness of more than 3 HB.

Optionally, in steps S1 and S3, the flexible film paste and the hardened film paste are formed on the same side of the flexible glass substrate, and the formed flexible film layer is located between the flexible glass substrate and the hardened film layer.

Optionally, the first pre-curing, the second pre-curing, the first curing and the second curing are each independently thermal curing and/or photo curing.

Optionally, the coating forms of the first coater and the second coater are respectively and independently selected from one or more of blade coating, slit coating and wire rod coating.

Optionally, the method further comprises:

prior to step S1, transferring the flexible glass substrate to the first coater using a first pick and transfer device;

before step S2, transferring the first precursor to the first pre-curing oven and the first curing oven in sequence by using a second grasping and transferring device;

prior to step S3, transferring the second precursor to the second coater using a third pick and transfer device;

before step S4, transferring the third precursor to the second pre-curing oven and the second curing oven in sequence by using a fourth grabbing and transferring device;

after step S4, removing the flexible composite glass using a fifth pick and transfer device;

wherein the first, second, third, fourth and fifth grabbing and conveying devices are the same or different and are each independently a three-axis robot and/or a robotic arm.

A second aspect of the present disclosure provides a flexible composite glass made using the method of the first aspect of the present disclosure;

optionally, the thickness of the flexible composite glass is 25-150 μm, preferably 30-80 μm.

Optionally, the minimum bend radius of the flexible composite glass is 1-5 mm.

According to the technical scheme, the flexible film slurry and the hardened film slurry are directly and sequentially coated and cured on the flexible glass substrate by the slurry coating method, so that the direct and tight connection between the film and the flexible glass substrate and between the film and the film is realized, the step of adding an adhesive is omitted, the process is simplified, and the purposes of improving the yield of products and reducing the generation cost are achieved; meanwhile, automatic equipment combining a mechanical structure and an electrical system is used for grabbing, conveying, carrying and the like of the glass, automatic batch production can be achieved, and the problems of low yield and overhigh labor participation are solved.

Additional features and advantages of the disclosure will be set forth in the detailed description which follows.

Drawings

The accompanying drawings, which are included to provide a further understanding of the disclosure and are incorporated in and constitute a part of this specification, illustrate embodiments of the disclosure and together with the description serve to explain the disclosure without limiting the disclosure. In the drawings:

fig. 1 is a process flow diagram for making a flexible composite glass according to one embodiment of the present disclosure.

Description of the reference numerals

1 flexible glass substrate 2 first coater feed 3 coating of flexible film slurry

4 first coating machine blanking 5 first precuring 6 first curing

7 feeding of second coating machine, 8 coating of hardened film slurry, 9 coating of second coating machine and blanking of second coating machine

10 second precure 11 second cure 12 clean

13 inspection 14 packaging

Detailed Description

The following detailed description of specific embodiments of the present disclosure is provided in connection with the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating the present disclosure, are given by way of illustration and explanation only, not limitation.

The present disclosure provides in a first aspect a method of making a flexible composite glass, the method comprising the steps of:

s1 coating a flexible glass substrate with a flexible film slurry on a first coater to form a first precursor;

s2, performing first precuring on the first precursor in a first precuring furnace, and then performing first curing in the first curing furnace to form a second precursor coated with a flexible film layer;

s3 coating the second precursor with a hardening film slurry on a second coating machine to form a third precursor;

s4, carrying out second precuring on the third precursor in a second precuring furnace, and then carrying out second curing in the second curing furnace to form the flexible composite glass coated with the flexible film layer and the hardening film layer in sequence;

the viscosity of the flexible film slurry at 24 ℃ is 200-.

The production process of the flexible composite glass disclosed by the invention utilizes the characteristic of relatively high adhesion force when the slurry is solidified to form a film, and the slurry is directly used for sequentially forming the film on the glass substrate and the film, so that the process is simple and the yield is high. The automatic production is realized by using modes such as transferring by using automatic equipment, the manual participation is reduced, the production cost is reduced, and meanwhile, the mass production can be realized.

According to the present disclosure, the first curing oven, the second curing oven, the first pre-curing oven and the second pre-curing oven in steps S2 and S4 may be the same device or different devices, and other devices may be adopted to meet the requirements of pre-curing and curing, and are not limited herein. In order to secure the curing speed, the first pre-curing and the first curing of step S2 and the second pre-curing and the second curing of step S4 are sequentially performed in two ovens, respectively.

According to the present disclosure, the first coater for coating the flexible film slurry and the second coater for coating the hardened film slurry may be the same or different, and the types are not limited, and it is sufficient to realize coating of the flexible film slurry and the hardened film slurry.

In one embodiment of the present disclosure, the thickness of the flexible glass substrate is 15 to 110 μm, preferably 25 to 70 μm, and particularly, the thickness of the flexible glass substrate may be 30 μm.

In one embodiment of the present disclosure, the flexible film paste comprises: one or more of polyimide, polyethylene terephthalate and polypropylene film, and the flexible film slurry contains a solvent, such as dimethylacetamide; the hardened film paste includes: polyethylene terephthalate and/or polyurethane, and a solvent, which may be, for example, dimethylacetamide, is included in the hardened film paste.

In one embodiment of the present disclosure, the viscosity of the flexible film slurry at 24 ℃ is preferably 3000-; the viscosity of the hardened film slurry at 24 ℃ is preferably 3000-8000 cps. The slurry in the viscosity range has good film forming effect.

In order to ensure that the prepared flexible composite glass can meet the requirements of subsequent application, in one embodiment of the disclosure, the flexible film slurry has a bending frequency of more than 20 ten thousand times after film formation, and the minimum bending radius is 1-5mm, preferably 1.5-3 mm; the surface pencil hardness is 0-1 HB; the bending times of the hardened film slurry after film forming are more than 20 ten thousand, the minimum bending radius is 1-5mm, and the optimized bending radius is 1.5-3 mm; the surface pencil hardness is more than 3 HB. Wherein, the property of the flexible film slurry after film forming and the property of the hardened film slurry after film forming are both the property of the slurry after solidification, and the flexible film slurry does not contain a flexible glass substrate.

In an embodiment of the present disclosure, in steps S1 and S3, the flexible film paste and the hardened film paste are formed into a film on the same side of the flexible glass substrate, and the formed flexible film layer is located between the flexible glass substrate and the hardened film layer, that is, the prepared flexible composite glass structure sequentially comprises the flexible glass substrate + the flexible film layer + the hardened film layer.

In one embodiment of the present disclosure, the first pre-cure, the second pre-cure, the method of first curing and the second curing are each independently thermal curing and/or photo curing. The specific pre-curing and curing process is determined by the nature of the slurry. The light curing comprises ultraviolet curing for 1-20 min. The conditions for thermal curing were: the temperature is 50-300 ℃ and the time is 0.4-3 h. Preferably, the first pre-curing method is thermal curing, the temperature is 50-120 ℃, and the time is 0.4-2 h; the second pre-curing method is thermal curing, the temperature is 50-120 ℃, and the time is 0.4-2.5 h; the first curing method is thermal curing, the temperature is 50-300 ℃, and the time is 0.4-3 h; the second curing method is ultraviolet curing for 1-20 min.

In one embodiment of the present disclosure, the coating forms of the first coater and the second coater are each independently selected from one or more of blade coating, slot coating, and wire bar coating, preferably slot coating.

To enable automated operations, in one embodiment of the present disclosure, the method further comprises:

prior to step S1, transferring the flexible glass substrate to a first coater using a first pick and transfer device;

before step S2, transferring the first precursor to a first pre-curing oven and a first curing oven in sequence by using a second grabbing and transferring device;

prior to step S3, transferring the second precursor to a second coater using a third pick and transfer device;

before step S4, transferring the third precursor to a second pre-curing oven and a second curing oven in sequence by using a fourth grabbing and transferring device;

after step S4, removing the flexible composite glass using a fifth pick and transfer device;

wherein the first, second, third, fourth and fifth gripping and conveying devices are the same or different, may be conventional in the art, and are each independently a three-axis robot arm and/or a robotic band robot arm. Preferably, all gripping and conveying means select the same equipment.

In one embodiment of the present disclosure, the method of making a flexible composite glass further comprises cleaning, inspecting, and packaging after the flexible film layer and the hardened film layer are formed.

In one embodiment of the present disclosure, as shown in fig. 1, a first coater feed 2 is prepared before the flexible glass substrate 1 is taken out by an automated apparatus and sent to a coater. The thickness of the flexible glass substrate 1 was 30 μm. And (3) placing the conveyed flexible glass substrate 1 on a coating machine through a three-axis manipulator or a robot with a manipulator arm, and coating the flexible film slurry 3. The flexible film slurry comprises: polyimide, polyethylene terephthalate, polypropylene film and dimethylacetamide, with a viscosity at 24 ℃ of 3000-8000 cps. The first coating machine selects a mechanical structure suitable for the production line flow operation, and the coating form of the first coating machine is slit coating. After the coating of the flexible film slurry 3 is completed, the first coater blanking 4 is performed using the same equipment as the first coater feeding 2. And conveying the flexible glass substrate coated with the flexible film slurry to a first pre-curing furnace for first pre-curing treatment, wherein the method is thermal curing, the temperature is 50-120 ℃, and the time is 0.4-2 h. And after the first precuring is finished, the mixture enters a first curing furnace for first curing 6. The first curing 6 is thermal curing at 50-300 deg.c for 0.4-3 hr. The flexible film slurry subjected to the first pre-curing and the first curing becomes a flexible film layer and is bonded with a flexible glass substrate to form the composite glass covered with the flexible film layer.

The composite glass coated with the flexible film layer is conveyed to a second coating machine through automation equipment, and is placed on the second coating machine in a mode of a three-axis manipulator or a robot with a manipulator arm, and the feeding 7 of the second coating machine is carried out by adopting the same equipment as the feeding 2 of the first coating machine. Subsequently, a hardened film paste coating 8 is performed, the hardened film paste comprising: polyethylene terephthalate, polyurethane and dimethylacetamide, with a viscosity at 24 ℃ of 3000-8000 cps. The second coater may be the same as or different from the first coater, and only slurry coating needs to be achieved. The second coater is in the form of slot coating. And transferring and carrying the composite glass coated with the hardened film slurry by automatic equipment to realize blanking 9 of a second coating machine, and transferring the composite glass to a second pre-curing furnace to perform second pre-curing 10, wherein the second pre-curing 10 is performed in a heat curing mode, the temperature is 50-120 ℃, and the time is 0.4-2.5 h. And transferring the composite glass subjected to the second pre-curing to a second curing furnace for second curing 11, wherein the second curing 11 is ultraviolet curing for 1-20 min. A composite glass product of a flexible glass substrate, a flexible film layer and a hardening film layer is formed, no binder is added between the two layers of films and between the films and the glass substrate, and the two layers of films are positioned on the same side of glass.

And (3) sequentially cleaning 12, inspecting 13 and packaging 14 the prepared flexible composite glass to obtain a finished product of the flexible composite glass.

A second aspect of the present disclosure is a flexible composite glass made by the method of the first aspect of the present disclosure.

In one embodiment of the present disclosure, the flexible composite glass has a thickness of 25 to 150 μm, preferably 30 to 80 μm.

In one embodiment of the present disclosure, the minimum bend radius of the flexible composite glass is 1-5mm, preferably 1.5-3 mm.

In the following examples and test examples, reagents, materials and instruments used therefor are commercially available unless otherwise specified.

The bending times test method comprises the following steps: fixing two ends of the flexible composite glass, extruding until the bending radius is 1.5-3mm, then loosening and recovering, and circulating the step until the bending times are 20 ten thousand or the glass is broken;

minimum bend radius test method: the research of representing the flexibility and influencing factors of the ultrathin glass based on the two-point bending method is that glass and enamel are treated, 2019 and 47 (6): 1 to 6;

pencil hardness test method: reference to GB T6739-;

viscosity test method: reference is made to GB T10247-.

Examples 1-4 are provided to illustrate the flexible composite glass of the present disclosure and the method of making the same.

Example 1

And (3) taking out the flexible glass substrate through an automatic device and preparing the first coating machine for feeding before sending the flexible glass substrate to the first coating machine. The thickness of the flexible glass substrate was 30 μm. And placing the conveyed flexible glass substrate on a first coating machine through a three-axis manipulator or a robot with a manipulator arm to coat the flexible film slurry. The flexible film slurry comprises the following components: polyimide, polyethylene terephthalate, polypropylene film and dimethylacetamide, having a viscosity of 9000cps at 24 ℃. The first coating machine selects a mechanical structure suitable for the production line flow operation, and the coating form of the first coating machine is slit coating. And after the flexible film slurry is coated, the first coating machine is used for blanking by using the same equipment as the first coating machine for feeding. And conveying the flexible glass substrate coated with the flexible film slurry to a first pre-curing furnace for first pre-curing treatment, wherein the method is thermal curing, the temperature is 100 ℃, and the time is 1 h. And after the first precuring is finished, the mixture enters a second curing furnace for first curing. The first curing mode is thermal curing, the temperature is 200 ℃, and the time is 1.5 h. The flexible film slurry subjected to the first pre-curing and the first curing becomes a flexible film and is bonded with a flexible glass substrate to form the composite glass coated with the flexible film layer.

The composite glass coated with the flexible film layer is conveyed to a second coating machine through automation equipment, and is placed on the second coating machine through a three-axis manipulator or a robot with a manipulator arm, and the second coating machine is fed. And then coating a hardened film slurry, wherein the hardened film slurry comprises the following components: polyethylene terephthalate, polyurethane and dimethylacetamide, having a viscosity of 9000cps at 24 ℃. The second coater is the same as the first coater. The second coater is in the form of slot coating. And transferring and carrying the composite glass coated with the hardened film slurry by automatic equipment to realize blanking of a second coating machine, and transferring the composite glass to a second pre-curing furnace for second pre-curing, wherein the second pre-curing mode is thermosetting, the temperature is 110 ℃, and the time is 1.8 h. And transferring the composite glass subjected to the second pre-curing to a second curing furnace for second curing, wherein the second curing mode is ultraviolet curing, and the time is 13 min.

And sequentially cleaning, inspecting and packaging the prepared flexible composite glass crude product to finally obtain a flexible composite glass finished product A1.

The prepared flexible composite glass product A1, a flexible film and a hardened film were subjected to performance tests, and the results are shown in Table 1.

Example 2

A flexible composite glass A2 was produced in the same manner as in example 1, except that the viscosity of the flexible film paste was 9000cps at 24 ℃ and the viscosity of the hardened film paste was 6000cps at 24 ℃. The prepared flexible composite glass product A2, a flexible film and a hardened film were subjected to performance tests, and the results are shown in Table 1.

Example 3

A flexible composite glass A3 was produced in the same manner as in example 1, except that the viscosity at 24 ℃ of the flexible film paste was 6000cps and the viscosity at 24 ℃ of the hardened film paste was 9000 cps. The prepared flexible composite glass product A3, a flexible film and a hardened film were subjected to performance tests, and the results are shown in Table 1.

Example 4

A flexible composite glass A4 was produced in the same manner as in example 1, except that the viscosity of the flexible film paste was 6000cps at 24 ℃ and the viscosity of the hardened film paste was 6000cps at 24 ℃. The prepared flexible composite glass product A4, a flexible film and a hardened film were subjected to performance tests, and the results are shown in Table 1.

Examples 1-4 adjustment of the viscosity of the flexible film slurry and the hardened film slurry was achieved by adjusting the ratio of the solvents.

TABLE 1

As can be seen from the data in Table 1, in the preferred viscosity range, the viscosity of the flexible film slurry at 24 deg.C is 3000-8000 cps; when the viscosity of the hardened film slurry is 3000-8000cps at 24 ℃, the minimum bending radius of the prepared flexible composite glass is smaller, and the performance is more excellent. According to the method for preparing the flexible composite glass, the flexible composite glass with good performance can be obtained, the use of an adhesive is avoided, the production process is simplified, the automatic production is realized, and the yield is improved.

The preferred embodiments of the present disclosure are described in detail with reference to the accompanying drawings, however, the present disclosure is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present disclosure within the technical idea of the present disclosure, and these simple modifications all belong to the protection scope of the present disclosure.

It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. In order to avoid unnecessary repetition, various possible combinations will not be separately described in this disclosure.

In addition, any combination of various embodiments of the present disclosure may be made, and the same should be considered as the disclosure of the present disclosure, as long as it does not depart from the spirit of the present disclosure.