Super-flexible and ultrathin hybrid glass and low-temperature large-area preparation method thereof

Abstract

The invention belongs to the field of advanced materials, and particularly relates to super-flexible and ultrathin hybrid glass and a low-temperature large-area preparation method thereof, and the hybrid glass comprises the following raw materials: oligomeric silsesquioxane, inorganic nanoparticles and a high-molecular polymer porous film. The ultra-flexible and ultra-thin hybrid glass prepared by the invention can be processed and formed at room temperature or lower temperature, compared with the existing commercial ultra-thin glass, the flexibility of the ultra-thin hybrid glass is remarkably improved, the ultra-thin hybrid glass is thinner, the problem that the traditional glass is fragile and the technical challenge in a thinning process are overcome, and the ultra-flexible and ultra-thin hybrid glass has good application prospects. The electronic equipment can be lightened and thinned, and the service life of the electronic equipment can be prolonged.

Description

Technical Field

[0001] The present invention belongs to the field of advanced materials, and in particular relates to an ultra-flexible and ultra-thin hybrid glass and a low-temperature large-area preparation method thereof. Background Art

[0002] In recent years, electronic devices are gradually developing from fixed to bendable, rollable and foldable, which puts forward new requirements for the cover materials of display devices. The ideal cover material needs to have not only high transparency and scratch resistance like glass, but also flexibility like polymer film. At present, there are two main mainstream solutions: one is to use ultra-thin glass (UTG), the preparation method of which is usually to thin silicate glass to 50μm or even 30μm by high-temperature melting and stretching, thereby giving it bending properties; the other is to coat hard coatings on the surface of polymer films such as transparent polyimide (CPI) and polyethylene terephthalate (PET) to enhance their scratch resistance. However, polymer films perform poorly in creep resistance and are prone to wrinkles and creases, which seriously affect the display effect, high-grade feel and reliability of the device during use. Therefore, UTG has gradually become the mainstream choice for current flexible cover solutions.

[0003] Currently, commercial ultra-thin glass is mainly produced by melting inorganic glass (such as soda-lime-silicon, borosilicate, aluminosilicate and lithium aluminosilicate glass) at a temperature above 1000°C and thinning it into a shape. Although these materials have excellent transparency, hardness and bendability, their application still faces the following major problems: (1) large thickness and high density. The thickness of existing commercial ultra-thin glass is usually more than 30 μm and the density is greater than 2.2 g / cm 3 , which limits the lightweight design of terminal products; (2) It is brittle and has poor flexibility. The elongation at break of existing commercial ultra-thin glass is less than 0.5%, the elastic recovery is only 60%, and it is fragile. In addition, its large thickness leads to a large bending radius, which restricts the bending performance and reliability of terminal products; (3) The processing temperature is high and the energy consumption is high. Existing commercial ultra-thin glass needs to be melted at a high temperature of more than 1000℃ for subsequent processing. This high-energy consumption process is inconsistent with the concept of low-carbon economic development.

[0004] Therefore, how to develop new solutions to prepare more flexible and thinner ultra-thin glass at low temperatures is an urgent problem that needs to be solved. Summary of the invention

[0005] In order to solve the above problems, the present invention provides an ultra-flexible and ultra-thin hybrid glass, wherein the raw materials of the hybrid glass include oligomeric silsesquioxane, inorganic nanoparticles and a high molecular polymer porous film.

[0006] In some embodiments, the oligomeric silsesquioxane, inorganic nanoparticles and high molecular weight polymer porous film are cross-linked and cured to form an organic-inorganic hybrid cross-linked network.

[0007] In some embodiments, the cross-linking and curing includes cross-linking and curing inside the high molecular polymer porous film.

[0008] In some embodiments, the raw materials of the hybrid glass further include an initiator.

[0009] In some embodiments, the mass ratio of oligomeric silsesquioxane to inorganic nanoparticles is 5-90:10-80, preferably 20-75:25-80.

[0010] In some embodiments, the oligomeric silsesquioxane includes at least one of a random oligomeric silsesquioxane, a ladder oligomeric silsesquioxane, or a cage oligomeric silsesquioxane.

[0011] In some embodiments, the three-dimensional topological structure formulas of the random oligomeric silsesquioxane, ladder oligomeric silsesquioxane and cage oligomeric silsesquioxane are shown in Formula I, Formula II and Formula III, respectively:

[0012]

[0013] In the above formula, R are each the same or different and are selected from (When R is all of this structure, the corresponding compound is of formula I-1, II-1 or III-1), (When R is all of this structure, the corresponding compound is of formula I-2, II-2 or III-2), (When R is all of this structure, the corresponding compound is of formula I-3, II-3 or III-3), (When R is all of this structure, the corresponding compound is of formula I-4, II-4 or III-4), (When R is all of this structure, the corresponding compound is of formula I-5, II-5 or III-5), (When R is all of this structure, the corresponding compound is of formula I-6, II-6 or III-6), (When R is all of this structure, the corresponding compound is of formula I-7, II-7 or III-7), (When R is all of this structure, the corresponding compound is of formula I-8, II-8 or III-8), (When R is all of this structure, the corresponding compound is of formula I-9, II-9 or III-9), (When R is all of this structure, the corresponding compound is of formula I-10, II-10 or III-10), (When R is all of this structure, the corresponding compound is of formula I-11, II-11 or III-11), (When R is all of this structure, the corresponding compound is of formula I-12, II-12 or III-12), (When R is all of this structure, the corresponding compound is formula I-13, II-13 or III-13) or (When R are all of this structure, the corresponding compound is Formula I-4, II-4 or III-4), wherein R1 are each the same or different and are selected from

[0014] In some embodiments, the inorganic nanoparticles include at least one of silica particles, titania particles, zirconium oxide particles, calcium carbonate particles, or zinc oxide particles.

[0015] In some embodiments, the inorganic nanoparticles are silica particles.

[0016] In some embodiments, the inorganic nanoparticles have a size of 1 to 1000 nm.

[0017] In a preferred embodiment, the size of the inorganic nanoparticles is 20 to 500 nm, more preferably 10 to 50 nm.

[0018] In some embodiments, the high molecular polymer porous film includes at least one of polyethylene, polypropylene, nylon, polyurethane, polytetrafluoroethylene or polyvinylidene fluoride porous films.

[0019] In some embodiments, the porosity of the high molecular polymer porous film is greater than 10%.

[0020] In a preferred embodiment, the porosity of the high molecular polymer porous film is 20 to 90%, and more preferably 50 to 80%.

[0021] In some embodiments, the thickness of the high molecular polymer porous film is 20 nm to 100 μm.

[0022] In a preferred embodiment, the thickness of the high molecular polymer porous film is 0.5 μm to 50 μm, and more preferably 3 μm to 20 μm.

[0023] In some embodiments, the initiator is at least one of a thermal initiator, triethylamine, a platinum catalyst, or a photoinitiator.

[0024] In some embodiments, the thermal initiator includes azobisisobutyronitrile, azobisisobutyramidine hydrochloride, or azobisisopropylimidazoline hydrochloride.

[0025] In some embodiments, the photoinitiator includes 2-hydroxy-2-methylphenylpropanone, 1-hydroxycyclohexylphenylketone, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone, benzoin dimethyl ether, triphenylsulfonium hexafluoroantimonate, or 2,2-diethoxyacetophenone.

[0026] In a preferred embodiment, the initiator is triphenylsulfonium hexafluoroantimonate.

[0027] In some embodiments, the ultra-flexible, ultra-thin hybrid glass has a thickness of 0.8-50 μm.

[0028] In some embodiments, the ultra-flexible, ultra-thin hybrid glass also has a light transmittance greater than 90%.

[0029] The present invention also provides a method for preparing the ultra-flexible and ultra-thin hybrid glass as described herein, the method comprising the following steps:

[0030] (a) mixing oligomeric silsesquioxane and inorganic nanoparticles in a solvent, and removing the solvent to obtain an oligomeric silsesquioxane slurry containing inorganic nanoparticles;

[0031] (b) coating the inorganic nanoparticle-containing oligomeric silsesquioxane slurry obtained in step (a) on a polymer porous film, allowing the slurry to fully enter the polymer porous film and expel air, thereby obtaining a polymer porous film composited with inorganic nanoparticles and oligomeric silsesquioxane;

[0032] (c) curing the porous polymer film composited with inorganic nanoparticles and oligomeric silsesquioxane obtained in step (b) to obtain an ultra-flexible and ultra-thin hybrid glass;

[0033] Furthermore, the mass fraction of the oligomeric silsesquioxane in the hybrid glass raw material is greater than 5%; preferably, the mass fraction of the oligomeric silsesquioxane in the hybrid glass raw material is greater than 50%; more preferably, it is 60-70%.

[0034] In some embodiments, the mass fraction of the inorganic nanoparticles in the hybrid glass raw material is 5-80%; preferably, the mass fraction of the inorganic nanoparticles in the hybrid glass raw material is above 10%; more preferably, it is 20%-40%.

[0035] In some embodiments, the mass ratio of the oligomeric silsesquioxane to the inorganic nanoparticles is 5-90:10-80, preferably 20-75:25-80.

[0036] In some embodiments, the method further comprises, in step (a), adding an initiator to the solvent and mixing the mixture thoroughly.

[0037] In some embodiments, the mass fraction of the initiator in the hybrid glass raw material is 0.01-5%; preferably, the mass fraction of the initiator in the hybrid glass raw material is 0.5-3%; more preferably, 1-2%.

[0038] In some embodiments, the solvent includes at least one of the following: dichloromethane, chloroform, toluene, xylene, ether, tetrahydrofuran, acetone, methyl ethyl ketone, ethyl acetate, butyl acetate, N,N-dimethylformamide, N,N-dimethylacetamide, acetonitrile, benzonitrile, methanol or ethanol.

[0039] In some embodiments, the coating is performed by roller coating.

[0040] In some embodiments, the curing comprises light curing or heat curing.

[0041] In some embodiments, the thickness of the prepared ultra-flexible and ultra-thin hybrid glass can be controlled by controlling the mass ratio of the oligomeric silsesquioxane slurry containing inorganic nanoparticles and the high molecular weight polymer porous film and the pressure of the roller coating.

[0042] In some embodiments, the thickness of the prepared ultra-flexible, ultra-thin hybrid glass is 0.8-50 μm.

[0043] The ultra-flexible and ultra-thin hybrid glass prepared by the present invention can be processed and formed at room temperature or lower temperature, with a thickness of 0.8 to 50 μm, an elongation at break of 0.8 to 10%, a bending radius of curvature as low as 0.3 to 0.5 mm, a light transmittance of 92%, a hardness of 1.1 to 5 GPa, and a modulus of 5 to 30 GPa. Compared with existing commercial ultra-thin glass, the flexibility of this ultra-thin hybrid glass has been significantly improved, and a thinner thickness has been achieved, overcoming the problem of the fragility of traditional glass and the technical challenges in the thinning process, which is conducive to the thinning of electronic devices and extending the service life of electronic devices.

[0044] Compared with the prior art, the present invention has the following beneficial effects:

[0045] 1. The present invention uses a polymer porous film as a support carrier, and composites a slurry composed of oligomeric silsesquioxane and inorganic nanoparticles with it to form an interconnected network, which is cross-linked and cured to form a mechanically interlocked organic-inorganic hybrid cross-linked material - ultra-thin hybrid glass. Among them, oligomeric silsesquioxane and inorganic nanoparticles provide high hardness after cross-linking, and the polymer micro-nano film provides flexibility, so that the cured ultra-thin hybrid glass has the hardness of inorganic glass and the flexibility of polymer.

[0046] 2. Since the transmittance, hardness and function of the material can be regulated by regulating the types and relative proportions of oligomeric silsesquioxane and nanoparticles, the flexible ultra-thin hybrid glass involved in the present invention not only has high transparency, but also has the advantages of adjustable mechanical properties and functionality.

[0047] 3. The thickness of existing ultra-thin glass is greater than 30μm, and it is still a challenge to achieve large-area preparation of thinner ultra-thin glass. Since polymer micro-nano porous membranes can be processed over a large area, and the thickness and porosity can be adjusted, the ultra-thin hybrid glass of the present invention can be prepared over a wide range and over a large area within a thickness range of 20nm to 100μm.

[0048] 4. The processing of existing ultra-thin glass requires melting the glass at a high temperature of more than 1000°C and then thinning it into shape. The ultra-thin hybrid glass involved in the present invention can be processed and formed at room temperature or a lower temperature below 100°C, and has the advantage of low energy consumption.

[0049] In summary, the present invention provides a simple and efficient low-temperature, large-area preparation method for ultra-flexible, ultra-thin hybrid glass. The flexibility and thickness far exceed those of existing commercial ultra-thin glass, overcoming the brittle characteristics of traditional glass and the challenges of thinning process, and can provide strong support for the development of the field of flexible electronics. BRIEF DESCRIPTION OF THE DRAWINGS

[0050] Figure 1 The schematic diagram of the process of preparing ultra-flexible and ultra-thin hybrid glass of the present invention is shown; first, the inorganic nanoparticles and oligomeric silsesquioxane are evenly mixed and an initiator is added, and then the polysilsesquioxane monomer containing the inorganic nanoparticles is roll-coated and infiltrated to allow it to fully enter the porous film of the high molecular polymer, and then the target material, i.e., ultra-flexible and ultra-thin hybrid glass, is obtained by curing.

[0051] Figure 2 The continuous bending test results of the commercially purchased ultra-thin glass of Comparative Example 1 of the present invention and the ultra-flexible, ultra-thin hybrid glass prepared in Example 2 are shown.

[0052] Figure 3 The falling ball impact resistance test results of the commercially purchased ultra-thin glass of Comparative Example 1 of the present invention and the ultra-flexible, ultra-thin hybrid glass prepared in Example 2 are shown. DETAILED DESCRIPTION

[0053] The present invention is further described below with reference to specific examples, but the examples do not limit the present invention in any form. Unless otherwise specified, the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in the art.

[0054] Example 1

[0055] (1) By mass, 3-(2,3-epoxypropyloxy)propyl cage oligomeric silsesquioxane (the structural formula of which is shown in Formula III-1, 99 parts) and an initiator (triphenylsulfonium hexafluoroantimonate, 1 part) were mixed uniformly to form a transparent and viscous slurry A;

[0056] (2) Slurry A was roll-coated on a polyethylene porous film (3 μm thick, 70% porosity) to allow it to fully penetrate into the polyethylene porous film and exclude air. After UV (365 nm) curing for 3 minutes, the target material was obtained.

[0057] Example 2

[0058] (1) Add 3-(2,3-epoxypropoxy)propyl cage oligomeric silsesquioxane (75 parts, with a structural formula as shown in Formula III-1) and nano-silica (25 parts, with a particle size of ∼20 nm) to ethanol (20 mL) by mass, mix them evenly under high-speed stirring, and then remove the ethanol to obtain a transparent and viscous slurry A;

[0059] (2) Slurry A (99 parts) and initiator (triphenylsulfonium hexafluoroantimonate, 1 part) were mixed uniformly to form a transparent and viscous slurry B;

[0060] (3) Slurry B was roller-coated on a polyethylene porous film (3 μm thick, 70% porosity) to allow it to fully penetrate into the polyethylene porous film and exclude air. After UV (365 nm) curing for 3 minutes, the target material was obtained.

[0061] Example 3

[0062] The difference from Example 2 is that:

[0063] In step 1, the number of portions of the nano-silicon dioxide is replaced with 50 portions.

[0064] Example 4

[0065] The difference from Example 2 is that:

[0066] In step 1, the number of parts of the nano-silicon dioxide is replaced with 80 parts.

[0067] Example 5

[0068] The difference from Example 2 is that:

[0069] In step 1, the particle size of the nano-silica is replaced to ˜100 nm.

[0070] Example 6

[0071] The difference from Example 2 is that:

[0072] In step 1, the particle size of the nano-silica is replaced to 200 nm.

[0073] Example 7

[0074] The difference from Example 2 is that:

[0075] In step 1, the particle size of the nano-silica is replaced to 500 nm.

[0076] Example 8

[0077] The difference from Example 2 is that:

[0078] In step 1, the 3-(2,3-epoxypropoxy)propyl cage oligomeric silsesquioxane is replaced with 3-(2,3-epoxypropoxy)propyl ladder oligomeric silsesquioxane (the structural formula of which is shown in Formula II-1).

[0079] Example 9

[0080] The difference from Example 2 is that:

[0081] In step 1, the 3-(2,3-epoxypropoxy)propyl cage oligomeric silsesquioxane is replaced with 3-(2,3-epoxypropoxy)propyl random oligomeric silsesquioxane (the structural formula of which is shown in Formula I-1).

[0082] Example 10

[0083] The difference from Example 2 is that:

[0084] In step 1, the 3-(2,3-epoxypropyloxy)propyl cage oligomeric silsesquioxane is replaced with 2-(3,4-epoxycyclohexyl)ethyl cage oligomeric silsesquioxane (the structural formula is shown in Formula III-2).

[0085] Embodiment 11

[0086] The difference from Example 2 is that:

[0087] In step 3, the thickness of the polyethylene porous film is replaced with 0.5 μm.

[0088] Example 12

[0089] The difference from Example 2 is that:

[0090] In step 3, the thickness of the polyethylene porous film is replaced with 20 μm.

[0091] Embodiment 13

[0092] The difference from Example 2 is that:

[0093] In step 3, the thickness of the polyethylene porous film is replaced with 45 μm.

[0094] Embodiment 14

[0095] The difference from Example 2 is that:

[0096] In step 3, the thickness of the polyethylene porous film is replaced with 95 μm.

[0097] Embodiment 15

[0098] The difference from Example 2 is that:

[0099] In step 3, the polyethylene porous film is replaced with a polypropylene porous film.

[0100] Example 16

[0101] The difference from Example 2 is that:

[0102] In step 3, the polyethylene porous film is replaced with a nylon porous film.

[0103] Embodiment 17

[0104] The difference from Example 2 is that:

[0105] In step 3, the polyethylene porous film is replaced with a polyurethane porous film.

[0106] Embodiment 18

[0107] The difference from Example 2 is that:

[0108] In step 3, the polyethylene porous film is replaced with a polymethyl methacrylate porous film.

[0109] Embodiment 19

[0110] (1) Add 3-(methacryloyloxy)propyl cage-shaped oligomeric silsesquioxane (75 parts, with a structural formula as shown in Formula III-3) and nano-silica (25 parts, with a particle size of ˜20 nm) to ethanol (20 mL) by mass, mix them evenly under high-speed stirring, and then remove the ethanol to obtain a transparent and viscous slurry A;

[0111] (2) Slurry A (99 parts) and initiator (phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, 1 part) were mixed uniformly to form a transparent and viscous slurry B;

[0112] (3) Slurry B was roller-coated on a polyethylene porous film (3 μm thick, 70% porosity) to allow it to fully penetrate into the polyethylene porous film and exclude air. After UV curing (365 nm) for 5 minutes in a nitrogen atmosphere, the target material was obtained.

[0113] Embodiment 20

[0114] The difference from Example 19 is:

[0115] In step 1, the 3-(methacryloyloxy)propyl cage oligomeric silsesquioxane is replaced with 3-(acryloyloxy)propyl cage oligomeric silsesquioxane (the structural formula of which is shown in Formula III-4).

[0116] Embodiment 21

[0117] The difference from Example 19 is:

[0118] In step 1, the nano-silicon dioxide is replaced by nano-titanium dioxide (particle size ˜20 nm).

[0119] Embodiment 22

[0120] The difference from Example 19 is:

[0121] In step 1, the nano-silicon dioxide is replaced with nano-zirconium oxide (particle size ˜20 nm).

[0122] Embodiment 23

[0123] The difference from Example 19 is:

[0124] In step 1, the nano-silicon dioxide is replaced by nano-calcium carbonate (particle size ˜20 nm).

[0125] Embodiment 24

[0126] The difference from Example 19 is:

[0127] In step 1, the nano silicon dioxide is replaced by nano zinc oxide (particle size ˜20 nm).

[0128] Embodiment 25

[0129] (1) Adding vinyl ladder oligomeric silsesquioxane (50 parts by mass, with a structural formula as shown in Formula II-5) and hydrogen-containing ladder oligomeric silsesquioxane (50 parts by mass, with a structural formula as shown in Formula II-6) to toluene (20 mL) for dissolution, and then removing toluene to obtain a transparent and viscous slurry A;

[0130] (2) Slurry A (75 parts) and nano-silicon dioxide (25 parts, particle size ˜20 nm) were added to ethanol (20 mL), mixed evenly under high-speed stirring, and then the ethanol was removed to obtain a transparent and viscous slurry B;

[0131] (3) Slurry B (99.99 parts) and initiator (platinum catalyst, 0.01 parts) were mixed uniformly to form a transparent and viscous slurry C;

[0132] (4) Slurry C is coated on a polytetrafluoroethylene porous film (thickness 3 μm, porosity 70%) with a roller, and the slurry is fully penetrated into the polyethylene porous film and the air is expelled. After curing at 80° C. for 120 minutes under a nitrogen atmosphere, the target material is obtained.

[0133] Embodiment 26

[0134] (1) By mass, 3-(2,3-epoxypropoxy)propyl cage oligomeric silsesquioxane (40 parts, the structural formula of which is shown in formula III-1), 3-mercaptopropyl cage oligomeric silsesquioxane (35 parts, the structural formula of which is shown in formula III-7) and nano-silica (25 parts, particle size of which is ˜20 nm) are added to ethanol (20 mL), mixed evenly under high-speed stirring, and then the ethanol is removed to obtain a transparent and viscous slurry A;

[0135] (2) Slurry A (99.5 parts) and initiator (triethylamine, 0.5 parts) were cooled to 0°C and mixed to form a transparent and viscous slurry B;

[0136] (3) Slurry B is coated on a polyethylene porous film (3 μm thick, 70% porosity) by a roller, and the slurry is fully absorbed into the polyethylene porous film and the air is expelled. After curing at 50° C. for 120 minutes, the target material is obtained.

[0137] Embodiment 27

[0138] The difference from Example 27 is:

[0139] In step 1, the 3-mercaptopropyl cage-type oligomeric silsesquioxane is replaced with 3-aminopropyl cage-type oligomeric silsesquioxane (structural formula shown in III-8).

[0140] Embodiment 28

[0141] (1) Adding alkoxy cage oligomeric silsesquioxane (75 parts, with a structural formula as shown in Formula III-9) and nano-silica (25 parts, with a particle size of ˜20 nm) to toluene (20 mL) by mass, mixing the mixture evenly under high-speed stirring, and then removing the toluene to obtain a transparent and viscous slurry A;

[0142] (2) Slurry A is roller-coated on a polyvinylidene fluoride porous film (8 μm thick, 70% porosity) to allow it to fully penetrate into the polyvinylidene fluoride porous film. After curing at 85° C. for 120 minutes in an environment with a humidity of 85%, the target material is obtained.

[0143] Embodiment 29

[0144] The difference from Example 28 is that:

[0145] In step 1, the structural formula of the alkoxy cage oligomeric silsesquioxane is replaced from formula III-9 to formula III-10.

[0146] Embodiment 30

[0147] (1) By mass, alkoxy cage oligomeric silsesquioxane (40 parts, the structural formula of which is shown in Formula III-9), trifluoropropyl cage oligomeric silsesquioxane (35 parts, the structural formula of which is shown in Formula III-11) and nano-silica (25 parts, particle size ˜20 nm) are added to toluene (20 mL), mixed evenly under high-speed stirring, and then toluene is removed to obtain a transparent viscous slurry A;

[0148] (2) Slurry A is roller-coated on a polytetrafluoroethylene porous film (thickness 8 μm, porosity 60%) to allow it to fully penetrate into the polyvinylidene fluoride porous film. After curing at 85° C. for 120 minutes in an environment with a humidity of 85%, the target material is obtained.

[0149] Embodiment 31

[0150] The difference from Example 30 is:

[0151] In step 1, the trifluoropropyl cage-shaped oligomeric silsesquioxane is replaced with 1H,1H,2H,2H-perfluorohexyl cage-shaped oligomeric silsesquioxane (structural formula shown in III-12).

[0152] Embodiment 32

[0153] The difference from Example 30 is:

[0154] In step 1, the trifluoropropyl cage-shaped oligomeric silsesquioxane is replaced with 1H,1H,2H,2H-perfluorooctyl cage-shaped oligomeric silsesquioxane (structural formula shown in III-13).

[0155] Embodiment 33

[0156] The difference from Example 30 is:

[0157] In step 1, the trifluoropropyl cage-shaped oligomeric silsesquioxane is replaced with 1H,1H,2H,2H-perfluorodecyl cage-shaped oligomeric silsesquioxane (structural formula shown in III-14).

[0158] Comparative Example 1

[0159] The commercially available ultra-thin glass has a thickness of 30 μm.

[0160] Test Case

[0161] The hybrid glasses prepared in Examples 1-33 and the ultra-thin glass of Comparative Example 1 were tested for performance. The specific performance testing method is as follows:

[0162] (1) Thickness test

[0163] The thickness characterization was performed using the Dektak XT step profiler from Bruker, USA.

[0164] (2) Transmittance test

[0165] The transmittance characterization was tested by the UV-3600 UV-visible light tester produced by Shimadzu Corporation of Japan.

[0166] (3) Hardness test

[0167] The hardness characterization was carried out by using the TI 980 nanoindenter from Bruker, USA.

[0168] (4) Modulus test

[0169] The modulus characterization comes from the tensile test, and the tensile stress-strain curve is tested by an EM6.501-W tensile testing machine from Tesmart, Shenzhen, China.

[0170] (5) Elongation at break test

[0171] The elongation at break was characterized from the tensile test, and the tensile stress-strain curve was tested by an EM6.501-W tensile testing machine from Tesmart, Shenzhen, China.

[0172] (6) Dynamic bending performance test

[0173] The continuous bending experiment was tested by the KZ-FD2 small unidirectional folding cycle tester produced by China Kezhizhu Company.

[0174] (7) Minimum bending radius

[0175] The minimum bending radius of curvature is obtained by testing in continuous bending experiments.

[0176] (8) Drop ball impact test

[0177] The drop ball impact test is tested by adjusting the drop height of a 50g stainless steel ball.

[0178] (9) Water contact angle test

[0179] The water contact angle was tested by DSA25 equipment from KRUSS, Germany.

[0180] Among them, the ultra-flexible, ultra-thin hybrid glass prepared in Example 2 was compared with the commercially purchased ultra-thin glass of Comparative Example 1 in the continuous bending test and the falling ball impact test. The commercially purchased ultra-thin glass showed reliable bending stability at a bending radius of 1.5 mm, but under more stringent bending conditions (when the bending radius of curvature was less than 1 mm), the ultra-thin glass broke after only one bending. At the same time, due to the brittleness of the glass itself and the residual compressive stress inside the glass during the high-temperature processing process, the ultra-thin glass is very likely to shatter when impacted. The specific results are as follows: Figure 2 and Figure 3 As shown, Figure 2 In the comparative example 1, the commercially purchased ultra-thin glass was continuously bent at a bending radius of 0.5 mm, and it broke after only one bending; the ultra-flexible and ultra-thin hybrid glass prepared in Example 2 was bent continuously for 500,000 times under the same bending conditions, and the surface of the material remained intact without any breakage or creases, indicating that the ultra-flexible and ultra-thin hybrid glass described in the present invention has excellent flexibility, which is far superior to the existing commercial ultra-thin glass. Figure 3 In the experiment, the commercially purchased ultra-thin glass of Comparative Example 1 was broken at a falling ball impact height of 14 cm, wherein the mass of the falling ball was 50 g; in the same falling ball impact experiment, the ultra-flexible and ultra-thin hybrid glass prepared in Example 2 was subjected to a falling ball impact height of 150 cm, and only slight dents appeared on the surface of the material without any breakage, indicating that the ultra-flexible and ultra-thin hybrid glass of the present invention has excellent toughness, which is far superior to the existing commercial ultra-thin glass.

[0181] The results of the performance tests on the hybrid glasses prepared in Examples 1-33 are detailed in Table 1 below.

[0182] Table 1: Performance test results of ultra-flexible and ultra-thin hybrid glass

[0183]

[0184]

[0185]

[0186]

[0187] According to the performance test results of the ultra-flexible and ultra-thin hybrid glass of Examples 1 to 33 in Table 1, the present invention uses oligomeric silsesquioxane and inorganic nanoparticles to form a transparent slurry, which is then poured into the interior of a polymer porous film. After solidification, a mechanically interlocked organic-inorganic hybrid cross-linked network is formed, so that the prepared hybrid glass is not only transparent and has high hardness, but also has excellent flexibility and hydrophobicity. The reason is that, first, the slurry composed of oligomeric silsesquioxane and inorganic nanoparticles contains both organic material components and inorganic material components, and can form a nanoscale organic-inorganic hybrid network after solidification, which has excellent transparency, hardness and modulus; second, through the adjustment of the formula, the refractive index of the slurry composed of oligomeric silsesquioxane and inorganic nanoparticles can be made equivalent to that of a polymer porous film, thereby avoiding the scattering of visible light by the polymer porous film, so that the composite hybrid glass has high transparency; third, the polymer porous film has It has excellent flexibility and good mechanical strength, can dissipate the energy of the material when it is bent or impacted, avoid stress concentration, and thus show excellent bending and impact resistance; Fourth, since the thickness and porosity of the polymer micro-nano ultra-thin film are easy to control and convenient for large-area preparation, the mechanical properties, thickness and width of the ultra-thin hybrid glass involved in the present invention can be prepared as needed; Fifth, since the types of oligomeric silsesquioxanes are diverse and the surface functional groups are adjustable, the surface hydrophilicity and hydrophobicity of the ultra-thin hybrid glass involved in the present invention can be adjusted within a certain range.

[0188] It should be noted that the preferred embodiments of the present invention are given in the specification and drawings of the present invention. However, the present invention can be implemented in many different forms and is not limited to the embodiments described in this specification. These embodiments are not used as additional limitations on the content of the present invention. The purpose of providing these embodiments is to make the understanding of the disclosure of the present invention more thorough and comprehensive. In addition, the above-mentioned technical features continue to be combined with each other to form various embodiments not listed above, which are all regarded as the scope of the present invention; further, for ordinary technicians in this field, they can be improved or transformed according to the above description, and all these improvements and transformations should belong to the protection scope of the claims attached to the present invention.

Claims

1. An ultra-flexible, ultra-thin hybrid glass, characterized in that: The raw materials of the hybrid glass include oligomeric silsesquioxane, inorganic nanoparticles and high molecular polymer porous film.

2. The hybrid glass according to claim 1, characterized in that: The oligomeric silsesquioxane, inorganic nanoparticles and high molecular polymer porous film are cross-linked and cured to form an organic-inorganic hybrid cross-linked network; Furthermore, the cross-linking and curing includes cross-linking and curing inside the high molecular polymer porous film.

3. The hybrid glass according to claim 1 or 2, characterized in that: The raw materials of the hybrid glass also include an initiator.

4. The hybrid glass according to claim 1 or 2, characterized in that: The mass ratio of the oligomeric silsesquioxane to the inorganic nanoparticles is 5-90:10-80, preferably 20-75:25-80.

5. Hybrid glass according to any one of the preceding claims, characterized in that The oligomeric silsesquioxane includes at least one of a random oligomeric silsesquioxane, a ladder oligomeric silsesquioxane, or a cage oligomeric silsesquioxane.

6. The hybrid glass according to claim 5, characterized in that: The three-dimensional topological structure general formulas of the random oligomeric silsesquioxane, ladder oligomeric silsesquioxane and cage oligomeric silsesquioxane are shown in Formula I, Formula II and Formula III respectively: In the above formula, R are each the same or different and are selected from Wherein, R1 are each the same or different and are selected from 7. Hybrid glass according to any one of the preceding claims, characterized in that The inorganic nanoparticles include at least one of silicon dioxide particles, titanium dioxide particles, zirconium oxide particles, calcium carbonate particles or zinc oxide particles; Furthermore, the inorganic nanoparticles are silicon dioxide particles; Furthermore, the size of the inorganic nanoparticles is 1 to 1000 nm; Preferably, the size of the inorganic nanoparticles is 20 to 500 nm; more preferably, 10 to 50 nm.

8. Hybrid glass according to any one of the preceding claims, characterized in that The high molecular polymer porous film includes at least one of polyethylene, polypropylene, nylon, polyurethane, polytetrafluoroethylene or polyvinylidene fluoride porous films; Furthermore, the porosity of the polymer porous film is greater than 10%; Preferably, the porosity of the polymer porous film is 20 to 90%; more preferably 50 to 80%; Furthermore, the thickness of the high molecular polymer porous film is 20nm to 100μm; Preferably, the thickness of the high molecular polymer porous film is 0.5 μm to 50 μm; more preferably 3 μm to 20 μm; Furthermore, the thickness of the hybrid glass is 0.8-50 μm; Further, the initiator is at least one of a thermal initiator, triethylamine, a platinum catalyst or a photoinitiator; Further, the thermal initiator includes azobisisobutyronitrile, azobisisobutyramidine hydrochloride or azobisisopropylimidazoline hydrochloride; Further, the photoinitiator includes 2-hydroxy-2-methylphenylacetone, 1-hydroxycyclohexylphenyl ketone, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone, benzoin dimethyl ether, triphenylsulfonium hexafluoroantimonate or 2,2-diethoxyacetophenone; Preferably, the initiator is triphenylsulfonium hexafluoroantimonate.

9. Hybrid glass according to any one of the preceding claims, characterized in that The ultra-flexible, ultra-thin hybrid glass also has a light transmittance greater than 90%.

10. The method for preparing the ultra-flexible and ultra-thin hybrid glass according to any one of claims 1 to 9, characterized in that: The method comprises the following steps: (a) mixing oligomeric silsesquioxane and inorganic nanoparticles in a solvent, and removing the solvent to obtain an oligomeric silsesquioxane slurry containing inorganic nanoparticles; (b) coating the inorganic nanoparticle-containing oligomeric silsesquioxane slurry obtained in step (a) on a polymer porous film, allowing the slurry to fully enter the polymer porous film and expel air, thereby obtaining a polymer porous film composited with inorganic nanoparticles and oligomeric silsesquioxane; (c) curing the porous polymer film composited with inorganic nanoparticles and oligomeric silsesquioxane obtained in step (b) to obtain an ultra-flexible and ultra-thin hybrid glass; Furthermore, the mass fraction of the oligomeric silsesquioxane in the hybrid glass raw material is 5% or more; preferably, the mass fraction of the oligomeric silsesquioxane in the hybrid glass raw material is 50% or more; more preferably, 60-70%; Furthermore, the mass fraction of the inorganic nanoparticles in the hybrid glass raw material is 5 to 80%; preferably, the mass fraction of the inorganic nanoparticles in the hybrid glass raw material is more than 10%; more preferably, it is 20% to 40%; Further, the mass ratio of the oligomeric silsesquioxane to the inorganic nanoparticles is 5-90:10-80, preferably 20-75:25-80; Furthermore, the method further comprises, in step (a), adding an initiator to the solvent and mixing the mixture thoroughly; Furthermore, the mass fraction of the initiator in the hybrid glass raw material is 0.01-5%; preferably, the mass fraction of the initiator in the hybrid glass raw material is 0.5-3%; more preferably, 1-2%; Further, the solvent includes at least one of the following substances: dichloromethane, chloroform, toluene, xylene, ether, tetrahydrofuran, acetone, methyl ethyl ketone, ethyl acetate, butyl acetate, N,N-dimethylformamide, N,N-dimethylacetamide, acetonitrile, benzonitrile, methanol or ethanol; Furthermore, the coating is carried out by roller coating; Further, the curing includes light curing or heat curing; Further, the heating curing is carried out at 50-90°C; Furthermore, the thickness of the prepared ultra-flexible and ultra-thin hybrid glass is 0.8-50 μm.

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