CN112174519A

CN112174519A - Composite glass plate and preparation method and application thereof

Info

Publication number: CN112174519A
Application number: CN202010946925.0A
Authority: CN
Inventors: 李青; 李赫然; 王博; 胡恒广; 闫冬成; 史伟华; 张广涛; 田鹏; 郝艺
Original assignee: Dongxu Optoelectronic Technology Co Ltd; Hebei Guangxing Semiconductor Technology Co Ltd
Current assignee: Dongxu Optoelectronic Technology Co Ltd; Hebei Guangxing Semiconductor Technology Co Ltd
Priority date: 2020-09-10
Filing date: 2020-09-10
Publication date: 2021-01-05
Anticipated expiration: 2040-09-10
Also published as: CN112174519B

Abstract

The invention relates to the technical field of electronic glass, and discloses a composite glass plate, a preparation method and application thereof. The composite glass plate comprises a glass substrate, a supporting layer and an intermediate layer positioned between the glass substrate and the supporting layer, wherein the intermediate layer is in a liquid state and contains one or more of fluorine oil, silicone oil, ionic liquid, liquid resin and liquid silicone rubber. The composite glass plate provided by the invention is simple in preparation method, and the supporting layer and the middle layer can be repeatedly utilized, so that the composite glass plate is energy-saving and environment-friendly.

Description

Composite glass plate and preparation method and application thereof

Technical Field

The invention relates to the technical field of electronic glass, in particular to a composite glass plate and a preparation method and application thereof.

Background

The display technology is gradually developed, and meanwhile, the market has higher demands for the lightness and thinness of display devices, and the raw materials for producing the display devices are also required to meet the demands for lightness and thinness.

Some high-end machines in the existing panel factories need to carry out thinning treatment on display devices, and a chemical thinning process is generally adopted. However, the chemical thinning process requires a large amount of strong acid such as hydrofluoric acid, which not only has high processing cost, but also does not meet the requirements of energy conservation and environmental protection. With the increase of global environmental protection, the production mode of chemical thinning is gradually limited or prohibited. Some glass substrate manufacturers can directly mass-produce thin glass substrates of 0.25mm or less. And if the panel factory directly adopts the thin glass substrate below 0.25mm to produce, because the base plate is too thin, self supporting strength can not bear the dead weight, and it is too big to hang down, leads to the panel to produce the line can't cross the piece, can't satisfy the requirement that current panel produced the line.

At present, the solution adopted in the industry is mainly to laminate a thin glass substrate and a thicker glass to form a composite glass plate for use, and the lamination adopts the modes of direct vacuum lamination, high-temperature-resistant organic silicon resin lamination, inorganic layer lamination and the like, but the modes still have many defects and are mostly not practical. For example, defects such as bubbles and Newton's rings can be generated after direct vacuum lamination, and problems such as partial peeling and the like occur in the processes of sheet taking, storage and conveying; meanwhile, the equipment required by vacuum lamination is complex, the investment is large, and the cost is high; the vacuum laminated composite board has enhanced laminating force after a high-temperature manufacturing process, and cannot be peeled off, so that peeling and fragmentation are caused. After the high-temperature resistant organic silicon resin is attached, the adhesive force is increased through a high-temperature treatment process, so that the stripping is difficult, the stripping fragments are caused, and the residual glue left on the surface of the thin glass substrate is difficult to clean; meanwhile, the synthesis process of the organic silicon resin is complex, the performance is unstable, various volatile organic compounds exist in a relatively closed space, potential safety hazards exist, and the health of operators is damaged. Inorganic layer laminating needs large-scale evaporation equipment, and the investment is high, with high costs, and the laminating effect is not good, and the bubble problem is difficult to solve, and peels off the process complicacy, is difficult to popularize and apply in actual production line.

Under the background, how to research and develop new products and new processes and reasonably apply the ultra-thin glass substrate becomes a difficult problem to be overcome in the electronic display industry chain.

Disclosure of Invention

The invention aims to overcome the technical problems in the prior art and provide the composite glass plate, the preparation method and the application.

In order to achieve the above object, an aspect of the present invention provides a composite glass plate comprising a glass substrate, a support layer, and an intermediate layer disposed between the glass substrate and the support layer, wherein the intermediate layer is in a liquid state, and the intermediate layer contains one or more components of fluorine oil, silicone oil, ionic liquid, liquid resin, and liquid silicone rubber.

Preferably, the peel force of the composite glass sheet is less than 100N/m, more preferably less than 50N/m.

Preferably, the fluorine oil is selected from one or more of a perfluorinated hydrocarbon oil, a chlorofluorocarbon oil and a perfluorinated ether oil.

Preferably, the silicone oil is selected from one or more of methyl silicone oil, phenyl silicone oil and aryl silicone oil.

Preferably, the ionic liquid is selected from one or more of imidazole compounds, pyrrole compounds, pyridine compounds, piperidine compounds and quaternary ammonium salt ionic liquids.

Preferably, the liquid resin is a rosin resin.

Preferably, the liquid silicone rubber is a polymer of a linear polyorganosiloxane.

Preferably, the intermediate layer has a resistance temperature of greater than 270 ℃, more preferably greater than 360 ℃.

Preferably, the viscosity of the intermediate layer is 0.1 to 20000cps at 25 ℃.

Preferably, the interlayer has a water content of less than 200 ppm.

Preferably, the intermediate layer has a visible light transmittance of greater than 85% at 25-450 ℃.

Preferably, the refractive index of the intermediate layer is 1.2 to 1.8.

Preferably, the thickness of the intermediate layer is 0.001 to 100 μm.

Preferably, the thickness of the glass substrate is 0.25mm or less.

Preferably, the support layer is made of one or more materials selected from glass, metal, organic polymer material, carbon fiber composite material, and graphene composite material.

Preferably, the thickness of the support layer is 0.2-1.1 mm.

Preferably, the young's modulus of the support layer is greater than 65 GPa.

Preferably, the support layer is glass, and the glass contains 66-73 mol% of SiO calculated by oxide based on the total mole number of the components of the glass₂11-15 mol% of Al₂O₃0-11 mol% of B₂O₃1-10 mol% of MgO, 2-10 mol% of CaO, 0-6 mol% of SrO, 0-10 mol% of BaO, 0-2 mol% of ZnO and 0-0.7 mol% of Re₂O₃And less than 0.05 mol% of R₂And O, wherein Re is a rare earth element, and R is an alkali metal.

Preferably, the support layer is glass, and the glass contains 60 to 74 mol% of SiO calculated by oxide based on the total moles of the components of the glass₂8-18 mol% of Al₂O₃1-15 mol% of B₂O₃+P₂O₅4-15 mol% of Na₂O, 0-10 mol% of Li₂O, 0-10 mol% of K₂O, 0.5-10 mol% MgO + TiO₂0 to 4 mol% of ZnO and 0 to 4 wt% of Y₂O₃+La₂O₃+Nd₂O₃。

Preferably, the length and width of the composite glass sheet are greater than 300mm, more preferably greater than 1000 mm.

Preferably, the length of the glass substrate is less than or equal to the length of the support layer.

Preferably, the width of the glass substrate is less than or equal to the width of the support layer.

Preferably, the length of the glass substrate is 0.05-20mm less than the length of the support layer.

Preferably, the width of the glass substrate is 0.05-20mm smaller than the width of the support layer.

In a second aspect, the present invention provides a method of making a composite glass sheet according to the present invention, the method comprising the steps of:

1) applying the components of the intermediate layer to one surface of a support layer and/or a glass substrate;

2) and attaching the supporting layer to the glass substrate.

Preferably, the process is carried out under heated conditions.

Preferably, the heating temperature is 50-360 ℃.

In a third aspect, the invention provides the use of the composite glass sheet according to the invention for the manufacture of a flat/flexible display substrate and/or carrier sheet.

Specifically, compared with the prior art, the invention has the following main advantages:

(1) strong acid such as hydrofluoric acid is not used, so that the environment pollution is avoided;

(2) the curing process is not needed, and the attaching and stripping processes are simple and easy to implement;

(3) the production equipment is simple, the preparation method is simple, and the investment cost of a production line is reduced;

(4) the vacuum bubble removal can be realized, the quality control is easier to carry out, and the yield is high;

(5) the supporting layer can be repeatedly used, so that the production cost is reduced, and the repair cost is low;

(6) the middle layer can be recycled and purified, which is beneficial to environmental protection and further reduces the cost;

(7) the flexible ultrathin glass can be produced roll to roll, and the automation level is greatly improved.

Drawings

FIG. 1 is a schematic view of the basic structure of a composite glass according to an embodiment of the present invention;

FIG. 2 is a schematic view of the basic structure of another embodiment of the composite glass of the present invention.

Description of the reference numerals

1-1, glass substrate 1-2, intermediate layer 1-3, supporting layer

2-1, 2-2 glass substrates, 2-3 intermediate layers and supporting layers

Detailed Description

The following detailed description of embodiments of the invention refers to the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.

The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.

In the present invention, the use of directional terms such as "upper, lower, left, right" generally means upper, lower, left, right in the drawings, and "inner, outer" means inner and outer of the corresponding structures, unless otherwise specified.

In a first aspect, the present invention provides a composite glass plate, comprising a glass substrate, a support layer and an intermediate layer located between the glass substrate and the support layer, wherein the intermediate layer is in a liquid state, and the intermediate layer contains one or more components selected from fluoro oil, silicone oil, ionic liquid, liquid resin and liquid silicone rubber.

The glass substrate and the supporting layer are attached by utilizing the liquid layer between the glass substrate and the supporting layer, so that a whole is formed, the supporting layer can be recycled, the middle layer can be recycled, purified and reused, the environment is protected, and meanwhile, the production cost is further reduced. And the sagging amount of the composite glass plate during point supporting meets the requirements of panel manufacturing process, and the production line application of the ultrathin glass substrate can be realized.

In the present invention, the peeling force is a force value required to peel the glass substrate and the supporting layer apart. In view of the subsequent in-line application of the composite glass and the ease of peeling, the composite glass sheet in the present invention preferably has a peeling force of less than 100N/m, more preferably less than 50N/m, still more preferably less than 36N/m, and still more preferably less than 18N/m, to avoid peeling debris during the glass process.

In the invention, the intermediate layer is in a liquid state and contains one or more of fluorine oil, silicone oil, ionic liquid, liquid resin and liquid silicone rubber, and the liquid intermediate layer plays roles of filling, adsorption, lamination, permeability increase and buffering on the glass substrate and the supporting layer, so that the composite glass plate forms an organic whole and meets the application requirement of a subsequent production line.

In the present invention, the fluorine oil refers to a synthetic lubricating oil containing fluorine in the molecule, for example, a fluorocarbon or a chlorofluorocarbon formed by substituting hydrogen in an alkane with fluorine or fluorine, chlorine, and preferably, the fluorine oil is selected from one or more of a perfluorocarbon oil, a chlorofluorocarbon oil, and a perfluoroether oil. In the invention, the middle layer still has excellent chemical stability when being heated at high temperature by adopting fluorine oil.

In the present invention, the silicone oil refers to a linear polysiloxane product which remains liquid at room temperature, and includes both methyl silicone oil and modified silicone oil, preferably, the silicone oil is selected from one or more of methyl silicone oil, phenyl silicone oil and aryl silicone oil. In the present invention, the phenyl silicone oil is a benzyl silicone oil obtained by replacing a part of methyl groups in a dimethyl silicone oil with phenyl groups. The more the phenyl group content in the benzyl silicone oil, the more excellent the thermal stability. In the invention, the aryl silicone oil is a product of replacing a part of methyl of dimethyl organic silicone oil with a functional group or substituent derived from a simple aromatic ring, and can also be derived from phenyl silicone oil.

In the invention, the ionic liquid is mainly an ionic liquid which is liquid at normal temperature, and preferably, the ionic liquid is one or more selected from imidazole compounds, pyrrole compounds, pyridine compounds, piperidine compounds and quaternary ammonium salt ionic liquids. Specifically, for example, the imidazole compound may be tetrafluoroboric acid type imidazole, 1-butyl-3-methylimidazolium hexafluorophosphate (chemical formula [ bimm ]]PF₆) Or 2-methylimidazole; the pyrrole compound can be dipyrromethane, alkyl pyrrole or N-methyl pyrrolidone; the pyridine compound can be trifluoromethyl pyridine, N-butyl pyridine tetra fluoro salt or trimethyl pyridine; the piperidine compound can be 2-piperidine methyl formate or 1-propyl-1-methyl piperidine bis-trifluoromethanesulfonimide salt; the quaternary ammonium salt ionic liquid is also called quaternary ammonium salt and is in ammonium ionsIs substituted with a hydrocarbon group, and a compound of the formula R₄NX, wherein four alkyl groups R can be the same or different, the negative ion X can be a halogen negative ion, an acid radical negative ion or a tributylmethylammonium bistrifluoromethanesulfonylimide salt. The ionic liquids can be prepared by synthetic methods commonly used by those skilled in the art, or can be obtained commercially.

In the present invention, preferably, the liquid resin is a liquid rosin resin. In the present invention, the liquid rosin resin means: rosin is used as main raw material, triethylene glycol and rosin resin acid are selected to react, and the reaction product is a non-drying viscous liquid flow. Specifically, in the embodiment of the present invention, the liquid rosin resin composition may contain, for example, in percentage by weight: 50-70 wt% of epoxy resin, 20-30 wt% of rosin, 5-10 wt% of glycerol, 2-8 wt% of fumaric acid, 1-5 wt% of sodium silicate, 0-6 wt% of sodium dodecyl benzene sulfonate and 5-10 wt% of water. In one embodiment of the present invention (example 5), epoxy resin 53 wt%, rosin 22 wt%, glycerin 8 wt%, fumaric acid 5 wt%, sodium silicate 2.5 wt%, sodium dodecylbenzenesulfonate 3.5 wt%, and water 6 wt%.

In the present invention, preferably, the liquid silicone rubber is a polymer of a linear polyorganosiloxane. In the present invention, the liquid silicone rubber is a liquid having a certain viscosity, which is prepared by adding a crosslinking agent, a reinforcing filler and other compounding agents to a linear polyorganosiloxane as a base polymer, and compounding and vulcanizing the mixture. Specifically, the liquid silicone rubber may contain, for example, in percentage by weight: 45-65 wt% of vinyl polysiloxane, 15-25 wt% of glycerol, 5-20 wt% of tetramethyl tetravinylcyclotetrasiloxane, 1.5-15 wt% of tetramethyl divinyl disiloxane, 0-10 wt% of white carbon black and 1-5 wt% of silane coupling agent. In one embodiment (example 6) of the present invention, 54 wt% of vinyl polysiloxane, 18 wt% of glycerol, 12.2 wt% of tetramethyltetravinylcyclotetrasiloxane, 7.2 wt% of tetramethyldivinyldisiloxane, 5.6 wt% of white carbon black, and 3 wt% of silane coupling agent are used.

In the present invention, the particle size of the white carbon black is preferably less than 5 μm, more preferably less than 2 μm; by further controlling the particle size of the white carbon black, the influence on the performance of the composite glass plate caused by uneven thickness of the intermediate layer is avoided.

In the present invention, the intermediate layer preferably withstands a temperature of more than 270 ℃, more preferably more than 360 ℃, further preferably withstands a high temperature of 450 ℃ or more, and further preferably withstands a high temperature of 600 ℃ or more. The above-mentioned resistance temperature of more than 360 ℃ means that the intermediate layer is resistant to a high temperature of 360 ℃ or more in a nitrogen atmosphere without undergoing self chemical change or chemical bonding.

In the present invention, in order to further satisfy the processability of the composite glass sheet and facilitate the subsequent peeling, it is preferable that the viscosity of the intermediate layer is 0.1 to 20000cps, more preferably 10 to 10000cps, further preferably 100-.

In order to further reduce bubbles generated in the composite glass plate and ensure the yield of the composite glass plate, in the invention, the water content of the intermediate layer is preferably less than 200 ppm; more preferably, the interlayer has a water content of less than 100 ppm. Through the water content in control intermediate level, can avoid the production of laminating in-process bubble, influence the laminating effect, further guarantee the yield of compound glass board.

In the present invention, in order to further satisfy the process performance requirements of the composite glass plate, it is preferable that the visible light transmittance of the interlayer is greater than 85%, more preferably greater than 90%, at 25-450 ℃.

In the present invention, in order to further satisfy the process performance requirements of the composite glass sheet, it is preferable that the refractive index of the intermediate layer is 1.2 to 1.8, more preferably 1.3 to 1.7, and still more preferably 1.4 to 1.6 at normal temperature.

In the present invention, the thickness of the intermediate layer is preferably 0.001 to 100. mu.m, more preferably 0.01 to 50 μm.

The glass substrate may be flat glass for electronic display or flexible glass, for example, glass substrates for display devices such as LCD, OLED, plasma display, quantum dot display, Micro LED, electronic paper, and the like.

In order to satisfy the requirement of the thickness of the thin glass substrate, in the present invention, the thickness of the glass substrate is preferably 0.25mm or less, more preferably 0.2mm or less, and further preferably 0.15mm or less. In the present invention, it is preferable that the glass substrate contains 66 to 73 mol% of SiO in terms of oxide based on the total number of moles of each component of the glass substrate₂11-15 mol% of Al₂O₃0-11 mol% of B₂O₃1-10 mol% of MgO, 2-10 mol% of CaO, 0-6 mol% of SrO, 0-10 mol% of BaO, 0-2 mol% of ZnO and 0-0.7 mol% of Re₂O₃And less than 0.05 mol% of R₂And O, wherein Re is a rare earth element, and R is an alkali metal.

In order to satisfy the thickness requirement of the thin glass substrate, in the present invention, it is preferable that the glass substrate contains 60 to 74 mol% of SiO in terms of oxides based on the total number of moles of each component of the glass substrate₂8-18 mol% of Al₂O₃1-15 mol% of B₂O₃+P₂O₅4-15 mol% of Na₂O, 0-10 mol% of Li₂O, 0-10 mol% of K₂O, 0.5-10 mol% MgO + TiO₂0 to 4 mol% of ZnO and 0 to 4 wt% of Y₂O₃+La₂O₃+Nd₂O₃。

The supporting layer is mainly a rigid plate for supporting and bearing, and in the present invention, the supporting layer is preferably made of one or more materials selected from glass, metal, organic polymer materials, carbon fiber composites, and graphene composites. In a specific embodiment of the present invention, the support layer is made of glass.

The glass used as the support layer is not particularly limited, and includes, but is not limited to, alkali-free glass, alkali-containing glass, and chemically strengthened glass.

In the present invention, it is preferable that the thermal expansion coefficient of the above-mentioned glass support layer material is matched with that of the glass substrate with a relative deviation of not more than 10%, more preferably not more than 5%.

In the present invention, preferably, the branchThe support layer is glass and contains 66-73 mol% of SiO calculated by oxide and based on the total mole number of all the components of the support layer₂11-15 mol% of Al₂O₃0-11 mol% of B₂O₃1-10 mol% of MgO, 2-10 mol% of CaO, 0-6 mol% of SrO, 0-10 mol% of BaO, 0-2 mol% of ZnO and 0-0.7 mol% of Re₂O₃And less than 0.05 mol% of R₂And O, wherein Re is a rare earth element, and R is an alkali metal.

In the present invention, it is preferable that the support layer is glass, and the support layer contains 60 to 74 mol% of SiO, in terms of oxide, based on the total number of moles of each component of the support layer₂8-18 mol% of Al₂O₃1-15 mol% of B₂O₃+P₂O₅4-15 mol% of Na₂O, 0-10 mol% of Li₂O, 0-10 mol% of K₂O, 0.5-10 mol% MgO + TiO₂0 to 4mol percent of ZnO and 0 to 4wt percent of Y₂O₃+La₂O₃+Nd₂O₃。

In the present invention, the thickness of the support layer is preferably 0.2 to 1.1mm, more preferably 0.3 to 0.8mm, and further preferably 0.35 to 0.7 mm.

In order to further ensure that the composite glass plate has a sag reaching the requirements of panel manufacturing process when supported at a point, in the present invention, the young's modulus of the support layer is preferably greater than 65GPa, more preferably greater than 68GPa, and even more preferably greater than 70 GPa.

In order to meet the requirements of practical application, in the invention, the length and the width of the composite glass plate are preferably more than 300mm, and more preferably more than 1000 mm. In particular, the length and width of the support layer are greater than 300mm, more preferably greater than 1000 mm; the length and the width of the glass substrate are larger than 300mm, and more preferably larger than 1000mm, so that the size requirement of the G5 glass substrate for generation line is further met, a panel manufacturer production line is adapted, and the production efficiency is improved.

In order to facilitate the peeling and recycling of the subsequent composite glass plate, in the present invention, the length of the glass substrate is preferably equal to or less than the length of the support layer.

In order to further facilitate the peeling and recycling of the subsequent composite glass plate, in the invention, the length of the glass substrate is preferably 0.05-20mm smaller than that of the support layer; more preferably, the length of the glass substrate is 0.1 to 10mm less than the length of the support layer; further preferably, the length of the glass substrate is 0.2 to 6mm smaller than the length of the support layer. By satisfying the above requirements, the damage of the glass substrate can be avoided to the greatest extent, and the yield can be improved.

In order to facilitate the peeling and recycling of the subsequent composite glass plate, in the present invention, the width of the glass substrate is preferably equal to or less than the width of the support layer.

In order to further facilitate the peeling and recycling of the subsequent composite glass plate, in the invention, the width of the glass substrate is preferably 0.05-20mm smaller than that of the support layer; more preferably, the width of the glass substrate is 0.1 to 10mm smaller than the width of the support layer; further preferably, the width of the glass substrate is 0.2 to 6mm smaller than the width of the support layer. By satisfying the above requirements, the damage of the glass substrate can be avoided to the greatest extent, and the yield can be improved.

2) and attaching the supporting layer to the glass substrate.

According to the preparation method, the composite glass plate meeting the requirements of a (thin substrate) panel production line can be obtained only by laminating the supporting layer coated with the liquid intermediate layer component and/or the glass substrate, and strong acid substances such as hydrofluoric acid are not used in the laminating process, so that high cost and high pollution caused by chemical thinning are avoided; the method also avoids various defects and shortcomings generated by the direct vacuum bonding, high-temperature-resistant organic silicon resin bonding, inorganic layer bonding and other bonding processes, avoids high cost caused by research and development of a new production line, obviously improves the production efficiency and the product yield, and has excellent economic benefit.

In the coating in step 1), specifically, the liquid component of the intermediate layer may be coated on only one surface of the glass substrate, and then the coated surface is attached to the support layer; or coating the liquid component of the middle layer on only one surface of the support layer, and then attaching the coating surface to the glass substrate; or the liquid components of the intermediate layer can be respectively coated on one surface of the support layer and one surface of the glass substrate, and then the coating surfaces of the support layer and the glass substrate are jointed to obtain the composite glass substrate.

The coating method in step 1) is not particularly limited, and examples thereof include slit coating, spray coating, roll coating, wire bar coating, and blade coating.

The coating in step 1) may be carried out under heating conditions, and specifically, for example, the support layer may be heated, or the glass substrate may be heated, or the components of the intermediate layer may be heated. In the method of the present invention, the heating temperature is preferably 50 to 360 ℃, more preferably 70 to 270 ℃, still more preferably 80 to 180 ℃, and still more preferably 100-150 ℃. The generation of bubbles is further reduced through heating, and the yield of the composite glass plate is improved.

The bonding in step 2) may be performed, for example, by closely bonding the support layer and the glass substrate in a vacuum or air atmosphere, specifically, bonding may be started from one side or one corner until the entire substrate is bonded. In the bonding process, pressure can be applied from the outer side of the support layer and/or the glass substrate, so that bonding efficiency is improved, and internal air bubbles are promoted to be discharged. The medium for applying pressure can be selected from a rubber disc, a rubber sheet or a rubber roller, and preferably the rubber roller is used for rolling, so that the number of bubbles with the inner diameter of more than 0.02mm in the composite glass plate is less than or equal to 1/m²。

In terms of the surface flatness of the composite glass sheet, in the method of the present invention, preferably, the method may further include a step of performing a homogenization treatment after the attachment. The step can be selectively increased or decreased according to the surface flatness of the composite glass plate.

The above-mentioned homogenization treatment can be carried out under the same heating conditions as in step 1).

If necessary, the laminated composite glass plate may be subjected to vacuum defoaming, wherein the vacuum degree may be 1 × 10^-4-200Pa, preferably from 0.01 to 150Pa, more preferably from 1 to 100 Pa.

During the vacuum debubbling process, pressurization may be selected. Specifically, pressure is applied to both sides of the composite glass sheet to facilitate internal bubble venting. The pressure application position may be, for example, a full-surface pressure application position, or may be a position where pressure is first applied from the middle portion and gradually moved to both sides to promote faster discharge of the internal air bubbles.

The above-mentioned laminating need not to carry out limit portion grinding and polishing again after finishing, also need not to carry out physics attenuate, chemical attenuate and handle, can send to panel producer to put into production after processes such as washing, inspection, packing, transportation to peel off the composite glass board of accomplishing the panel processing procedure, retrieval and utilization is carried out to intermediate level and supporting layer. Taking a TFT-LCD as an example, the method specifically comprises the following steps:

1. panel manufacturing process: after the attached composite glass plate is subjected to Array process and CF process, functional components are formed on the surface of a glass substrate, then an LCD online attaching process is carried out, a box forming process is completed, and then a stripping process is carried out.

2. A stripping procedure: fixing the display device with the support layer by using a vacuum objective table, sucking the upper support layer to be peeled by using a vacuum sucker, and peeling from one side or one corner until the support plate is completely peeled. When peeling is started, a gap is cut at one side or one corner by using the thin blade, so that the panel is prevented from being damaged due to overlarge initial peeling force.

3. A cleaning procedure: after the peeling, the interlayer liquid component remaining on the surface of the glass substrate constituting the display device is cleaned by a method such as air knife, ultrasonic cleaning, organic solvent cleaning, alkaline cleaning, pure water rinsing, or the like. After cleaning, functional devices made of the glass substrate enter the next procedure, and liquid components in the middle layer are recovered.

4. And (3) recycling: the intermediate layer liquid component remaining on the surface of the support layer is cleaned by using methods such as air knife cleaning, ultrasonic cleaning, organic solvent cleaning, alkaline cleaning solution cleaning, pure water rinsing and the like. After being cleaned, the adhesive tape can be repeatedly used and attached again.

The flexible ultrathin glass produced by the preparation method in a roll-to-roll mode can greatly improve the automation level.

The present invention will be described in detail below by way of examples. In the following examples, each material used was commercially available unless otherwise specified, and the method used was a conventional method in the art unless otherwise specified.

The Young modulus is measured by GB/T37780-2019, the refractive index is measured by an Abbe refractometer, the visible light transmittance is measured by a spectrophotometer, the tolerance temperature of the middle layer is measured by the same process conditions as that of a large-size panel production line (1100mm multiplied by 1300mm), a heat treatment device is used for measuring, the viscosity is measured by a rotary viscometer, and the stripping force is measured by a stripping force tester (model DXL-A, equipped with a 100N high-precision mechanical sensor).

Example 1

As shown in FIG. 1, the support layer 1-3 is an alkali-free glass (hereinafter referred to as a 0.5T glass support layer) having a length of 1300mm, a width of 1100mm and a thickness of 0.5mm, the glass substrate 1-1 is an alkali-free glass (hereinafter referred to as a 0.15T glass substrate) having a length of 1295mm, a width of 1095mm and a thickness of 0.15mm, and the intermediate layer 1-2 is an alkyl quaternary ammonium salt ionic liquid. Wherein the 0.15T glass substrate and the 0.5T glass supporting layer are made of the same glass, and the glass comprises 67.4mol percent of SiO calculated by oxide and based on the total molar weight of the 0.15T glass substrate₂11.1 mol% of Al₂O₃9.8 mol% of B₂O₃2.3 mol% MgO, 8.8 mol% CaO, 0.5 mol% SrO, 0.05 mol% ZnO and less than 0.05 mol% R₂O, wherein R is alkali metal (specifically Li, Na and K).

The Young modulus of the glass is 73GPa, the refractive index is 1.52, and the visible light transmittance at the wavelength of 380-780nm is 91.6%.

After the 0.5T glass supporting layer is ground, polished and cleaned, quaternary ammonium salt ionic liquid is uniformly coated on one surface of the supporting layer by a wire bar knife coating method, and the thickness of the supporting layer is 5 mu m. Under the non-vacuum condition, a 0.15T glass substrate is attached from one side, and air between the glass plates is discharged by rolling through a rubber roller, so that the number of bubbles with the inner diameter of more than 0.02mm in the composite glass plate is 0/m²。

After the lamination, a pressurizing and vacuum bubble discharging process is performed, wherein the vacuum degree is 10Pa, pressure is applied from the middle part, and the air bubbles gradually move to two sides to promote the inner bubbles to be discharged more quickly.

The length and width of the 0.15T glass substrate are both 5mm smaller than the 0.5T glass support layer. The edge shape is embodied, the 0.15T glass substrate is 2.5mm smaller than the 0.5T glass supporting layer, so that the 0.5T glass supporting layer can protect the 0.15T glass substrate, the damage of 0.15T thin glass is avoided to the greatest extent, and the yield is improved. The properties of the intermediate layer are shown in table 1.

And (3) TFT-LCD panel manufacturing process: after the Array process and the CF process, functional components are formed on the surface of the glass substrate, then the LCD on-line process is carried out to complete the box forming process, and then the stripping process is carried out.

A stripping procedure: the vacuum stage is used for fixing the display device with the 0.5T glass supporting layer, the vacuum chuck is used for sucking the upper 0.5T glass supporting layer to be peeled, and the peeling is started from one side until the 0.5T glass supporting layer is completely peeled. At the start of the peeling, a slit can be cut on one side by means of a specially made thin blade to facilitate the directional peeling. At a peel rate of 20mm/min, a peel force of 12N/m was measured.

A cleaning procedure: after the peeling, the quaternary ammonium salt ionic liquid remaining on the surface of the 0.15T glass substrate constituting the display device was cleaned by a combination of methods such as air knife cleaning, ultrasonic cleaning, organic solvent cleaning, and pure water rinsing. And after cleaning, the functional device made of the glass substrate enters the next procedure.

And (3) recycling: and cleaning the residual quaternary ammonium salt ionic liquid on the surface of the 0.5T glass supporting layer by using an air knife, ultrasonic cleaning, organic solvent cleaning and pure water washing. After the cleaning, the adhesive tape can be repeatedly utilized and attached again. The recycling of the 0.5T glass supporting layer can reduce the production cost, save energy, reduce consumption and protect the environment.

And (3) recycling: the quaternary ammonium salt ionic liquid is collected and can be reused after purification, so that the cost is further reduced, the resources are saved, and the environment is protected.

Example 2

As shown in FIG. 2, the support layer 2-3 is an alkali-free glass (hereinafter referred to as a 0.6T glass support layer) having a length of 1300mm, a width of 1100mm and a thickness of 0.6mm, the glass substrate 2-1 is an alkali-free glass (hereinafter referred to as a 0.2T glass substrate) having a length of 1294mm, a width of 1094mm and a thickness of 0.2mm, and the intermediate layer 2-2 is trifluoropropylmethylsilicone oil. Wherein the 0.2T glass substrate and the 0.6T glass supporting layer are made of the same glass, and the glass comprises 67.5mol percent of SiO calculated by oxide and based on the total molar weight of the 0.2T glass substrate₂13.2 mol% of Al₂O₃9.5 mol% of B₂O₃1.6 mol% MgO, 3.4 mol% CaO, 2.6 mol% SrO, 1.2 mol% BaO, 0.9 mol% ZnO and less than 0.05 mol% R₂O, wherein R is alkali metal (specifically Li, Na and K).

The Young modulus of the glass is 78GPa, the refractive index is 1.52, and the visible light transmittance at the wavelength of 380-780nm is 91.8%.

After edge grinding, edge polishing and overall cleaning of the 0.6T glass supporting layer, silicone oil was uniformly coated on one surface by a doctor blade coating method to a thickness of 5 μm. In the vacuum cavity, a 0.2T glass substrate is attached from one side, and the outer surface is pressed by a film, so that the number of bubbles with the inner diameter larger than 0.02mm in the composite glass plate is 0/m²。

Before coating the silicone oil, a filtering device is added to filter impurities in the silicone oil. In the process of applying the silicone oil, the 0.6T glass support layer and the silicone oil were heated to a heating temperature of 105 ℃. After the lamination, vacuum bubble removal is carried out, and the vacuum degree is 1 Pa.

The length and the width of the 0.2T glass substrate are 6mm smaller than those of the 0.6T glass supporting layer, the shape of the edge is reflected, and the 0.2T glass substrate is 3mm smaller than that of the 0.6T glass supporting layer, so that the 0.6T glass supporting layer can protect the 0.2T glass substrate, the damage of 0.2T thin glass is avoided to the greatest extent, and the yield is improved. The properties of the intermediate layer are shown in table 1.

And (3) OLED panel manufacturing process: the laminated composite glass plate is subjected to processing in each step to complete encapsulation, and then subjected to a peeling step.

A stripping procedure: the vacuum carrier is used for fixing a display device with two 0.6T glass supporting layers on a vacuum object stage, the upper 0.6T glass supporting layer to be stripped is sucked by a vacuum sucker, and the stripping is started from one corner until the carrier is completely stripped. When the peeling is started, a gap is cut at one corner by a special thin blade, which is beneficial to directional peeling and avoids the damage to the panel caused by overlarge peeling force. The peel force was 10N/m.

A cleaning procedure: after the peeling, the silicone oil remaining on the surface of the 0.2T glass substrate constituting the display device was cleaned by a combination of methods such as air knife cleaning, ultrasonic cleaning, alkaline cleaning solution cleaning, and pure water rinsing. And after cleaning, the functional device made of the glass substrate enters the next procedure.

And (3) recycling: and (3) residual silicone oil on the surface of the 0.6T glass supporting layer is cleaned by using an air knife, ultrasonic cleaning, alkaline cleaning solution cleaning and pure water washing. After the cleaning, can reuse, laminate again. The recycling of the 0.6T glass supporting layer can reduce the production cost, save energy, reduce consumption and protect the environment.

And (3) recycling: the silicone oil is collected and can be reused after purification, so that the cost is further reduced, the resources are saved, and the environment is protected.

Example 3

The procedure is as in example 1, except that the quaternary ammonium salt ionic liquid is replaced with a fluoro oil.

After the 0.5T glass supporting layer is ground, polished and cleaned, a plurality of pieces of fluorine oil are uniformly coated on one surface of the supporting layer by a multi-head dispenser. Adhering a 0.15T glass substrate along the coating direction of a dispenser from one side under the non-vacuum condition, rolling by using a rubber roller, and discharging between the glass platesSo that the number of bubbles with the inner diameter of the composite glass plate larger than 0.02mm is less than 2/m²。

The length and width of the 0.15T glass substrate are 6mm smaller than those of the 0.5T glass support layer. The edge shape is embodied, the 0.15T glass substrate is smaller than the 0.5T glass supporting layer by 3mm, so that the 0.5T glass supporting layer can protect the 0.15T glass substrate, the damage of 0.15T thin glass is avoided to the maximum extent, and the yield is improved. The properties of the intermediate layer are shown in table 1.

A stripping procedure: the vacuum stage is used for fixing the display device with the 0.5T glass supporting layer, the vacuum chuck is used for sucking the upper 0.5T glass supporting layer to be peeled, and the peeling is started from one side until the 0.5T glass supporting layer is completely peeled. At the start of the peeling, a slit can be cut on one side by means of a specially made thin blade to facilitate the directional peeling. At a peel rate of 20mm/min, the peel force was 15N/m.

A cleaning procedure: after the peeling, the fluorine oil remaining on the surface of the 0.15T glass substrate constituting the display device was cleaned by a combination of methods such as air knife cleaning, ultrasonic cleaning, organic solvent cleaning, and pure water rinsing. And after cleaning, the functional device made of the glass substrate enters the next procedure.

And (3) recycling: and cleaning residual fluorine oil on the surface of the 0.5T glass support layer by using an air knife, ultrasonic cleaning, organic solvent cleaning and pure water washing. After the cleaning, the adhesive tape can be repeatedly utilized and attached again. The recycling of the 0.5T glass supporting layer can reduce the production cost, save energy, reduce consumption and protect the environment.

And (3) recycling: the fluorine oil is collected and can be reused after purification, so that the cost is further reduced, the resource is saved, and the environment is protected.

Example 4

The procedure is as in example 1, except that the quaternary ammonium ionic liquid is replaced with phenyl silicone oil.

After the 0.5T glass support layer was ground, polished and cleaned, phenyl silicone oil was uniformly coated on one surface to a thickness of 5 μm by a slit coating method. Under the non-vacuum condition, a 0.2T glass substrate is attached from one side, and air between the glass plates is discharged by using a rubber roller for rolling, so that the number of bubbles with the inner diameter of more than 0.02mm in the composite glass plate is less than 2/m²。

The length and width of the 0.2T glass substrate are 8mm smaller than those of the 0.5T glass support layer. The edge shape is embodied, the 0.2T glass substrate is 4mm smaller than the 0.5T glass supporting layer, so that the 0.5T glass supporting layer can protect the 0.2T glass substrate, the damage of 0.2T thin glass is avoided to the maximum extent, and the yield is improved. The properties of the intermediate layer are shown in table 1.

A stripping procedure: the vacuum stage is used for fixing the display device with the 0.5T glass supporting layer, the vacuum chuck is used for sucking the upper 0.5T glass supporting layer to be peeled, and the peeling is started from one side until the 0.5T glass supporting layer is completely peeled. At the start of the peeling, a slit can be cut on one side by means of a specially made thin blade to facilitate the directional peeling. At a peel rate of 20mm/min, the peel force was 18N/m.

A cleaning procedure: after the peeling, the phenyl silicone oil remaining on the surface of the 0.2T glass substrate constituting the display device was cleaned by a combination of methods such as air knife cleaning, ultrasonic cleaning, organic solvent cleaning, and pure water rinsing. And after cleaning, the functional device made of the glass substrate enters the next procedure.

And (3) recycling: and (3) cleaning the residual phenyl silicone oil on the surface of the 0.5T glass support layer by using an air knife, ultrasonic cleaning, organic solvent cleaning and pure water washing. After the cleaning, the adhesive tape can be repeatedly utilized and attached again. The recycling of the 0.5T glass supporting layer can reduce the production cost, save energy, reduce consumption and protect the environment.

And (3) recycling: the phenyl silicone oil is collected and can be reused after purification, so that the cost is further reduced, the resources are saved, and the environment is protected.

Example 5

The procedure is as in example 1, except that the quaternary ammonium salt ionic liquid is replaced with a liquid rosin resin.

After the 0.4T glass support layer was ground, polished and washed, a liquid rosin resin was uniformly coated on one surface thereof by blade coating with a doctor blade to a thickness of 8 μm. Under the non-vacuum condition, a 0.1T glass substrate is attached from one side, and air between the glass plates is discharged by using a rubber roller for rolling, so that the number of bubbles with the inner diameter of more than 0.02mm in the composite glass plate is less than 2/m²。

The length and width of the 0.1T glass substrate are 8mm smaller than those of the 0.4T glass support layer. The edge shape is embodied, the 0.1T glass substrate is 4mm smaller than the 0.4T glass supporting layer, so that the 0.4T glass supporting layer can protect the 0.1T glass substrate, the damage of 0.1T thin glass is avoided to the greatest extent, and the yield is improved. The properties of the intermediate layer are shown in table 1.

A stripping procedure: the vacuum stage is used for fixing the display device with the 0.4T glass supporting layer, the vacuum chuck is used for sucking the upper 0.4T glass supporting layer to be peeled, and the peeling is started from one side until the 0.4T glass supporting layer is completely peeled. At the start of the peeling, a slit can be cut on one side by means of a specially made thin blade to facilitate the directional peeling. The peel force was 20N/m at a peel rate of 20 mm/min.

A cleaning procedure: after the peeling, the residual liquid rosin resin on the surface of the 0.1T glass substrate constituting the display device was cleaned by a combination of methods such as air knife cleaning, ultrasonic cleaning, organic solvent cleaning, and pure water rinsing. And after cleaning, the functional device made of the glass substrate enters the next procedure.

And (3) recycling: the residual liquid rosin resin on the surface of the 0.4T glass supporting layer was cleaned using an air knife, ultrasonic cleaning, organic solvent cleaning and pure water rinsing. After the cleaning, the adhesive tape can be repeatedly utilized and attached again. The recycling of the 0.4T glass supporting layer can reduce the production cost, save energy, reduce consumption and protect the environment.

And (3) recycling: the liquid rosin resin is collected and can be reused after purification and purification, so that the cost is further reduced, the resources are saved, and the environment is protected.

Example 6

The procedure is as in example 1 except that the quaternary ammonium ionic liquid is replaced with liquid silicone rubber.

After the 0.5T glass support layer was ground, polished and cleaned, a liquid silicone rubber was uniformly coated on one surface thereof with a thickness of 12 μm using a roll coater. Under the non-vacuum condition, a 0.2T glass substrate is attached from one side, and air between the glass plates is discharged by using a rubber roller for rolling, so that the number of bubbles with the inner diameter of more than 0.02mm in the composite glass plate is less than 2/m²。

After the lamination, a pressurizing and vacuum bubble discharging process is carried out, wherein the vacuum degree is 5Pa, pressure is applied from the middle part, and the air bubbles gradually move to two sides, so that the inner bubbles are promoted to be discharged more quickly.

The length and width of the 0.2T glass substrate are both 5mm smaller than the 0.5T glass support layer. The edge shape is embodied, the 0.2T glass substrate is 2.5mm smaller than the 0.5T glass supporting layer, so that the 0.5T glass supporting layer can protect the 0.2T glass substrate, the damage of 0.2T thin glass is avoided to the greatest extent, and the yield is improved. The properties of the intermediate layer are shown in table 1.

A stripping procedure: the vacuum stage is used for fixing the display device with the 0.5T glass supporting layer, the vacuum chuck is used for sucking the upper 0.5T glass supporting layer to be peeled, and the peeling is started from one side until the 0.5T glass supporting layer is completely peeled. At the start of the peeling, a slit can be cut on one side by means of a specially made thin blade to facilitate the directional peeling. At a peel rate of 20mm/min, the peel force was 30N/m.

A cleaning procedure: after the peeling, the liquid silicone rubber remaining on the surface of the 0.2T glass substrate constituting the display device was cleaned by a combination of methods such as air knife, ultrasonic cleaning, organic solvent cleaning, and pure water rinsing. And after cleaning, the functional device made of the glass substrate enters the next procedure.

And (3) recycling: and cleaning the residual liquid silicone rubber on the surface of the 0.5T glass supporting layer by using an air knife, ultrasonic cleaning, organic solvent cleaning and pure water washing. After the cleaning, the adhesive tape can be repeatedly utilized and attached again. The recycling of the 0.5T glass supporting layer can reduce the production cost, save energy, reduce consumption and protect the environment.

And (3) recycling: the liquid silicon rubber is collected and can be reused after purification, so that the cost is further reduced, the resources are saved, and the environment is protected.

TABLE 1

Although the embodiments of the present invention have been described in detail with reference to the accompanying drawings, the embodiments of the present invention are not limited to the details of the above embodiments, and various simple modifications can be made to the technical solutions of the embodiments of the present invention within the technical idea of the embodiments of the present invention, and the simple modifications all belong to the protection scope of the embodiments of the present invention.

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, the embodiments of the present invention do not describe every possible combination.

In addition, any combination of various different implementation manners of the embodiments of the present invention is also possible, and the embodiments of the present invention should be considered as disclosed in the embodiments of the present invention as long as the combination does not depart from the spirit of the embodiments of the present invention.

Claims

1. The composite glass plate comprises a glass substrate, a supporting layer and an intermediate layer positioned between the glass substrate and the supporting layer, and is characterized in that the intermediate layer is in a liquid state and contains one or more of fluorine oil, silicone oil, ionic liquid, liquid resin and liquid silicone rubber.

2. Composite glass pane according to claim 1, wherein the peel force of the composite glass pane is less than 100N/m, preferably less than 50N/m.

3. The composite glass sheet of claim 1, wherein the fluorine oil is selected from one or more of a perfluorocarbon oil, a chlorofluorocarbon oil, and a perfluoroether oil;

preferably, the silicone oil is selected from one or more of methyl silicone oil, phenyl silicone oil and aryl silicone oil;

preferably, the ionic liquid is selected from one or more of imidazole compounds, pyrrole compounds, pyridine compounds, piperidine compounds and quaternary ammonium salt ionic liquid;

preferably, the liquid resin is a rosin resin;

4. A composite glass sheet according to any of claims 1 to 3, wherein the interlayer withstands temperatures greater than 270 ℃, preferably greater than 360 ℃;

preferably, the viscosity of the intermediate layer is 0.1 to 20000cps at 25 ℃;

preferably, the interlayer has a water content of less than 200 ppm;

preferably, the intermediate layer has a visible light transmittance of greater than 85% at 25-450 ℃;

preferably, the refractive index of the intermediate layer is 1.2 to 1.8;

preferably, the thickness of the intermediate layer is 0.001 to 100 μm.

5. The composite glass sheet according to claim 1, wherein the glass substrate has a thickness of 0.25mm or less;

preferably, the support layer is made of one or more materials selected from glass, metal, organic polymer material, carbon fiber composite material and graphene composite material;

preferably, the thickness of the support layer is 0.2-1.1 mm;

preferably, the young's modulus of the support layer is greater than 65 GPa.

6. The composite glass sheet of claim 5, wherein the support layer is glass,

the glass contains 66 to 73mol percent of SiO calculated by oxide based on the total mole number of all components of the glass₂11-15 mol% of Al₂O₃0-11 mol% of B₂O₃1-10 mol% of MgO, 2-10 mol% of CaO, 0-6 mol% of SrO, 0-10 mol% of BaO, 0-2 mol% of ZnO and 0-0.7 mol% of Re₂O₃And less than 0.05 mol% of R₂And O, wherein Re is a rare earth element, and R is an alkali metal.

7. The composite glass sheet of claim 5, wherein the support layer is a glass comprising 60-74 mol% SiO, calculated as the oxide, based on the total moles of the glass components₂8-18 mol% of Al₂O₃1-15 mol% of B₂O₃+P₂O₅4-15 mol% of Na₂O, 0-10 mol% of Li₂O, 0-10 mol% of K₂O, 0.5-10 mol% MgO + TiO₂0 to 4mol percent of ZnO and 0 to 4wt percent of Y₂O₃+La₂O₃+Nd₂O₃。

8. Composite glass sheet according to any one of claims 5 to 7, wherein the length and width of the composite glass sheet are greater than 300mm, preferably greater than 1000 mm;

preferably, the length of the glass substrate is less than or equal to that of the support layer;

9. The composite glass sheet of claim 8, wherein the length of the glass substrate is 0.05-20mm less than the length of the support layer;

10. A method of making a composite glass sheet according to any of claims 1 to 9, comprising the steps of:

2) and attaching the supporting layer to the glass substrate.

11. The production method according to claim 10, wherein the method is carried out under heating;

preferably, the heating temperature is 50-360 ℃.

12. Use of a composite glass sheet according to any one of claims 1 to 9 for the preparation of a flat/flexible display substrate and/or carrier sheet.