High-impact ultrathin flexible glass coating and preparation process thereof

Abstract

The invention discloses a high-impact-resistance ultrathin flexible glass coating and a preparation process thereof.The high-impact-resistance ultrathin flexible glass coating comprises a viscosity promoting layer, a composite buffer layer is arranged on one side of the viscosity promoting layer, a dry hard coating is arranged on the side, away from the viscosity promoting layer, of the composite buffer layer, and an anti-reflection layer is arranged on the side, away from the composite buffer layer, of the dry hard coating; an antibacterial fingerprint-resistant coating is arranged on one side, far away from the dry hard coating, of the anti-reflection layer. According to the invention, the matrix adopts the high-toughness polyurethane-acrylate copolymer, the molecular chain segment has good flexibility, and impact energy can be absorbed through chain segment deformation; the added acrylate microspheres and core-shell SiO2 rubber particles form a'micro buffer unit ', and when being impacted, the microspheres / particles can disperse stress through compression and deformation, so that the situation that the coating or glass is broken due to stress concentration is avoided; the nano reinforced particles further improve the mechanical stability of the composite material and prevent fatigue failure of the buffer layer in repeated bending.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of flexible glass coating, in particular to a high-impact-resistant ultra-thin flexible glass coating and a preparation process thereof. BACKGROUND

[0002] UTG (ultra-thin glass) is extremely thin and has poor inherent impact resistance, so it is prone to breakage or damage when subjected to external forces. In order to improve its impact resistance, technicians attempt to add a special coating to the surface. In order to increase hardness, wear resistance and impact resistance and other properties, the existing UTG (ultra-thin flexible glass) usually needs to be protected by a multi-layer coating on the surface, such as a hard coating (hard coating) and a special protective film on the UTG, and a protective film or cushion layer (such as PET) may also be added below. Although this multi-layer protective structure improves the protection capability of the UTG, it also increases the thickness, resulting in a complex process, rising costs, and may affect the flexibility and bending performance. If a single coating material can provide good protection, it will simplify the production process, reduce costs, maintain the lightness and thinness of the product, and at the same time improve the service life and reliability of the UTG.

[0003] The existing publication No. CN120554946A discloses an ultra-thin glass UTG protective coating and a flexible electronic product glass containing the protective coating. The protective coating includes a network polymer having the following structural formula (I), the network polymer has a plurality of acrylate-modified polyurethane chains and a plurality of carbon chains, the acrylate-modified polyurethane chains and the carbon chains are alternately connected to form a network, and the plurality of carbon chains are straight chains or branched chains, and their lengths are the same or different. The protective coating can improve the impact resistance of the ultra-thin glass by more than 200%, and at the same time has excellent visible light transmittance. SUMMARY

[0004] The purpose of the present application is to provide a high-impact-resistant ultra-thin flexible glass coating and a preparation process thereof to solve the problems in the prior art.

[0005] To achieve the above-mentioned purpose, the present application provides the following technical scheme: a high-impact-resistant ultra-thin flexible glass coating, comprising an adhesion promoting layer, a composite buffer layer is arranged on one side of the adhesion promoting layer, a dry hard coating layer is arranged on the side of the composite buffer layer away from the adhesion promoting layer, an anti-reflection layer is arranged on the side of the dry hard coating layer away from the composite buffer layer, and an antibacterial and anti-fingerprint coating layer is arranged on the side of the anti-reflection layer away from the dry hard coating layer.

[0006] Preferably, the adhesion promoting layer is formed by mixing one or two kinds of diluted amino coupling agent and mercapto coupling agent, adding a dispersant and a stabilizer, and then coating and curing.

[0007] Preferably, the composite buffer layer is mixed by high-toughness polyurethane-acrylate copolymer, acrylate microspheres, nano-enhanced particles and additives, and the thickness of the composite buffer layer is 20-40μm.

[0008] Preferably, the dry hard coating layer is mixed by fluorine-modified polysiloxane resin, nano-silicon carbide particles and solvent, and the thickness of the dry hard coating layer is 5-12μm.

[0009] Preferably, the anti-reflection layer is a composite coating layer of nano-SiO2 and TiO2, and the thickness of the anti-reflection layer is 300-500nm.

[0010] Preferably, the antibacterial and anti-fingerprint coating layer is mixed by fluorine-containing polysiloxane resin, nitrogen-doped titanium dioxide and nano-silver particles, and the thickness of the antibacterial and anti-fingerprint coating layer is 100-200nm.

[0011] A preparation process of a high-impact ultra-thin flexible glass coating layer, comprising the following steps:

[0012] S1, substrate pretreatment: using a radio frequency plasma device to remove oil stains, impurities and hydroxyl groups on the surface of the ultra-thin glass; immersing the glass in a 5% γ-aminopropyl triethoxysilane ethanol solution to form a silane coupling agent molecular layer;

[0013] S2, preparation of adhesion promotion layer: mixing 40% amino silane coupling agent, 35% polyurethane-modified acrylate resin, 15% nano-Al2O3 particles, 0.5% leveling agent and 9.5% propylene glycol methyl ether acetate; coating by a micro-gravure coater; curing by a medium-pressure mercury lamp, and then drying;

[0014] S3, preparation of composite buffer layer: mixing 50% hydroxyl-terminated polybutadiene-modified epoxy resin, 15% acrylate microspheres, 12% core-shell SiO2 rubber particles, 3% photoinitiator 1-hydroxycyclohexyl phenyl ketone and 20% butyl acetate; coating by a slot coater; curing by a double-curing process;

[0015] S4, preparation of dry hard coating layer: mixing 60% hexafunctional polyurethane acrylate, 20% nano-SiC particles, 15% fluorine-modified polysiloxane, 3% photoinitiator and 2% methyl isobutyl ketone; coating by a comma doctor blade coater; curing by an LED light source;

[0016] S5, preparation of anti-reflection layer: using a pull-up coater to realize uniform film formation in cooperation with a rotating platform; baking at 120℃ for 30min after coating; sintering at 450℃ for 1h;

[0017] S6, antibacterial anti-fingerprint layer preparation: fluorine-containing polysiloxane resin 60%, nitrogen-doped TiO2 15%, nano silver particles 3%, photoinitiator 2%, isopropanol 20% are mixed; spray through ultrasonic precision spray gun, and finally UV curing and thermal curing are carried out.

[0018] Compared with the prior art, the beneficial effects of the present application are:

[0019] 1. The "elasticity-toughness synergistic structure" of the composite buffer layer: the matrix uses high-toughness polyurethane-acrylate copolymer, and the molecular chain segment has good flexibility and can absorb impact energy through chain segment deformation; the added acrylate microspheres and core-shell SiO2 rubber particles form "microscopic buffer units", which can disperse stress through compression and deformation when impacted, avoiding stress concentration leading to coating or glass breakage; the nano-enhanced particles further improve the mechanical stability of the composite material, preventing fatigue failure of the buffer layer in repeated bending.

[0020] 2. The coating is firmly combined with the glass substrate and each layer, and will not delaminate or fall off during long-term use. Radio frequency plasma removes oil stains and hydroxyl groups on the surface of the glass, reducing interface defects; gamma-aminopropyl triethoxysilane pretreatment forms "molecular bridges", with one end of the siloxyl group reacting with the glass surface hydroxyl group (forming a Si-O-Si bond) and the other end of the amino group reacting with the resin of the subsequent adhesion promoting layer, realizing chemical level bonding. The "two-way bonding design" of the adhesion promoting layer: amino type / mercapto type coupling agent is used, one end of which can react with the silane layer on the surface of the glass, and the other end forms a chemical bond with the polyurethane-acrylate copolymer of the composite buffer layer; the added nano Al2O3 particles enhance the mechanical anchoring effect of the interface, further improving the interlayer bonding force.

[0021] 3. High surface hardness, can resist scratches from keys, sand, and other hard objects, and is not prone to scratches during long-term use. The dry hard coating is a "hardness core layer": the matrix uses fluorine-modified polysiloxane resin, which contains rigid silicon-oxygen bonds (Si-O) in the molecule, giving the coating high hardness; nano SiC particles (Mohs hardness 9.5, second only to diamond) are used to enhance the wear resistance of the coating through "particle strengthening effect" - nano SiC is uniformly dispersed in the resin, which can block the diffusion of scratching stress and reduce surface wear. The curing process enhances the hardness: LED light source curing allows the resin molecules to fully crosslink, forming a dense three-dimensional network structure, further improving the scratch resistance of the coating.

[0022] 4. A composite coating of nano-SiO2 (refractive index ~1.45) and TiO2 (refractive index ~2.3) is used. By adjusting the ratio of the two materials and the coating thickness (300-500nm, close to 1 / 4 of the wavelength of visible light), the interference effect of light is used to cancel the reflected light. When the phase difference of the reflected light on the upper and lower surfaces of the coating is 180°, the reflected light cancels each other out, thereby reducing reflection and improving light transmittance.

[0023] 5. The "dual-function synergy" of the antibacterial and anti-fingerprint coating: Fluorinated polysiloxane resin has extremely low surface energy (the strong electronegativity of fluorine results in low surface tension), making it difficult for oils and sweat in fingerprints to adhere and easy to wipe away; nitrogen-doped TiO2 generates hydroxyl radicals (·OH) under light, which can damage bacterial cell membranes and proteins; nano-silver particles (Ag) + By binding to the sulfhydryl groups of bacterial enzyme proteins, it inhibits bacterial metabolism, and the two work synergistically to achieve broad-spectrum antibacterial activity. Attached Figure Description

[0024] The accompanying drawings are provided to further illustrate the invention and form part of the specification. They are used in conjunction with embodiments of the invention to explain the invention and do not constitute a limitation thereof. In the drawings:

[0025] Figure 1 This is a schematic diagram of the structure of the present invention.

[0026] In the diagram: 1. Adhesion promoting layer; 2. Composite buffer layer; 3. Dry hardening coating; 4. Anti-reflective layer; 5. Antibacterial and anti-fingerprint coating. Detailed Implementation

[0027] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only a part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention. Therefore, the following detailed description of the embodiments of the present invention provided in the accompanying drawings is not intended to limit the scope of the claimed invention, but merely to illustrate selected embodiments of the invention.

[0028] Please see Figure 1 In this embodiment of the invention, a high-impact ultra-thin flexible glass coating includes an adhesion promoting layer 1, a composite buffer layer 2 disposed on one side of the adhesion promoting layer 1, a dry hardening coating 3 disposed on the side of the composite buffer layer 2 away from the adhesion promoting layer 1, an anti-reflective layer 4 disposed on the side of the dry hardening coating 3 away from the composite buffer layer 2, and an antibacterial and anti-fingerprint coating 5 disposed on the side of the anti-reflective layer 4 away from the dry hardening coating 3.

[0029] The adhesion promoting layer 1 is formed by mixing amino coupling agent, mercapto coupling agent, dispersant and stabilizer after dilution, and then coating and curing. The thickness of the adhesion promoting layer 1 is 3-8 μm.

[0030] The composite buffer layer 2 is formed by mixing high-toughness polyurethane-acrylate copolymer, acrylate microspheres, nano-enhanced particles and additives. The thickness of the composite buffer layer 2 is 20-40 μm. The "elastic-tough synergistic structure" of the composite buffer layer 2: the matrix uses high-toughness polyurethane-acrylate copolymer, which has good flexibility and can absorb impact energy through chain segment deformation; the added acrylate microspheres and core-shell SiO2 rubber particles form "microscopic buffer units", which can disperse stress through compression and deformation when impacted, avoiding stress concentration leading to coating or glass breakage; the nano-enhanced particles further improve the mechanical stability of the composite material to prevent fatigue failure of the buffer layer in repeated bending.

[0031] The dry hard coating layer 3 is formed by mixing fluorine-modified polysiloxane resin, nano-silicon carbide particles and solvent. The thickness of the dry hard coating layer 3 is 5-12 μm. The dry hard coating layer 3 is a "hardness core layer": the matrix uses fluorine-modified polysiloxane resin containing rigid silicon-oxygen bonds (Si-O) to give the coating high hardness; the nano-SiC particles (Mohs hardness 9.5, second only to diamond) are added to improve the wear resistance of the coating through "particle strengthening effect" - the uniform dispersion of nano-SiC in the resin can block the diffusion of scratching stress and reduce surface wear. The curing process enhances the hardness: LED light source curing allows the resin molecules to fully crosslink, forming a dense three-dimensional network structure that further improves the scratch resistance of the coating.

[0032] The anti-reflective layer 4 uses a composite coating of nano-SiO2 and TiO2. The thickness of the anti-reflective layer 4 is 300-500 nm. The "optical interference design" of the anti-reflective layer 4: a composite coating of nano-SiO2 (refractive index ~1.45) and TiO2 (refractive index ~2.3) is used to offset reflected light through the interference effect of light - when the phase difference of reflected light on the upper and lower surfaces of the coating is 180°, the reflected light cancels each other out, thereby reducing reflection and improving transmission.

[0033] The antibacterial anti-fingerprint coating 5 is mixed by fluorine-containing polysiloxane resin, nitrogen-doped titanium dioxide and nano-silver particles, and the thickness of the antibacterial anti-fingerprint coating 5 is 100-200 nm. The fluorine-containing polysiloxane resin has very low surface energy (the strong electronegativity of fluorine element makes the surface tension low), and the oil and sweat in the fingerprint are difficult to adhere and easy to be wiped; the nitrogen-doped TiO2 generates hydroxyl radicals (·OH) under light, which can destroy the bacterial cell membrane and protein; the nano-silver particles (Ag + ) inhibit bacterial metabolism by combining with the sulfhydryl of bacterial enzyme protein, and both achieve broad-spectrum antibacterial through synergy.

[0034] A preparation process of a high-impact ultra-thin flexible glass coating, comprising the following steps:

[0035] S1, substrate pretreatment: using a radio frequency plasma device to remove oil stains, impurities and hydroxyl groups on the surface of the ultra-thin glass; immersing the glass into a 5% γ-aminopropyl triethoxysilane ethanol solution to form a silane coupling agent molecular layer;

[0036] S2, preparation of adhesion promotion layer 1: mixing 40% amino silane coupling agent, 35% polyurethane modified acrylate resin, 15% nano Al2O3 particles, 0.5% leveling agent + 9.5% propylene glycol methyl ether acetate; coating by micro-gravure coater; curing by medium pressure mercury lamp, and then drying;

[0037] S3, preparation of composite buffer layer 2: mixing 50% hydroxyl-terminated polybutadiene modified epoxy resin, 15% acrylate microspheres, 12% core-shell SiO2 rubber particles, 3% photoinitiator 1-hydroxycyclohexyl phenyl ketone, and 20% butyl acetate; coating by slot coater; curing by double curing process;

[0038] S4, preparation of dry hard coating layer 3: mixing 60% hexafunctional polyurethane acrylate, 20% nano SiC particles, 15% fluorine modified polysiloxane, 3% photoinitiator, and 2% methyl isobutyl ketone; coating by comma blade coater; curing by LED light source;

[0039] S5, preparation of anti-reflection layer 4: using a pull-up coater to realize uniform film formation with a rotating platform; baking at 120°C for 30 min after coating; sintering at 450°C for 1 h;

[0040] S6, preparation of antibacterial anti-fingerprint layer: mixing 60% fluorine-containing polysiloxane resin, 15% nitrogen-doped TiO2, 3% nano-silver particles, 2% photoinitiator, and 20% isopropyl alcohol; spraying by ultrasonic precision spray gun, and finally UV curing and thermal curing.

[0041] The working principle of the present application is: the "elasticity-toughness synergistic structure" of the composite buffer layer 2: the matrix uses high-toughness polyurethane-acrylate copolymer, the molecular chain segment has good flexibility, and can absorb impact energy through chain segment deformation; the added acrylate microspheres and core-shell SiO2 rubber particles form "microscopic buffer units", when impacted, the microspheres / particles can disperse stress through compression and deformation, avoiding stress concentration leading to coating or glass breakage; nano-enhanced particles further improve the mechanical stability of the composite material, preventing the buffer layer from fatigue failure in repeated bending.

[0042] The coating is firmly combined with the glass substrate and each layer, and will not delaminate or fall off during long-term use. Radio frequency plasma removes oil stains and hydroxyl groups on the surface of the glass, reducing interface defects; gamma-aminopropyl triethoxysilane pretreatment forms "molecular bridges", the silicon group at one end reacts with the hydroxyl group on the surface of the glass (forming a Si-O-Si bond), and the amino group at the other end can react with the resin of the subsequent adhesion promotion layer, achieving chemical level bonding. The "two-way bonding design" of the adhesion promotion layer 1: amino type / mercapto type coupling agent is used, one end of which can react with the silane layer on the surface of the glass, and the other end forms a chemical bond with the polyurethane-acrylate copolymer of the composite buffer layer; the added nano Al2O3 particles enhance the mechanical anchoring effect of the interface, further improving the interlayer bonding force.

[0043] The surface hardness is high, which can resist scratches from hard objects such as keys and sand, and is not easy to produce scratches during long-term use. The dry hard coating 3 is the "hardness core layer": the matrix uses fluorine-modified polysiloxane resin, which contains rigid silicon-oxygen bonds (Si-O) in the molecule, giving the coating high hardness; combined with nano SiC particles (Mohs hardness 9.5, second only to diamond), the coating wear resistance is improved through "particle strengthening effect" - nano SiC is uniformly dispersed in the resin, which can block the diffusion of scratching stress and reduce surface wear. The curing process enhances the hardness: LED light source curing makes the resin molecules fully crosslink, forming a dense three-dimensional network structure, further improving the scratch resistance of the coating.

[0044] The surface reflectivity is reduced and the visible light transmittance is improved, which is suitable for display screens, optical devices and other scenarios. The "optical interference design" of the anti-reflection layer 4: a composite coating of nano SiO2 (refractive index ~1.45) and TiO2 (refractive index ~2.3) is used, by adjusting the ratio of the two materials and the coating thickness (300-500 nm, close to 1 / 4 of the wavelength of visible light), the interference effect of light is used to cancel the reflected light - when the phase difference of the reflected light on the upper and lower surfaces of the coating is 180°, the reflected light cancels each other out, thereby reducing reflection and improving light transmittance.

[0045] The "dual-function synergism" of the antibacterial anti-fingerprint coating 5: the fluorine-containing polysiloxane resin has very low surface energy (the strong electronegativity of fluorine element makes the surface tension low), and the oil and sweat in the fingerprints are difficult to adhere and easy to be wiped; the nitrogen-doped TiO2 generates hydroxyl radicals (·OH) under light, which can destroy the bacterial cell membrane and protein; the nano-silver particles (Ag + ) inhibit bacterial metabolism by combining with the sulfhydryl of bacterial enzyme protein, and the two achieve broad-spectrum antibacterial through synergism.

[0046] Finally, it should be noted that: the above only for the preferred embodiments of the present application, and not for limiting the present application, although the foregoing embodiments of the present application are described in detail, for those skilled in the art, it still can be modified, or part of the technical features of the equivalent replacement of the technical solutions recorded in the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. within the spirit and principles of the present application shall be included in the protection scope of the present application.

Claims

1. A high impact ultra-thin flexible glass coating, characterized in that, The application relates to a glass substrate with an anti-fingerprint and antibacterial coating, which comprises a viscosity promoting layer (1), a composite buffer layer (2) arranged on one side of the viscosity promoting layer (1), a dry hard coating layer (3) arranged on the side, away from the composite buffer layer (2), of the composite buffer layer (2), an anti-reflection layer (4) arranged on the side, away from the dry hard coating layer (3), of the dry hard coating layer (3), and an anti-fingerprint and antibacterial coating layer (5) arranged on the side, away from the anti-reflection layer (4), of the anti-reflection layer (4).

2. The high impact ultra-thin flexible glass coating of claim 1, wherein, The viscosity promoting layer (1) is formed by mixing one or two kinds of diluted amino coupling agent and mercapto coupling agent, adding a dispersant and a stabilizer, and then coating and curing.

3. The high impact ultra-thin flexible glass coating of claim 1, wherein, The composite buffer layer (2) is formed by mixing high-toughness polyurethane-acrylate copolymer, acrylate microspheres, nano-enhanced particles and an auxiliary agent.

4. The high impact ultra-thin flexible glass coating of claim 1, wherein, The dry hard coating layer (3) is formed by mixing fluorine-modified polysiloxane resin, nano-silicon carbide particles and a solvent.

5. The high impact ultra-thin flexible glass coating of claim 1, wherein, The anti-reflection layer (4) is formed by using nano-SiO2 and TiO2 composite coating.

6. The high impact ultra-thin flexible glass coating of claim 1, wherein, The anti-fingerprint and antibacterial coating layer (5) is formed by mixing fluorine-containing polysiloxane resin, nitrogen-doped titanium dioxide and nano-silver particles.

7. A process for making a high impact ultra-thin flexible glass coating, characterized in that, The application further discloses a preparation method of the glass substrate with an anti-fingerprint and antibacterial coating. S1, substrate pretreatment: removing oil stains, impurities and hydroxyl groups on the surface of the ultra-thin glass by using a radio frequency plasma device; S2, viscosity promoting layer (1) preparation: mixing 40% of amino silane coupling agent, 35% of polyurethane-modified acrylate resin, 15% of nano-Al2O3 particles, 0.5% of a leveling agent and 9.5% of propylene glycol methyl ether acetate; coating by using a micro-gravure coater; curing by using a medium-pressure mercury lamp, and then drying; S3, composite buffer layer (2) preparation: mixing 50% of hydroxyl-terminated polybutadiene-modified epoxy resin, 15% of acrylate microspheres, 12% of core-shell SiO2 rubber particles, 3% of a photoinitiator (1-hydroxycyclohexyl phenyl ketone) and 20% of butyl acetate; S4, dry hard coating layer (3) preparation: mixing 60% of a hexafunctional polyurethane acrylate, 20% of nano-SiC particles, 15% of fluorine-modified polysiloxane, 3% of a photoinitiator and 2% of methyl isobutyl ketone; coating by using a comma doctor blade coater; and curing by using an LED light source; S5, anti-reflection layer (4) preparation: using a pulling-coating machine to realize uniform film forming by cooperating with a rotating platform; baking at 120 DEG C for 30 min after coating; and sintering at 450 DEG C for 1 h; S6, anti-fingerprint and antibacterial layer preparation: mixing 60% of fluorine-containing polysiloxane resin, 15% of nitrogen-doped TiO2, 3% of nano-silver particles, 2% of a photoinitiator and 20% of isopropyl alcohol; spraying by using an ultrasonic precision spray gun; and finally UV curing and thermal curing. S1, substrate pretreatment: removing oil stains, impurities and hydroxyl groups on the surface of the ultra-thin glass by using a radio frequency plasma device; S2, viscosity promoting layer (1) preparation: mixing 40% of amino silane coupling agent, 35% of polyurethane-modified acrylate resin, 15% of nano-Al2O3 particles, 0.5% of a leveling agent and 9.5% of propylene glycol methyl ether acetate; coating by using a micro-gravure coater; curing by using a medium-pressure mercury lamp, and then drying; S3, composite buffer layer (2) preparation: mixing 50% of hydroxyl-terminated polybutadiene-modified epoxy resin, 15% of acrylate microspheres, 12% of core-shell SiO2 rubber particles, 3% of a photoinitiator (1-hydroxycyclohexyl phenyl ketone) and 20% of butyl acetate; S4, dry hard coating layer (3) preparation: mixing 60% of a hexafunctional polyurethane acrylate, 20% of nano-SiC particles, 15% of fluorine-modified polysiloxane, 3% of a photoinitiator and 2% of methyl isobutyl ketone; coating by using a comma doctor blade coater; and curing by using an LED light source; S5, anti-reflection layer (4) preparation: using a pulling-coating machine to realize uniform film forming by cooperating with a rotating platform; baking at 120 DEG C for 30 min after coating; and sintering at 450 DEG C for 1 h; S6, anti-fingerprint and antibacterial layer preparation: mixing 60% of fluorine-containing polysiloxane resin, 15% of nitrogen-doped TiO2, 3% of nano-silver particles, 2% of a photoinitiator and 20% of isopropyl alcohol; spraying by using an ultrasonic precision spray gun; and finally UV curing and thermal curing.

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