Coating Liquid Used For Forming Ultraviolet Absorption Coating And Ultraviolet Absorption Glass

Abstract

Provided is an ultraviolet absorption glass comprising: a glass substrate, and an ultraviolet absorption coating arranged on at least one surface of the glass substrate, wherein the ultraviolet absorption coating comprises silicon dioxide, an ultraviolet absorber, and MOz used for storing and releasing electrons excited by ultraviolet light in the ultraviolet absorber. The ultraviolet absorption glass is low cost and has good resistance to discoloration and devitrification.

Claims

1. An ultraviolet absorption glass comprising: a glass substrate, and an ultraviolet absorption coating arranged on at least one surface of the glass substrate, wherein the ultraviolet absorption coating comprises silicon dioxide, an ultraviolet absorber, and MOz used for storing and releasing electrons excited by ultraviolet light in the ultraviolet absorber, and wherein MOz is at least one compound selected from the group consisting of VO.sub.5/2, MnO.sub.2, FeO.sub.3/2, CoO.sub.4/3, NiO, YO.sub.3/2, ZrO.sub.2, NbO.sub.5/2, MoO.sub.3, RuO.sub.2, RhO.sub.3/2, PdO, TaO.sub.5/2, WO.sub.3, ReO.sub.3, OsO.sub.4, IrO.sub.2, GaO.sub.3/2, InO.sub.3/2, SnO.sub.2, SbO.sub.5/2 and BiO.sub.5/2.

2. The ultraviolet absorption glass according to claim 1, wherein in the ultraviolet absorption coating, a molar ratio of MOz to silicon dioxide is in a range of 1/300-1/100.

3. The ultraviolet absorption glass according to claim 2, wherein in the ultraviolet absorption coating, a molar ratio of MOz to silicon dioxide is in a range of 1/180-1/120.

4. The ultraviolet absorption glass according to claim 1, wherein in the ultraviolet absorption coating, a molar ratio of MOz to ultraviolet absorber is in a range of 1/20-1/10.

5. The ultraviolet absorption glass according to claim 4, wherein in the ultraviolet absorption coating, a molar ratio of MOz to ultraviolet absorber is in a range of 1/18-1/12.

6. The ultraviolet absorption glass according to claim 1, wherein a color difference between the ultraviolet absorption glass and the glass substrate is in a range of ΔE*ab≤2.0.

7. The ultraviolet absorption glass according to claim 1, wherein the ultraviolet absorber is benzophenone ultraviolet absorber, benzimidazole ultraviolet absorber or triazine ultraviolet absorber.

8. The ultraviolet absorption glass according to claim 1, wherein the ultraviolet absorption coating further comprises H.sup.+ or an alkali metal ion.

9. The ultraviolet absorption glass according to claim 1, wherein the ultraviolet absorption coating is formed by drying a coating liquid at a temperature between 100° C. and 200° C.

10. The ultraviolet absorption glass according to claim 9, wherein the coating liquid comprises partially hydrolyzed condensates of a silane compound, an ultraviolet absorber, a precursor of MOz, deionized water and at least one alcohol, and wherein the precursor is soluble in deionized water and/or the alcohol to produce MOz.

11. The ultraviolet absorption glass according to claim 10, wherein the precursor is at least one compound selected from the group consisting of LiVO.sub.3, HMnO.sub.4, Na.sub.2FeO.sub.4, Li.sub.2MoO.sub.4, H.sub.2RuO.sub.4, Na.sub.2WO.sub.4, H.sub.2ReO.sub.4, K.sub.2OsO.sub.4, NaGaO.sub.2, Na.sub.2SnO.sub.3.

12. The ultraviolet absorption glass according to claim 10, wherein the alcohol is selected from ethanol and isopropanol.

13. The ultraviolet absorption glass according to claim 1, wherein the glass substrate is a green float glass.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0041] FIG. 1 shows an ultraviolet absorption glass of the present invention, where element 1 is a glass substrate, and element 2 is an ultraviolet absorption coating.

DETAILED DESCRIPTION

[0042] Further description of the present invention will be illustrated, which combined with embodiments in the drawings.

[0043] The coating liquid used for forming ultraviolet absorption coating of the present invention comprises partially hydrolyzed condensates of a silane compound and an ultraviolet absorber. The partially hydrolyzed condensates of a silane compound contain silicon dioxide, which can be used for improving hardness and adhesion to the glass substrate of the ultraviolet absorption coating which is formed by the coating liquid, thereby ensuring high durability of the ultraviolet absorption coating. An ultraviolet absorber absorbs ultraviolet (UV) light and blocks the UV light coming into the vehicle or the house, avoiding damage to human health and aging of the decoration.

[0044] The term “partially hydrolyzed condensates” refers to oligomers (polymers) generated by hydrolysis and dehydration-condensation of an organic silane compound, which is generally polymerizing and dissolved in a solvent to an extent. The partially hydrolyzed condensates containing organic oxy group or silanol group are able to hydrolysis and condensate further to give final substance. The silane compound is at least one compound selected from the group consisting of tetramethoxysilane, tetraethoxysilane, trimethoxysilane, triethoxysilane and dimethoxydimethylsilane. In general, a single silane compound produces partially hydrolyzed condensates, while two or more silane compounds produce partial hydrolyzed co-condensates as their co-condensates. They are collectively referred to as “partially hydrolyzed condensate” in the present invention.

[0045] It is well known in the prior art that an ultraviolet absorption glass containing a surface coating of silicon dioxide (SiO.sub.2) and ultraviolet absorber absorbs the ultraviolet light. However, after being used for a period of time, the surface coating tends to become discolored or devitrified, resulting in discoloration or devitrification of the ultraviolet absorption glass, even a yellow appearance of a part of the glass. After absorbing the ultraviolet light, outer electrons of the ultraviolet absorber molecule jump from the ground state to an excited state (anti-bonding orbital), being raised to an excited state. The excited electrons can not be transferred. When the excited electrons accumulate and reach the capacity of ultraviolet absorber molecule, ultraviolet absorber or silicon dioxide will be destroyed, leading to discoloration or devitrification and a yellow appearance of the glass. Actually, such ultraviolet absorption glass has poor weather resistance in practical use. Therefore, the coating liquid used for forming ultraviolet absorption coating of the present invention further comprises AxMOy, where A is hydrogen or alkali metal, O is oxygen, M is at least one element selected from the group consisting of vanadium (V), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), ruthenium (Ru), rhodium (Rh), palladium (Pd), tantalum (Ta), tungsten (W), rhenium (Re), osmium (Os), iridium (Ir), gallium (Ga), indium (In), stannum (Sn), antimony (Sb) and bismuth (Bi), x is in a range of 1≤x≤2, y is in a range of 1≤y≤4. The MOz is used for storing and releasing electrons that excited by ultraviolet lights in the ultraviolet absorber.

[0046] Further, the coating liquid used for forming ultraviolet absorption coating further comprises deionized water and at least one of alcohol as solvent. Preferably, the alcohol in the coating liquid is ethanol and isopropanol, since both of the two alcohols are capable of dissolving the ultraviolet absorber and have a lower boiling point.

[0047] In addition, the coating liquid used for forming ultraviolet absorption coating further comprises a silane additive which is capable of improving adhesion of the coating liquid to the glass substrate. The silane additive is at least one compound selected from the group consisting of N-[3-(trimethoxysilyl)propyl]ethylenediamine, [3-(methacryloyloxy)propyl]trimethoxysilane, [3-(2-aminoethyl)aminopropyl]trimethoxysilane and [3-(methacryloyloxy)propyl]triethoxysilane. These silane additives can be purchased commercially, such KH470 (Nanjing Shuguang Company), KH560 (Nanjing Shuguang Company), KBM603 (Shin-Etsu Chemicals) or A1120 (Momentive Chemicals), etc.

[0048] In practical applications, the AxMOy is preferably at least one compound selected from the group consisting of lithium vanadate (LiVO.sub.3), permanganic acid (HMnO.sub.4), sodium ferrate (Na.sub.2FeO.sub.4), lithium cobaltate (LiCoO.sub.2), lithium nickelate (LiNiO.sub.2), sodium yttrium oxide (NaYO.sub.2) sodium zirconate (Na.sub.2ZrO.sub.3), lithium niobate (LiNbO.sub.3), lithium molybdate (Li.sub.2MoO.sub.4), ruthenium acid (H.sub.2RuO.sub.4), lithium rhodate (LiRhO.sub.2), lithium palladate (Li.sub.2PdO.sub.3), lithium tantalate (LiTaO.sub.3), sodium tungstate (Na.sub.2WO.sub.4), rhenium acid (H.sub.2ReO.sub.4), potassium osmate (K.sub.2OsO.sub.4), potassium iridate (KIrO.sub.3), sodium gallate (NaGaO.sub.2), sodium indium oxide (NaInO.sub.2), sodium stannate (Na.sub.2SnO.sub.3), sodium antimonate (NaSbO.sub.3) and sodium bismuthate (NaBiO.sub.3). These compounds provide a better effect to the coating liquid used for forming ultraviolet absorption coating.

[0049] Furthermore, the ultraviolet absorber is benzophenone ultraviolet absorbers, benzimidazole-based ultraviolet absorber or triazine-based ultraviolet absorber.

[0050] As a benzophenone ultraviolet absorber, it specifically includes 2,4-dihydroxy benzophenone, 2, 2′, 3 (or 4, 5, 6)-trihydroxybenzophenone, 2,2′,4,4′-tetrahydroxybenzophenone, 2,4-dihydroxy-T, 4′-dimethoxybenzophenone, 2-hydroxy-4-(octyloxy)benzophenone, etc.

[0051] As a benzimidazole ultraviolet absorber, it specifically includes 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol (UV absorber, commercial name is UV-234), 2-(5-chloro (2H)-benzotriazole-2-yl)-4-methyl-6-(tert-butyl) phenol, octyl-3-[3-t-4-hydroxy-5-[5-chloro-2H-benzotriazol-2-yl] propionate, 2-(2H-benzotriazol-2-yl)-4,6-di-t-pentyl phenol, 2-(2-hydroxy-5-methylphenyl) benzotriazole, 2-[2-hydroxy-3-(3,4,5,6-tetrahydrophthalic imide-methyl)-5-methylphenyl] benzotriazole, 2-(2-hydroxy-5-t-octylphenyl) benzotriazole, 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole, methyl-3-(3-(2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyphenyl) propionate, 2-(2H-benzotriazol-2-yl)-4,6-bis (1-methyl-1-phenylethyl) phenol, 2-(2H-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl) phenol, etc.

[0052] As a triazine ultraviolet absorber, it specifically includes 2-[4-[(2-hydroxy-3-dodecyloxypropyl) oxy]-2-hydroxyphenyl]-4,6-bis (2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-(2′-ethyl) hexyl) oxy]-2-hydroxyphenyl]-4,6-bis (2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis (2-hydroxy-4-butoxyphenyl)-6-(2,4-bis-butoxyphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-[1-octyl-carbethoxy] phenyl)-4,6-bis (4-phenylphenyl)-1,3,5-triazine, TINUVIN477 (commercial name, from Ciba Japan Company), etc.

[0053] The organic ultraviolet absorbers can absorb ultraviolet light of wide wavelength range. In the present invention, the ultraviolet absorbers may be used alone, or in a combination of two or more according to the actual need.

[0054] The coating liquid is applied on the glass substrate to form ultraviolet absorption coating, preparing ultraviolet absorption glass. As shown in FIG. 1, the ultraviolet absorption glass comprises glass substrate 1 and ultraviolet absorption coating 2, where the ultraviolet absorption coating 2 is arranged on at least one surface of the glass substrate 1. The ultraviolet absorption coating 2 containing silicon dioxide (SiO.sub.2) and ultraviolet absorber further comprises MOz used for storing and releasing electrons that excited by ultraviolet lights in the ultraviolet absorber, wherein O is oxygen, M is at least one element selected from the group consisting of vanadium (V), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), ruthenium (Ru), rhodium (Rh), palladium (Pd), tantalum (Ta), tungsten (W), rhenium (Re), osmium (Os), iridium (Ir), gallium (Ga), indium (In), stannum (Sn), antimony (Sb) and bismuth (Bi), O is oxygen, and z is in a range of 1≤z≤4.

[0055] In the process where the ultraviolet absorber absorbs the UV light, the ultraviolet absorber produces excited electrons and the excited electrons are gradually stored in MOz (1≤z≤4). The reaction equation (1) occurs:

MOz+ne.sup.−+nA.sup.+.fwdarw.AnMOz  (1),

[0056] where O is oxygen, A is hydrogen or alkali metal, M is at least one element selected from the group consisting of vanadium (V), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), ruthenium (Ru), rhodium (Rh), palladium (Pd), tantalum (Ta), tungsten (W), rhenium (Re), osmium (Os), iridium (Ir), gallium (Ga), indium (in), stannum (Sn), antimony (Sb) and bismuth (Bi), z is in a range of 1≤z≤4, n is in a range of 1≤n≤2.

[0057] When there is no ultraviolet light, that is, the ultraviolet absorber coating does not absorb the ultraviolet light, and the excited electrons previously stored in MOz (1≤z≤4) are released. The reaction equation (2) occurs:

AnMOz.fwdarw.MOz+ne.sup.−+nA.sup.+  (2).

[0058] Equation (2) is deemed to be a reverse reaction of equation (1), where the notations are consistent with that in equation (1). Therefore, the notations will not be illustrated in detail herein.

[0059] At the same time, the electrons released in reaction (2) diffuse to the surface of ultraviolet absorption glass, being consumed by O.sub.2 of the air adsorbed on the surface of the glass. The reaction equation (3) occurs:

O.sub.2+2e.sup.−.fwdarw.2O−  (3).

[0060] It can be known from the reaction equation (1), (2) and (3) that when the ultraviolet absorption coating 2 arranged on ultraviolet absorption glass is exposed to the UV light, such as in a sunny day, MOz will absorb and store the excited electrons. When there is no UV light, such as at a dark night, MOz will gradually release the electrons previously absorbed and stored in the daytime. The process is equivalent to transferring the excited electrons, thus avoiding the electrons accumulating and destroying the silicon dioxide and ultraviolet absorber in the ultraviolet absorption coating, not to cause discoloration or devitrification to ultraviolet absorption coating and ultraviolet absorption glass.

[0061] In practical applications, the MOz is at least one compound selected from the group consisting of vanadium pentoxide (VO.sub.5/2), manganese dioxide (MnO.sub.2), iron(III) oxide (FeO.sub.3/2), cobalt oxide (II,III) (CoO.sub.4/3), nickel(II) oxide (NiO), yttrium(III) oxide (YO.sub.3/2), zirconium dioxide (ZrO.sub.2), niobium pentoxide (NbO.sub.5/2), molybdenum(VI) oxide (MoO.sub.3), ruthenium dioxide (RuO.sub.2), rhodium(III) oxide (RhO.sub.3/2), palladium(II) oxide (PdO), tantalum pentoxide (TaO.sub.5/2), tungsten(VI) oxide (WO.sub.3), rhenium trioxide (ReO.sub.3), osmium (VIII) oxide (OsO.sub.4), iridium dioxide (IrO.sub.2), gallium(III) oxide (GaO.sub.3/2), indium (III) oxide (InO.sub.3/2), tin(IV) oxide (SnO.sub.2), antimony pentoxide (SbO.sub.5/2) and bismuth pentoxide (BiO.sub.5/2). These compounds provide a better effect to the ultraviolet absorption glass arranged with the coating.

[0062] The MOz listed above will reduce color difference ΔE*ab between the ultraviolet absorption glass and the glass substrate 1. For example, using white float glass or green float glass as the glass substrate 1 will achieve a color difference ΔE*ab between the ultraviolet absorption glass and the glass substrate 1 under 2.0 (ΔE*ab≤2.0). In accordance with practice, vanadium pentoxide (VO.sub.5/2), iron(III) oxide (FeO.sub.3/2), cobalt oxide (II,III) (CoO.sub.4/3), yttrium(III) oxide (YO.sub.3/2), niobium pentoxide (NbO.sub.5/2), rhodium(III) oxide (RhO.sub.3/2), tantalum pentoxide (TaO.sub.5/2), gallium(III) oxide (GaO.sub.3/2), indium (III) oxide (InO.sub.3/2), antimony pentoxide (SbO.sub.5/2) and bismuth pentoxide (BiO.sub.5/2) are written as V.sub.2O.sub.5, Fe.sub.2O.sub.3, Co.sub.3O.sub.4, Y.sub.2O.sub.3, Nb.sub.2O.sub.5, Rh.sub.2O.sub.3, Ta.sub.2O.sub.5, Ga.sub.2O.sub.3, In.sub.2O.sub.3, Sb.sub.2O.sub.5 and Bi.sub.2O.sub.5, being consistent with the form of MOz without changing its actual meaning.

[0063] Furthermore, the ultraviolet absorber is benzophenone ultraviolet absorber, benzimidazole ultraviolet absorber or triazine ultraviolet absorber.

[0064] As a benzophenone ultraviolet absorber, it specifically includes 2,4-dihydroxy benzophenone, 2, 2′, 3 (or 4/5/6)-trihydroxybenzophenone, 2,2′,4,4′-tetrahydroxybenzophenone, 2,4-dihydroxy-2′, 4′-dimethoxybenzophenone, 2-hydroxy-4-(octyloxy)benzophenone, etc.

[0065] As a benzimidazole ultraviolet absorber, it specifically includes 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol (UV absorber, commercial name is UV-234), 2-(5-chloro (2H)-benzotriazole-2-yl)-4-methyl-6-(tert-butyl) phenol, octyl-3-[3-t-4-hydroxy-5-[5-chloro-2H-benzotriazol-2-yl] propionate, 2-(2H-benzotriazol-2-yl)-4,6-di-t-pentyl phenol, 2-(2-hydroxy-5-methylphenyl) benzotriazole, 2-[2-hydroxy-3-(3,4,5,6-tetrahydrophthalic imide-methyl)-5-methylphenyl] benzotriazole, 2-(2-hydroxy-5-t-octylphenyl) benzotriazole, 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole, methyl-3-(3-(2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyphenyl) propionate, 2-(2H-benzotriazol-2-yl)-4,6-bis (1-methyl-1-phenylethyl) phenol, 2-(2H-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl) phenol, etc.

[0066] As a triazine ultraviolet absorber, it specifically includes 2-[4-[(2-hydroxy-3-dodecyloxypropyl) oxy]-2-hydroxyphenyl]-4,6-bis (2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-(2′-ethyl) hexyl) oxy]-2-hydroxyphenyl]-4,6-bis (2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis (2-hydroxy-4-butoxyphenyl)-6-(2,4-bis-butoxyphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-[1-octyl-carbethoxy] phenyl)-4,6-bis (4-phenylphenyl)-1,3,5-triazine, TINUVIN477 (commercial name, from Ciba Japan Company), etc.

[0067] The organic ultraviolet absorbers can absorb ultraviolet light of wide wavelength range. In the present invention, the ultraviolet absorbers may be used alone, or in a combination of two or more according to the actual need.

[0068] In the present invention, silicon dioxide is used for improving hardness and adhesion to the glass substrate 1 of the ultraviolet absorption coating 2 which is formed by the coating liquid, thereby ensuring high durability of the ultraviolet absorption coating 2. Preferably, in an ultraviolet absorption coating 2, a molar ratio of MOz to silicon dioxide is in a range of 1/300-1/100. More preferably, in the ultraviolet absorption coating 2, a molar ratio of MOz to silicon dioxide is in a range of 1/180-1/120.

[0069] In the present invention, an ultraviolet absorber absorbs ultraviolet light and blocks the UV light coming into the vehicle or the house, avoiding damage to people and aging of the decoration. Preferably, in an ultraviolet absorption coating, a molar ratio of MOz to ultraviolet absorber is in a range of 1/20-1/10. More preferably, in the ultraviolet absorption coating 2, a molar ratio of MOz to silicon dioxide is in a range of 1/18-1/12.

[0070] A coating liquid used for forming an ultraviolet absorption coating and an ultraviolet absorption glass arranged with the ultraviolet absorption coating are described above in detail. Furthermore, the present invention provides a method for preparing the ultraviolet absorption glass, comprising the following steps.

[0071] Step 1: providing silane compound and AxMOy as raw material, providing deionized water and at least one alcohol as a solvent, stirring and ultrasonically dispersing the raw material and solvent, wherein A is hydrogen or an alkali metal, O is oxygen, M is at least one element selected from the group consisting of vanadium (V), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), ruthenium (Ru), rhodium (Rh), palladium (Pd), tantalum (Ta), tungsten (W), rhenium (Re), osmium (Os), iridium (Ir), gallium (Ga), indium (In), tin (Sn), antimony (Sb) and bismuth (Bi), x is in a range of 1≤x≤2, y is in a range of 1≤y≤4.

[0072] The silane compound is at least one compound selected from but not limited to the group consisting of tetramethoxysilane, tetraethoxysilane, trimethoxysilane, triethoxysilane and dimethoxydimethylsilane. Any other colloid substance that produces partially hydrolyzed condensate via hydrolysis or a series of reaction can be selected.

[0073] As a solvent, the alcohol may be but not limited to ethanol and isopropanol, other alcohols can also be selected according to actual need.

[0074] AxMOy is preferably at least one compound selected from the group consisting of lithium vanadate (LiVO.sub.3), permanganic acid (HMnO.sub.4), sodium ferrate (Na.sub.2FeO.sub.4), lithium cobaltate (LiCoO.sub.2), lithium nickelate (LiNiO.sub.2), sodium yttrium oxide (NaYO.sub.2) sodium zirconate (Na.sub.2ZrO.sub.3), lithium niobate (LiNbO.sub.3), lithium molybdate (Li.sub.2MoO.sub.4), ruthenium acid (H.sub.2RuO.sub.4), lithium rhodate (LiRhO.sub.2), lithium palladate (Li.sub.2PdO.sub.3), lithium tantalate (LiTaO.sub.3), sodium tungstate (Na.sub.2WO.sub.4), rhenium acid (H.sub.2ReO.sub.4), potassium osmate (K.sub.2OsO.sub.4), potassium iridate (KIrO.sub.3), sodium gallate (NaGaO.sub.2), sodium indium oxide (NaInO.sub.2), sodium stannate (Na.sub.2SnO.sub.3), sodium antimonate (NaSbO.sub.3) and sodium bismuthate (NaBiO.sub.3).

[0075] Step 2: after the step of stirring and ultrasonically dispersing, conducting a hydrolysis reaction and a condensation reaction between the raw material and solvent to produce a colloid B containing silicon dioxide in a form of a partially hydrolyzed condensate.

[0076] As a matrix of the final ultraviolet absorption coating, silicon dioxide improves hardness and adhesion to the glass substrate of the ultraviolet absorption coating which is formed by the coating liquid, thereby ensuring high durability of the ultraviolet absorption coating.

[0077] Step 3: adding an ultraviolet absorber and a silane additive to the colloid B while stirring to dissolve the ultraviolet absorber, then obtaining a coating liquid C used for forming an ultraviolet absorption coating.

[0078] The silane additive is at least one compound selected from the group consisting of N-[3-(trimethoxysilyl)propyl]ethylenediamine, [3-(methacryloyloxy)propyl]trimethoxysilane, [3-(2-aminoethyl)aminopropyl] trimethoxysilane and [3-(methacryloyloxy)propyl]triethoxysilane.

[0079] The ultraviolet absorber is benzophenone ultraviolet absorber, benzimidazole ultraviolet absorber or triazine ultraviolet absorber. These three ultraviolet absorbers have been described in detail in the above description, it is not further described herein.

[0080] Step 4: preparing a glass substrate, applying the coating liquid C uniformly on at least one surface of the glass substrate.

[0081] The glass substrate is preferably but not limited to a white float glass or a green float glass. Any glass sheet prepared by other methods that meet the requirements will be selected as the glass substrate of the present invention.

[0082] At the same time, the coating liquid C can be uniformly applied on the glass substrate in different ways, such as spraying, wiping, flow coating, brushing and dipping that optionally combines with ultrasound, centrifugation or rotation techniques. Since the coating technique is known in the art, it is not further described herein.

[0083] Step 5: drying the coating liquid C at a temperature of 100° C.-200° C. to form an ultraviolet absorption coating containing MOz on a surface of the glass substrate, O is oxygen, M is at least one element selected from the group consisting of vanadium (V), manganese (Mn), iron (Fe), cobalt (Co), Nickel (Ni), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), ruthenium (Ru), rhodium (Rh), palladium (Pd), tantalum (Ta), tungsten (W), rhenium (Re), osmium (Os), iridium (Ir), gallium (Ga), indium (in), tin (Sn), antimony (Sb) and bismuth (Bi), z is in a range of 1≤z≤4, thereby obtaining an ultraviolet absorption glass.

[0084] The MOz is at least one compound selected from the group consisting of vanadium pentoxide (VO.sub.5/2), manganese dioxide (MnO.sub.2), iron(III) oxide (FeO.sub.3/2), cobalt oxide (II,III) (CoO.sub.4/3), nickel(II) oxide (NiO), yttrium(III) oxide (YO.sub.3/2), zirconium dioxide (ZrO.sub.2), niobium pentoxide (NbO.sub.5/2), molybdenum(VI) oxide (MoO.sub.3), ruthenium dioxide (RuO.sub.2), rhodium(III) oxide (RhO.sub.3/2), palladium(II) oxide (PdO), tantalum pentoxide (TaO.sub.5/2), tungsten(VI) oxide (WO.sub.3), rhenium trioxide (ReO.sub.3), osmium (VIII) oxide (OsO.sub.4), iridium dioxide (IrO.sub.2), gallium(III) oxide (GaO.sub.3/2), indium (III) oxide (InO.sub.3/2), tin(IV) oxide (SnO.sub.2), antimony pentoxide (SbO.sub.5/2) and bismuth pentoxide (BiO.sub.5/2).

[0085] The step of drying the coating liquid C is conducted for 30 to 120 minutes. It is understood that the time for drying depends on the different coating liquid C, so that the time for drying is determined according to the actual conditions.

EXAMPLES

[0086] Further description of the present invention will be illustrated, which combined with embodiments. It will be understood that the embodiments are illustrative and that the invention scope is not so limited.

[0087] As the compounds MOz are similar in reaction mechanism, tungsten trioxide (WO.sub.3) is used as an example to explain the present invention. Other MOz compounds will not be illustrated in detail herein.

Example 1

[0088] 10 g of TEOS and 0.1 g of sodium tungstate (Na.sub.2WO.sub.4) were used as raw material, while ethanol, isopropanol and deionized water were used as solvent. The raw material and solvent were stirred and ultrasonically dispersed. After the step of stirring and ultrasonically dispersing, a hydrolysis reaction and a condensation reaction were conducted between the raw material and solvent to produce a colloid B containing silicon dioxide in a form of a partially hydrolyzed condensate. To 20 g of colloid B, 1.2 g of UV absorber 2,4-dihydroxy-T, 4′-dimethoxybenzophenone and 0.02 g of KH560 (purchased from Nanjing Shuguang Company) were added while stirring to dissolve the UV absorber. A stirring was continued for 2 hours to obtain a coating liquid C used for forming an ultraviolet absorption coating.

[0089] A white float glass (FUYAO 3.2C) was provided as a glass substrate. The white float glass has a thickness of 3.2 mm, a color of L*=95.67, a*=−1.53, b*=1.28, a size of 150 mm×150 mm, and a UV-blocking rate of 31.67%. 2.3 g of the coating liquid C were uniformly applied on the surface of the glass substrate, and then dried at 150° C. for 1 hour to obtain an ultraviolet absorption glass arranged with the ultraviolet absorption coating, where a molar ratio of tungsten trioxide (WO.sub.3) to silicon dioxide (SiO.sub.2) is 1:158.7, a molar ratio of tungsten trioxide (WO.sub.3) to the ultraviolet absorber is 1:16.1. The ultraviolet absorption glass was evaluated according to the performance evaluation method described below, and the evaluation results are shown in Table 1.

[0090] Performance Evaluation

[0091] (1) UV-blocking rate: a transmission spectrum of a wavelength of 250 nm-2500 nm was generated by using a spectrophotometer (Mode: Perkin Elmer Lambda 950).

[0092] Lta was calculated according to ASTM E308-01 standard. Tuv and Te were calculated according to ISO9050-2003(E) standard. Tir was calculated according to TL957-2011 standard. Tuv was a calculated value of UV transmittance of a wavelength of 300 nm-380 nm. UV-blocking rate=100%-UV transmittance. UV transmittance was an average value calculated from 5 points of one sample.

[0093] (2) Color difference between ultraviolet absorption glass and glass substrate ΔE*ab: a transmission spectrum of a wavelength of 250 nm-2500 nm was generated by using a spectrophotometer (Mode: Perkin Elmer Lambda 950).

[0094] L*, a* and b* were calculated according to CIE 1976 standard: average values of L*, a* and b* calculated from 5 points of one glass substrate were denoted by L*1, a*1, b*1, respectively; average value of L*, a* and b* calculated from 5 points of one ultraviolet absorption glass were denoted by L*2, a*2, b*2, respectively. Lightness difference, color difference and total color difference ΔE*ab were given by

Lightness difference:ΔL*=L*1−L*2

Color difference:Δa*=a*1−a*2

Δb*=b*1−b*2

Total color difference:ΔE*ab=[(ΔL*).sup.2+(Δa*).sup.2+(Δb*).sup.2].sup.1/2.

[0095] (3) Weather resistance test: the glass substrate and the ultraviolet absorption glass were simultaneously put into the xenon lamp aging test apparatus (Model: CI4000, United States) subjected to the weather resistance test under the following conditions: cycle: drying for 102 min and raining for 18 min; wavelength: 300-400 nm; radiation intensity: (60±2) w/m.sup.2, black board temperature: (65±3°) C., tank temperature: (38±3°) C., relative humidity: (50±10)%, testing time: 1000 hours. After the weather resistance test, the samples were evaluated by step (1) and (2), UV-blocking rate and color difference ΔE*ab between the ultraviolet absorption glass and the glass substrate were calculated.

Example 2

[0096] A green float glass (FUYAO 3.2G) was provided as a glass substrate. The green float glass has a thickness of 3.2 mm, a color of L*=93.02, a*=−4.57, b*=1.62, a size of 150 mm×150 mm, and a UV-blocking rate of 59.11%. The glass substrate was treated in the same manner that of Example 1 to produce an ultraviolet absorption glass arranged with the ultraviolet absorption coating. The ultraviolet absorption glass was evaluated according to the performance evaluation method described in Example 1, and the evaluation results are shown in Table 1.

Example 3

[0097] A green float glass (FUYAO 3.2SG) was provided as a glass substrate. The green float glass has a thickness of 3.2 mm, a color of L*=89.47, a*=−7.23, b*=4.25, a size of 150 mm×150 mm, and a UV-blocking rate of 76.49%. The glass substrate was treated in the same manner that of Example 1 to produce an ultraviolet absorption glass arranged with the ultraviolet absorption coating. The ultraviolet absorption glass was evaluated according to the performance evaluation method described in Example 1, and the evaluation results are shown in Table 1.

Example 4

[0098] A white float glass (FUYAO 3.2C) was provided as a glass substrate. The white float glass has a thickness of 3.2 mm, a color of L*=95.53, a*=−1.13, b*=0.18, a size of 150 mm×150 mm, and a UV-blocking rate of 31.67%. In this embodiment, the glass substrate is treated without applying the ultraviolet absorption coating liquid of the present invention (deemed as a common glass). The common glass was evaluated according to the performance evaluation method described in Example 1, and the evaluation results are shown in Table 1.

Example 5

[0099] A green float glass (FUYAO 3.2G) was provided as a glass substrate. The green float glass has a thickness of 3.2 mm, a color of L*=92.98, a*=−4.15, b*=0.61, a size of 150 mm×150 mm, and a UV-blocking rate of 59.11%. In this embodiment, the glass substrate is treated without applying the ultraviolet absorption coating liquid of the present invention (deemed as a common glass). The common glass was evaluated according to the performance evaluation method described in Example 1, and the evaluation results are shown in Table 1.

Example 6

[0100] A green float glass (FUYAO solar 3.2SG) was provided as a glass substrate. The green float glass has a thickness of 3.2 mm, a color of L*=89.33, a*=−6.67, b*=3.16, a size of 150 mm×150 mm, and a UV-blocking rate of 76.49%. In this embodiment, the glass substrate is treated without applying the ultraviolet absorption coating liquid of the present invention (deemed as a common glass). The common glass was evaluated according to the performance evaluation method described in Example 1, and the evaluation results are shown in Table 1.

TABLE-US-00001 TABLE 1 Performance evaluation results of the ultraviolet absorption glass of Example 1-6 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Lta 89.25% 82.99% 75.24% 88.86% 82.86% 74.89% Tuv 0.15% 0.55% 0.28% 68.33% 40.89% 23.51% Te 79.06% 60.68% 47.46% 81.93% 62.84% 48.85% Tir 77.23% 47.36% 30.02% 76.59% 47.16% 29.83% L* 95.67 93.02 89.47 95.53 92.98 89.33 a* −1.53 −4.57 −7.23 −1.13 −4.15 −6.77 b* 1.28 1.62 4.25 0.18 0.61 3.16 Before.sup.1* UV-blocking rate 99.85% 99.45% 99.72% 31.67% 59.11% 76.49% decision ∘ ∘ ∘ x x x ΔE*ab 1.18 1.09 1.19 — — — decision ∘ ∘ ∘ — — — After.sup.2* UV-blocking rate 99.83% 99.45% 99.70% 31.68% 59.10% 76.49% decision ∘ ∘ ∘ x x x ΔE*ab 1.22 1.11 1.24 0.01 0.02 0.02 decision ∘ ∘ ∘ ∘ ∘ ∘ Note: Before.sup.1*: before weather resistance test; After.sup.2*: after weather resistance test.

[0101] In the above table, Lta is visible light transmittance of a wavelength of 380 nm-780 nm. Tuv is UV transmittance of a wavelength of 300 nm-380 nm. Te is total solar energy transmittance of a wavelength of 300 nm-2500 nm. Tir is infrared ray transmittance of a wavelength of 780 nm-2500 nm. UV-blocking rate=100%-UV transmittance, i.e. UV-blocking rate=100%-Tuv. The notation “o” represents “pass”, the notation “x” represents “fail”, and the notation “A” represents approach to a boundary value.

[0102] It can be seen from table 1 that the coating liquid used for forming ultraviolet absorption coating of the present invention can be used for various glass substrates, such as white float glass, green float glass, etc. An ultraviolet absorption coating forms on the surface of the glass substrate to bring a better UV-blocking rate and weather resistance to ultraviolet absorption glass.

Example 7

[0103] 10 g of TEOS and 0.099 g of sodium tungstate (Na.sub.2WO.sub.4) were used as raw material, while ethanol, isopropanol and deionized water were used as solvent. The raw material and solvent were stirred and ultrasonically dispersed. After the step of stirring and ultrasonically dispersing, a hydrolysis reaction and a condensation reaction were conducted between the raw material and solvent to produce a colloid B containing silicon dioxide in a form of partially hydrolyzed condensate. To 20 g of colloid B, 1.201 g of UV absorber 2,4-dihydroxy-2′, 4′-dimethoxybenzophenone and 0.02 g of KH560 (purchased from Nanjing Shuguang Company) were added while stirring to dissolve the UV absorber. A stirring was continued for 2 hours to obtain a coating liquid C used for forming an ultraviolet absorption coating.

[0104] A green float glass (FUYAO 3.2G) was provided as a glass substrate. The green float glass has a thickness of 3.2 mm, a size of 150 mm×150 mm, and a UV-blocking rate of 59.11%. 2.3 g of the coating liquid C were uniformly applied on the surface of the glass substrate, and then dried at 150° C. for 1 hour to obtain an ultraviolet absorption glass arranged with the ultraviolet absorption coating, where a molar ratio of tungsten trioxide (WO.sub.3) to silicon dioxide (SiO.sub.2) is 1:158.6, a molar ratio of tungsten trioxide (WO.sub.3) to the ultraviolet absorber is 1:16.1. The ultraviolet absorption glass was evaluated according to the performance evaluation method described in Example 1, and the evaluation results are shown in Table 2.

Example 8

[0105] The embodiment was prepared in the manner similar to that of Example 7, except that the sodium tungstate (Na.sub.2WO.sub.4) was added in an amount sufficient to adjust the molar ratio of tungsten trioxide (WO.sub.3) to silicon dioxide (SiO.sub.2) to a value of 1:350. An ultraviolet absorption glass arranged with the ultraviolet absorption coating was obtained. The ultraviolet absorption glass was evaluated according to the performance evaluation method described in Example 1, and the evaluation results are shown in Table 2.

Example 9

[0106] The embodiment was prepared in the manner similar to that of Example 7, except that the sodium tungstate (Na.sub.2WO.sub.4) was added in an amount sufficient to adjust the molar ratio of tungsten trioxide (WO.sub.3) to silicon dioxide (SiO.sub.2) to a value of 1:300. An ultraviolet absorption glass arranged with the ultraviolet absorption coating was obtained. The ultraviolet absorption glass was evaluated according to the performance evaluation method described in Example 1, and the evaluation results are shown in Table 2.

Example 10

[0107] The embodiment was prepared in the manner similar to that of Example 7, except that the sodium tungstate (Na.sub.2WO.sub.4) was added in an amount sufficient to adjust the molar ratio of tungsten trioxide (WO.sub.3) to silicon dioxide (SiO.sub.2) to a value of 1:180. An ultraviolet absorption glass arranged with the ultraviolet absorption coating was obtained. The ultraviolet absorption glass was evaluated according to the performance evaluation method described in Example 1, and the evaluation results are shown in Table 2.

Example 11

[0108] The embodiment was prepared in the manner similar to that of Example 7, except that the sodium tungstate (Na.sub.2WO.sub.4) was added in an amount sufficient to adjust the molar ratio of tungsten trioxide (WO.sub.3) to silicon dioxide (SiO.sub.2) to a value of 1:120. An ultraviolet absorption glass arranged with the ultraviolet absorption coating was obtained. The ultraviolet absorption glass was evaluated according to the performance evaluation method described in Example 1, and the evaluation results are shown in Table 2.

Example 12

[0109] The embodiment was prepared in the manner similar to that of Example 7, except that the sodium tungstate (Na.sub.2WO.sub.4) was added in an amount sufficient to adjust the molar ratio of tungsten trioxide (WO.sub.3) to silicon dioxide (SiO.sub.2) to a value of 1:100. An ultraviolet absorption glass arranged with the ultraviolet absorption coating was obtained. The ultraviolet absorption glass was evaluated according to the performance evaluation method described in Example 1, and the evaluation results are shown in Table 2.

Example 13

[0110] The embodiment was prepared in the manner similar to that of Example 7, except that the sodium tungstate (Na.sub.2WO.sub.4) was added in an amount sufficient to adjust the molar ratio of tungsten trioxide (WO.sub.3) to silicon dioxide (SiO.sub.2) to a value of 1:80. An ultraviolet absorption glass arranged with the ultraviolet absorption coating was obtained. The ultraviolet absorption glass was evaluated according to the performance evaluation method described in Example 1, and the evaluation results are shown in Table 2.

Example 14

[0111] The embodiment was prepared in the manner similar to that of Example 7, except that the ultraviolet absorber was added in an amount sufficient to adjust the molar ratio of tungsten trioxide (WO.sub.3) to ultraviolet absorber to a value of 1:25. An ultraviolet absorption glass arranged with the ultraviolet absorption coating was obtained. The ultraviolet absorption glass was evaluated according to the performance evaluation method described in Example 1, and the evaluation results are shown in Table 2.

Example 15

[0112] The embodiment was prepared in the manner similar to that of Example 7, except that the ultraviolet absorber was added in an amount sufficient to adjust the molar ratio of tungsten trioxide (WO.sub.3) to ultraviolet absorber to a value of 1:20. An ultraviolet absorption glass arranged with the ultraviolet absorption coating was obtained. The ultraviolet absorption glass was evaluated according to the performance evaluation method described in Example 1, and the evaluation results are shown in Table 2.

Example 16

[0113] The embodiment was prepared in the manner similar to that of Example 7, except that the ultraviolet absorber was added in an amount sufficient to adjust the molar ratio of tungsten trioxide (WO.sub.3) to ultraviolet absorber to a value of 1:18. An ultraviolet absorption glass arranged with the ultraviolet absorption coating was obtained. The ultraviolet absorption glass was evaluated according to the performance evaluation method described in Example 1, and the evaluation results are shown in Table 2.

Example 17

[0114] The embodiment was prepared in the manner similar to that of Example 7, except that the ultraviolet absorber was added in an amount sufficient to adjust the molar ratio of tungsten trioxide (WO.sub.3) to ultraviolet absorber to a value of 1:12. An ultraviolet absorption glass arranged with the ultraviolet absorption coating was obtained. The ultraviolet absorption glass was evaluated according to the performance evaluation method described in Example 1, and the evaluation results are shown in Table 2.

Example 18

[0115] The embodiment was prepared in the manner similar to that of Example 7, except that the ultraviolet absorber was added in an amount sufficient to adjust the molar ratio of tungsten trioxide (WO.sub.3) to ultraviolet absorber to a value of 1:10. An ultraviolet absorption glass arranged with the ultraviolet absorption coating was obtained. The ultraviolet absorption glass was evaluated according to the performance evaluation method described in Example 1, and the evaluation results are shown in Table 2.

Example 19

[0116] The embodiment was prepared in the manner similar to that of Example 7, except that the ultraviolet absorber was added in an amount sufficient to adjust the molar ratio of tungsten trioxide (WO.sub.3) to ultraviolet absorber to a value of 1:6. An ultraviolet absorption glass arranged with the ultraviolet absorption coating was obtained. The ultraviolet absorption glass was evaluated according to the performance evaluation method described in Example 1, and the evaluation results are shown in Table 2.

TABLE-US-00002 TABLE 2 Performance evaluation results of the ultraviolet absorption glass of Example 7-19 Before weather resistance test After weather resistance test UV-blocking rate decision ΔE*ab decision UV-blocking rate decision ΔE*ab decision Example 7 99.44% ∘ 1.1 ∘ 99.38% ∘ 1.12 ∘ Example 8 99.49% ∘ 0.75 ∘ 98.11% x 5.77 x Example 9 99.40% ∘ 0.77 ∘ 99.03% ∘ 1.39 Δ Example 10 99.43% ∘ 0.80 ∘ 99.19% ∘ 1.16 ∘ Example 11 99.56% ∘ 1.14 ∘ 99.56% ∘ 1.21 ∘ Example 12 99.48% ∘ 1.18 ∘ 99.47% ∘ 1.36 Δ Example 13 99.44% ∘ 2.12 x 99.42% ∘ 3.14 x Example 14 99.81% ∘ 0.87 ∘ 99.43% ∘ 2.10 x Example 15 99.75% ∘ 0.80 ∘ 99.50% ∘ 1.39 Δ Example 16 99.72% ∘ 0.81 ∘ 99.50% ∘ 1.17 ∘ Example 17 99.22% ∘ 0.77 ∘ 99.00% ∘ 1.10 ∘ Example 18 99.10% Δ 0.77 ∘ 99.02% Δ 0.97 ∘ Example 19 98.13% x 0.72 ∘ 97.91% x 0.93 ∘

[0117] Compared Example 7 with 8-13, it can be seen from table 2 that a molar ratio of WO.sub.3 to silicon dioxide in a range of 1/300-1/100, preferably 1/180-1/120 will bring a better UV-blocking rate and weather resistance to ultraviolet absorption glass.

[0118] Compared Example 7 with 14-19, it can be seen from table 2 that a molar ratio of WO.sub.3 to ultraviolet absorber in a range of 1/20-1/10, preferably 1/18-1/12 will bring a better UV-blocking rate and weather resistance to ultraviolet absorption glass.

Example 20

[0119] The embodiment was prepared in the manner similar to that of Example 7, except that sodium tungstate (Na.sub.2WO.sub.4) and the ultraviolet absorber were not added. A coating glass arranged with a coating was obtained. The coating glass was evaluated according to the performance evaluation method described in Example 1, and the evaluation results are shown in Table 3.

Example 21

[0120] The embodiment was prepared in the manner similar to that of Example 7, except that the ultraviolet absorber was not added. A coating glass arranged with a coating was obtained. The coating glass was evaluated according to the performance evaluation method described in Example 1, and the evaluation results are shown in Table 3.

TABLE-US-00003 TABLE 3 Performance evaluation results of the glass obtained from Example 20-21 Lta Tuv Te Tir L* a* b* Example 20 83.35% 41.42% 63.05% 47.10% 93.20 −4.18 0.55 Example 21 83.57% 42.01% 62.82% 47.12% 93.29 −4.22 0.61

[0121] It can be seen from table 3 that a coating glass without adding sodium tungstate (Na.sub.2WO.sub.4) and ultraviolet absorber (i.e. the coating contains no WO.sub.3 and ultraviolet absorber) has no UV-blocking and IR-blocking function. Similarly, the coating glass adding Na.sub.2WO.sub.4 without the ultraviolet absorber (i.e. the coating contains WO.sub.3 but no ultraviolet absorber) has no UV-blocking and IR-blocking function. It indicates that the WO.sub.3 blocks neither ultraviolet light nor infrared ray, but plays an important role in storing and releasing the electrons excited by the UV light in the ultraviolet absorber.

[0122] While the present invention has been described with reference to particular embodiments, it will be understood that the embodiments are illustrative and that the invention scope is not so limited. Alternative embodiments of the present invention will become apparent to those having ordinary skill in the art to which the present invention pertains. Such alternate embodiments are considered to be encompassed within the scope of the present invention. Accordingly, the scope of the present invention is described by the appended claims and is supported by the foregoing description.