CN112479602A

CN112479602A - Film-coated product, preparation method thereof and electronic equipment shell

Info

Publication number: CN112479602A
Application number: CN202011033092.5A
Authority: CN
Inventors: 马兰; 许海波; 陈梁
Original assignee: BYD Co Ltd
Current assignee: BYD Co Ltd
Priority date: 2020-09-27
Filing date: 2020-09-27
Publication date: 2021-03-12
Anticipated expiration: 2040-09-27
Also published as: CN112479602B

Abstract

The invention provides a film-coated product which comprises a base material, a buffer layer and a film-coated layer, wherein the buffer layer covers at least part of the surface of the base material, the film-coated layer covers the surface of the buffer layer, which is far away from the base material, the buffer layer is obtained by hydrolyzing and condensing a buffer coating agent, and the buffer coating agent comprises micromolecular siloxane shown in a structural formula 1 and/or a structural formula 2:

Description

Film-coated product, preparation method thereof and electronic equipment shell

Technical Field

The invention belongs to the technical field of material processing, and particularly relates to a film-coated product, a preparation method thereof and an electronic equipment shell.

Background

Common electronic device housing materials, such as glass, plastic, or metal, require high impact strength under a thin condition, and the impact force of the existing materials is difficult to meet the impact strength requirement, and additional processing is required to improve the strength.

Taking glass as an example, the glass has excellent light transmission performance, mechanical performance and chemical stability, and is widely applied to the fields of electronic industry, building industry, optical industry and the like. At present, the thickness of glass products is developed towards thinner and thinner, but the thinner the thickness of glass is, the lower the strength and impact resistance of glass is. The glass is cracked because the microcracks on the surface of the glass cause stress concentration at the tips of the cracks and expand until the glass is cracked when being impacted by external force. Particularly, after the decorative film layer or the functional film layer is vacuum evaporated or sputtered on the surface of the glass, the film layer often has large internal stress and interacts with the microcracks of the glass substrate, so that the glass substrate is warped or distorted and deformed, the microcracks are more easily expanded to the fracture of the glass, and the impact resistance of the glass product is greatly reduced.

The existing protective coating liquid taking tetraethoxysilane as a main component has a complex preparation process and needs high-temperature curing at 140-. The film layer formed by curing the tetraethoxysilane has higher rigidity and is not beneficial to buffering the stress between the base material and the coating layer.

Disclosure of Invention

The invention provides a coated product and a preparation method thereof, aiming at the problem of poor impact resistance of the coated product caused by coating stress on the existing substrate.

The technical scheme adopted by the invention for solving the technical problems is as follows:

in one aspect, the invention provides a coated product comprising a substrate, a buffer layer and a coating layer, wherein the buffer layer covers at least part of the surface of the substrate, the coating layer covers the surface of the buffer layer away from the substrate, the buffer layer is obtained by hydrolysis and condensation of a buffer coating agent, and the buffer coating agent comprises micromolecular siloxane shown in a structural formula 1 and/or a structural formula 2:

wherein R is₁、R₅And R₆Each independently selected from H, - (CH)₂)_XR₉or-NHR₁₀Wherein x is 0-8, R₉And R₁₀Each independently selected from the group consisting of: h, an alkylene oxide group having at least 3 carbon atoms, a linear or branched aminoalkyl group having at least 2 carbon atoms, a mercaptoalkyl group, a vinyl group, a carbamate group, an acryloxy group, an acrylamide group, a phenylalkyl group, an isocyanatoalkyl group, or a ureidoalkyl group;

R₂、R₃、R₄、R₇and R₈Each independently selected from straight or branched chain alkyl of 1 to 4 carbon atoms or H.

Optionally, the substrate is selected from one or more of glass, ceramic, metal, plastic, and sapphire.

Optionally, R₁、R₅And R₆Each independently selected from H, - (CH)₂)_XR₉Wherein R is₉Selected from the group consisting of an alkylene oxide group having at least 3 carbon atoms, a linear or branched aminoalkyl group having at least 2 carbon atoms, and an isocyanatoalkyl group having at least 2 carbon atoms.

Optionally, the alkylene oxide group having at least 3 carbon atoms includes an alkylene oxide group containing an-N-heteroatom.

Optionally, the alkylene oxide group having at least 3 carbon atoms includes one or more of a glycidoxy group, a epoxybutoxy group, a epoxypentyloxy group, a glycidylamino group, a epoxybutylamino group, a epoxypentylamino group, a epoxypropyl group, a epoxybutyl group, and a epoxypentyl group.

Optionally, the molecular weight of the small molecular silane is 100-2000.

Optionally, the Young modulus of the buffer layer is 1-40 GPa, and the hardness is 0.1-20 GPa.

Optionally, the Young modulus of the buffer layer is 1-20 GPa, and the hardness is 0.1-10 GPa.

Optionally, the thickness of the buffer layer is 10-2000 nm.

Optionally, the thickness of the buffer layer is 50-500 nm.

Optionally, the buffer coating agent further comprises tetraethyl orthosilicate, and the mass ratio of the tetraethyl orthosilicate to the micromolecule siloxane shown in the structural formula 1 and/or the structural formula 2 is 0-10: 50-70.

Optionally, the film-coated product further comprises a first transition layer, the first transition layer is positioned between the buffer layer and the substrate, and the first transition layer comprises Si and/or SiO₂。

Optionally, the coating layer includes at least one optical film layer stacked on top of each other, and at least one of the optical film layers is selected from Nb independently₂O₅、MgF₂、Al₂O₃、TiO₂、SiO₂、Si₃N₄One or more of AlN, Al, Si, Cr, Nb, In, Sn and lanthanum titanate.

Optionally, the film-coated product further comprises a second transition layer, the second transition layer is located between the buffer layer and the film coating layer, and the second transition layer comprises Si and/or SiO₂。

In another aspect, the present invention provides a method for preparing a film-coated article as described above, comprising the following steps:

coating a buffer coating agent on at least part of the surface of a substrate, wherein the buffer coating agent comprises micromolecular siloxane shown as a structural formula 1 and/or a structural formula 2, the micromolecular siloxane is filled into the microcracks on the surface of the substrate, and the tips of the microcracks are passivated through hydrolytic condensation to obtain a buffer layer covered on the surface of the substrate:

wherein R is₁、R₅And R₆Each independently selected from H, - (CH)₂)_XR₉or-NHR₁₀Wherein x is 0-8, R₉And R₁₀Each independently selected from the group consisting of: h, an epoxyalkyl group having at least 3 carbon atoms, a linear or branched aminoalkyl group having at least 2 carbon atoms, a mercaptoalkyl group, a vinyl group, a carbamate group, a propane groupAlkenoyloxy, acrylamido, phenylalkyl, isocyanatoalkyl, or ureidoalkyl;

R₂、R₃、R₄、R₇and R₈Each independently selected from straight or branched chain alkyl of 1 to 4 carbon atoms or H;

and depositing a coating layer on the surface of the buffer layer.

Optionally, the buffer coating agent further comprises a solvent, and the buffer coating agent comprises the following components in parts by weight:

50-70 parts of micromolecular siloxane and 60-90 parts of solvent.

Optionally, the solvent comprises the following components by weight: 50-70 parts of an alcohol solvent and 10-20 parts of an alcohol ether solvent;

the alcohol solvent comprises one or more of methanol, ethanol and isopropanol;

the alcohol ether solvent comprises propylene glycol methyl ether.

Optionally, the buffer coating agent further comprises 0.1-1 part by weight of a leveling agent;

the leveling agent comprises one or more of polydimethylsiloxane, polymethylphenylsiloxane, polyester modified organosiloxane and polyvinylpyrrolidone.

Optionally, the substrate is subjected to surface hydroxylation treatment after the substrate is subjected to surface cleaning before the buffer coating agent is applied.

Optionally, before applying the buffer coating agent, a first transition layer is deposited on the surface of the substrate, said first transition layer comprising Si and/or SiO₂And coating a buffer coating agent on the surface of the first transition layer.

Optionally, before the hydrolytic condensation, the substrate coated with the buffer coating agent is placed in a vacuum environment, the temperature is 50-100 ℃, and the duration time is 10-30 min.

Optionally, during the hydrolysis condensation operation, the substrate is placed under the conditions that the humidity is greater than 50% and the temperature is 50-70 ℃ for hydrolysis reaction for 10-30 min, and after the hydrolysis reaction is completed, the temperature is raised to 100-120 ℃ for condensation reaction.

Alternatively to this, the first and second parts may,depositing a coating layer on the surface of the buffer layer in a vacuum coating mode, wherein the coating layer comprises at least one optical film layer arranged in a stacked mode, and at least one optical film layer is respectively and independently selected from Nb₂O₅、MgF₂、Al₂O₃、TiO₂、SiO₂、Si₃N₄One or more of AlN, Al, Si, Cr, Nb, In, Sn and lanthanum titanate.

Optionally, before depositing the coating layer, depositing a second transition layer on the surface of the buffer layer, wherein the second transition layer comprises Si and/or SiO₂And depositing a coating layer on the surface of the second transition layer.

In another aspect, the invention provides an electronic device housing comprising the film-covered article as described above.

Optionally, the electronic device casing is sequentially provided with the film coating layer, the buffer layer and the base material from inside to outside.

According to the film-coated product provided by the invention, the buffer coating agent containing the micromolecule silane shown in the structural formula 1 and/or the structural formula 2 is coated on the surface of the substrate, and the buffer coating agent is deposited at the tips of the microcracks on the surface of the substrate under the capillary action due to better wettability with the substrate, and the micromolecule siloxane provided by the invention has the structure as R₂、R₃、 R₄、R₇And R₈The Si-O bond absorbs water molecules in the environment and is hydrolyzed to generate Si-OH groups, can carry out dehydration condensation, and simultaneously the small molecule siloxane has the structure as R₁、R₅And R₆The unhydrolyzed organic group in the hydrolysis reaction can generate steric hindrance effect when Si-OH groups between adjacent micromolecule siloxane are subjected to dehydration condensation, and finally a net structure with a certain crosslinking degree is generated, the surface of the net structure is attached with hydroxyl and the unhydrolyzed organic group, and the attached hydroxyl can be subjected to dehydration condensation with-OH on the surface of the microcrack of the substrate to form a connecting bond, so that the tip of the microcrack on the surface of the substrate is passivated. Unhydrolyzed organic groups generate steric hindrance effect when Si-OH groups between adjacent small molecular siloxane are subjected to dehydration condensation, the crosslinking degree of a net structure is reduced, namely the particle size of the formed particles is smaller,and the tip of the microcrack is filled. The unhydrolyzed organic group can also endow the buffer layer with certain flexibility, the flexible buffer layer plays a role in buffering between the base material and the coating layer, the influence of the self stress of the coating layer on the base material is effectively relieved, and the impact resistance of the base material is improved.

Detailed Description

In order to make the technical problems, technical solutions and advantageous effects solved by the present invention more apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

The embodiment of the invention provides a film-coated product which comprises a base material, a buffer layer and a film coating layer, wherein the buffer layer covers at least part of the surface of the base material, the film coating layer covers the surface of the buffer layer, which is far away from the base material, the buffer layer is obtained by hydrolyzing and condensing a buffer coating agent, and the buffer coating agent comprises micromolecular siloxane shown in a structural formula 1 and/or a structural formula 2:

The invention provides a small molecule siloxane as R₂、R₃、R₄、R₇And R₈The Si-O bond absorbs water molecules in the environment and is hydrolyzed to generate Si-OH groups, can carry out dehydration condensation, and simultaneously the small molecule siloxane has the structure as R₁、R₅And R₆The unhydrolyzed organic group in the hydrolysis reaction can generate steric hindrance effect when Si-OH groups between adjacent micromolecule siloxane are subjected to dehydration condensation, and finally a net structure with a certain crosslinking degree is generated, the surface of the net structure is attached with hydroxyl and the unhydrolyzed organic group, and the attached hydroxyl can be subjected to dehydration condensation with-OH on the surface of the microcrack of the substrate to form a connecting bond, so that the tip of the microcrack on the surface of the substrate is passivated. Unhydrolyzed organic groups generate steric hindrance effect when Si-OH groups between adjacent micromolecular siloxane are subjected to dehydration condensation, and the crosslinking degree of a net structure is reduced, namely the particle size of formed particles is smaller, so that the filling of the tips of microcracks is facilitated. The unhydrolyzed organic group can also endow the buffer layer with certain flexibility, the flexible buffer layer plays a role in buffering between the base material and the coating layer, the influence of the self stress of the coating layer on the base material is effectively relieved, and the impact resistance of the base material is improved.

In some embodiments, the substrate is selected from one or more of glass, ceramic, metal, plastic, sapphire.

In a preferred embodiment, the substrate is selected from glass.

In some embodiments, the glass is selected from raw glass, soda lime glass, high alumina glass, fully tempered glass, semi-tempered glass, or heat strengthened glass.

The buffer coating agent provided by the invention is especially suitable for microcrack filling treatment on the surface of glass, and because Si-OH is formed on the surface of the glass and can be subjected to dehydration condensation with Si-OH groups obtained after hydrolysis of micromolecular siloxane, Si-O-Si bonds with higher bonding force are further formed, the bonding force between the buffer layer and a substrate is ensured, and the formed buffer layer is also beneficial to maintaining the characteristics of high light transmittance and low haze of the glass.

In some embodiments, the number of carbon atoms in the epoxyalkyl group is 3 to 5.

In some embodiments, the epoxyalkyl group having at least 3 carbon atoms comprises an-N-heteroatom containing epoxyalkyl group.

In some embodiments, the alkylene oxide group having at least 3 carbon atoms includes one or more of a glycidoxy group, a epoxybutoxy group, a cyclopentoxy group, a glycidylamino group, a oxetanylamino group, a cyclopentylamino group, a glycidyloxy group, a epoxybutyl group, a epoxypentyl group.

In some embodiments, x ═ 1-5, R₉And R₁₀Each independently selected from the group consisting of: h, an alkylene oxide group having 3 to 5 carbon atoms, a linear or branched aminoalkyl group having 2 to 5 carbon atoms, an acryloxy group, a phenylalkyl group, an isocyanatoalkyl group, or a ureidoalkyl group.

In some embodiments, the small molecule silane has a molecular weight of 100-1000.

In some embodiments, the Young's modulus of the buffer layer is 1-40 GPa, and the hardness is 0.1-20 GPa.

In a preferred embodiment, the Young modulus of the buffer layer is 1-20 GPa, and the hardness is 0.1-10 GPa.

The buffer layer needs to have certain rigidity and flexibility, and is beneficial to generating corresponding deformation under the stress action of the functional or decorative film layer to improve the shock resistance. Therefore, the Young modulus and the hardness have a certain range, and if the Young modulus is too small, the flexibility of the film layer is not enough, so that the shock resistance is not favorably improved; if the Young's modulus is too large, the rigidity of the film layer is not enough, which is not favorable for the adhesion between the buffer layer and the base material. If the hardness is too high, the flexibility of the film layer is not enough, which is not beneficial to improving the shock resistance; if the hardness is too low, the rigidity of the film layer is not sufficient, which is not favorable for the adhesion between the buffer layer and the base material.

In some embodiments, the buffer layer has a thickness of 10 to 2000 nm.

In a preferred embodiment, the thickness of the buffer layer is 50-1100 nm; further preferably, the thickness of the buffer layer is 50 to 500 nm.

When the thickness of the buffer layer is too low, an effective continuous film layer cannot be formed, and the stress buffering effect between the substrate and the coating layer is insufficient; when the thickness of the buffer layer is too high, the bonding strength between the base material and the coating layer can be influenced, the durability of the coated product is not favorably improved, particularly when the thickness of the film layer of the buffer layer reaches 2000nm, the impact resistance of the buffer layer to the base material is improved to the maximum value, the impact resistance of the base material is not increased any more when the film thickness is further increased, the material cost is increased, and the bonding strength between the base material and the coating layer is influenced.

In some embodiments, the buffer layer is directly attached to the surface of the substrate.

In other embodiments, the coated article further comprises a first transition layer between the buffer layer and the substrate, the first transition layer comprising Si and/or SiO₂。

The thickness of the first transition layer is 5-50 nm.

Si or SiO deposited in the first transition layer as opposed to directly attached₂As a porous columnar crystal structure, the contact area between the buffer layer and the substrate is increased; meanwhile, the Si content in the first transition layer is higher than that in the base material, so that the Si-O-Si bonding quantity between the buffer layer and the base material is increased, and the adhesive force is improved.

In some embodiments, the buffer coating agent further comprises tetraethyl orthosilicate, and the mass ratio of the tetraethyl orthosilicate to the small-molecule siloxane shown in the structural formula 1 and/or the structural formula 2 is 0-10: 50-70.

The proper amount of the tetraethyl orthosilicate can improve the hardness of the buffer layer to a certain extent, and further improve the impact resistance of the base material, and if the amount of the tetraethyl orthosilicate is too high, the flexibility of the buffer layer is insufficient, and the permeation efficiency of the buffer coating agent to microcracks on the surface of the base material is affected.

In some embodiments, the coating layer includes a decorative film layer and/or a functional film layer.

The coating layer comprises at least one optical film layer arranged in a stacked mode, and each optical film layer is selected from Nb independently₂O₅、MgF₂、Al₂O₃、TiO₂、SiO₂、Si₃N₄One or more of AlN, Al, Si, Cr, Nb, In, Sn and lanthanum titanate.

The thickness of the coating layer is 100-500 nm.

In some embodiments, the coating is directly attached to the surface of the buffer layer.

In other embodiments, the coated article further comprises a second transition layer between the buffer layer and the coating layer, the second transition layer comprising Si and/or SiO₂。

The thickness of the second transition layer is 5-50 nm.

The Si or SiO in the second transition layer functions in a similar manner to the first transition layer with respect to the direct attachment₂The contact area between the buffer layer and the coating layer can be increased, the Si-O-Si bonding quantity between the buffer layer and the coating layer is increased, and the adhesive force is improved.

Another embodiment of the present invention provides a method for preparing a film-coated article as described above, comprising the following steps:

wherein R is₁、R₅And R₆Each independently selected from H, - (CH)₂)_XR₉or-NHR₁₀Wherein x is 0-8, R₉And R₁₀Each independently selected from the group consisting of: h, an alkylene oxide group having at least 3 carbon atoms, a linear or branched aminoalkyl group having at least 2 carbon atoms, a mercaptoalkyl group, a vinyl group, a carbamate group, an acryloxy group, an acrylamide group, a phenylalkyl group, an isocyanatoalkyl group orUreidoalkyl;

and depositing a coating layer on the surface of the buffer layer.

In some embodiments, the buffer coating agent further comprises a solvent for dispersing the small molecule siloxane, and the buffer coating agent is prepared to have a flowing state, and the flowing of the buffer coating agent on the surface of the substrate enables the small molecule siloxane to be uniformly coated on the surface of the substrate.

Specifically, the buffer coating agent comprises the following components in parts by weight:

50-70 parts of micromolecular siloxane and 60-90 parts of solvent.

In some embodiments, the solvent comprises the following components by weight: 50-70 parts of an alcohol solvent and 10-20 parts of an alcohol ether solvent;

the alcohol solvent comprises one or more of methanol, ethanol and isopropanol;

the alcohol ether solvent comprises propylene glycol methyl ether.

The preferable alcohol solvent and alcohol ether solvent have stronger volatility and lower boiling point, and the solvent in the buffer coating agent can be removed in a heating mode, if the solvent which is difficult to volatilize is adopted, the solvent in the buffer layer is easy to remain, and the strength of the buffer layer is influenced.

In some embodiments, the buffer coating agent further comprises 0.1 to 1 part by weight of a leveling agent;

The leveling agent is used for improving the leveling performance of the buffer coating agent on the surface of the base material, and preferably adopts a siloxane leveling agent, and the siloxane leveling agent can participate in the hydrolysis condensation reaction of the small molecular silane while improving the leveling performance, participate in the formation of the buffer layer, and avoid the influence on the impact resistance of the buffer layer.

In some embodiments, the buffer coating agent is prepared by the following preparation method:

baking the micromolecular silane under a vacuum condition to remove impurities such as water and the like in the micromolecular silane, and then mixing the solvent, the micromolecular silane and the flatting agent.

In some embodiments, the buffer coating agent is applied by a method selected from spin coating, dip coating, or spray coating.

In some embodiments, the substrate is subjected to a surface hydroxylation treatment after the substrate has been surface cleaned prior to application of the buffer coating agent.

The surface cleaning operation of the substrate comprises: soaking and washing a base material in a liquid detergent solution, and then repeatedly washing the base material by using deionized water to remove organic dirt on the surface; secondly, soaking and scrubbing the base material in NaOH solution, and fully cleaning the base material with deionized water; thirdly, ultrasonic cleaning is carried out in ethanol solution; fourthly, the base material is transferred into deionized water solution for ultrasonic cleaning and drying.

The surface hydroxylation treatment of the substrate comprises: and (3) putting the dried base material into an activated ion machine for treatment, and carrying out surface hydroxylation treatment.

Since the number of hanging hydroxyl groups on the surface of the substrate is small, the surface of the substrate is subjected to hydroxylation treatment, so that the wettability of the buffer coating agent on the substrate can be effectively improved, and when the small-molecule silane is subjected to dehydration condensation, the hydroxyl groups on the surface of the substrate are bonded with the small-molecule silane, so that the bonding strength between the substrate and the buffer layer is improved.

In some embodiments, a first transition layer comprising Si and/or SiO is deposited on the substrate surface prior to applying the buffer coating agent₂And coating a buffer coating agent on the surface of the first transition layer.

The first transition layer can be prepared by physical vapor deposition, evaporation coating or magnetron sputtering.

In some embodiments, the substrate coated with the buffer coating agent is placed in a vacuum environment at a temperature of 50 to 100 ℃ for 10 to 30min before the hydrolytic condensation.

As the micro cracks on the surface of the base material are filled with air, the air can obstruct the inflow of the buffer coating agent to a certain extent, thereby influencing the reinforcing effect of the buffer coating agent on the base material, as a further improvement of the invention, the base material coated with the buffer coating agent is placed in a vacuum environment, and under the vacuum condition, the pressure difference exists between the air bubbles in the micro cracks and the surface of the buffer coating agent, thereby being beneficial to the air bubbles in the micro cracks to be removed and the buffer coating agent to be invaded, and simultaneously being convenient for the solvent in the buffer coating agent to be removed under the heating condition.

In some embodiments, the hydrolysis and condensation process is performed by placing the substrate under a humidity of greater than 50% and a temperature of 50-70 ℃ for hydrolysis reaction for 10-30 min, and heating the substrate to 100-120 ℃ after the hydrolysis reaction is completed for condensation reaction.

In some embodiments, a coating layer is deposited on the surface of the buffer layer by vacuum coating, the coating layer comprises at least one optical film layer arranged in a stacked mode, and at least one optical film layer is selected from Nb independently₂O₅、MgF₂、Al₂O₃、TiO₂、SiO₂、Si₃N₄One or more of AlN, Al, Si, Cr, Nb, In, Sn and lanthanum titanate.

In some embodiments, a second transition layer is deposited on the surface of the buffer layer prior to depositing the coating layer, the second transition layer comprising Si and/or SiO₂And depositing a coating layer on the surface of the second transition layer.

The second transition layer can be prepared by physical vapor deposition, evaporation coating or magnetron sputtering.

Another embodiment of the present invention provides an electronic device housing comprising the film-covered article described above.

In some embodiments, the electronic device housing is provided with the film coating layer, the buffer layer and the substrate in sequence from inside to outside.

The present invention will be further illustrated by the following examples.

Example 1

This example is used to illustrate a coated article and a method for making the same, which includes the following steps:

(1) preparation of the buffer coating agent: firstly, 3- (2, 3-epoxypropoxy) propyl trimethoxy silane (molecular weight: 236) is put into a vacuum oven and baked for 30min at 100 ℃ to remove impurities such as water and the like in the vacuum oven; then mixing 20 mass percent of 3- (2, 3-epoxypropoxy) propyl trimethoxy silane, 40 mass percent of ethanol, 25 mass percent of isopropanol, 15 mass percent of propylene glycol methyl ether and 0.5 mass percent of polydimethylsiloxane leveling agent, and placing the mixture into a reaction bottle to stir for 1 hour;

(2) cleaning and surface hydroxylation treatment of glass: soaking and washing ultrathin toughened glass with the thickness of 0.7mm in a liquid detergent for 10min, and repeatedly washing the ultrathin toughened glass with deionized water to remove organic dirt on the surface; secondly, soaking and scrubbing the glass in 30 wt% NaOH solution for 3min, and fully cleaning the glass with deionized water; thirdly, ultrasonic cleaning is carried out for 10min in ethanol solution; and fourthly, transferring the mixture into deionized water solution for ultrasonic cleaning for 10min, and drying. Fifthly, the dried glass is put into an activated ion machine for treatment for 1min, and surface hydroxylation treatment is carried out.

(3) Coating of the buffer layer: clamping the washed glass on a lifting rod of a coating film drawing machine by adopting a dipping-drawing method, wherein the descending speed is 1mm/S, the soaking time is 30S, the drawing speed is 0.25mm/S, after a buffer layer is coated, putting the glass into a vacuum oven for vacuumizing treatment, keeping the temperature at 80 ℃ for 20min to volatilize a solvent, then removing the vacuum, transferring a glass sample into an oven with the humidity of 55% and the temperature of 60 ℃ for hydrolysis reaction for 20min, and then raising the temperature to 100 ℃ for condensation reaction for 30min to obtain a glass product S1.

(4) Deposition of functional film layer: sequentially depositing SiO on the buffer layer by adopting a magnetron sputtering vacuum coating method₂/TiO₂/SiO₂/TiO₂/SiO₂/TiO₂/SiO₂The optical film layer (total thickness 200nm) was used to obtain a glass article S1'.

Example 2

(3) Coating of the buffer layer: clamping the washed glass on a lifting rod of a coating film drawing machine by adopting a dipping-drawing method, wherein the descending speed is 1mm/S, the soaking time is 30S, the drawing speed is 0.25mm/S, after a buffer layer is coated, putting the glass into a vacuum oven for vacuumizing treatment, keeping the temperature at 80 ℃ for 20min to volatilize a solvent, then removing the vacuum, transferring a glass sample into an oven with the humidity of 55% and the temperature of 60 ℃ for hydrolysis reaction for 20min, and then raising the temperature to 100 ℃ for condensation reaction for 30min to obtain a glass product S2.

(4) Deposition of functional film layer: sequentially depositing SiO on the buffer layer by adopting a magnetron sputtering vacuum coating method₂/TiO₂/SiO₂/TiO₂/SiO₂/TiO₂/SiO₂An optical film layer (total thickness 500nm) was formed to obtain a glass article S2'.

Example 3

(3) Coating of the buffer layer: clamping the washed glass on a lifting rod of a coating film drawing machine by adopting a dipping-drawing method, wherein the descending speed is 1mm/S, the soaking time is 30S, the drawing speed is 0.8mm/S, after a buffer layer is coated, putting the glass into a vacuum oven for vacuumizing treatment, keeping the temperature at 80 ℃ for 20min to volatilize a solvent, then removing the vacuum, transferring a glass sample into an oven with the humidity of 55% and the temperature of 60 ℃ for hydrolysis reaction for 20min, and then raising the temperature to 100 ℃ for condensation reaction for 30min to obtain a glass product S3.

(4) Deposition of functional film layer: sequentially depositing SiO on the buffer layer by adopting a magnetron sputtering vacuum coating method₂/TiO₂/SiO₂/TiO₂/SiO₂/TiO₂/SiO₂The optical film layer (total thickness 200nm) was used to obtain a glass article S3'.

Example 4

(3) Coating of the buffer layer: clamping the washed glass on a lifting rod of a coating film drawing machine by adopting a dipping-drawing method, wherein the descending speed is 1mm/S, the soaking time is 30S, the drawing speed is 0.8mm/S, after a buffer layer is coated, putting the glass into a vacuum oven for vacuumizing treatment, keeping the temperature at 80 ℃ for 20min to volatilize a solvent, then removing the vacuum, transferring a glass sample into an oven with the humidity of 55% and the temperature of 60 ℃ for hydrolysis reaction for 20min, and then raising the temperature to 100 ℃ for condensation reaction for 30min to obtain a glass product S4.

(4) Deposition of functional film layer: sequentially depositing SiO on the buffer layer by adopting a magnetron sputtering vacuum coating method₂/TiO₂/SiO₂/TiO₂/SiO₂/TiO₂/SiO₂An optical film layer (total thickness 500nm) was formed to obtain a glass article S4'.

Example 5

(3) Coating of the buffer layer: clamping the washed glass on a lifting rod of a coating film drawing machine by adopting a dipping-drawing method, wherein the descending speed is 1mm/S, the soaking time is 30S, the drawing speed is 2.5mm/S, after a buffer layer is coated, putting the glass into a vacuum oven for vacuumizing treatment, keeping the temperature at 80 ℃ for 20min to volatilize a solvent, then removing the vacuum, transferring a glass sample into an oven with the humidity of 55% and the temperature of 60 ℃ for hydrolysis reaction for 20min, and then raising the temperature to 100 ℃ for condensation reaction for 30min to obtain a glass product S5.

(4) Deposition of functional film layer: sequentially depositing SiO on the buffer layer by adopting a magnetron sputtering vacuum coating method₂/TiO₂/SiO₂/TiO₂/SiO₂/TiO₂/SiO₂The optical film layer (total thickness 200nm) was used to obtain a glass article S5'.

Example 6

(3) Coating of the buffer layer: clamping the washed glass on a lifting rod of a coating film drawing machine by adopting a dipping-drawing method, wherein the descending speed is 1mm/S, the soaking time is 30S, the drawing speed is 2.5mm/S, after a buffer layer is coated, putting the glass into a vacuum oven for vacuumizing treatment, keeping the temperature at 80 ℃ for 20min to volatilize a solvent, then removing the vacuum, transferring a glass sample into an oven with the humidity of 55% and the temperature of 60 ℃ for hydrolysis reaction for 20min, and then raising the temperature to 100 ℃ for condensation reaction for 30min to obtain a glass product S6.

(4) Deposition of functional film layer: sequentially depositing SiO on the buffer layer by adopting a magnetron sputtering vacuum coating method₂/TiO₂/SiO₂/TiO₂/SiO₂/TiO₂/SiO₂An optical film layer (total thickness 500nm) was formed to obtain a glass article S6'.

Example 7

(3) Coating of the buffer layer: clamping the washed glass on a lifting rod of a coating film drawing machine by adopting a dipping-drawing method, wherein the descending speed is 1mm/S, the soaking time is 30S, the drawing speed is 4mm/S, after a buffer layer is coated, putting the glass into a vacuum oven for vacuumizing treatment, keeping the temperature at 80 ℃ for 20min to volatilize a solvent, then removing the vacuum, transferring a glass sample into an oven with the humidity of 55% and the temperature of 60 ℃ for hydrolysis reaction for 20min, and then raising the temperature to 100 ℃ for condensation reaction for 30min to obtain a glass product S7.

(4) Deposition of functional film layer: sequentially depositing SiO on the buffer layer by adopting a magnetron sputtering vacuum coating method₂/TiO₂/SiO₂/TiO₂/SiO₂/TiO₂/SiO₂The optical film layer (total thickness 200nm) was used to obtain a glass article S7'.

Example 8

(3) Coating of the buffer layer: clamping the washed glass on a lifting rod of a coating film drawing machine by adopting a dipping-drawing method, wherein the descending speed is 1mm/S, the soaking time is 30S, the drawing speed is 4mm/S, after a buffer layer is coated, putting the glass into a vacuum oven for vacuumizing treatment, keeping the temperature at 80 ℃ for 20min to volatilize a solvent, then removing the vacuum, transferring a glass sample into an oven with the humidity of 55% and the temperature of 60 ℃ for hydrolysis reaction for 20min, and then raising the temperature to 100 ℃ for condensation reaction for 30min to obtain a glass product S8.

(4) Deposition of functional film layer: sequentially depositing SiO on the buffer layer by adopting a magnetron sputtering vacuum coating method₂/TiO₂/SiO₂/TiO₂/SiO₂/TiO₂/SiO₂An optical film layer (total thickness 500nm) was formed to obtain a glass article S8'.

Example 9

(3) Coating of the buffer layer: clamping the washed glass on a lifting rod of a coating film drawing machine by adopting a dipping-drawing method, wherein the descending speed is 1mm/S, the soaking time is 30S, the drawing speed is 10mm/S, after a buffer layer is coated, putting the glass into a vacuum oven for vacuumizing treatment, keeping the temperature at 80 ℃ for 20min to volatilize a solvent, then removing the vacuum, transferring a glass sample into an oven with the humidity of 55% and the temperature of 60 ℃ for hydrolysis reaction for 20min, and then raising the temperature to 100 ℃ for condensation reaction for 30min to obtain a glass product S9.

(4) Deposition of functional film layer: sequentially depositing SiO on the buffer layer by adopting a magnetron sputtering vacuum coating method₂/TiO₂/SiO₂/TiO₂/SiO₂/TiO₂/SiO₂The optical film layer (total thickness 200nm) was used to obtain a glass article S9'.

Example 10

(3) Coating of the buffer layer: clamping the washed glass on a lifting rod of a coating film drawing machine by adopting a dipping-drawing method, wherein the descending speed is 1mm/S, the soaking time is 30S, the drawing speed is 10mm/S, after a buffer layer is coated, putting the glass into a vacuum oven for vacuumizing treatment, keeping the temperature at 80 ℃ for 20min to volatilize a solvent, then removing the vacuum, transferring a glass sample into an oven with the humidity of 55% and the temperature of 60 ℃ for hydrolysis reaction for 20min, and then raising the temperature to 100 ℃ for condensation reaction for 30min to obtain a glass product S10.

(4) Deposition of functional film layer: sequentially depositing SiO on the buffer layer by adopting a magnetron sputtering vacuum coating method₂/TiO₂/SiO₂/TiO₂/SiO₂/TiO₂/SiO₂An optical film layer (total thickness 500nm) was formed to obtain a glass article S10'.

Example 11

(1) preparation of buffer layer coating agent: firstly, putting trimethoxy silane (molecular weight: 122) in a vacuum oven to bake for 30min at 100 ℃ to remove impurities such as water and the like in the trimethoxy silane; then 10 percent of isocyanic acid propyl triethoxy silane, 10 percent of aminopropyl triethoxy silane, 35 percent of ethanol, 30 percent of isopropanol, 15 percent of propylene glycol methyl ether and 0.2 percent of polyester modified organic siloxane flatting agent are mixed and placed in a reaction bottle to be stirred for 1 hour;

(3) Coating of the buffer layer: placing the washed glass on a horizontal table top by adopting a spraying method, spraying by using a handheld spray gun at proper air pressure, atomization degree and moving speed, placing the obtained glass sheet into a vacuum oven for vacuumizing treatment, keeping the temperature at 80 ℃ for 20min to volatilize a solvent, then removing the vacuum, transferring a glass sample into an oven with the humidity of 55% and the temperature of 60 ℃ for hydrolysis reaction for 20min, and raising the temperature to 100 ℃ for condensation reaction for 30min to obtain a glass product S11.

(4) Deposition of functional film layer: sequentially depositing SiO on the buffer layer by adopting a magnetron sputtering vacuum coating method₂/TiO₂/SiO₂/TiO₂/SiO₂/TiO₂/SiO₂An optical film layer (total thickness 500nm) was formed to obtain a glass article S11'.

Example 12

(1) preparation of the buffer coating agent: firstly, respectively placing gamma-aminopropyldiethoxysilane (molecular weight: 177) and gamma-aminopropyltriethoxysilane (molecular weight: 221) in a vacuum oven to bake for 30min at 100 ℃ so as to remove impurities such as water and the like in the vacuum oven; then mixing 10% of gamma-aminopropyldiethoxysilane, 10% of gamma-aminopropyltriethoxysilane, 35% of ethanol, 30% of isopropanol, 15% of propylene glycol monomethyl ether and 0.3% of polydimethylsiloxane leveling agent in percentage by mass, placing the mixture in a reaction bottle, and stirring for 1 hour;

(3) Coating of the buffer layer: placing the washed glass on a horizontal table top by adopting a spraying method, spraying by using a handheld spray gun at proper air pressure, atomization degree and moving speed, placing the obtained glass sheet into a vacuum oven for vacuumizing treatment, keeping the temperature at 80 ℃ for 20min to volatilize a solvent, then removing the vacuum, transferring a glass sample into an oven with the humidity of 55% and the temperature of 60 ℃ for hydrolysis reaction for 20min, and raising the temperature to 100 ℃ for condensation reaction for 30min to obtain a glass product S12.

(4) Deposition of decorative film layer: sequentially depositing SiO on the buffer layer by adopting a magnetron sputtering vacuum coating method₂/Al₂O₃/SiO₂/Al₂O₃/SiO₂/Al₂O₃/SiO₂Film layer (total thickness 500nm), glass product S12' was obtained.

Example 13

(1) preparation of buffer layer coating agent: firstly, respectively placing isopropyltriethoxysilane (molecular weight: 247) and [3- (triethoxysilyl) propyl ] ethyl carbamate (molecular weight: 293) in a vacuum oven and baking for 30min at 100 ℃ to remove impurities such as water and the like in the vacuum oven; then 10 percent of isocyanic acid propyl triethoxy silane, 10 percent of aminopropyl triethoxy silane, 35 percent of ethanol, 30 percent of isopropanol, 15 percent of propylene glycol methyl ether and 0.2 percent of polyester modified organic siloxane flatting agent are mixed and placed in a reaction bottle to be stirred for 1 hour;

(3) Coating of the buffer layer: placing the washed glass on a horizontal table top by adopting a spraying method, spraying by using a handheld spray gun at proper air pressure, atomization degree and moving speed, placing the obtained glass sheet into a vacuum oven for vacuumizing treatment, keeping the temperature at 80 ℃ for 20min to volatilize a solvent, then removing the vacuum, transferring a glass sample into an oven with the humidity of 55% and the temperature of 60 ℃ for hydrolysis reaction for 20min, and raising the temperature to 100 ℃ for condensation reaction for 30min to obtain a glass product S13.

(4) Deposition of functional film layer: sequentially depositing SiO on the buffer layer by adopting a magnetron sputtering vacuum coating method₂/TiO₂/SiO₂/TiO₂/SiO₂/TiO₂/SiO₂An optical film layer (total thickness 500nm) was formed to obtain a glass article S13'.

Example 14

(1) preparation of buffer layer coating agent: firstly, respectively placing aminobutylaminopropylbutoxysilane (molecular weight: 451) and tetraethyl orthosilicate (molecular weight: 208) in a vacuum oven to bake for 30min at 100 ℃ so as to remove impurities such as water and the like in the vacuum oven; then mixing 18% of aminobutylaminopropylbutoxysilane, 2% of tetraethyl orthosilicate, 35% of ethanol, 30% of isopropanol, 15% of propylene glycol monomethyl ether and 0.2% of polyester modified organosiloxane leveling agent in percentage by mass, placing the mixture in a reaction bottle, and stirring for 1 hour;

(3) Coating of the buffer layer: placing the washed glass on a horizontal table top by adopting a spraying method, spraying by using a handheld spray gun at proper air pressure, atomization degree and moving speed, placing the obtained glass sheet into a vacuum oven for vacuumizing treatment, keeping the temperature at 80 ℃ for 20min to volatilize a solvent, then removing the vacuum, transferring a glass sample into an oven with the humidity of 55% and the temperature of 60 ℃ for hydrolysis reaction for 20min, and raising the temperature to 100 ℃ for condensation reaction for 30min to obtain a glass product S14.

(4) Deposition of functional film layer: sequentially depositing SiO on the buffer layer by adopting a magnetron sputtering vacuum coating method₂/TiO₂/SiO₂/TiO₂/SiO₂/TiO₂/SiO₂An optical film layer (total thickness 500nm) was formed to obtain a glass article S14'.

Example 15

(3) Deposition of a first transition layer: depositing a layer of SiO with the thickness of 10nm on the surface of the glass in a PVD mode₂As a first transition layer.

(4) Coating of the buffer layer: placing the washed glass on a horizontal table top by adopting a spraying method, spraying by using a handheld spray gun at proper air pressure, atomization degree and moving speed, placing the obtained glass sheet into a vacuum oven for vacuumizing treatment, keeping the temperature at 80 ℃ for 20min to volatilize a solvent, then removing the vacuum, transferring a glass sample into an oven with the humidity of 55% and the temperature of 60 ℃ for hydrolysis reaction for 20min, and raising the temperature to 100 ℃ for condensation reaction for 30min to obtain a glass product S15.

(5) Deposition of functional film layer: sequentially depositing SiO on the buffer layer by adopting a magnetron sputtering vacuum coating method₂/TiO₂/SiO₂/TiO₂/SiO₂/TiO₂/SiO₂An optical film layer (total thickness 500nm) was formed to obtain a glass article S15'.

Example 16

(3) Coating of the buffer layer: the method comprises the steps of placing washed glass on a horizontal table top by adopting a spraying method, spraying by using a handheld spray gun at proper air pressure, atomization degree and moving speed, placing the obtained glass sheet into a vacuum oven for vacuumizing treatment, keeping the temperature of 80 ℃ for 20min to volatilize a solvent, then removing the vacuum, transferring a glass sample into an oven with the humidity of 55% and the temperature of 60 ℃ for hydrolysis reaction for 20min, and raising the temperature to 100 ℃ for condensation reaction for 30 min.

(4) Deposition of a second transition layer: depositing a layer of SiO with the thickness of 10nm on the surface of the buffer layer in a PVD (physical vapor deposition) mode₂As a second transition layer, a glass article S16 was produced.

(5) Deposition of functional film layer: sequentially depositing SiO on the buffer layer by adopting a magnetron sputtering vacuum coating method₂/TiO₂/SiO₂/TiO₂/SiO₂/TiO₂/SiO₂An optical film layer (total thickness 500nm) was formed to obtain a glass article S16'.

Example 17

(4) Coating of the buffer layer: the method comprises the steps of placing washed glass on a horizontal table top by adopting a spraying method, spraying by using a handheld spray gun at proper air pressure, atomization degree and moving speed, placing the obtained glass sheet into a vacuum oven for vacuumizing treatment, keeping the temperature of 80 ℃ for 20min to volatilize a solvent, then removing the vacuum, transferring a glass sample into an oven with the humidity of 55% and the temperature of 60 ℃ for hydrolysis reaction for 20min, and raising the temperature to 100 ℃ for condensation reaction for 30 min.

(5) Deposition of a second transition layer: depositing a layer of SiO with the thickness of 10nm on the surface of the buffer layer in a PVD (physical vapor deposition) mode₂As a second transition layer, a glass article S17 was produced.

(6) Deposition of functional film layer: sequentially depositing SiO on the buffer layer by adopting a magnetron sputtering vacuum coating method₂/TiO₂/SiO₂/TiO₂/SiO₂/TiO₂/SiO₂An optical film layer (total thickness 500nm) was formed to obtain a glass article S17'.

Comparative example 1

This comparative example is used for comparative illustration of the coated article and the method of preparation disclosed by the present invention, comprising the following steps:

(1) cleaning and activating ion treatment of glass: soaking and washing ultrathin toughened glass with the thickness of 0.7mm in a liquid detergent for 10min, and repeatedly washing the ultrathin toughened glass with deionized water to remove organic dirt on the surface; secondly, soaking and scrubbing the glass in 30 wt% NaOH solution for 3min, and fully cleaning the glass with deionized water; thirdly, ultrasonic cleaning is carried out for 10min in ethanol solution; and fourthly, transferring the mixture into deionized water solution for ultrasonic cleaning for 10min, and drying. Fifthly, the dried glass is put into an activated ion machine for treatment for 1min, and surface hydroxylation treatment is carried out, thus obtaining the glass product D1.

Comparative example 2

This comparative example is used for comparative illustration of a coated article and a method of making the same disclosed by the present invention, comprising the following steps:

(1) cleaning and activating ion treatment of glass: soaking and washing ultrathin toughened glass with the thickness of 0.7mm in a liquid detergent for 10min, and repeatedly washing the ultrathin toughened glass with deionized water to remove organic dirt on the surface; secondly, soaking and scrubbing the glass in 30 wt% NaOH solution for 3min, and fully cleaning the glass with deionized water; thirdly, ultrasonic cleaning is carried out for 10min in ethanol solution; and fourthly, transferring the mixture into deionized water solution for ultrasonic cleaning for 10min, and drying. Fifthly, the dried glass is put into an activated ion machine for treatment for 1min, and surface hydroxylation treatment is carried out.

(2) Deposition of functional film layer: sequentially depositing SiO on the clean glass by adopting a magnetron sputtering vacuum coating method₂/TiO₂/SiO₂/TiO₂/SiO₂/TiO₂/SiO₂The optical film layer (total thickness 200nm) gave a glass article D2.

Comparative example 3

(2) Deposition of functional film layer: sequentially depositing SiO on the clean glass by adopting a magnetron sputtering vacuum coating method₂/TiO₂/SiO₂/TiO₂/SiO₂/TiO₂/SiO₂The optical film layer (total thickness 500nm) gave a glass article D3.

Comparative example 4

This comparative example, which is intended to illustrate by way of comparison a glass article and method of making the same as disclosed herein, includes most of the operating steps of example 3, except that:

tetraethoxysilane was used instead of 3- (2, 3-glycidoxy) propyltrimethoxysilane in example 3.

Glass article D4 with a buffer layer and glass article D4' with a deposited functional film layer were produced on the basis of the above.

Comparative example 5

This comparative example, which is intended to illustrate by way of comparison a glass article and method of making the same as disclosed herein, includes most of the operating steps of example 2, except that:

tetraethoxysilane was used instead of 3- (2, 3-glycidoxy) propyltrimethoxysilane in example 2.

Glass article D5 with a buffer layer and glass article D5' with a deposited functional film layer were produced on the basis of the above.

Performance testing

The glass articles prepared as described above were subjected to the following performance tests:

film thickness test

The glass products D4, D5, S1, S2, S3, S4, S5, S6, S7, S8, S9, S10, S11, S12, S13, S14, S15, S16 and S17 are subjected to a film thickness test of the buffer layer, the film thickness test adopts an SEM-FIB cutting technology, and a layer of PET is plated before FIB cutting in order to prevent the protective film from being damaged during cutting and to enable the thickness of the protective film to be observed more visually. Three places are selected for cutting test of the film thickness of the same sample, and the average value is obtained. The test results of the examples and comparative examples are as follows:

sample name	Thickness of buffer layer \ nm
		D4	164.52
D5	46.38
		S1	47.53
S2	44.62
		S3	153.61
S4	157.82
		S5	487.91
S6	522.09
		S7	1033.57
S8	976.52
		S9	1956.87
S10	2124.96
		S11	1873.41
S12	1582.54
		S13	1531.54
S14	1541.58
		S15	1554.26
S16	1492.78
		S17	1496.51

Young's modulus and hardness test

And D4, D5, S1, S2, S3, S4, S5, S6, S7, S8, S9, S10, S11, S12, S13, S14, S15, S16 and S17 of the glass products are subjected to Young modulus and hardness tests of the buffer layer, the nano-mechanical property of the film layer is measured by adopting a nano-indenter, a diamond triangular pyramid Berkovich indenter is adopted for indentation tests, and the radius of curvature of the tip of the indenter is less than 20 nanometers. Each sample was subjected to at least 15 different position effective indentation tests, respectively, with the spacing of the indentations being maintained at least 30 times the maximum indentation depth to prevent interplay of the indentation stress fields. And then, the Young modulus and the hardness value of the film are obtained through model calculation by drawing a Young modulus-displacement curve and a hardness-displacement curve. The buffer layer test results obtained were as follows:

sample name	Young's modulus \ GPa	Hardness \ GPa
			D4	43.12	21.26
D5	41.54	23.78
			S1	5.22	0.77
S2	4.42	0.69
			S3	6.53	0.58
S4	7.83	0.83
			S5	7.31	0.73
S6	5.81	0.77
			S7	8.75	0.86
S8	7.59	0.71
			S9	11.34	0.83
S10	13.82	1.04
			S11	16.73	1.34
S12	17.95	1.51
			S13	18.81	2.67
S14	17.37	2.87
			S15	16.95	1.74
S16	15.64	1.80
			S17	17.71	2.67

Ball drop test

Carrying out ball falling tests on glass products S1 ', S2 ', S3 ', S4 ', S5 ', S6 ', S7 ', S8 ', S9 ', S10 ', S11 ', S12 ', S13 ', S14 ', S15 ', S16 ', S17 ', D1, D2, D3, D4 ' and D5 ', fixing the glass products with optical film layers facing downwards to a ball falling test jig, carrying out free falling body impact tests on steel balls with the mass of 32g +/-1 g and the diameter of 20mm, selecting different heights to test the glass surfaces, and sequentially carrying out test height from low to high on the test center point of each glass surface (15.5cm-22cm-31.5 cm-37 cm-40.5cm-47cm-55cm-60cm-65cm-70cm-75cm-80cm-85cm-90 cm-95 cm-105cm-110cm-115cm-120 cm-130 cm-140 cm), finishing the test when the glass surface has cracks, recording the height of the steel ball when the glass surface has cracks, and taking the average value of the height of the steel ball when the steel ball has cracks after 3 times of tests; the test results of the examples and comparative examples are as follows:

sample name	Height/cm of test
		D1	125
D2	65
		D3	40.5
D4’	80
		D5’	47
S1’	90
		S2’	60
S3’	105
		S4’	80
S5’	125
		S6’	100
S7’	140
		S8’	120
S9’	140 has not been broken
		S10’	140
S11’	130
		S12’	130
S13’	135
		S14’	130
S15’	130
		S16’	135
S17’	135

From the above test results, compared with the glass product D1 without the buffer layer, the glass products D2 and D3 directly covering the glass with other functional film layers or decorative film layers can further deteriorate the impact resistance, and the glass products S1 ', S2 ', S3 ', S4 ', S5 ', S6 ', S7 ', S8 ', S9 ', S10 ', S11 ', S12 ', S13 ', S14 ', S15 ', S16 ' and S17 ' treated by the buffer layer provided by the present invention can effectively alleviate the deterioration of the functional film layer or decorative film layer on the glass performance, and is favorable for eliminating the stress of the functional film layer or decorative film layer.

Cohesion test

Dry and water boiling check tests were performed on the glass articles S1 ', S2 ', S3 ', S4 ', S5 ', S6 ', S7 ', S8 ', S9 ', S10 ', S11 ', S12 ', S13 ', S14 ', S15 ', S16 ', S17 ', D4, D5.

Dry hundred grids: using a cutting knife or a single-edge knife to cut 10X 10 continuous 1X 1mm on the optical film layer of the glass product²The small square grids are used for brushing fragments in a test area with a brush; then the 3M adhesive tape is pressed on the upper part of the grid area to ensure that the adhesive tape is contacted with the film layerAnd the adhesive tape is well held, the adhesive tape is quickly pulled down within 0.5-1.0s at an angle as close to 60 degrees as possible, the falling state of the film layer is checked, and the judgment is carried out according to qualified criteria.

Boiling in water for hundreds of grids: placing the glass product in a water bath kettle at 80 ℃ with the optical film layer facing upwards, taking out after 30min, standing for 2h, wiping off water on the surface of the sample by using a dust-free cloth, and repeating the operation of drying the glass product in a hundred grids. Specific evaluation criteria are as follows:

level 0: the product is completely smooth without any grid layering;

level 1: small blocks are stripped at the intersection, and the influence area is less than 5%;

and 2, stage: the crossing points are stripped along the edges, and the influence area is 5-15%;

and 3, level: peeling off the whole strip along the edge, and/or partially or completely different lattices, wherein the influence area is 15-35%;

4, level: the whole edge is stripped, and some lattices are partially or partially stripped, so that the influence area is 35-65%;

and 5, stage: any exfoliation rating greater than 4;

with grades 0 and 1 being considered passed and the others being considered failed.

The test results in the table show that the glass product treated by the buffer layer provided by the invention still has good film stability after being boiled for a long time, which indicates that the buffer layer provided by the invention not only has strong bonding strength with glass, but also has good bonding strength with a coating layer, and is beneficial to the adhesion of a functional film layer and a decorative film layer.

The result of the comparative bonding force test and the result of the falling ball test show that the improvement of the impact resistance of the glass product is facilitated along with the increase of the thickness of the buffer layer, the reduction of the bonding force between the substrate and the coating layer can be caused, and when the thickness of the buffer layer is between 50nm and 500nm, the obtained glass product can have both the excellent impact resistance and the good bonding strength between the film layers. Set up first transition layer and second transition layer simultaneously and can effectively compensate because the too big cohesion degradation problem between the rete that brings of thickness of buffer layer.

The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.

Claims

1. A film-coated product is characterized by comprising a substrate, a buffer layer and a film coating layer, wherein the buffer layer covers at least part of the surface of the substrate, the film coating layer covers the surface of the buffer layer, which deviates from the substrate, the buffer layer is obtained by hydrolysis and condensation of a buffer coating agent, and the buffer coating agent comprises micromolecular siloxane shown in a structural formula 1 and/or a structural formula 2:

wherein R is₁、R₅And R₆Each independently selected from H, - (CH)₂)_XR₉or-NHR₁₀Wherein x is 0-8, R₉And R₁₀Each independently selected from the group consisting of: h; an alkylene oxide group having at least 3 carbon atoms; a linear or branched aminoalkyl, mercaptoalkyl, vinyl, carbamate, acryloxy, acrylamido, phenylalkyl, isocyanatoalkyl, or ureidoalkyl group having at least 2 carbon atoms;

2. The coated article of claim 1, wherein the substrate is selected from one or more of glass, ceramic, metal, plastic, and sapphire.

3. The coated article of claim 1, wherein R is₁、R₅And R₆Each independently selected from H, - (CH)₂)_XR₉Wherein R is₉Selected from the group consisting of an alkylene oxide group having at least 3 carbon atoms, a linear or branched aminoalkyl group having at least 2 carbon atoms, and an isocyanatoalkyl group having at least 2 carbon atoms.

4. The coated article of claim 1 or 3, wherein the epoxyalkyl group having at least 3 carbon atoms comprises an-N-heteroatom-containing epoxyalkyl group.

5. The coated article of claim 1 or 3, wherein the alkylene oxide group having at least 3 carbon atoms comprises one or more of a glycidoxy group, a epoxybutoxy group, a glycidoxy group, a glycidylamino group, a epoxybutylamino group, a epoxypentylamino group, a epoxypropyl group, a epoxybutyl group, and a epoxypentyl group.

6. The coated article of claim 1, wherein the small molecule silane has a molecular weight of 100 to 1000.

7. The coated article according to claim 1, wherein the buffer layer has a Young's modulus of 1 to 40GPa and a hardness of 0.1 to 20 GPa.

8. The coated article according to claim 7, wherein the buffer layer has a Young's modulus of 1 to 20GPa and a hardness of 0.1 to 10 GPa.

9. The coated article according to claim 1, wherein the buffer layer has a thickness of 10 to 2000 nm.

10. The coated article according to claim 9, wherein the buffer layer has a thickness of 50 to 500 nm.

11. The film-coated article according to claim 1, wherein the buffer coating agent further comprises tetraethyl orthosilicate, and the mass ratio of the tetraethyl orthosilicate to the small-molecule siloxane represented by the structural formula 1 and/or the structural formula 2 is 0.01-10: 50-70.

12. The coated article of claim 1, further comprising a first transition layer between the buffer layer and the substrate, the first transition layer comprising Si and/or SiO₂。

13. The coated article of claim 1 wherein the coating layer comprises at least one optical film layer disposed in a stack, at least one of the optical film layers each being independently selected from Nb₂O₅、MgF₂、Al₂O₃、TiO₂、SiO₂、Si₃N₄One or more of AlN, Al, Si, Cr, Nb, In, Sn and lanthanum titanate.

14. The film-covered article of claim 13, further comprising a second transition layer, said second transition layer being disposed between said buffer layer and said coating layer, said second transition layer comprising Si and/or SiO₂。

15. The method for producing a film-covered article according to any one of claims 1 to 13, characterized by comprising the following steps:

and depositing a coating layer on the surface of the buffer layer.

16. The method of claim 15, wherein the buffer coating agent further comprises a solvent, and the buffer coating agent comprises the following components by weight:

50-70 parts of micromolecular siloxane and 60-90 parts of solvent.

17. The method of producing a coated article according to claim 16, wherein the solvent comprises the following components by weight: 50-70 parts of an alcohol solvent and 10-20 parts of an alcohol ether solvent;

the alcohol solvent comprises one or more of methanol, ethanol and isopropanol;

the alcohol ether solvent comprises propylene glycol methyl ether.

18. The film-coated article according to claim 16, wherein the buffer coating agent further comprises 0.1 to 1 part by weight of a leveling agent;

19. The method for producing a coated article according to claim 15, wherein the surface of the substrate is cleaned before the buffer coating agent is applied, and then the substrate is subjected to a surface hydroxylation treatment.

20. The method for producing a coated article according to claim 15, wherein the substrate coated with the buffer coating agent is placed in a vacuum environment at a temperature of 50 to 100 ℃ for a duration of 10 to 30min before the hydrolytic condensation.

21. The method for producing a coated article according to claim 15, wherein a first transition layer comprising Si and/or SiO is deposited on the surface of the substrate before the buffer coating agent is applied₂And coating a buffer coating agent on the surface of the first transition layer.

22. The method for producing a coated product according to claim 15 or 21, wherein the hydrolysis and condensation are carried out by subjecting the substrate to a hydrolysis reaction at a temperature of 50 to 70 ℃ for 10 to 30min at a humidity of more than 50%, and heating the substrate to 100 to 120 ℃ after the hydrolysis reaction.

23. The method of claim 15, wherein the buffer layer is vacuum coated to deposit a coating comprising at least one optical layer disposed in a stack, at least one of the optical layers being independently selected from Nb₂O₅、MgF₂、Al₂O₃、TiO₂、SiO₂、Si₃N₄One or more of AlN, Al, Si, Cr, Nb, In, Sn and lanthanum titanate.

24. The method of claim 15 or 23, wherein a second transition layer is deposited on the surface of the buffer layer prior to depositing the coating layer, the second transition layer comprising Si and/or SiO₂And depositing a coating layer on the surface of the second transition layer.

25. An electronic device case comprising the film-coated product according to any one of claims 1 to 13.

26. The electronic device enclosure of claim 25, wherein said coating layer, said buffer layer and said substrate are disposed in sequence from inside to outside of said electronic device enclosure.