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CN-122010409-A - Special protective glass and preparation method thereof

CN122010409ACN 122010409 ACN122010409 ACN 122010409ACN-122010409-A

Abstract

The invention relates to the technical field of special glass, and discloses special protective glass and a preparation method thereof, wherein the special protective glass comprises a glass substrate and a self-healing coating coated on the surface of the glass substrate; the glass substrate is composed of oxides of a silicon source, an aluminum source, a lithium source, a sodium source, a magnesium source, a zirconium source, a phosphorus source, a titanium source, a cerium source and a tin source, the self-healing coating comprises an organosiloxane film forming component, a crosslinking component, a silane anchoring component and nano particles, the crosslinking component comprises a boric acid ester bond crosslinking structure and a disulfide bond crosslinking structure, the silane anchoring component comprises at least one molecule with a trialkoxy silicon group at the tail end, and the self-healing coating is combined with silanol groups on the surface of the glass substrate through siloxane bonds to form an interface covalent bonding layer. The invention can realize effective repair after the glass has cracks, not only ensures the optical performance, but also enhances the mechanical strength of the glass.

Inventors

  • LI LEI

Assignees

  • 河北傲团科技有限公司

Dates

Publication Date
20260512
Application Date
20260224

Claims (10)

  1. 1. The special protective glass is characterized by comprising a glass substrate and a self-healing coating coated on the surface of the glass substrate; The glass substrate is composed of 55.0-68.0 parts by weight of SiO 2 , 12.0-20.0 parts by weight of Al 2 O 3 , 2.5-6.0 parts by weight of Li 2 O, 6.0-13.0 parts by weight of Na 2 O, 0.5-4.5 parts by weight of MgO, 0.5-3.0 parts by weight of ZrO 2 , 0.10-1.00 parts by weight of P 2 O 5 , 0.00-2.00 parts by weight of TiO 2 , 0.05-0.60 parts by weight of CeO 2 and 0.05-0.40 parts by weight of SnO 2 ; the self-healing coating comprises an organosiloxane film forming component, a crosslinking component, a silane anchoring component and nanoparticles; The crosslinking component comprises a boric acid ester bond crosslinking structure and a disulfide bond crosslinking structure; The silane anchoring component comprises at least one molecule with trialkoxy silicon groups at the tail end, and the self-healing coating is combined with silanol groups on the surface of the glass substrate through a silicon-oxygen bond to form an interface covalent bonding layer; The dry film thickness of the self-healing coating is 1.5-8.0 μm, and the D50 of the nano particles is 5-20nm.
  2. 2. The special protective glass according to claim 1, wherein the organosiloxane film forming component in the self-healing coating is at least one of hydroxyl-terminated polydimethylsiloxane and organosilsesquioxane; The crosslinking component comprises a borate crosslinking agent and a disulfide crosslinking agent, wherein the borate crosslinking agent is difunctional phenylborate or difunctional alkylborate, and the disulfide crosslinking agent is dihydroxydisulfide or diamine disulfide; The nanometer particles are nanometer ZrO 2 particles or nanometer SiO 2 particles.
  3. 3. The special protective glass according to claim 1, wherein the organic siloxane film forming component in the self-healing coating is 55-78wt%, the crosslinking component is 8-25wt%, the silane anchoring component is 3-12wt% and the nano particles are 1-10wt%, based on the total dry film mass of the self-healing coating.
  4. 4. The special protective glass according to claim 3, wherein the mass ratio of hydroxyl-terminated polydimethylsiloxane to organosilsesquioxane in the organosiloxane film-forming component is 3-15:1, the mass ratio of borate cross-linking agent to disulfide cross-linking agent in the cross-linking component is 1-4:1, the silane anchoring component comprises bis (triethoxysilyl) ethane to 3-glycidoxypropyl trimethoxysilane, the mass ratio of bis (triethoxysilyl) ethane to 3-glycidoxypropyl trimethoxysilane is 0.5-3:1, and the nanoparticle surface is silanized and modified by one or more molecules of bis (triethoxysilyl) ethane to 3-glycidoxypropyl trimethoxysilane, wherein the silanization modification amount is 0.5-5wt% of the mass of the nanoparticle.
  5. 5. A method for producing the special cover glass according to any one of claims 1 to 4, comprising the steps of: S1, weighing raw materials of a silicon source, an aluminum source, a lithium source, a sodium source, a magnesium source, a zirconium source, a phosphorus source, a titanium source, a cerium source and a tin source according to a formula of a glass substrate, and mixing to obtain a batch; s2, melting and clarifying the batch materials in an electric melting furnace at 1550-1680 ℃, and introducing dry oxygen into the glass liquid in the clarification stage and maintaining the dew point of a hearth to be not higher than-40 ℃ to obtain clarified glass liquid; s3, carrying out overflow downdraw forming or tape casting forming on the clarified glass liquid to obtain a glass substrate blank, and carrying out annealing treatment on the glass substrate blank to obtain an annealed glass substrate; S4, placing the annealed glass substrate in potassium nitrate molten salt for ion exchange strengthening treatment to obtain a strengthened glass substrate; S5, performing plasma activation treatment on the surface of the reinforced glass substrate and forming a surface silanol group enriched layer; s6, coating a primer solution containing a silane anchoring component on the surface silanol-group enriched layer and curing to obtain an interface primer layer; And S7, coating a self-healing coating precursor on the interface base coat, and forming a film and curing to obtain the special protective glass.
  6. 6. The method for producing a cover glass according to claim 5, wherein the melting time in step S2 is 2.5 to 6.0 hours, the clarification stage adopts gas bubbling clarification, the bubbling gas is a mixed gas of dry oxygen and dry nitrogen, the oxygen volume fraction in the mixed gas is 10 to 60%, and the bubbling flow rate is 0.2 to 2.0L/min.
  7. 7. The method for producing a cover glass according to claim 5, wherein the molten salt for ion exchange strengthening treatment in step S4 is a potassium nitrate molten salt, the ion exchange strengthening treatment temperature is 380 to 450 ℃, the ion exchange strengthening treatment time is 2 to 16 hours, and the strengthened glass substrate is subjected to desalting cleaning and drying treatment after the ion exchange strengthening treatment.
  8. 8. The method according to claim 5, wherein the plasma activation treatment in step S5 is performed by using oxygen plasma or argon-oxygen mixed plasma, the radio frequency power is 50-250W, and the treatment time is 30-300S.
  9. 9. The method according to claim 5, wherein the primer in step S6 contains a bifunctional silane molecule, the bifunctional silane molecule is at least one of bis (triethoxysilyl) ethane and 3-glycidoxypropyl trimethoxysilane, the curing temperature of the primer is 80-140 ℃, and the curing time is 10-60min.
  10. 10. The method according to claim 5, wherein the self-healing coating precursor in step S7 comprises an organosiloxane film forming component, a crosslinking component, a silane anchoring component and nanoparticles; The film forming mode in the step S7 is dip-coating film forming, and the dip-coating pulling speed is 20-180mm/min; The curing mode in the step S7 comprises ultraviolet curing and heat curing, wherein the ultraviolet irradiation energy is 0.3-2.5J/cm < 2 >, the heat curing temperature is 80-140 ℃ and the heat curing time is 10-90min.

Description

Special protective glass and preparation method thereof Technical Field The invention relates to the technical field of special glass, in particular to special protective glass and a preparation method thereof. Background The special glass is widely applied in a plurality of fields of modern industry, construction, automobiles, optical equipment and the like. It is required not only to have excellent optical properties such as high transparency, low optical distortion, uniform refractive index, etc., but also to have certain mechanical strength, abrasion resistance and corrosion resistance to cope with complex environmental conditions. However, in practical application, although the mechanical strength and the wear resistance of the special glass are improved to some extent, in use, when cracks appear on the surface of the glass due to the impact of external force, the cracks may cause the optical performance to be reduced, the structural strength to be reduced and the service life to be reduced as time passes. Although existing glass surface strengthening techniques, such as surface hardening treatment, ion exchange strengthening, etc., can improve scratch resistance and impact resistance of glass to some extent, these techniques have limitations in facing crack repair. Once a crack occurs on the surface of the glass, conventional glass repair techniques often fail to effectively restore its optical properties and surface smoothness, thereby affecting the overall performance of the glass. Disclosure of Invention The invention aims to provide special protective glass and a preparation method thereof, which aim to prolong the service life and durability of the special protective glass and realize effective repair after the glass is cracked. The invention provides special protective glass, which comprises a glass substrate and a self-healing coating coated on the surface of the glass substrate; The glass substrate is composed of 55.0-68.0 parts by weight of SiO 2, 12.0-20.0 parts by weight of Al 2O3, 2.5-6.0 parts by weight of Li 2 O, 6.0-13.0 parts by weight of Na 2 O, 0.5-4.5 parts by weight of MgO, 0.5-3.0 parts by weight of ZrO 2, 0.10-1.00 parts by weight of P 2O5, 0.00-2.00 parts by weight of TiO 2, 0.05-0.60 parts by weight of CeO 2 and 0.05-0.40 parts by weight of SnO 2; the self-healing coating comprises an organosiloxane film forming component, a crosslinking component, a silane anchoring component and nanoparticles; The crosslinking component comprises a boric acid ester bond crosslinking structure and a disulfide bond crosslinking structure; The silane anchoring component comprises at least one molecule with trialkoxy silicon groups at the tail end, and the self-healing coating is combined with silanol groups on the surface of the glass substrate through a silicon-oxygen bond to form an interface covalent bonding layer; The dry film thickness of the self-healing coating is 1.5-8.0 μm, and the D50 of the nano particles is 5-20nm. Further, the organosiloxane film-forming component in the self-healing coating is at least one of hydroxyl-terminated polydimethylsiloxane and organosilicon silsesquioxane; The crosslinking component comprises a borate crosslinking agent and a disulfide crosslinking agent, wherein the borate crosslinking agent is difunctional phenylborate or difunctional alkylborate, and the disulfide crosslinking agent is dihydroxydisulfide or diamine disulfide; The nanometer particles are nanometer ZrO 2 particles or nanometer SiO 2 particles. Further, based on the total dry film mass of the self-healing coating, the organic siloxane film forming component in the self-healing coating is 55-78wt%, the crosslinking component is 8-25wt%, the silane anchoring component is 3-12wt% and the nano particle is 1-10wt%. Further, the mass ratio of hydroxyl-terminated polydimethylsiloxane to organosilsesquioxane in the organosiloxane film-forming component is 3-15:1, the mass ratio of borate crosslinking agent to disulfide crosslinking agent in the crosslinking component is 1-4:1, the silane anchoring component comprises bis (triethoxysilyl) ethane and 3-glycidoxypropyl trimethoxysilane, the mass ratio of bis (triethoxysilyl) ethane to 3-glycidoxypropyl trimethoxysilane is 0.5-3:1, the surfaces of the nanoparticles are subjected to silanization modification through one or more molecules in the bis (triethoxysilyl) ethane and 3-glycidoxypropyl trimethoxysilane, and the silanization modification amount is 0.5-5wt% of the mass of the nanoparticles. On the other hand, the invention provides a preparation method of special protective glass, which comprises the following steps: S1, weighing raw materials of a silicon source, an aluminum source, a lithium source, a sodium source, a magnesium source, a zirconium source, a phosphorus source, a titanium source, a cerium source and a tin source according to a formula of a glass substrate, and mixing to obtain a batch; s2, melting and clarifying the batch materi