WO2006137454A1 - Transparent article and process for production thereof - Google Patents

Abstract

A transparent article comprising a substrate (1) and an organic-inorganic composite film (2) formed on the substrate (1), the organic-inorganic composite film (2) comprising silica as the inorganic oxide (main ingredient) and a light absorbent as at least a part of the organic substance, and the composite film (2) being not delaminated from the substrate (1) after subjecting the article to Taber abrasion test according to Japanese Industrial Standards (JIS) R 3212. The composite film (2) is formed from a coating solution containing a silicon alkoxide, a strong acid, water, an alcohol and an organic substance by sol-gel method. At least a part of the organic substance is a light absorbent. In the solution, for example, the content of the silicon alkoxide exceeds 3% by mass in terms of SiO2 concentration, the molar concentration of protons by mass falls within the range from 0.001 to 0.2 mol/kg, and the number of moles of water is four times the total number of moles of the silicon atoms contained in the silicon alkoxide or higher. By employing the sol-gel method, a film having an excellent mechanical strength can be produced without the need of heating the substrate to a temperature higher than 400°C even when the film thickness is increased to 250 nm or more.

Description

 Specification

 Transparent article and method for producing the same

 Technical field

 [0001] The present invention relates to a transparent article including a transparent substrate and a thin film formed on the transparent substrate, and the thin film including a light absorber which is an organic substance. The present invention also relates to a method for producing this transparent article by the sol-gel method.

 Background art

 [0002] Glass materials are generally hard and are also used in the form of a film covering a substrate. However, if a glassy film is to be obtained, the melting method requires high-temperature treatment, which limits the materials constituting the substrate and the film.

 [0003] In the sol-gel method, a metal organic or inorganic compound solution is used as a starting material, and the metal oxide or hydroxide fine particles are dissolved in the solution by hydrolysis and condensation polymerization of the compound in the solution. In this method, the sol is further solidified by gelling, and the gel is heated as necessary to obtain an oxide solid.

 [0004] The sol-gel method makes it possible to produce a glassy film at a low temperature. A method for forming a silica-based film by the sol-gel method is disclosed in, for example, Japanese Patent Application Laid-Open No. 11-269657.

 [0005] Generally, a silica-based film formed by a sol-gel method is inferior in mechanical strength as compared to a glassy film obtained by a melting method.

 [0006] In JP-A-11-269657, at least one of silicon alkoxide and its hydrolyzate (including partially hydrolyzed hydrolyzate) is 0.0010 to 3% by weight in terms of silica, acid 0.001 A method of forming a silica-based film by applying an alcohol solution containing 0 to 1.0 N and water of 0 to 10% by weight to a substrate as a coating solution is disclosed.

[0007] The silica-based film obtained by this method has a strength enough to withstand the dry cloth abrasion test, and although it is not sufficient, it is a good mechanical film as a film obtained by the sol-gel method. Has strength. However, a silica-based film that can be formed by the method disclosed in Japanese Patent Application Laid-Open No. 11-269657 is limited to a maximum thickness of 250 ηm in order to ensure a practical appearance. The thickness of the silica-based film formed by the sol-gel method is usually 100 to 20 About Onm.

 [0008] By applying the coating liquid a plurality of times to form a multilayer film, the silica-based film can be thickened. However, the adhesion at the interface of each layer is lowered, and the wear resistance of the silica-based film may be lowered. There is also a problem that the manufacturing process of the silica film is complicated.

 [0009] Because of the circumstances as described above, it has been difficult to obtain a silica-based film excellent in mechanical strength and thick enough to have a film thickness exceeding 250 nm by the sol-gel method.

 [0010] A technique for forming an organic-inorganic composite film in which an inorganic material and an organic material are combined by a sol-gel method has been proposed. Since the sol-gel method is characterized by film formation at a low temperature, a silica-based film containing an organic substance can be formed. The organic-inorganic composite film by the sol-gel method is disclosed, for example, in JP-A-3-212451, JP-A-3-56535, and JP-A-2002-338304.

 [0011] In order to improve the mechanical strength of the silica-based film by the sol-gel method, it is desirable to heat-treat the silica-based film at 450 ° C or higher. However, if the organic-inorganic composite film is heat-treated at such a high temperature, organic substances in the film are decomposed. The restriction that the heat treatment must be performed within a range in which the organic substance does not decompose limits the improvement of the mechanical strength of the film to be formed even in the liquid phase film forming method other than the sol-gel method. For this reason, it has been considered difficult to form a silica-based film having excellent mechanical strength when an organic substance is included.

 [0012] For various purposes, a film containing a light absorber, which is an organic substance, may be formed on a transparent substrate such as glass or resin. Such a film is formed according to the absorption wavelength of the light absorber, such as a colored coating, a polarizing plate, a color conversion filter (Japanese Patent Laid-Open No. 2000-182780), an optical filter (Japanese Patent Laid-Open No. 2005-189738), a color filter ( Many applications such as an optical recording medium represented by an optical disc (Japanese Patent Laid-Open No. 20003-217174) and a light emitting element (Japanese Patent Laid-Open No. 2000-150156) and an optical recording medium (Japanese Patent Laid-Open No. 20003-217174) have been made.

 Disclosure of the invention

 [0013] An object of the present invention is to provide a silica-based film having excellent mechanical strength while containing a light absorber that is an organic substance.

[0014] The present invention relates to a transparent substrate, an organic substance and an inorganic acid formed on the surface of the transparent substrate. The organic-inorganic composite film includes silica as the inorganic oxide, the organic-inorganic composite film includes the silica as a main component, and the organic-inorganic composite film. After the Taber abrasion test specified in JIS R 3212 performed on the surface of the composite film, the organic-inorganic composite film does not peel from the transparent substrate, and at least a part of the organic substance is a UV absorber. Provide the goods.

 [0015] Another aspect of the present invention is a transparent article comprising a transparent substrate and an organic-inorganic composite film containing an organic material and an inorganic oxide formed on the surface of the transparent substrate. The inorganic-inorganic composite film contains silica as the inorganic oxide, the organic-inorganic composite film is mainly composed of the silica, and is subjected to the Taber abrasion test specified in JIS R 3212 performed on the surface of the organic-inorganic composite film. Later, there is provided a transparent article in which the organic-inorganic composite film does not peel from the transparent substrate and at least a part of the organic substance is an organic dye.

 In the present specification, the main component means that the content is the highest and the component is! The content is evaluated on a mass% basis. The Taber abrasion test according to JIS R 3212 can be performed using a commercially available Taber abrasion tester. This test is a wear test at a rotation speed of 1000 times while applying a load of 500g weight as specified in the above 6JIS.

 [0017] Another aspect of the present invention includes a transparent substrate, and an organic-inorganic composite film containing an organic material and an inorganic oxide formed on the surface of the transparent substrate. The method for producing a transparent article, comprising silica as the inorganic acid compound, wherein the organic-inorganic composite film is mainly composed of the silica, and at least a part of the organic material is an ultraviolet absorber. Applying the formation solution of the organic-inorganic composite film on the surface, and removing at least a part of the liquid component contained in the formation solution from the formation solution applied to the transparent substrate, Includes silicon alkoxide, strong acid, water, alcohol, and organic substance, and at least a part of the organic substance is an ultraviolet absorber, and the silicon alkoxide has a concentration power. When the silicon atom contained in is converted to SiO, it is expressed by the SiO concentration and exceeds 3% by mass.

 twenty two

The concentration of water is in the range of 0.001-0.2 molZkg, expressed by the mass concentration of protons assuming that the strong acid protons are completely dissociated. 4 times or more the total number of moles of silicon atoms contained in the alkoxide, Provided is a method for producing a transparent article, in which at least a part of a liquid component contained in a forming solution applied to the transparent substrate is removed while maintaining the bright substrate at a temperature of 400 ° C or lower.

[0018] From another aspect, the present invention includes a transparent substrate, and an organic-inorganic composite film containing an organic material and an inorganic oxide formed on the surface of the transparent substrate. A method for producing a transparent article, comprising silica as the inorganic acid compound, wherein the organic-inorganic composite film comprises the silica as a main component, and at least a part of the organic material is an organic dye. Applying the formation solution of the organic-inorganic composite film to the surface, and removing at least a part of the liquid component contained in the formation solution from the formation solution applied to the transparent substrate. Includes a silicon alkoxide, a strong acid, water, alcohol, and an organic substance, and includes an organic dye as the organic substance, and the silicon alkoxide has a concentration of the silicon alkoxide. A near-atomic to the SiO

 2 When expressed in terms of SiO concentration when converted, it exceeds 3% by mass, and the concentration of the strong acid is

 2

 Acid power It is in the range of 0.001 to 0.2 molZkg expressed by the molar concentration of protons when it is assumed that protons are completely dissociated, and the number of moles of water is the silicon contained in the silicon alkoxide. At least a part of the liquid component contained in the forming solution applied to the transparent substrate is removed while maintaining the transparent substrate at a temperature of 400 ° C or lower, which is 4 times or more the total number of moles of atoms. A method for producing a transparent article is provided.

 [0019] According to the present invention, an organic-inorganic composite film having excellent mechanical strength and high light absorption ability can be formed by the sol-gel method even when the film thickness is greater than 250 nm. Despite containing an organic substance, the organic-inorganic composite film according to the present invention can have excellent wear resistance comparable to a glass plate obtained by a melting method.

 [0020] According to the production method of the present invention, it is possible to form a film having excellent mechanical strength and high light absorption ability by, for example, applying a forming solution once to a thickness exceeding 250 ηm.

Brief Description of Drawings

FIG. 1 is a cross-sectional view showing an example of a transparent article of the present invention.

[FIG. 2] FIG. 2 shows an example of a usage state of the backlight for a liquid crystal display panel of the present invention. FIG.

 FIG. 3 is a cross-sectional view showing an example of a usage state of the liquid crystal display panel of the present invention.

 BEST MODE FOR CARRYING OUT THE INVENTION

[0022] Hereinafter, the sol-gel process will be described first.

 [0023] In the case of a sol-gel method using silicon alkoxide as a starting material, silicon alkoxide contained in a film-forming solution (coating solution) is subjected to hydrolysis reaction and condensation in the presence of water and a catalyst in the coating solution. Through the polymerization reaction, it becomes an oligomer through a siloxane bond, and the coating solution becomes a sol state along with this.

 [0024] The coating solution in a sol state is applied to a substrate (transparent substrate), and an organic solvent such as alcohol and water are volatilized from the applied coating solution. In this drying step, the oligomer is concentrated, the condensation polymerization reaction proceeds, the molecular weight increases, and the fluidity is eventually lost. Thus, a film having a semi-solid gel force is formed on the substrate. Immediately after Gelui, organic solvent and water are filled in the gaps in the network of siloxane bonds. When the solvent or water volatilizes from the gel, the siloxane polymer shrinks, the condensation polymerization reaction further proceeds, and the film is cured.

 [0025] In the gel obtained by the conventional sol-gel method, the gap left after the organic solvent and water are removed remains as pores without being completely filled even after heat treatment up to about 400 ° C. Was. If pores remain, the mechanical strength of the membrane will not be high enough. For this reason, conventionally, in order to obtain a hard film, a heat treatment at a high temperature exceeding 400 ° C., for example, 450 ° C. or higher, preferably 500 ° C. or higher is required.

 [0026] The relationship between the reaction and temperature in the heat treatment of the silica-based film by the sol-gel method will be described in more detail. The heat treatment at about 100 to 150 ° C evaporates the solvent and water contained in the coating solution. In the heat treatment at about 250 to 400 ° C, if the organic material is contained in the raw material, the organic material is decomposed and evaporated. When heat-treated at a temperature exceeding 400 ° C, organic materials usually do not remain in the film. In heat treatment at about 500 ° C or higher, the gel skeleton contracts and the film becomes dense.

[0027] As described above, in a normal sol-gel reaction, immediately after gelation, the formed net The organic solvent and water are filled in the gaps of the cake. It is known that the size of this gap depends on the form of polymerization of the silicon alkoxide in the solution.

 [0028] The form of polymerization varies greatly depending on the pH of the solution. In an acidic solution, oligomers of silicon alkoxide tend to grow linearly. When such a liquid is applied to the substrate, the linear oligomers are folded to form a network structure, and the resulting film becomes a dense film with relatively small gaps. However, since the linear polymer is solidified in a folded state, the microstructure is not strong and cracks easily occur when solvent and water volatilize through gaps.

 [0029] On the other hand, spherical oligomers are likely to grow in an alkaline liquid. When such a liquid is applied to the substrate, a structure in which spherical oligomers are connected to each other is formed, and a film having a relatively large gap is formed. Since this gap is formed by bonding and growing spherical oligomers, cracks are unlikely to occur when the solvent or water volatilizes from the gap.

 [0030] The present inventor forms a dense and crack-free film as a thick film under certain conditions by appropriately adjusting the concentration of strong acid and the amount of water in an acidic region where a relatively dense film can be formed. The present invention has been completed by finding the knowledge that it can be performed and further developing this knowledge.

 [0031] It is known that the isoelectric point of silanol is 2. This is because the pH of the coating solution

 2 indicates that silanol can be present most stably in the liquid. That is, even when a large amount of hydrolyzed silicon alkoxide is present in the solution, if the pH of the solution is about 2, the probability that an oligomer is formed by the dehydration condensation polymerization reaction is very low. As a result, it becomes easy to exist in the coating liquid in a hydrolyzed silicon alkoxide monomer or in a low polymerization state.

[0032] In the region where the pH is about 2, silicon alkoxide is stabilized in a state where one alkoxyl group per molecule is hydrolyzed to form silanol. For example, tetraalkoxysilane has four alkoxyl groups, one of which is hydrolyzed and stabilized in the form of silanol.

[0033] When the strong acid is added to the sol-gel solution and the proton of the strong acid is completely dissociated, the molar mass of proton (hereinafter, simply referred to as “proton concentration”) is: 001-0.

2molZkg, preferably about 0.001-0.ImolZkg, the pH of the solution is It will be about 3 to 1. When the pH is adjusted to this range, silicon alkoxide can be stably present as a monomer or a low-polymerized silanol in the coating solution.

 [0034] The coating liquid contains a mixed solvent of water and alcohol, and other solvents can be added as necessary. In the case of such a mixed solvent, a strong acid is used, and By adjusting the proton molar concentration in the above range when it is assumed that the proton is completely dissociated, a liquid having a pH of about 2 can be obtained.

 In calculating the molar concentration of protons, it is not necessary to consider protons having an acid dissociation index of 1S 4 or higher in water of the acid used. For example, since the acid dissociation index of acetic acid, which is a weak acid, in water is 4.8, even if acetic acid is included in the coating solution, the proton of acetic acid is not included in the above proton concentration.

 [0036] Further, for example, there are three stages of dissociation of phosphoric acid, and three protons may be dissociated per molecule. However, the first-stage dissociation index is 2.15, which can be regarded as a strong acid, but the second-stage dissociation index is 7.2, and the third-stage dissociation index is even higher. Therefore, the above proton concentration premised on dissociation from a strong acid should be calculated assuming that only one proton dissociates from one molecule of phosphoric acid. Phosphoric acid after the dissociation of one proton is not a strong acid. It is not necessary to consider the second and subsequent proton dissociation. In the present specification, the strong acid specifically refers to an acid having protons having an acid dissociation exponential force in water.

 [0037] The reason for defining the proton concentration as the concentration when the proton of the strong acid is completely dissociated is that the degree of dissociation of the strong acid is accurately obtained in a mixture of an organic solvent such as alcohol and water. This is because it is difficult.

 [0038] When the pH of the coating solution is maintained at about 1 to 3 and applied to the substrate surface and dried in this manner, the silicon alkoxide in a low polymerization state is densely filled, so that the pores are small. A dense film can be obtained.

[0039] This film is dense. Due to insufficient hydrolysis and polycondensation reaction of silicon alkoxide, heating at a low temperature range of 200 to 300 ° C does not exceed a certain hardness. . Therefore, it was decided to add water excessively with respect to the silicon alkoxide so that it proceeds easily after the coating of the coating liquid with the hydrolysis and condensation polymerization reaction force of the silicon alkoxide. Hydrolysis and polycondensation reactions are easy to proceed! Then, the film becomes hard without being heated to a high temperature. Specifically, the maximum number of moles required for hydrolysis relative to the total number of moles of silicon atoms contained in the silicon alkoxide, that is,

It is assumed that water with a mole number more than 4 times is added. The upper limit of the amount of water added can be, for example, 20 times.

 [0040] When the coating solution is dried, water is also evaporated in parallel with the volatilization of the solvent. Considering this, the number of moles of water is preferably more than 4 times, for example, 5 to 20 times the total number of moles of silicon atoms.

 [0041] In silicon alkoxide, up to four alkoxyl groups can be bonded to one silicon atom. An alkoxide having a small number of alkoxyl groups reduces the number of moles of water required for hydrolysis. In addition, tetraalkoxysilane in which four alkoxyl groups are bonded to a silicon atom may be a polymer (for example, “Ethylsilicate manufactured by Colcoat”).

40 ”), the total number of moles of water required for hydrolysis is less than four times that of silicon atoms (assuming that the number of moles of Si in the polymer is n (n≥2)) The stoichiometric amount of water required for hydrolysis is (2n + 2) moles). The higher the degree of polymerization, the lower the number of moles of water required for hydrolysis. Therefore, in reality, the number of moles of water required for hydrolysis of silicon alkoxide may be less than four times the total number of moles of silicon atoms contained in silicon alkoxide. In consideration of the preferable condition, in the method according to the present invention, the coating solution contains water having a mole number more than 4 times the total mole number of silicon atoms.

[0042] When water exceeding the stoichiometric amount required for hydrolysis is added, capillary shrinkage due to evaporation of water in the drying process increases, and silicon alkoxide tends to diffuse and concentrate. Hydrolysis and condensation polymerization reactions are promoted. As the solvent volatilizes and water evaporates, the pH of the applied coating solution fluctuates in the above range. This is another factor that promotes hydrolysis and polycondensation reactions. Thus, when a dense film is formed and the hydrolysis and polycondensation reactions are sufficiently advanced, a hard film is formed. As a result, a single-layer film having excellent mechanical strength can be obtained by heat treatment at a lower temperature than in the past.

When this method is used, a silica-based film having excellent mechanical strength can be obtained even if it is thick. In order to obtain a thick film, for example, the silicon atom contained in the silicon alkoxide is adjusted according to the SiO concentration when converted to SiO so that the silicon alkoxide concentration is relatively high.

 Prepare the coating solution so that it exceeds 3% by weight.

[0044] In the method according to the present invention, since it is sufficient to perform baking at a lower temperature than in the past, even when an organic substance typified by a light absorber is added to the coating liquid, the organic substance remains without being decomposed in the film. Thus, according to the present invention, it is possible to form a silica-based film having excellent mechanical strength and high light absorption ability. This silica film itself is excellent in mechanical strength. Therefore, it is not necessary to form a hard coat layer or the like on the silica film in order to obtain practical mechanical strength. Thus, the organic-inorganic composite film of the present invention is excellent in mechanical strength even if it is a single layer.

 [0045] A hydrophilic organic polymer may be further added to the coating solution. The hydrophilic organic polymer suppresses the occurrence of cracks that may occur as the liquid components contained in the applied coating liquid evaporate. In addition, the hydrophilic organic polymer is interposed between the silica particles generated in the liquid, and alleviates the influence of film shrinkage due to evaporation of the liquid component. Thus, it is considered that when the hydrophilic organic polymer is added, excessive curing shrinkage of the film can be suppressed, so that the stress in the film is relieved. The hydrophilic organic polymer plays a role of suppressing the shrinkage of the film and maintaining the mechanical strength of the film.

 [0046] In the method according to the present invention, it is sufficient to heat the film at a lower temperature than in the prior art, and thus the hydrophilic organic polymer remains in the film even after heating. For this reason, even if the film is thicker, it is possible to obtain a film having excellent mechanical strength in a state where the hydrophilic organic polymer is present in the film. As described above, the organic-inorganic composite film may contain a hydrophilic organic polymer as an organic substance.

 [0047] The hydrophilic organic polymer may be added to the coating solution in advance. In the organic-inorganic composite film formed from this coating solution, it is considered that organic and inorganic substances are complexed at the molecular level.

 [0048] Referring to various experimental results, the hydrophilic organic polymer seems to suppress the growth of silica particles formed by the sol-gel reaction, and suppress the porosity of the film.

[0049] Examples of hydrophilic organic polymers include polymers containing polyoxyalkylene groups. . Examples of the hydrophilic organic polymer containing a polyoxyalkylene group include polyethylene glycol and polyether type surfactants.

 [0050] In the coating liquid, a hydrophilic organic polymer having an ultraviolet absorbing ability may be added as an ultraviolet absorbent, or a hydrophilic organic polymer having no ultraviolet absorbing ability may be added.

 [0051] Examples of hydrophilic organic polymers that do not have the ability to absorb ultraviolet rays include polymers containing polyoxyalkylene groups (polyalkylene oxide structures), polybulur prolactams, PVP (polyvinylpyrrolidone) and butyl ether. A copolymer etc. can be illustrated.

 [0052] The coating liquid may contain other components, for example, a phosphorus source such as phosphoric acid, phosphate, and phosphate ester.

 [0053] By improving the sol-gel method as described above, according to the present invention, the substrate strength does not peel even when the Taber abrasion test stipulated in JIS R 3212 is applied even though it contains organic matter. An article in which an organic-inorganic composite film having a light absorbing ability is formed is provided.

 [0054] The film thickness of the organic-inorganic composite film is, for example, more than 250 nm and not more than 5 μm, preferably more than 300 nm and not more than 5 μm, and more preferably not less than 500 nm and not more than 5 μm. This film thickness may be 4 m or less, or more than 1 m.

 [0055] According to the present invention, the haze ratio of the portion to which the Taber abrasion test is applied, which is measured after the Taber abrasion test, can be 4% or less, further 3% or less. This is a mechanical strength corresponding to a glassy film obtained by the melting method.

 [0056] In the organic-inorganic composite film according to the present invention, the mass of an organic substance typified by a light absorber (for example, an ultraviolet absorber, an organic dye) is 0.1 to 40% with respect to the total mass of the organic-inorganic composite film, In particular, it is preferably 2 to 40%. The organic-inorganic composite film according to the present invention may contain phosphorus.

[0057] The organic-inorganic composite film according to the present invention may contain fine particles. By adding fine particles, a function can be added to the film. In the present specification, “fine particles” are used as a term meaning particles having a particle diameter of 5 nm or more. The particle size of the “fine particles” is 5 nm to 10 / zm, preferably 5 nm to 300 nm. The fine particles are not particularly limited. For example, organic fine particles, conductive oxide fine particles (for example, indium stannate fine particles, antimony tin oxide) Fine particles). Examples of the organic fine particles include latex.

 [0058] According to the present invention, while containing 1% by mass or more of fine particles, the haze ratio power of the portion to which the Taber abrasion test is applied, which is measured after the Taber abrasion test, is preferably 3% or less. It is also possible to form an organic / inorganic composite film.

 [0059] In the method of the present invention, a coating solution containing silicon alkoxide, strong acid, water and alcohol, and further containing an organic substance is used. At least a part of the organic substance is a light absorber. Another part of the organic substance may be a hydrophilic organic polymer that does not have ultraviolet absorbing ability. The hydrophilic organic polymer is usually added as a component separate from the strong acid, but a polymer that functions as a strong acid, for example, a polymer containing a phosphate group, is added as at least a part of the strong acid. Also good.

 [0060] The ultraviolet absorber is a component that increases the absorption of the film in the ultraviolet region (the boundary on the long wavelength side is 400 nm). The ultraviolet absorber is, for example, at least one compound selected from benzotriazole, benzophenone, hydroxyphenol triazine, and cyanoacrylate. Some of these compounds are sold as dyes, but in consideration of general classification, they are not considered as organic dyes in this specification. The UV absorber is at least one organic dye selected from polymethine, imidazoline, coumarin, naphthalimide, perylene, azo, isoindolinone, quinophthalone and quinoline strengths. Moyo!ヽ. When an organic dye having ultraviolet absorbing ability is used, ultraviolet rays on the long wavelength side can be more reliably shielded. The polymethine organic dye contains at least one organic dye selected from cyanine-based, merocyanine-based, stiltyl-based and rhodocyanine-based forces. The azo organic dye includes a stilbene organic dye.

[0061] In this specification, an organic dye is used as a term meaning an organic substance having absorption at a wavelength of 300 nm to 2500 nm. The organic dye may contain, for example, organic dyes having the above-described ultraviolet absorbing ability such as polymethine having absorption at a wavelength of 300 nm to 400 nm. Organic dyes are also, for example, organic dyes that do not have UV-absorbing ability, more specifically, those that do not have UV-absorbing ability, visible light range (400 to 700 nm) and Z or near infrared range (700 to 2500 nm). May be an organic dye having absorption. Organic The dye may contain an organic dye having absorption in the near infrared region.

 [0062] Since the organic dye and the light absorber that is Z or an ultraviolet absorber can be sufficiently dissolved and dispersed in the coating liquid, the light absorber is not contained as fine particles in the organic-inorganic composite film of the present invention. Also good. Thus, the organic-inorganic composite film of the present invention may be a film that does not contain fine particles.

 [0063] In addition to the ultraviolet absorber, the organic substance may further contain at least one selected from an organic dye having no ultraviolet absorbing ability and a hydrophilic organic polymer having no ultraviolet absorbing ability.

 [0064] The organic-inorganic composite film or coating liquid may contain, as an organic substance, an organic dye having absorption in the near infrared region in addition to the ultraviolet absorber. Further, the coating solution of the organic / inorganic composite film may contain, in addition to the ultraviolet absorber, at least one selected from indium stannate and antimony stannate fine particles as fine particles. . In addition, the organic-inorganic composite film or coating liquid contains, as an organic substance, an organic dye having absorption in the near-infrared region in addition to an ultraviolet absorber, and as fine particles, indium stannate and antimony stannate. It may contain at least one selected from fine particles.

 [0065] In the present specification, whether or not an organic substance has an ultraviolet absorbing ability is determined based on whether or not it has absorption at a wavelength of 400 nm or less. In addition, whether or not organic substances have absorption in the near infrared region is determined based on whether or not they have absorption in the wavelength range of 700 to 2500 nm.

 [0066] The silicon alkoxide is preferably at least one selected from tetraalkoxysilane and its polymer strength. Silicon alkoxides and polymers thereof may contain hydrolyzed alkoxyl groups.

 [0067] The concentration of silicon alkoxide is expressed as the SiO concentration when silicon atoms contained in the silicon alkoxide are converted to SiO, and it is sufficient if it is 3% by mass or more.

twenty two

 % Or less, 14 mass% or less, or even less than 14 mass%. If the silicon alkoxide concentration in the coating solution is too high, cracks may occur that cause the substrate to peel off.

[0068] The organic substance concentration is the same as the concentration of silicon alkoxide expressed by SiO concentration. It is good to set it as 60 mass% or less with respect to this SiO. The concentration of organic matter is 0

twenty two

 It is preferable to be 1% by mass or more, particularly 5% by mass or more.

[0069] In the drying step in the method of the present invention, at least a part, preferably substantially all, of the liquid components of the forming solution applied onto the substrate, for example, water and alcohol, are removed.

 [0070] The drying step includes an air drying step performed at room temperature (for example, 20 ° C), and a heat treatment step performed in an atmosphere at a temperature higher than room temperature and not higher than 300 ° C, for example, 100 to 200 ° C. Are preferably included in this order. The air-drying process should be performed in an atmosphere where the relative humidity is controlled to 40% or less, and even 30% or less. By controlling the relative humidity to the above level, the occurrence of film cracks can be prevented more reliably. The lower limit of the relative humidity in the air drying process is not particularly limited, and may be 15% or even 20%. In the air drying process, the force varies depending on the application method of the forming solution. In any application method, there is an air drying time of at least several seconds (for example, 2 to 3 seconds or more). The upper limit of the air drying time is, for example, several minutes to several tens of minutes or less, for example, 5 minutes, 10 minutes, 20 minutes, etc., depending on the convenience of the batch in the manufacturing process, and may be 24 hours or less.

 [0071] It is preferable to control the atmosphere in contact with the substrate during application of the forming solution. In the method of the present invention, the forming solution is preferably applied to the transparent substrate while maintaining the relative humidity of the atmosphere at 40% or less. If the relative humidity of the atmosphere during application is too high, the film may not be sufficiently densified and cracks may occur in the film.

 [0072] According to the present invention, the step of applying the forming solution and the step of removing at least a part of the liquid component contained in the applied forming solution are performed once each. For example, it is possible to form a single-layer organic-inorganic composite film that is thick to some extent when the film thickness is, for example, more than 250 nm and not more than 5 m.

[0073] Examples of the strong acid used in the production method of the present invention include hydrochloric acid, nitric acid, trichloroacetic acid, trifluoroacetic acid, sulfuric acid, phosphoric acid, methanesulfonic acid, paratoluenesulfonic acid, and oxalic acid. Of the strong acids, volatile acids can be preferably used because they do not volatilize when heated and do not remain in the cured film. It is known that if acid remains in the cured film, it may hinder the bonding of inorganic components and the film hardness may decrease. [0074] The organic-inorganic composite film according to the present invention has a film hardness comparable to that of molten glass by heat treatment at a relatively low temperature. Even if this organic-inorganic composite film is applied to window glass for automobiles or buildings, it can withstand practical use.

[0075] Many organic substances start to decompose at a temperature of 200 to 300 ° C. Even if it is an inorganic substance, for example, indium stannate oxide (ITO) fine particles have a reduced heat shielding ability when heated to 250 ° C or higher.

 In the present invention, the transparent substrate may be heated when removing the liquid component, if necessary. In this case, the heating temperature of the transparent substrate should be adjusted as appropriate according to the heat resistance of the functional material. In the present invention, it is possible to sufficiently harden the organic-inorganic composite film even by heating at 100 to 300 ° C.

 [0077] Examples of the transparent substrate include glass plates and resin plates. Use of a transparent substrate having a thickness exceeding 0.1 mm, further 0.3 mm or more, particularly 0.5 mm or more can more reliably prevent cracks and film peeling after the Taber abrasion test. The upper limit of the thickness of the substrate is not particularly limited, but may be, for example, 20 mm or less, and further 10 mm or less.

[0078] According to the present invention, it is possible to provide a transparent article having a visible light transmittance of 70% or more, preferably 85% or more while exhibiting excellent ultraviolet absorbing ability. However, the term “transparent article” as used in this specification means an article having transparency that allows the opposite side to be seen through the article, and its visible light transmittance is limited to the above. Do not mean. In the present invention, not only this but also various glass plates except for a glass plate strengthened by a rapid cooling treatment may be used as a transparent substrate. . The rapid cooling process is a process in which a heated glass plate is rapidly cooled with its surface force (usually air is blown onto the surface of the glass plate) to form a compressive stress layer on the surface of the glass plate.

 [0079] In order to further improve the ultraviolet shielding performance of the transparent article, a glass plate having a glass composition containing an ultraviolet absorbing component may be used as the transparent substrate. Examples of the ultraviolet absorbing component include at least one selected from acid-titanium and acid-cerium forces. As a transparent substrate, a glass plate with a higher content of Fe 2 O, which is an ultraviolet absorbing component, than usual is used.

 twenty three

It may be used. As such a glass plate, a glass group containing 0.2% by mass or more of Fe 2 O is used. A glass plate having a composition is preferred. Glass plates containing UV-absorbing components have a UV transmittance of 5-40%, a light transmittance of 20-50% at a wavelength of 370 nm, and a visible light transmittance of 70% when formed to a thickness of 3.1 mm. It is preferable to have the above composition.

 [0080] The transparent article according to the present invention has an ultraviolet transmittance of 1.1% or less, and in some cases 0.8% or less, by using, for example, the above glass plate containing an ultraviolet absorbing component as a transparent substrate. The light transmittance at a wavelength of 370 nm may be 2.0% or less, and in some cases, 1.6% or less.

 [0081] Even if the transmittance of ultraviolet light is low, if the transmittance of light on the long wavelength side in the ultraviolet region is high, the effect of being affected by the shielding rate of light on the long wavelength side in the ultraviolet region, such as the sun protection effect. You cannot get enough fruit. When the transparent article according to the present invention is used as a window glass, a high prevention effect can be obtained for sunburn that promotes skin aging and induces skin cancer. Thus, the transparent article according to the present invention may be a window glass for vehicles or buildings. In this case, the transparent substrate is preferably a glass plate.

 [0082] The transparent article of the present invention is not limited to a high ultraviolet shielding ability but can also have a high shielding ability and a near infrared ray and visible light having a predetermined wavelength.

 [0083] The visible light (blue light) of Takagi Nergi is similar to ultraviolet rays, for example, adjustment of biological rhythm represented by the body clock, secretion of growth hormone, cyclic activity of gonadal, blood pressure adjustment, immune It affects the function of maintaining the vital functions of the hypothalamus and the pituitary system. For example, looking at intense blue light at night will disturb the body clock. Also, for example, short-wavelength light below blue light is imaged slightly in front of the retina, so it scatters before reaching the retina and feels dazzling, or causes stress and causes immune deficiency. Sometimes. According to the transparent article of the present invention, it is possible to remarkably shield short-wavelength light of blue light or less that has a great adverse effect on a living body, and provide a healthy and comfortable space.

[0084] The wavelength of the optical signal used in the remote operation terminal of the electronic device is in the range of 800 to 1200 nm. For this reason, for example, if near-infrared light (wavelength 700 to 1200 nm) on the short wavelength side that generates plasma display power leaks into the usage environment of the terminal, the electronic device cannot correctly read the signal from the terminal and malfunctions. Sometimes. In addition, the spectral sensitivity of image sensors such as cameras and light-receiving elements such as automatic exposure meters is in the near infrared range, If the near-infrared light is not eliminated, it will cause problems such as insufficient exposure and color balance with the human visual sensitivity. According to the transparent article of the present invention, near-infrared light on the short wavelength side can be selectively shielded, and malfunction of electronic equipment and malfunction of the image sensor and the light receiving element can be prevented. In addition, according to the transparent article of the present invention, it is possible to shield the heat rays contained in the sunlight by remarkably shielding near infrared rays (wavelength 700 to 2500 nm).

As shown in FIG. 1, the transparent article of the present invention is obtained by forming an organic-inorganic composite film 2 on a transparent substrate 1.

 [0086] The present invention can also be applied to, for example, provision of a liquid crystal display knock light, a liquid crystal display panel, and the like in which deterioration of the resin component due to ultraviolet rays is prevented. In a liquid crystal display composed of many resin parts, deterioration of the resin parts due to ultraviolet rays contained in the light from the backlight may cause problems. The organic-inorganic composite film according to the present invention is not limited in its application, but can exert a remarkable effect in a device containing a resin such as a liquid crystal display.

 As shown in FIG. 2, a backlight 100 for a liquid crystal display according to the present invention includes a substrate 10 having a light emitting surface 11, and an organic / inorganic material including an organic substance and an inorganic oxide formed on the light emitting surface 11 of the substrate 10. And the organic-inorganic composite film 20 contains silica as an inorganic oxide, and the organic-inorganic composite film 20 contains silica as a main component and is performed on the surface of the organic-inorganic composite film 20. After the Taber abrasion test stipulated in JIS R 3212, the organic-inorganic composite film 20 is not peeled off from the substrate 10, and at least a part of the organic substance is a UV absorber. The backlight 100 for a liquid crystal display is disposed on the back side of the liquid crystal display panel 250 so that the organic-inorganic composite film 20 faces.

Further, as shown in FIG. 3, a liquid crystal display panel 200 according to the present invention includes a liquid crystal panel 30 having a light transmission surface 31, and organic and inorganic oxides formed on the transmission surface 31 of the liquid crystal panel 30. The organic-inorganic composite film 20 containing silica, the organic-inorganic composite film 20 containing silica as an inorganic oxide, the organic-inorganic composite film 20 containing silica as a main component, and the surface of the organic-inorganic composite film 20 The organic / inorganic composite film 20 does not peel off from the liquid crystal panel 30 after the Taber abrasion test specified in JIS R 3212, and at least a part of the organic material is a UV absorber. LCD panel 20 If the organic / inorganic composite film 20 having the ultraviolet shielding ability is formed on the surface 31 where the surface on which ultraviolet rays enter the inside of 0 is the transmission surface 31, deterioration of the resin inside the display can be suppressed. The liquid crystal display panel 200 is disposed such that the transmission surface 31 faces the backlight 150 for liquid crystal display.

 [0089] Hereinafter, the present invention will be described in more detail by way of examples.

 [0090] (Example A1)

 In Example A1, a benzotriazole ultraviolet absorber (hydrophilic organic polymer) was used as the ultraviolet absorber.

[0091] 16.61 g of pure water, benzotriazole UV absorber (TINUVIN 1130 manufactured by Ciba 'Specialty' Chemicals) 3. 90 g, ethyl alcohol (manufactured by Katayama Chemical) 46. 89 g, ethyl silicate 40 (manufactured by Colcoat) 32. 50 g, concentrated hydrochloric acid (35 mass _^0/0, Kanto Ltd. I匕学) 0. 10 g of the mixed-and stirred to obtain a formed solution. Table 1 shows the silicon alkoxide (silica conversion), proton concentration, water content, etc. in this solution. The water content is calculated by adding the water (0.35 mass%) contained in ethyl alcohol. The proton concentration was calculated assuming that all protons contained in hydrochloric acid were dissociated. The calculation method of water content and proton concentration is the same in all of the following Examples and Comparative Examples.

 [0092] "Ethyl silicate 40" used here is represented by the following formula (1), and has a silica content (SiO

 ) Is a colorless and transparent liquid containing 40% by mass. Furthermore, the chain structure

2

 In addition to the condensation polymer, a condensation polymer having a branched or cyclic structure is also included. Silicon alkoxide polymers represented by “ethyl silicate 40” are excellent in silica supply efficiency, viscosity, specific gravity, storage stability, etc., and are easy to handle during use. Use it as a part or whole.

 CH CH 0 (Si (OCH CH)) OCH CH (1)

 3 2 2 3 2 η 2 3

 Where the average value of η is 5.

[0093] Next! On a soda-lime silicate glass substrate (100 X 100 mm, thickness: 3. lmm) washed, a relative humidity (hereinafter referred to simply as “humidity”) 30% at room temperature and a forming solution Was applied by flow coating. As it was, it was dried at room temperature (20 ° C) for about 30 minutes, then put in an oven preheated to 200 ° C, heated for 15 minutes, and then cooled. The resulting film has a thickness of 2500η It was a film with high transparency of m.

[0094] The composition of the soda-lime silicate glass substrate is as follows (unit: mass%).

 SiO: 72.3%, A1 0: 1.4%, MgO: 4. l%, CaO: 8. l%, NaO: 13.1%, K

2 2 3 2

O: 0.7%, total iron oxide converted to Fe O: 0.08%, SO: 0.2%.

 2 2 3 3

 Hereinafter, a glass substrate having the composition is referred to as an FL substrate.

 [0096] The hardness of the film was evaluated by a wear test in accordance with JIS R 3212. That is, using a commercially available Taber abrasion tester (TABER INDUSTRIES 5150 ABRASER), the wear was performed 1000 times with a load of 500 g, and the haze ratio before and after the abrasion test was measured. Table 2 shows the film thickness, the presence or absence of cracks, the haze ratio before and after the Taber test, and the presence or absence of film peeling after the Taber test. Table 2 also shows the haze ratio for the above FL substrate, which is a molten glass plate, as a blank. The haze ratio was measured using HGM-2DP manufactured by Suga Test Instruments Co., Ltd.

 [0097] The optical characteristics were measured using a spectrophotometer (UV-3000PC manufactured by Shimadzu Corporation), and the light transmittance at a wavelength of 365 nm, the visible light transmittance and the ultraviolet transmittance calculated according to JIS R 3106. Judged. Table 2 also shows the values of visible light transmittance, ultraviolet light transmittance, and transmittance at a wavelength of 365 nm.

 [0098] This glass plate with an ultraviolet absorbing film has sufficient utility as a window glass for automobiles and buildings where the haze ratio after the Taber test is sufficiently low at 3.5%. For window glass for automobiles, the haze ratio after the Taber test is required to be 4% or less.

 [0099] (Example A2)

 In Example A2, polyethylene glycol (PEG) was further added to the forming solution in Example A1. PEG is a hydrophilic organic polymer that does not have ultraviolet absorbing ability.

[0100] 18.02 g of pure water, benzotriazole ultraviolet absorber (TINUVIN 1130 manufactured by Ciba 'Specialty' Chemicals) 3.90 g, polyethylene glycol 400 (manufactured by Kanto Igaku) 0.26 g, ethyl alcohol (Katayama) (Chemical) 45.22 g, ethyl silicate 40 (Colcoat) 32.50 g, concentrated hydrochloric acid (35 mass%, manufactured by Kanto Chemical Co., Ltd.) 0.1 g were mixed and stirred to obtain a forming solution. Table 1 shows the concentration of each component in this solution. [0101] Next, in the same manner as in Example Al, a film was formed by applying the forming solution onto the cleaned FL substrate. Table 2 shows the film thickness and various characteristics of the glass plate with the UV absorbing film thus obtained.

 [0102] (Example A3)

 In Example A3, more phosphoric acid was added to the forming solution in Example A1.

 [0103] Pure water 16. 66 g, benzotriazole UV absorber (TINUVIN 1130 manufactured by Ciba 'Specialty' Chemicals) 3. 90 g, ethyl alcohol (made by Katayama Chemical) 46. 79 g, ethyl silicate 40 (manufactured by Colcoat) 32. 50 g, concentrated hydrochloric acid (35% by mass, manufactured by Kanto Chemical Co., Ltd.) 0.10 g, and phosphoric acid (85% by mass, manufactured by Kanto Chemical Co., Ltd.) 0.046 g were added and stirred to obtain a forming solution. Table 1 shows the concentration of each component in this solution.

 [0104] Next, in the same manner as in Example A1, a forming solution was applied onto the cleaned FL substrate to form a film. Table 2 shows the film thickness and various characteristics of the glass plate with the UV absorbing film thus obtained.

 [0105] (Example A4)

 In Example A4, the concentration of the benzotriazole ultraviolet absorber in the forming solution in Example A1 was increased, and the heating temperature after coating and drying at room temperature was lowered.

[0106] Pure water 16. 60 g, benzotriazole UV absorber (TINUVIN 1130 from Ciba 'Specialty' Chemicals) 5. 20 g, ethyl alcohol (Katayama Chemical) 45. 60 g, ethyl silicate 40 (Colcoat) 32. 50 g, concentrated hydrochloric acid (35 mass _^0/0, Kanto Ltd. I匕学) 0. 10 g of the mixed-and stirred to obtain a formed solution. Table 1 shows the concentration of each component in this solution.

 Next, the forming solution was applied on the cleaned FL substrate by a flow coating method at a humidity of 30% and at room temperature. As it was, it was dried at room temperature for about 30 minutes, then put into an oven preheated to 160 ° C., heated for 15 minutes, and then cooled. The film obtained was a high V film with a transparency of 3000 nm. Table 2 shows the film thickness and various characteristics of the glass plate with an ultraviolet absorbing film thus obtained.

 [Example A5]

In Example A5, a cyanine organic dye was used as an ultraviolet absorber, and a polyether phosphate ester polymer was further added. Polyether phosphate ester polymer is purple It is a hydrophilic organic polymer that does not have an external absorption capability.

 [0109] Pure water 19. 45g, cyanine organic pigment (NK-863, Hayashibara Biochemical Laboratories) 1. OOg, polyether phosphate ester polymer (Solsperse 41000, Nippon Lubrizol) 4. 55g, ethyl alcohol (Made by Katayama) 42.40g, Ethyl silicate 40 (Colcoat) 32.50g, Concentrated hydrochloric acid (35% by mass, manufactured by Kanto Science) 0.10g were mixed and stirred to obtain a forming solution. . Table 3 shows the concentration of each component in this solution.

 [0110] Next, the forming solution was applied on the cleaned FL substrate by a flow coating method at a humidity of 30% and at room temperature. As it was, it was dried at room temperature for about 30 minutes, put into an oven heated to 200 ° C in advance, heated for 15 minutes, and then cooled. The obtained film was a highly transparent film having a thickness of 3100 nm. Table 4 shows the film thickness and various characteristics of the glass plate with the UV absorbing film thus obtained.

 [0111] (Examples A6 to A8)

 In Examples A6 to A8, a glass plate with an ultraviolet absorbing film was obtained in the same manner as in Example A5 except for the heating temperature after coating and drying at room temperature (see Table 3). Table 4 shows the film thickness and various properties of each UV-absorbing film-coated glass plate.

 [0112] (Example A9)

 In Example A9, a benzotriazole ultraviolet absorber (ultraviolet absorber A) and a azo organic dye (ultraviolet absorber B) were used as the ultraviolet absorber.

 [0113] Pure water 16.83g, benzotriazole UV absorber (TINUVIN 1130 manufactured by Ciba 'Specialty' Chemicals) 4.00g, azo organic dye (Tokyo Chemical Industries AlizarinYellow GG) 0.08g, ethyl alcohol (Made by Katayama) 46.49g, Ethyl silicate 40 (Corcolate) 32.50g, Concentrated hydrochloric acid (35% by mass, Kanto 匕 gaku) 0.10g are mixed and stirred to form a solution. Got. Table 5 shows the concentration of each component in this solution.

[0114] Next, the forming solution was applied on the cleaned FL substrate by a flow coating method at a humidity of 30% and at room temperature. As it was, it was dried at room temperature for about 30 minutes, then put into an oven preheated to 110 ° C., heated for 60 minutes, and then cooled. The obtained film was a highly transparent film having a thickness of 2900 nm. Table 6 shows the film thickness and various characteristics of the glass plate with the UV absorbing film thus obtained. [0115] (Example A10)

 In Example AIO, a benzotriazole ultraviolet absorber (ultraviolet absorber A) and a cyanine organic dye (ultraviolet absorber B) were used as the ultraviolet absorber.

 [0116] 12.68 g of pure water, benzotriazole UV absorber (TINUVIN 1130 manufactured by Ciba 'Specialty' Chemicals) 3. OOg, cyanine organic dye (NK-863 manufactured by Hayashibara Biochemical Research Institute) 0.2 g , Ethyl alcohol (Katayama Igaku) 59.02g, Ethyl silicate 40 (Colcoat) 25.00g, Concentrated hydrochloric acid (35% by mass, Kanto Igaku) 0.10g were mixed and stirred to form A solution was obtained. Table 5 shows the concentration of each component in this solution.

 [0117] Next, the forming solution was applied on the cleaned FL substrate by a flow coating method at a humidity of 30% and at room temperature. As it was, it was dried at room temperature for about 30 minutes, put into an oven preheated to 140 ° C, heated for 15 minutes, and then cooled. The obtained film was a highly transparent film having a thickness of 1700 nm. Table 6 shows the film thickness and various characteristics of the glass plate with the UV absorbing film thus obtained.

 [0118] (Example Al l)

 In Example Al 1, the organic dye concentration in the forming solution in Example A10 was increased.

[0119] Pure water 12.68g, benzotriazole UV absorber (TINUVIN 1130 from Ciba 'Specialty' Chemicals) 3.00g, cyanine organic dye (NK-863, Hayashibara Biochemical Research Institute) 0. 3g , Ethyl alcohol (Katayama Igaku) 58. 92g, Ethyl silicate 40 (Colcoat) 25.00g, Concentrated hydrochloric acid (35% by mass, Kanto Igaku) 0.10g, mixed and stirred to form A solution was obtained. Table 5 shows the concentration of each component in this solution.

 Next, the forming solution was applied on the cleaned FL substrate by a flow coating method at a humidity of 30% and at room temperature. As it was, it was dried at room temperature for about 30 minutes, put into an oven preheated to 140 ° C, heated for 15 minutes, and then cooled. The obtained film was a highly transparent film having a thickness of 1800 nm. Table 6 shows the film thickness and various characteristics of the glass plate with the UV absorbing film thus obtained.

 [0121] (Example A12)

In Example A12, the SiO concentration in the forming solution in Example A10 was increased. [0122] 13.99 g of pure water, benzotriazole UV absorber (TINUVIN 1130 manufactured by Ciba 'Specialty' Chemicals) 3. OOg, cyanine organic dye (NK-863 manufactured by Hayashibara Biochemical Research Institute) 0.2 g , Ethyl alcohol (Katayama Igaku) 55.21g, Ethylsilicate 40 (Colcoat) 27.50g, Concentrated hydrochloric acid (35% by mass, Kanto Igaku) 0.10g are mixed and stirred to form A solution was obtained. Table 5 shows the concentration of each component in this solution.

 [0123] Next, the forming solution was applied on the cleaned FL substrate by a flow coating method at a humidity of 30% and at room temperature. As it was, it was dried at room temperature for about 30 minutes, put into an oven preheated to 140 ° C, heated for 15 minutes, and then cooled. The obtained film was a highly transparent film having a thickness of 1900 nm. Table 6 shows the film thickness and various characteristics of the glass plate with the UV absorbing film thus obtained.

 [0124] (Example A13)

 In Example A13, the concentration of the organic dye in the forming solution in Example A12 was increased, and PEG was added.

 [0125] 13.98 g of pure water, benzotriazole UV absorber (TINUVIN 1130 manufactured by Ciba 'Specialty' Chemicals) 3.00 g, shean organic pigment (NK 863 manufactured by Hayashibara Biochemical Research Institute) 0.25 g, Posiethylene guji INORE 200 (manufactured by Kanto Chemical Co., Ltd.) 0.60 g, ethenoreanolol n-le (manufactured by Katayama Chemical) 54. 57 g, ethyl silicate 40 (manufactured by Colcoat) 27. 50 g, concentrated hydrochloric acid (35% by mass, Kanto 匕Gaku) 0. 10 g was mixed and stirred to obtain a forming solution. Table 7 shows the concentration of each component in this solution.

 Next, the forming solution was applied on the cleaned FL substrate by a flow coating method at a humidity of 30% and at room temperature. As it was, it was dried at room temperature for about 30 minutes, put into an oven preheated to 140 ° C, heated for 15 minutes, and then cooled. The obtained film was a highly transparent film having a thickness of 2100 nm. Table 8 shows the film thickness and various characteristics of the glass plate with the UV absorbing film thus obtained.

 [Example A14]

 In Example A14, the SiO concentration in the forming solution in Example A13 was increased.

 2

[0128] Pure water 15. 30 g, benzotriazole UV absorber (TINUVIN 1130, manufactured by Ciba 'Specialty' Chemicals) 3.00 g, cyanine organic pigment (NK, manufactured by Hayashibara Biochemical Research Institute) 863) 0.25 g, Posiethylene gluene Monore 200 (Kanto Igaku) 0.60 g, Ethenoleanol n— (Katayama Igaku) 50. 75 g, Ethylsilicate 40 (Colcoat) 30.00 g, Concentrated hydrochloric acid (35 mass _^0/0, Kanto Ltd.匕学) 0. 10 g, added, and stirred to obtain a formed solution. Table 7 shows the concentration of each component in this solution.

 Next, the forming solution was applied on the cleaned FL substrate by a flow coating method at a humidity of 30% and at room temperature. As it was, it was dried at room temperature for about 30 minutes, put into an oven preheated to 140 ° C, heated for 15 minutes, and then cooled. The obtained film was a highly transparent film having a thickness of 2400 nm. Table 8 shows the film thickness and various characteristics of the glass plate with the UV absorbing film thus obtained.

 [0130] (Example A15)

 In Example A15, the SiO concentration in the forming solution in Example A14 was further increased.

 2

 It was.

 [0131] Pure water 16.62g, benzotriazole UV absorber (TINUVIN 1130 from Ciba 'Specialty' Chemicals) 3.00g, cyanine organic dye (NK 863, Hayashibara Biochemical Laboratories) 0.25g, Posiethylene guji INORE 200 (manufactured by Kanto Igaku) 0.60 g, ethenorea norenol (manufactured by Katayama Igaku) 46. 93 g, ethyl silicate 40 (manufactured by Colcoat) 32. 50 g, concentrated hydrochloric acid (35% by mass, Kanto) 0.1 g) was added and stirred to obtain a forming solution. Table 7 shows the concentration of each component in this solution.

 Next, the forming solution was applied on the cleaned FL substrate by a flow coating method at a humidity of 30% and at room temperature. As it was, it was dried at room temperature for about 30 minutes, put into an oven preheated to 140 ° C, heated for 15 minutes, and then cooled. The film obtained was a high V, film with a transparency of 2500 nm. Table 8 shows the film thickness and various characteristics of the glass plate with the UV absorbing film thus obtained.

 [0133] (Example A16)

 In Example A16, ITO fine particles were further added, and a polyether phosphate polymer was added.

[0134] 13.98 g of pure water, benzotriazole UV absorber (TINUVIN 1130 from Ciba 'Specialty' Chemicals) 3.00 g, cyanine organic dye (NK from Hayashibara Biochemical Research Institute) 863) 0.25 g, ethyl alcohol (made by Katayama Chemical) 54. 56 g, ITO fine particle dispersion (ethyl alcohol solution containing 40% by mass of ITO, manufactured by Mitsubishi Materials) 5. 63 g, polyethylene phosphate ester polymer (Nippon Lubriso) Ichiru Ltd. Solsperse 41000) 0. 60 g, E chill silicate 40 (manufactured by Colcoat) 21. 88 g, concentrated hydrochloric acid (35 mass _^0/0, manufactured by Kanto I匕学) mixing 0. 1 Og, stirred, forming solution Got. Table 9 shows the concentration of each component in this solution.

 Next, the forming solution was applied on the cleaned FL substrate by a flow coating method at a humidity of 30% and at room temperature. As it was, it was dried at room temperature for about 30 minutes, then put into an oven preheated to 140 ° C, heated for 15 minutes, and then cooled. The obtained film was a highly transparent film having a thickness of 2100 nm. Table 10 shows the film thickness and various properties of the glass plate with the ultraviolet absorbing film thus obtained. In this example and Example A17 described later, an FL substrate formed to be 305 × 305 mm was used.

 [0136] (Example A17)

 In Example A17, the concentration of the polyether phosphate polymer in the forming solution in Example A16 was reduced.

[0137] 13.98 g of pure water, benzotriazole ultraviolet absorber (TINUVIN 1130 manufactured by Ciba 'Specialty' Chemicals) 3.00 g, shean organic pigment (NK 863 manufactured by Hayashibara Biochemical Research Institute) 0.25 g, Ethyl alcohol (manufactured by Katayama Chemical) 54. 86 g, ITO fine particle dispersion (ethyl alcohol solution containing 40% by mass of ITO, manufactured by Mitsubishi Materials) 5. 63 g, polyether phosphate polymer (Solsperse 41000, manufactured by Nippon Lubrizol) 0. 30 g, stirred E chill silicate 40 (manufactured by Colcoat) 21. 88 g, concentrated hydrochloric acid (35 mass _^0/0, Kanto Ltd. I匕学) to 0. 1 0 g, mixed to obtain a film-forming solution. Table 9 shows the concentration of each component in this solution.

[0138] Next, in the same manner as in Example A16, a film was formed by applying the forming solution onto the cleaned FL substrate. Table 10 shows the film thickness and various characteristics of the glass plate with the UV absorbing film thus obtained.

[0139] The ultraviolet absorbing films obtained in Examples A16 and A17 contain ITO fine particles, and are excellent in the shielding ability of long-wavelength near infrared rays (wavelength 1200 to 2500 nm) in addition to the ultraviolet shielding ability. It was.

 [0140] When exposed to temperatures exceeding 200 ° C, the UV absorber made up of organic matter decomposes and the ITO fine particles are oxidized, reducing the UV shielding ability and the near-infrared shielding ability on the long wavelength side. It becomes easy. However, in Examples A16 and A17, a low firing temperature of 200 ° C. or less was applied, so the function of shielding ultraviolet rays and near-infrared rays on the long wavelength side was maintained high.

[0141] (Example A18)

 In Example A18, a polycarbonate substrate was used as the transparent substrate.

[0142] [Formation of primer layer]

 Mix and stir 99.50 g of ethyl alcohol (made by Katayama Chemical), 0.40 g of 3-aminopropyltriethoxysilane (made by Shin-Etsu Chemical), and 0.1 g of concentrated hydrochloric acid (35 mass%, made by Kanto Chemical Co., Ltd.). A forming solution was obtained. Table 11 shows 3-aminopropyltriethoxysilane (converted to aminoaminopropyl sesquioxane (RSiO)), proton concentration and water content in this solution. In addition, this

 1.5

 Again, the water content is calculated after the amount of water contained in ethyl alcohol is 0.35% by mass.

 [0143] Next, a forming solution was applied to the washed polycarbonate substrate (100 X 100 mm) by a flow coating method at a humidity of 30% and at room temperature. As it was, it was dried at room temperature for about 1 minute, put into an oven preheated to 110 ° C., heated for 30 minutes, and then cooled.

 [0144] [Formation of UV absorbing layer]

 17.28 g of pure water, benzotriazole UV absorber (TINUVIN 1130 manufactured by Ciba Specialty) Chemicals 5.00 g, ethyl alcohol (manufactured by Katayama Chemical) 43. 87 g, ethyl silicate 40 (manufactured by Colcoat) 33. 75 g Concentrated hydrochloric acid (35% by mass, manufactured by Kanto Chemical Co., Ltd.) (0.10 g) was mixed and stirred to obtain a forming solution. Table 12 shows the concentration of each component in this solution.

[0145] Next, the forming solution was applied by flow coating on a polycarbonate substrate on which the primer layer had been formed, at a humidity of 30% and at room temperature. After drying for about 30 minutes at room temperature, it was put in an oven preheated to 110 ° C., heated for 60 minutes, and then cooled. The obtained film was a highly transparent film. Table 13 shows the various properties of the resin board with an ultraviolet absorbing film thus obtained. [0146] When the film obtained in Example A18 was subjected to a tape peeling test, no film peeling occurred, and it was confirmed that in addition to wear resistance, the film was excellent in adhesion to the substrate. .

 [0147] Table 14 shows the film thickness and various characteristics of the glass plate with the ultraviolet absorbing film in which the ultraviolet absorbing film was formed on the FL substrate.

 [0148] (Example A19)

 In Example A19, a benzotriazole ultraviolet absorber (ultraviolet absorber A) and a cyanine organic dye (ultraviolet absorber B) were used as the ultraviolet absorber.

 [0149] Pure water 12.68g, benzotriazole UV absorber (TINUVIN 1130 manufactured by Ciba 'Specialty' Chemicals) 3. OOg, cyanine organic dye (NK-863, Hayashibara Biochemical Research Institute) 0.2g , Ethyl alcohol (Katayama Igaku) 59.02g, Ethyl silicate 40 (Colcoat) 25.00g, Concentrated hydrochloric acid (35% by mass, Kanto Igaku) 0.10g were mixed and stirred to form A solution was obtained. Table 17 shows the concentration of each component in this solution.

 [0150] The contents of the ultraviolet absorbers A and B in Table 17 are ratios relative to the whole solution. For example, in Example A19, the total amount of the UV absorber is 3.20% by mass. This content is determined by the concentration of silicon alkoxide expressed in terms of SiO concentration (

 2

 10.0%), which corresponds to 32.0% by mass. In any of the examples, the total mass of the ultraviolet absorbers A and B is 0.1 to 40% with respect to the total mass of the film.

 [0151] Next, the forming solution was applied to the washed soda-lime silicate glass substrate (100 X 100 mm; thickness 3.1 mm) at 30% humidity and room temperature by the flow coating method. This glass substrate has a glass composition containing an ultraviolet absorbing component, and itself has a predetermined ultraviolet shielding ability although not necessarily sufficient. Hereinafter, this glass substrate is referred to as a UV cut glass substrate. As it was, it was dried at room temperature (20 ° C) for about 30 minutes, then put in an oven preheated to 140 ° C, heated for 15 minutes, and then cooled. The obtained film was a highly transparent film having a thickness of 1700 nm.

[0152] The composition of the UV-cut glass substrates are as follows (unit: mass ^_0/0).

 SiO: 70%, Α1 Ο: 1.6%, MgO: 3.2%, CaO: 8.3%, Na 0: 14%, K O: 0

2 2 3 2 2

6%, Total iron oxide in terms of Fe 2 O: 0.9% (Fe O is 0.6% of the total composition), Ti

 2 3 2 3

O: 0.1%, CeO: 0.9%. [0153] Table 18 shows the film thickness and various properties of the glass plate with the ultraviolet absorbing film thus obtained. Table 18 also shows various characteristics of the UV-cut glass substrate, which is a molten glass plate, as a blank. The light transmittance at a wavelength of 370 nm was also measured using a spectrophotometer (manufactured by Shimadzu Corporation, UV-3000PC).

 [0154] (Example A20)

 In Example A20, the organic dye concentration in the forming solution in Example A19 was increased.

[0155] Pure water 12.68g, benzotriazole UV absorber (TINUVIN 1130 from Ciba Specialty) Chemicals 3. OOg, cyanine organic dye (NK-863, Hayashibara Biochemical Research Institute) 0. 3g , Ethyl alcohol (Katayama Igaku) 58. 92g, Ethyl silicate 40 (Colcoat) 25.00g, Concentrated hydrochloric acid (35% by mass, Kanto Igaku) 0.10g, mixed and stirred to form A solution was obtained. Table 17 shows the concentration of each component in this solution.

 [0156] Next, the forming solution was applied on the cleaned UV cut glass substrate by a flow coating method at a humidity of 30% and at room temperature. After drying for about 30 minutes at room temperature, it was put in an oven preheated to 140 ° C and heated for 15 minutes, and then cooled. The obtained film was a highly transparent film having a thickness of 1800 nm. Table 18 shows the film thickness and various characteristics of the glass plate with the UV absorbing film thus obtained.

 [Example A21]

 In Example A21, the SiO concentration in the forming solution in Example A19 was increased.

 2

 [0158] 13.99 g of pure water, benzotriazole UV absorber (TINUVIN 1130 manufactured by Ciba 'Specialty' Chemicals) 3.00 g, cyanine organic dye (NK-863 manufactured by Hayashibara Biochemical Research Institute) 0.2 g , Ethyl alcohol (Katayama Igaku) 55.21g, Ethylsilicate 40 (Colcoat) 27.50g, Concentrated hydrochloric acid (35% by mass, Kanto Igaku) 0.10g are mixed and stirred to form A solution was obtained. Table 17 shows the concentration of each component in this solution.

[0159] Next, the forming solution was applied on the cleaned UV cut glass substrate by a flow coat method at a humidity of 30% and at room temperature. After drying for about 30 minutes at room temperature, it was put in an oven preheated to 140 ° C and heated for 15 minutes, and then cooled. The obtained film was a highly transparent film having a thickness of 1900 nm. The film thickness and thickness of the glass plate with the ultraviolet absorbing film obtained in this way Table 18 shows the various characteristics.

[0160] (Example A22)

 In Example A22, the organic dye concentration in the forming solution in Example A21 was increased.

[0161] Pure water 13. 98 g, benzotriazole UV absorber (TINUVIN 1130 manufactured by Ciba 'Specialty' Chemicals) 3. OOg, cyanine organic dye (NK-863, Hayashibara Biochemical Research Institute) 0. 25 g , Ethyl alcohol (made by Katayama Igaku) 55.17g, ethyl silicate 40 (Colcoat) 27.50g, concentrated hydrochloric acid (35% by mass, manufactured by Kanto Igaku) 0.10g are mixed and stirred. An obtained solution was obtained. Table 17 shows the concentration of each component in this solution.

 [0162] Next, the forming solution was applied to the cleaned UV cut glass substrate by a flow coat method at a humidity of 30% and at room temperature. After drying for about 30 minutes at room temperature, it was put in an oven preheated to 140 ° C and heated for 15 minutes, and then cooled. The obtained film was a highly transparent film having a thickness of 1900 nm. Table 18 shows the various characteristics of the glass plate with the ultraviolet absorbing film thus obtained.

 [0163] (Example A23)

 In Example A23, the acid concentration in the forming solution in Example A22 was reduced.

 [0164] 14.02 g of pure water, benzotriazole UV absorber (TINUVIN 1130 manufactured by Ciba 'Specialty' Chemicals) 3.00 g, cyanine organic dye (NK-863 manufactured by Hayashibara Biochemical Research Institute) 0. 25 g , Ethyl alcohol (Katayama Igaku) 55. 18g, Ethyl silicate 40 (Colcoat) 27. 50g, Concentrated hydrochloric acid (35% by mass, Kanto Igaku) 0.05g are mixed and stirred. An obtained solution was obtained. Table 17 shows the concentration of each component in this solution.

 [0165] Next, the forming solution was applied on the cleaned UV cut glass substrate by a flow coating method at a humidity of 30% and at room temperature. After drying for about 30 minutes at room temperature, it was put in an oven preheated to 140 ° C and heated for 15 minutes, and then cooled. The obtained film was a highly transparent film having a thickness of 1900 nm. Table 18 shows the various characteristics of the glass plate with the ultraviolet absorbing film thus obtained.

 [Example A24]

In Example A24, the acid concentration in Example A22 was increased. [0167] 13.92 g of pure water, benzotriazole UV absorber (TINUVIN 1130 manufactured by Ciba 'Specialty' Chemicals) , Ethyl alcohol (made by Katayama Igaku) 55.13g, Ethylsilicate 40 (Colcoat) 27.50g, Concentrated hydrochloric acid (35% by mass, produced by Kanto Igaku) 0.20g are mixed and stirred. An obtained solution was obtained. Table 17 shows the concentration of each component in this solution.

 [0168] Next, the forming solution was applied on the cleaned UV cut glass substrate by a flow coat method at a humidity of 30% and at room temperature. After drying for about 30 minutes at room temperature, it was put in an oven preheated to 140 ° C and heated for 15 minutes, and then cooled. The obtained film was a highly transparent film having a thickness of 1900 nm. Table 18 shows the various characteristics of the glass plate with the ultraviolet absorbing film thus obtained.

 [0169] (Example A25)

 In Example A25, the acid concentration in the forming solution in Example A24 was further increased.

 [0170] 13.85 g of pure water, benzotriazole UV absorber (TINUVIN 1130 manufactured by Ciba 'Specialty' Chemicals) 3.00 g, cyanine organic dye (NK-863 manufactured by Hayashibara Biochemical Research Institute) 0. 25 g , Ethyl alcohol (made by Katayama Igaku) 55. 10 g, Ethyl silicate 40 (Colcoat) 27. 50 g, Concentrated hydrochloric acid (35% by mass, Kanto Igaku) 0.30 g are mixed and stirred. An obtained solution was obtained. Table 17 shows the concentration of each component in this solution.

 [0171] Next, the forming solution was applied on the cleaned UV cut glass substrate by a flow coat method at a humidity of 30% and at room temperature. After drying for about 30 minutes at room temperature, it was put in an oven preheated to 140 ° C and heated for 15 minutes, and then cooled. The obtained film was a highly transparent film having a thickness of 1900 nm. Table 18 shows the various characteristics of the glass plate with the ultraviolet absorbing film thus obtained.

 [Example A26]

 In Example A26, the acid concentration in the forming solution in Example A25 was further increased.

[0173] Pure water 13. 80g, benzotriazole UV absorber (TINUVIN 1130 from Ciba 'Specialty' Chemicals) 3.00g, cyanine organic dye (NK-863, Hayashibara Biochemical Research Institute) 0. 25g , Ethyl alcohol (Katayama Igaku) 55. 05g, Ethyl silicate 40 (Colcoat) 27. 50g, Concentrated hydrochloric acid (35% by mass, Kanto Igaku) 0.40g are mixed and stirred. An obtained solution was obtained. Table 17 shows the concentration of each component in this solution.

 [0174] Next, the forming solution was applied on the cleaned UV cut glass substrate by a flow coat method at a humidity of 30% and at room temperature. After drying for about 30 minutes at room temperature, it was put in an oven preheated to 140 ° C and heated for 15 minutes, and then cooled. The obtained film was a highly transparent film having a thickness of 1900 nm. Table 18 shows the various characteristics of the glass plate with the ultraviolet absorbing film thus obtained.

 [0175] (Example A27)

 In Example A27, the concentration of the UV absorber in the forming solution in Example A22 was lowered.

 [0176] Pure water 13. 98 g, benzotriazole UV absorber (TINUVIN 1130, manufactured by Ciba 'Specialty' Chemicals) 2. 50 g, shean organic pigment (NK-863, manufactured by Hayashibara Biochemical Research Institute) 0. 25 g , Ethyl alcohol (made by Katayama Igaku) 55.67g, Ethyl silicate 40 (Colcoat) 27.50g, Concentrated hydrochloric acid (35% by mass, produced by Kanto Igaku) 0.10g were mixed and stirred. An obtained solution was obtained. Table 17 shows the concentration of each component in this solution.

 [0177] Next, the forming solution was applied on the cleaned UV-cut glass substrate by a flow coat method at a humidity of 30% and at room temperature. After drying for about 30 minutes at room temperature, it was put in an oven preheated to 140 ° C and heated for 15 minutes, and then cooled. The obtained film was a highly transparent film having a thickness of 1900 nm. Table 18 shows the various characteristics of the glass plate with the ultraviolet absorbing film thus obtained.

 [0178] (Example A28)

 In Example A28, PEG was further added to the forming solution in Example A22.

 [0179] 13.98 g of pure water, benzotriazole UV absorber (TINUVIN 1130 manufactured by Ciba 'Specialty' Chemicals) 3.00 g, shean organic pigment (NK 863 manufactured by Hayashibara Biochemical Research Institute) 0.25 g, Posiethylene guji INORE 200 (manufactured by Kanto Chemical Co., Ltd.) 0.60 g, ethenoreanolol n-le (manufactured by Katayama Chemical) 54. 57 g, ethyl silicate 40 (manufactured by Colcoat) 27. 50 g, concentrated hydrochloric acid (35% by mass, Kanto 匕Gaku) 0. 10 g was mixed and stirred to obtain a forming solution. Table 19 shows the concentration of each component in this solution.

[0180] Next, on the cleaned UV-cut glass substrate, flow the forming solution at 30% humidity and room temperature. It was applied by a one-coat method. After drying for about 30 minutes at room temperature, it was put in an oven preheated to 140 ° C and heated for 15 minutes, and then cooled. The obtained film was a highly transparent film having a thickness of 2100 nm. Table 20 shows the various characteristics of the glass plate with the ultraviolet absorbing film thus obtained.

[0181] (Example A29)

 In Example A29, the SiO concentration in the forming solution in Example A28 was increased.

 2

 [0182] 15.30 g of pure water, benzotriazole UV absorber (TINUVIN 1130 manufactured by Ciba 'Specialty' Chemicals) 3.00 g, cyanine organic dye (NK 863 manufactured by Hayashibara Biochemical Research Institute) 0.25 g, Posiethylene guji INORE 200 (Kantoi Gakuen) 0.60g, ethenoreanore n- (Katayama Chemical) 50.75g, Ethylsilicate 40 (Colcoat) 30.00g, Concentrated hydrochloric acid (35% by mass, Kantoi) 0.1 g) was added and stirred to obtain a forming solution. Table 19 shows the concentration of each component in this solution.

 [0183] Next, the forming solution was applied on the cleaned UV cut glass substrate by a flow coating method at a humidity of 30% and at room temperature. After drying for about 30 minutes at room temperature, it was put in an oven preheated to 140 ° C and heated for 15 minutes, and then cooled. The obtained film was a highly transparent film having a thickness of 2400 nm. Table 20 shows the various characteristics of the glass plate with the ultraviolet absorbing film thus obtained.

 [0184] (Example A30)

 In Example A30, the SiO concentration in the forming solution in Example A29 was further increased.

 2

 It was.

 [0185] Pure water 16.62g, benzotriazole UV absorber (TINUVIN 1130 manufactured by Ciba 'Specialty' Chemicals) 3.00g, shean organic pigment (NK 863 manufactured by Hayashibara Biochemical Research Institute) 0.25g, Posiethylene guji INORE 200 (Kanto Chemical Co., Ltd.) 0.60g, ethenoreanolol n-le (Katayama Chemical Co., Ltd.) 46. 93g, Ethyl silicate 40 (Colcoat Co.) 32.50g, Concentrated hydrochloric acid (35% by mass, Kantoi) 0.1 g) was added and stirred to obtain a forming solution. Table 19 shows the concentration of each component in this solution.

[0186] Next, the forming solution was applied on the cleaned UV cut glass substrate by a flow coat method at a humidity of 30% and at room temperature. Continue to dry at room temperature for about 30 minutes, then preheat to 140 ° C. It was put into a heated oven, heated for 15 minutes, and then cooled. The obtained film was a highly transparent film of 2500 nm. Table 20 shows the various characteristics of the glass plate with the ultraviolet absorbing film thus obtained.

 [0187] (Example A31)

 In Example A31, the acid concentration in the forming solution in Example A28 was reduced.

 [0188] 14.02 g of pure water, benzotriazole UV absorber (TINUVIN 1130 manufactured by Ciba 'Speciality' Chemicals) 3. OOg, 0.25 g of cyanine organic dye (NK 863 manufactured by Hayashibara Biochemical Research Institute) Posiethylene guji INORE 200 (manufactured by Kanto Chemical Co., Ltd.) 0.30 g, ethinoreanolol n-le (manufactured by Katayama Chemical Co., Ltd.) 54. 88 g, ethyl silicate 40 (manufactured by Colcoat) 27. 50 g, concentrated hydrochloric acid (35% by mass, Kanto i *) 0.05 g) was mixed and stirred to obtain a forming solution. Table 19 shows the concentration of each component in this solution.

 [0189] Next, the forming solution was applied on the cleaned UV cut glass substrate by a flow coat method at a humidity of 30% and at room temperature. After drying for about 30 minutes at room temperature, it was put in an oven preheated to 140 ° C and heated for 15 minutes, and then cooled. The obtained film was a highly transparent film having a thickness of 2100 nm. Table 20 shows the various characteristics of the glass plate with the ultraviolet absorbing film thus obtained.

 [0190] (Example A32)

 In Example A32, the acid concentration in the forming solution in Example A28 was increased.

 [0191] 13.92 g of pure water, benzotriazole UV absorber (TINUVIN 1130 manufactured by Ciba 'Specialty' Chemicals) 3.00 g, cyanine organic dye (NK 863 manufactured by Hayashibara Biochemical Research Institute) 0.25 g, Posiethylene guji INORE 200 (manufactured by Kanto Chemical Co., Ltd.) 0.30 g, ethenoreanolol n-le (manufactured by Katayama Chemical Co., Ltd.) 54. 83 g, ethyl silicate 40 (manufactured by Colcoat) 27. 50 g, concentrated hydrochloric acid (35% by mass, Kanto i *) Gaku) 0.20 g was mixed and stirred to obtain a forming solution. Table 19 shows the concentration of each component in this solution.

[0192] Next, the forming solution was applied on the cleaned UV cut glass substrate by a flow coat method at a humidity of 30% and at room temperature. After drying for about 30 minutes at room temperature, it was put in an oven preheated to 140 ° C and heated for 15 minutes, and then cooled. The obtained film was a highly transparent film having a thickness of 2100 nm. Various characteristics of the glass plate with UV absorbing film thus obtained Is shown in Table 20.

 [Example A33]

 In Example A33, the acid concentration in the forming solution in Example A32 was further increased.

 [0194] 13.85 g of pure water, benzotriazole-based UV absorber (TINUVIN 1130 manufactured by Ciba 'Specialty' Chemicals) 3. OOg, 0.25 g of cyanine organic pigment (NK 863 manufactured by Hayashibara Biochemical Research Institute), Posiethylene guji INORE 200 (manufactured by Kanto Igaku) 0.30 g, ethenorea norenol (manufactured by Katayama Igaku) 54. 80 g, Ethyl silicate 40 (manufactured by Colcoat) 27. 50 g, concentrated hydrochloric acid (35% by mass, Kanto) 0.3 g) was mixed and stirred to obtain a forming solution. Table 19 shows the concentration of each component in this solution.

 [0195] Next, the forming solution was applied on the cleaned UV-cut glass substrate by a flow coating method at a humidity of 30% and at room temperature. After drying for about 30 minutes at room temperature, it was put in an oven preheated to 140 ° C and heated for 15 minutes, and then cooled. The obtained film was a highly transparent film having a thickness of 2100 nm. Table 20 shows the various characteristics of the glass plate with the ultraviolet absorbing film thus obtained.

 [0196] (Example A34)

 In Example A34, the acid concentration in the forming solution in Example A33 was further increased.

 [0197] 13.80 g of pure water, benzotriazole UV absorber (TINUVIN 1130 manufactured by Ciba 'Specialty' Chemicals) 3.00 g, shean organic pigment (NK 863 manufactured by Hayashibara Biochemical Research Institute) 0.25 g, Posiethylene guji INORE 200 (manufactured by Kanto Chemical Co., Ltd.) 0.30 g, ethenoreanolol n-le (manufactured by Katayama Chemical) 54. 75 g, ethyl silicate 40 (manufactured by KOLCOAT) 27. 50 g, concentrated hydrochloric acid (35% by mass, Kanto 匕0.44 g was mixed and stirred to obtain a forming solution. Table 19 shows the concentration of each component in this solution.

 [0198] Next, the forming solution was applied on the cleaned UV cut glass substrate by a flow coating method at a humidity of 30% and at room temperature. After drying for about 30 minutes at room temperature, it was put in an oven preheated to 140 ° C and heated for 15 minutes, and then cooled. The obtained film was a highly transparent film having a thickness of 2100 nm. Table 20 shows the various characteristics of the glass plate with the ultraviolet absorbing film thus obtained.

[0199] (Example A35) In Example A35, the concentration of the UV absorber in the forming solution in Example A28 was lowered.

 [0200] 14.04 g of pure water, benzotriazole UV absorber (TINUVIN 1130 manufactured by Ciba 'Specialty' Chemicals) 2. 50 g, 0.25 g of cyanine organic dye (NK 863 manufactured by Hayashibara Biochemical Research Institute), Posiethylene guji INORE 200 (manufactured by Kanto Igaku) 0.25 g, ethenorea nolenol n-le (made by Katayama Igaku) 55. 36 g, ethyl silicate 40 (manufactured by Colcoat) 27. 50 g, concentrated hydrochloric acid (35% by mass, Kanto) 0.1 g) was mixed and stirred to obtain a forming solution. Table 19 shows the concentration of each component in this solution.

 [0201] Next, the forming solution was applied to the cleaned UV cut glass substrate by a flow coat method at a humidity of 30% and at room temperature. After drying for about 30 minutes at room temperature, it was put in an oven preheated to 140 ° C and heated for 15 minutes, and then cooled. The obtained film was a highly transparent film having a film thickness of 2000 nm. Table 20 shows the various characteristics of the glass plate with the ultraviolet absorbing film thus obtained.

 [0202] (Example A36)

 In Example A36, the acid concentration in the forming solution in Example A35 was reduced.

 [0203] 14.02 g of pure water, benzotriazole UV absorber (TINUVIN 1130 manufactured by Ciba 'Specialty' Chemicals) 2. 50 g, 0.25 g of cyanine organic dye (NK 863 manufactured by Hayashibara Biochemical Research Institute), Posiethylene guji INORE 200 (manufactured by Kanto Chemical Co., Ltd.) 0.25 g, ethinoreanolol n-le (manufactured by Katayama Chemical Co., Ltd.) 55. 43 g, ethyl silicate 40 (manufactured by Colcoat) 27. 50 g, concentrated hydrochloric acid (35% by mass, Kanto i 匕) 0.05 g) was mixed and stirred to obtain a forming solution. Table 19 shows the concentration of each component in this solution.

 [0204] Next, the forming solution was applied on the cleaned UV cut glass substrate by a flow coat method at a humidity of 30% and at room temperature. After drying for about 30 minutes at room temperature, it was put in an oven preheated to 140 ° C and heated for 15 minutes, and then cooled. The obtained film was a highly transparent film having a film thickness of 2000 nm. Table 20 shows the various characteristics of the glass plate with the ultraviolet absorbing film thus obtained.

 [Example A37]

In Example A37, half (mass ratio) of the SiO raw material in the forming solution in Example A36 Tetraethoxysilane was used.

 [0206] Pure water 14. 05 g, benzotriazole UV absorber (TINUVIN 1130 manufactured by Ciba 'Specialty' Chemicals) 2. 50 g, shean organic pigment (NK 863 manufactured by Hayashibara Biochemical Research Institute) 0.25 g, Posiethylene gudge INORE 200 (manufactured by Kanto Chemical Co., Ltd.) 0.25 g, ethenoreanolol n-le (manufactured by Katayama Chemical) 50. 05 g, tetraethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) 19. 10 g, ethyl silicate 40 (manufactured by Colcoat) 13. 75 g of concentrated hydrochloric acid (35% by mass, manufactured by Kanto Chemical Co., Ltd.) of 0.05 g was mixed and stirred to obtain a forming solution. Table 19 shows the concentration of each component in this solution.

 [0207] Next, the forming solution was applied on the cleaned UV cut glass substrate by a flow coat method at a humidity of 30% and at room temperature. After drying for about 30 minutes at room temperature, it was put in an oven preheated to 140 ° C and heated for 15 minutes, and then cooled. The obtained film was a highly transparent film having a film thickness of 2000 nm. Table 20 shows the various characteristics of the glass plate with the ultraviolet absorbing film thus obtained.

 [Example A38]

 In Example A38, the SiO raw material in the forming solution in Example A36 was changed to tetraethoxysilane.

 2

 It was a run.

 [0209] Pure water 16.30g, benzotriazole UV absorber (TINUVIN 1130 manufactured by Ciba 'Specialty' Chemicals) 2. 50g, shean organic pigment (NK 863 manufactured by Hayashibara Biochemical Research Institute) 0.25g, Posiethylene guji INORE 200 (Kanto Chemical Co., Ltd.) 0.25 g, ethenoreanolol n— (Katayama Chemical Co., Ltd.) 42. 46 g, Tetraoxysilane (Shin-Etsu Chemical Co., Ltd.) 38. 19 g, Concentrated hydrochloric acid (35% by mass) 0.05 g) was mixed and stirred to obtain a forming solution. Table 19 shows the concentration of each component in this solution.

 [0210] Next, the forming solution was applied on the cleaned UV cut glass substrate by a flow coating method at a humidity of 30% and at room temperature. After drying for about 30 minutes at room temperature, it was put in an oven preheated to 140 ° C and heated for 15 minutes, and then cooled. The obtained film was a highly transparent film having a film thickness of 2000 nm. Table 20 shows the various characteristics of the glass plate with the ultraviolet absorbing film thus obtained.

 [0211] (Example A39)

In Example A39, a benzotriazole ultraviolet absorber (ultraviolet absorber A) and purple In addition to cyanine-based organic dyes (ultraviolet absorber B) having an external absorption capability, cyanine-based organic dyes having absorption in the near infrared region (organic dyes having absorption in the near infrared region) were used.

[0212] 7.94 g of pure water, benzotriazole UV absorber (TINUVIN 1130, manufactured by Ciba 'Specialty' Chemicals) 0.30 g, cyanine-based organic dye with UV absorption (Hayashibara Biochemical Laboratory, NK— 863) 0.25g, cyanine-based organic dye having absorption in the near infrared region (NK-125, Hayashibara Biochemical Laboratories) 0.10g, ethyl alcohol (made by Katayama Chemical) 72.26g, tetraethoxysilane (Shinetsu 19.10 g and concentrated hydrochloric acid (35% by mass, manufactured by Kanto Igaku) 0.05 g were mixed and stirred to obtain a forming solution. Table 23 shows the concentration of each component in this solution.

 [0213] Next, the forming solution was applied on the cleaned FL substrate by flow coating at 30% humidity and room temperature. As it was, it was dried at room temperature for about 30 minutes, put into an oven heated to 200 ° C in advance, heated for 15 minutes, and then cooled. The obtained film was a highly transparent film having a film thickness of 600 nm. Table 24 shows the various characteristics of the glass plate with organic-inorganic composite film thus obtained. Table 24 also shows various characteristics of the FL substrate as a blank. The minimum transmittance of light in the wavelength range of more than 700 nm and 12 OO nm or less was also measured using a spectrophotometer (manufactured by Shimadzu Corporation, UV-3000PC).

 [0214] (Example A40)

 In Example A40, the concentration of the organic dye having absorption in the near infrared region in the forming solution in Example A39 was decreased.

 [0215] 7.94 g of pure water, benzotriazole UV absorber (TINUVIN 1130 manufactured by Ciba 'Specialty' Chemicals) 0.30 g, cyanine-based organic dye with UV absorption (Hayashibara Biochemical Laboratory, NK— 863) 0.25 g, cyanine organic dye having absorption in the near infrared region (NK-125, Hayashibara Biochemical Laboratories) 0.20 g, ethyl alcohol (Katayama Chemical) 72. 16 g, tetraethoxysilane (Shinetsu 19.10 g and concentrated hydrochloric acid (35% by mass, manufactured by Kanto Igaku) 0.05 g were mixed and stirred to obtain a forming solution. Table 23 shows the concentration of each component in this solution.

[0216] Next, the forming solution was applied on the cleaned FL substrate by flow coating at 30% humidity and room temperature. After drying at room temperature for about 30 minutes, the temperature is raised to 200 ° C in advance. It was put into the oven and heated for 15 minutes and then cooled. The obtained film was a highly transparent film having a film thickness of 600 nm. Table 24 shows the various characteristics of the glass plate with organic-inorganic composite film thus obtained.

 [0217] (Example A41)

 In Example A41, the heating temperature after room temperature drying in Example A39 was lowered to 140 ° C. The obtained film was a highly transparent film having a thickness of 600 nm. Table 24 shows various properties of the glass plate with the organic-inorganic composite film thus obtained.

 [0218] As shown in Table 24, all of the organic-inorganic composite films obtained in Examples A39 to A41 have a short-wavelength near-infrared (wavelength 700 to 1200 nm) shielding ability in addition to the ultraviolet shielding ability. Was also excellent.

 [0219] (Example A42)

 In Example A42, ITO fine particles and a polyether phosphate ester polymer were added to the forming solution instead of the organic dye having absorption in the near infrared region.

 [0220] Pure water 31.14g, benzotriazole UV absorber (TINUVIN 1130 manufactured by Ciba 'Specialty' Chemicals) 0.30g, cyanine organic dye (NK 863 manufactured by Hayashibara Biochemical Research Institute) 0.25g, Ethyl alcohol (made by Katayama Chemical) 42.51g, ITO fine particle dispersion (ethyl alcohol solution containing 40% by mass of ITO, made by Mitsubishi Materials) 6.00g, polyether phosphate polymer (Solsperse 41000 made by Nippon Lubrizol) 0.60 g, tetraethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.), 19.10 g, concentrated hydrochloric acid (35 mass%, manufactured by Kanto Chemical Co., Ltd.), 0.1 g, were mixed and stirred to obtain a forming solution. Table 25 shows the concentration of each component in this solution.

 [0221] Next, the forming solution was applied on the cleaned FL substrate by a flow coating method at a humidity of 30% and at room temperature. As it was, it was dried at room temperature for about 30 minutes, put into an oven heated to 200 ° C in advance, heated for 15 minutes, and then cooled. The obtained film was a highly transparent film having a thickness of lOOOnm. Table 26 shows the various characteristics of the glass plate with organic-inorganic composite film thus obtained. Table 26 also shows various characteristics of the FL substrate as a blank.

 [0222] (Example A43)

In Example A43, the proton concentration in the forming solution in Example A42 was reduced. [0223] Pure water 31. 19 g, benzotriazole UV absorber (TINUVIN 1130 manufactured by Ciba 'Specialty' Chemicals) 0.30 g, cyanine organic dye (NK 863 manufactured by Hayashibara Biochemical Research Institute) 0.25 g, Ethyl alcohol (made by Katayama Chemical) 42.51g, ITO fine particle dispersion (ethyl alcohol solution containing 40% by mass of ITO, made by Mitsubishi Materials) 6.00g, polyether phosphate polymer (Solsperse 41000 made by Nippon Lubrizol) 0.060 g, tetraethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) 19.10 g and concentrated hydrochloric acid (35 mass%, manufactured by Kanto Chemical Co., Ltd.) 0.05 g were mixed and stirred to obtain a forming solution. Table 25 shows the concentration of each component in this solution.

 [0224] Next, the forming solution was applied on the cleaned FL substrate by a flow coating method at a humidity of 30% and at room temperature. As it was, it was dried at room temperature for about 30 minutes, put into an oven heated to 200 ° C in advance, heated for 15 minutes, and then cooled. The obtained film was a highly transparent film having a thickness of 900 nm. Table 26 shows the various characteristics of the glass plate with organic-inorganic composite film thus obtained.

 [0225] (Example A44)

 In Example A44, the SiO concentration in the forming solution in Example A42 was increased.

 2

 [0226] 34.00 g of pure water, benzotriazole UV absorber (TINUVIN 1130 manufactured by Ciba 'Specialty' Chemicals) 0.30 g, cyanine organic dye (NK 863 manufactured by Hayashibara Biochemical Research Institute) 0.25 g, Ethyl alcohol (made by Katayama Chemical) 37. 92g, ITO fine particle dispersion (ethyl alcohol solution containing 40% by mass of ITO, made by Mitsubishi Materials) 6.00g, polyether phosphate polymer (Solsperse 41000 made by Nippon Lubrizol) 0.060 g, tetraethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) 20.83 g, concentrated hydrochloric acid (35 mass%, manufactured by Kanto Chemical Co., Ltd.) 0.1 g were mixed and stirred to obtain a forming solution. Table 25 shows the concentration of each component in this solution.

[0227] Next, the forming solution was applied on the cleaned FL substrate by a flow coating method at a humidity of 30% and at room temperature. As it was, it was dried at room temperature for about 30 minutes, then put into an oven heated to 200 ° C in advance, heated for 15 minutes, and then cooled. The obtained film was a highly transparent film having a thickness of lOOOnm. Table 26 shows the various characteristics of the glass plate with organic-inorganic composite film thus obtained. [0228] (Example A45)

 In Example A45, the concentration of ITO fine particles in the forming solution in Example A42 was reduced.

 [0229] Pure water 31.12g, benzotriazole UV absorber (TINUVIN 1130 manufactured by Ciba 'Specialty' Chemicals) 0.30g, cyanine organic dye (NK 863 manufactured by Hayashibara Biochemical Research Institute) 0.25g, Ethyl alcohol (manufactured by Katayama Chemical) 46. 03g, ITO fine particle dispersion (ethyl alcohol solution containing 40% by mass of ITO, manufactured by Mitsubishi Materials) 2. 50g, polyether phosphate polymer (Solsperse 41000 manufactured by Nippon Lubrizol) 0.60 g, tetraethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) 19.10 g, concentrated hydrochloric acid (35 mass%, manufactured by Kanto Chemical Co., Ltd.) 0.1 g were mixed and stirred to obtain a forming solution. Table 25 shows the concentration of each component in this solution.

 [0230] Next, the forming solution was applied to the cleaned FL substrate by a flow coating method at a humidity of 30% and at room temperature. As it was, it was dried at room temperature for about 30 minutes, put into an oven heated to 200 ° C in advance, heated for 15 minutes, and then cooled. The obtained film was a highly transparent film having a thickness of 800 nm. Table 26 shows the various characteristics of the glass plate with organic-inorganic composite film thus obtained.

 [0231] (Example A46)

 In Example A46, the concentration of the ultraviolet absorber in the forming solution in Example A43 was increased, and the heating temperature after drying at room temperature was lowered.

 [0232] 13.98 g of pure water, benzotriazole UV absorber (TINUVIN 1130 manufactured by Ciba 'Specialty' Chemicals) 3.00 g, cyanine organic dye (NK 863 manufactured by Hayashibara Biochemical Research Institute) 0.25 g, Ethyl alcohol (manufactured by Katayama Chemical) 46. l lg, ITO fine particle dispersion (ethyl alcohol solution containing 40% by mass of ITO, manufactured by Mitsubishi Materials) 5. 63 g, polyether phosphate polymer (Solsperse 4100 manufactured by Nippon Lubrizol) ) 0.60 g, tetraethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) 30. 38 g, concentrated hydrochloric acid (35% by mass, manufactured by Kanto Chemical Co., Ltd.) 0.05 g were mixed and stirred to obtain a forming solution. Table 25 shows the concentration of each component in this solution.

[0233] Next, the formed solution was applied to the cleaned FL substrate at 30% humidity and room temperature using the flow coating method. And applied. As it was, it was dried at room temperature for about 30 minutes, put into an oven preheated to 140 ° C, heated for 15 minutes, and then cooled. The obtained film was a highly transparent film having a thickness of 1900 nm. Table 26 shows the various characteristics of the glass plate with organic-inorganic composite film thus obtained.

 [0234] As shown in Table 26, the ultraviolet absorbing films obtained in Examples A42 to A47 were excellent in the shielding ability of long-wavelength near infrared rays (wavelengths of 1200 to 2500 nm) in addition to the ultraviolet shielding ability.

 [0235] (Comparative Example A1)

 In Comparative Example A1, a polyether phosphate polymer was used instead of the benzotriazole ultraviolet absorber in Example A1.

 [0236] 19.45 g of pure water, polyether phosphate ester polymer (Japan Lubrizol Sol Snus 41000) 5. 20 g, ethino rareno reconole (manufactured by Katayama Igaku) 42. 75 g, ethino resilient To 40 (manufactured by Colcoat) 32.50 g and concentrated hydrochloric acid (35 mass%, manufactured by Kanto Chemical Co., Ltd.) 0.10 g were mixed and stirred to obtain a forming solution. Table 15 shows the concentration of each component in this solution.

 [0237] Next, the forming solution was applied on the cleaned FL substrate by a flow coating method at a humidity of 30% and at room temperature. As it was, it was dried at room temperature for about 30 minutes, put into an oven heated to 200 ° C in advance, heated for 15 minutes, and then cooled. The obtained film was a highly transparent film having a thickness of 3400 nm. However, this glass substrate with a film had poor ultraviolet shielding ability, with an ultraviolet transmittance of 66.7% and a light transmittance of 87.5% at a wavelength of 365 nm (see Table 16).

 [0238] (Comparative Example A2)

 In Comparative Example A2, no organic substance is added.

 [0239] 27.16 g of pure water, 27.49 g of ethyl alcohol (manufactured by Katayama Chemical), 45.14 g of tetraethoxysilane (manufactured by Shin-Etsu Chemical), concentrated hydrochloric acid (35 mass%, manufactured by Kanto Chemical) 0. 10 g and phosphoric acid (85% by mass, manufactured by Kanto Chemical Co., Ltd.) 0.1 l lg were mixed and stirred to obtain a forming solution. Table 15 shows the concentration of each component in this solution.

[0240] Next, the forming solution was applied on the cleaned FL substrate by flow coating at 30% humidity and room temperature. As it was, it was dried at room temperature for about 30 minutes, then put in an oven preheated to 200 ° C., heated for 40 minutes, and then cooled. As a result, cracks with peeling occur However, it was a force that was not established as a film.

 [0241] (Comparative Example A3)

 In Comparative Example A3, the proton concentration was decreased.

 [0242] Pure water 19.57 g, Polyethylene glycol 200 (Kanto Chemical Co., Ltd.) 1. 35 g, Ethyl alcohol (Katayama Chemical Co., Ltd.) 58. 25 g, Tetraethoxysilane (Shin-Etsu Chemical Co., Ltd.) 20. 83 g, Concentrated hydrochloric acid (35% by mass, manufactured by Kanto Yigaku) 0. OOlg was mixed and stirred to obtain a forming solution. Table 15 shows the concentration of each component in this solution.

 [0243] Next, an attempt was made to apply the forming solution onto the cleaned FL substrate. However, the solution was repelled from the substrate and was unable to form a film. This is thought to be because the hydrolysis of silicon alkoxide did not proceed sufficiently in a liquid with a low acid concentration.

 [0244] (Comparative Example A4)

 In Comparative Example A4, the water content was reduced.

[0245] 4.14 g of pure water, polyether phosphate ester polymer (Solus Nose 41000 manufactured by Nippon Lubrizol) 0.75 g, polyethylene glycol 200 (manufactured by Kanto Aisaku) 0.25 g, ethinoreal alcohol ( Katayama Chemical Co., Ltd.) 74. 03g, Tetraethoxysilane (Shin-Etsu Chemical Co., Ltd.) 20.83g, Concentrated Hydrochloric Acid (35% by mass, manufactured by Kanto Chemical Co., Ltd.) 0.10g were mixed and stirred to obtain a forming solution. . Table 15 shows the concentration of each component in this solution.

[0246] Next, a coating solution was applied on the cleaned FL substrate by a flow coating method at a humidity of 30% at room temperature. As it was, it was air-dried at room temperature for about 5 minutes, put in an oven preheated to 200 ° C, heated for 12 minutes, and then cooled.

[0247] The obtained film was a highly transparent film having a thickness of 600 nm, and no cracks accompanied by peeling were observed. However, when the Taber abrasion test was conducted, the film peeled after the Taber abrasion test (see Table 16).

[0248] (Comparative Example A5)

 In Comparative Example A5, a UV cut glass substrate was used instead of the FL substrate in Comparative Example A1.

[0249] Table 21 shows the concentration of each component in the forming solution. The obtained film was a highly transparent film having a thickness of 3400 nm. However, the glass plate with organic-inorganic composite film thus obtained is purple. The external light transmittance was 11.8%, and the light transmittance at a wavelength of 370nm was 32.3%.

[0250] (Comparative Example A6)

 In Comparative Example A6, a UV cut glass substrate was used instead of the FL substrate in Comparative Example A2.

 [0251] In this example, as with Comparative Example A2, cracks accompanied with peeling occurred, and the film did not hold as a film.

[0252] (Comparative Example A7)

 In Comparative Example A7, a UV cut glass substrate was used instead of the FL substrate in Comparative Example A3.

 [0253] In this example, as in Comparative Example A3, even if an attempt was made to apply the forming solution, the solution was repelled from the substrate and was unable to form a film.

[0254] (Comparative Example A8)

 In Comparative Example A8, a UV cut glass substrate was used instead of the FL substrate in Comparative Example A4.

 [0255] Table 21 shows the concentration of each component in the forming solution. The obtained film was a film having a high transparency with a thickness of 600 nm, and was strong without any cracks accompanying peeling. However, when the Taber abrasion test was conducted, the film peeled after the Taber abrasion test (see Table 22).

 [0256] (Example B1)

 In Example B1, a cyanine organic dye was used as the organic dye, and a polyether phosphate ester polymer was used as the hydrophilic organic polymer.

 [0257] Ethyl alcohol (Katayama Chemical Co., Ltd.) 42. 40 g, Ethyl silicate 40 (Colcoat Co.) 3 2. 50 g, Pure water 19. 45 g, Concentrated hydrochloric acid (35% by mass, Kanto Chemical Co., Ltd.) 0. 10 g , Polyether phosphate ester polymer (Solsperse 41000 manufactured by Nippon Lubrizol) 4.55 g, Cyan organic pigment (NK-863 manufactured by Hayashibara Biochemical Laboratories) 1. Add OOg, stir, and form solution Got. Table 27 shows the concentration of each component in this solution.

[0258] Next, the forming solution was applied on the cleaned UV cut glass substrate by a flow coat method at a humidity of 30% and at room temperature. Continue to dry at room temperature for about 30 minutes, then set to 200 ° C in advance. It was put into a heated oven, heated for 15 minutes, and then cooled. The obtained film was a highly transparent organic-inorganic composite film having a thickness of 3100 nm. Table 28 shows the film thickness and various characteristics of the glass plate with organic-inorganic composite film thus obtained.

 [0259] (Examples B2 to B4)

 In Examples B2 to B4, the heating temperature after drying at room temperature was lower than in Example B1.

 [0260] The obtained films were all highly transparent organic-inorganic composite films having a thickness of 3100 nm.

 Table 28 shows the film thickness and various characteristics of the glass plate with the organic-inorganic composite film thus obtained.

 [0261] As shown in Table 28, each of the glass plates with organic-inorganic composite films obtained in Examples B1 to B4 has high ultraviolet shielding ability and has a light transmittance of 2.5% at a wavelength of 370 nm. The light transmittance at a wavelength of 370 nm decreased by 25% or more due to the formation of the film.

 [0262] (Example B5)

 In Example B5, a cyanine organic dye was used as the organic dye, and a benzotriazole compound was used as the hydrophilic organic polymer.

 [0263] Pure water 12.68g, benzotriazole UV absorber (TINUVIN 1130 from Ciba 'Specialty' Chemicals) 3. OOg, cyanine organic dye (NK-863, Hayashibara Biochemical Research Institute) 0.2g , Ethyl alcohol (Katayama Igaku) 59.02g, Ethyl silicate 40 (Colcoat) 25.00g, Concentrated hydrochloric acid (35% by mass, Kanto Igaku) 0.10g was added, stirred and formed A solution was obtained. Table 29 shows the concentration of each component in this solution.

 [0264] Next, the forming solution was applied on the cleaned UV cut glass substrate by a flow coat method at a humidity of 30% and at room temperature. After drying for about 30 minutes at room temperature, it was put in an oven preheated to 140 ° C and heated for 15 minutes, and then cooled. The resulting film was a highly transparent organic-inorganic composite film having a thickness of 1900 nm. Table 30 shows the film thickness and various characteristics of the glass plate with the organic-inorganic composite film thus obtained.

 [0265] (Example B6)

 In Example B6, the organic dye concentration in the forming solution in Example B5 was increased.

[0266] Pure water 12.68g, benzotriazole UV absorber (TINUVIN 1130 manufactured by Ciba 'Specialty' Chemicals) 3.00g, cyanine organic dye (NK-863 manufactured by Hayashibara Biochemical Research Institute) 0. 3g , Ethyl alcohol (made by Katayama Igaku) 58. 92g, Ethyl silicate 40 (Col Coated) 25. OOg, concentrated hydrochloric acid (35% by mass, manufactured by Kanto Chemical Co., Ltd.) 0. lOg was added and stirred to obtain a forming solution. Table 29 shows the concentration of each component in this solution.

 [0267] Next, the forming solution was applied on the cleaned UV cut glass substrate by a flow coat method at a humidity of 30% and at room temperature. After drying for about 30 minutes at room temperature, it was put in an oven preheated to 140 ° C and heated for 15 minutes, and then cooled. The resulting film was a highly transparent organic-inorganic composite film having a thickness of 1900 nm. Table 30 shows the film thickness and various characteristics of the glass plate with the organic-inorganic composite film thus obtained.

 [0268] (Example B7)

 In Example B7, the SiO concentration in the forming solution in Example B5 was increased.

 2

 [0269] Pure water 13. 99 g, benzotriazole UV absorber (TINUVIN 1130 manufactured by Ciba 'Specialty' Chemicals) 3.00 g, shean organic pigment (NK-863 manufactured by Hayashibara Biochemical Research Institute) 0. 2 g , Ethyl alcohol (Katayama Igaku) 55.21g, ethyl silicate 40 (Colcoat) 27.50g, concentrated hydrochloric acid (35% by mass, Kanto Igaku) 0.10g was added, stirred and formed A solution was obtained. Table 29 shows the concentration of each component in this solution.

 [0270] Next, the forming solution was applied on the cleaned UV cut glass substrate by a flow coat method at a humidity of 30% and at room temperature. After drying for about 30 minutes at room temperature, it was put in an oven preheated to 140 ° C and heated for 15 minutes, and then cooled. The obtained film was a highly transparent organic-inorganic composite film having a thickness of 2100 nm. Table 30 shows the film thickness and various characteristics of the glass plate with the organic-inorganic composite film thus obtained.

 [0271] (Example B8)

 In Example B8, polyethylene glycol was further added as a hydrophilic organic polymer to the forming solution in Example B7, and the organic dye concentration in the forming solution was increased.

[0272] 13.98 g of pure water, benzotriazole UV absorber (TINUVIN 1130 manufactured by Ciba 'Specialty' Chemicals) 3.00 g, shean organic pigment (NK 863 manufactured by Hayashibara Biochemical Research Institute) 0.25 g, to E Chino rare Roh record Norre (Katayama made I匕学) 54. 57g, E Chino Les silicon gate 40 (manufactured by Colcoat) 27. 50g, concentrated hydrochloric acid (35 mass _^0/0, Kanto made I匕学) 0. 10g Then, polyethylene glycol 200 (manufactured by Kanto Chemical Co., Ltd.) (0.60 g) was added and stirred to obtain a forming solution. Each in this solution Table 29 shows the component concentrations.

 [0273] Next, the forming solution was applied on the cleaned UV cut glass substrate by a flow coat method at a humidity of 30% and at room temperature. After drying for about 30 minutes at room temperature, it was put in an oven preheated to 140 ° C and heated for 15 minutes, and then cooled. The obtained film was a highly transparent organic-inorganic composite film having a thickness of 2200 nm. Table 30 shows the film thickness and various characteristics of the glass plate with the organic-inorganic composite film thus obtained.

 [0274] (Example B9)

 In Example B9, an azo organic dye was used as the organic dye, and a benzotriazole compound was used as the hydrophilic organic polymer.

 [0275] Pure water 16.75 g, benzotriazole UV absorber (TINUVIN 1130 from Ciba 'Specialty' Chemicals) 4.00 g, azo organic dye (Tokyo Chemical Industries Alizarin Yellow GG) 0.084 g, ethyl Alcohol (made by Katayama Chemical Co., Ltd.) 46. 57g, Ethyl silicate 40 (Corcolate Co., Ltd.) 32. 50g, concentrated hydrochloric acid (35% by mass, manufactured by Kanto Chemical Co., Ltd.) 0.10g was added and stirred to form a solution. A liquid was obtained. Table 29 shows the concentration of each component in this solution.

 [0276] Next, the forming solution was applied on the cleaned UV-cut glass substrate by a flow coating method at a humidity of 30% and at room temperature. After drying for about 30 minutes at room temperature, it was put in an oven preheated to 110 ° C, heated for 60 minutes, and then cooled. The obtained film was a highly transparent organic-inorganic composite film having a thickness of 2700 nm. Table 30 shows the film thickness and various characteristics of the glass plate with the organic-inorganic composite film thus obtained.

 [0277] As shown in Table 30, each of the glass plates with organic-inorganic composite films obtained in Examples B5 to B9 has a high ultraviolet shielding ability, and has a light transmittance of 2.0% at a wavelength of 370 nm. The light transmittance at a wavelength of 370 nm decreased by 28% or more due to the formation of the film.

 [0278] (Example B10)

 In Example B10, a base styryl organic dye was used as the organic dye, and a polyether phosphate ester polymer was used as the hydrophilic organic polymer.

[0279] Ethyl alcohol (Katayama Chemical) 45. 48g, Ethyl silicate 40 (Colcoat) 3 2. 50g, Pure water 16.62g, Concentrated hydrochloric acid (35% by mass, Kanto Chemical Co., Ltd.) 0. 10g , Polyether phosphate ester polymer (Solsperse 41000 manufactured by Nippon Lubrizol) 5. 20 g, base Styryl organic pigment (NK-1977, Hayashibara Biochemical Laboratories) 0.10 g was added and stirred to obtain a forming solution. Table 31 shows the concentration of each component in this solution.

 [0280] Next, the forming solution was applied on the cleaned UV cut glass substrate by a flow coat method at a humidity of 30% and at room temperature. After drying for about 30 minutes at room temperature, it was put in an oven preheated to 200 ° C and heated for 15 minutes, and then cooled. The obtained film was a highly transparent organic-inorganic composite film having a thickness of 3400 nm. Table 32 shows the film thickness and various characteristics of the glass plate with organic-inorganic composite film thus obtained. This film was a pink colored film having a large absorption maximum near 550 nm.

 [0281] (Example B11)

 In Example B11, an organic dye having absorption in the near-infrared region was used as the organic dye, and a polyether phosphate ester polymer was used as the hydrophilic organic polymer.

 [0282] Ethyl alcohol (Katayama Chemical Co., Ltd.) 46. 13g, Ethyl silicate 40 (Colcoat) 3 2. 50g, Pure water 16.62g, Concentrated hydrochloric acid (35% by mass, Kanto Chemical Co., Ltd.) 0. 10g , Polyether phosphate ester polymer (Solsperse 41000, manufactured by Nippon Lubrizol) 4.55 g, organic dye having absorption in the near infrared region (IR-301, manufactured by Yamada Chemical Co., Ltd.) 0.10 g was added and stirred to form a solution. A liquid was obtained. Table 31 shows the concentration of each component in this solution.

 [0283] Next, the forming solution was applied on the cleaned UV cut glass substrate by a flow coating method at a humidity of 30% and at room temperature. After drying for about 30 minutes at room temperature, it was put into an oven preheated to 160 ° C, heated for 15 minutes, and then cooled. The obtained film was a highly transparent organic-inorganic composite film having a thickness of 3100 nm. Table 32 shows the film thickness and various characteristics of the glass plate with organic-inorganic composite film thus obtained. This film was a light blue colored film.

 [0284] (Example B12)

 In Example B12, a coumarin fluorescent dye was used as the organic dye, and a polyether phosphate ester polymer was used as the hydrophilic organic polymer.

[0285] Ethyl alcohol (Katayama Chemical) 27.07g, Tetraethoxysilane (Shin-Etsu Chemical Co., Ltd.) 36. l lg, Ethyl silicate 40 (Colcoat) 6. 50g, Pure water 25.62g, Concentrated Hydrochloric acid (35% by mass, manufactured by Kanto Chemical Co., Ltd.) 0.1 g, polyether phosphate ester polymer (Solsperse 41000 manufactured by Nippon Loop Resor) 4. 55 g, coumarin fluorescent dye (Hayashibara Biochemical Research Institute) NKX-1595) 0.05 g was added and stirred to obtain a forming solution. Table 33 shows the concentration of each component in this solution.

 [0286] Next, the forming solution was applied on the cleaned UV cut glass substrate by a flow coat method at a humidity of 30% and at room temperature. After drying for about 30 minutes at room temperature, it was put in an oven preheated to 140 ° C and heated for 15 minutes, and then cooled. The obtained film was a highly transparent organic-inorganic composite film having a thickness of 3100 nm. Table 34 shows the film thickness and various characteristics of the glass plate with organic-inorganic composite film thus obtained. This film was a film that emitted yellow light when irradiated with black light (UVL-56 manufactured by Funakoshi Co., Ltd.).

 [0287] (Example B13)

 In Example B13, the concentrations of the organic dye, hydrophilic organic polymer, and silicon alkoxide in the forming solution of Example B12 were reduced.

 [0288] Ethyl alcohol (manufactured by Katayama Chemical) 51.555g, tetraethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) 25.00g, ethyl siliques 40 (manufactured by Colcoat) 4.50g, pure water 17.58g, concentrated hydrochloric acid (35% by mass, manufactured by Kanto Chemical Co., Ltd.) 0. 10 g, polyether phosphate ester polymer (Nippon Loop Resor Solsperse 41000) 1. 26 g, coumarin fluorescent dye (NKX-1595, Hayashibara Biochemical Research Institute) 0.005 g was added and stirred to obtain a forming solution. Table 33 shows the concentration of each component in this solution.

 [0289] Next, the forming solution was applied on the cleaned UV cut glass substrate by a flow coat method at a humidity of 30% and at room temperature. After drying for about 30 minutes at room temperature, it was put in an oven preheated to 140 ° C and heated for 15 minutes, and then cooled. The obtained film was a highly transparent organic-inorganic composite film having a thickness of 1200 nm. Table 34 shows the film thickness and various characteristics of the glass plate with organic-inorganic composite film thus obtained. This film was also a film that emitted yellow light when irradiated with black light (UVL-56 manufactured by Funakoshi Co., Ltd.).

 [0290] (Examples B14 to B17)

 In Examples B14 to B17, an organic-inorganic composite film was formed in the same manner as in Example B13, except that the following organic dye was used in place of the coumarin fluorescent dye.

(Example B 14): Naphthalimide-based light-collecting dye (Lumogen F Viol et 570 manufactured by BASF Japan) (Example B15): Perylene-based condensing dye (Lumogen F Yellow 0 83 manufactured by BASF Japan)

 (Example B 16): Perylene-based condensing pigment (Lumogen F Red 300 manufactured by BASF Japan)

 (Example B 17): Perylene-based condensing dye (Lumogen F Orange 2 40 manufactured by BASF Japan)

 [0291] The obtained films were all organic-inorganic composite films having a film thickness of 1200 nm and high transparency.

 Table 34 shows the film thickness and various characteristics of the glass plate with the organic-inorganic composite film thus obtained. The V-shifted film was also a film that emitted light when irradiated with black light (UVL-56 manufactured by Funakoshi Co., Ltd.).

 [0292] (Example B18)

 In Example B18, an organic-inorganic composite film was formed on a polycarbonate resin substrate.

 [0293] <Formation of primer layer>

 99.50 g of ethyl alcohol (Katayama Chemical Co., Ltd.), 3-aminopropyltriethoxysilane (KBE-903 manufactured by Shin-Etsu Chemical Co., Ltd.) 0.40 g, concentrated hydrochloric acid (35% by mass, manufactured by Kanto Chemical Co., Ltd.) 10 g was added and stirred to obtain a forming solution. Table 35 shows the silicon alkoxide (converted to aminominopropyl sesquioxane (RSiO)), proton concentration and water content in this solution.

 1.5

Incidentally, here, the water content, calculated in terms of added moisture contained in ethyl alcohol as 0.35 mass _^0/0, Ru.

 [0294] Next, the forming solution was applied on a cleaned polycarbonate resin substrate (100 mm X 100 mm; thickness 3.0 mm) by flow coating at 30% humidity and room temperature. The primer layer was dried for about 1 minute at room temperature, put in an oven preheated to 110 ° C., heated for 30 minutes, and then cooled to form a primer layer.

 [0295] <Formation of organic-inorganic composite film>

On the primer layer, the same formation solution as in Example B12 (see Table 36) was applied by flow coating at 30% humidity and room temperature. As it was, it was dried at room temperature for about 30 minutes, put in an oven preheated to 110 ° C., heated for 60 minutes, and then cooled to form an organic-inorganic composite film. The obtained film was a highly transparent film having a thickness of 2800 nm. This way Table 37 shows the film thickness and various characteristics of the resin-coated resin board with organic-inorganic composite film. This film is also a film that emits yellow light when irradiated with black light (UVL-56 manufactured by Funakoshi Co., Ltd.).

 [0296] Further, when the obtained film was subjected to a tape peeling test according to the cross-cut tape method of JIS K 5400, film peeling did not occur at all, and in addition to wear resistance, the film was adhered to the resin substrate. It was confirmed that the properties were very excellent.

 [0297] This tape peeling test was performed as follows. First, use a cutter knife to cut in the vertical direction on the surface of the organic-inorganic composite film at intervals of 5 mm so as to penetrate the film and reach the resin substrate, and then in the horizontal direction perpendicular to the vertical direction. The same notch was made, and a sample having 9 grids of 5 mm square was produced. Next, the adhesive tape specified in JIS Z 1522 (-Chiban LP-24, Width: 24mm, Thickness: 0.054mm, Adhesive strength: 4. OlNZlOmm) is applied on this grid. Affixed to a length of about 50 mm. Thereafter, the adhesive tape was adhered to the sample by rubbing the surface of the adhesive tape with an eraser specified in JIS S 6050. After 1 to 2 minutes, the adhesive tape is peeled off instantaneously (for example, within 0.2 seconds) in the direction of 90 degrees with respect to the surface of the organic-inorganic composite film, and the state of the grid-like cut is observed. It was evaluated by.

 [0298] (Example B19)

 In Example B19, a cyanine organic dye having absorption in the near-infrared region was used as the organic dye, and a polyether phosphate ester polymer was used as the hydrophilic organic polymer.

 [0299] Ethyl alcohol (made by Katayama Chemical) 48.64g, tetraethoxysilane (made by Shin-Etsu Chemical Co., Ltd.) 31.25g, pure water 18.65g, concentrated hydrochloric acid (35% by mass, manufactured by Kanto Chemical Co., Ltd.) 0. 10g, Polyester phosphate polymer (Solse Nose 41000 made by Enomoto Lubrizol) 1.26g, cyanine-based organic dye having absorption in the near infrared region (NK-125, Hayashibara Biochemical Research Institute) 0. 10g Were added and stirred to obtain a forming solution. Table 38 shows the concentration of each component in this solution.

[0300] Next, the forming solution was applied onto the cleaned FL substrate by a flow coating method at a humidity of 30% and at room temperature. As it was, it was dried at room temperature for about 30 minutes, then put into an oven heated to 200 ° C in advance, heated for 15 minutes, and then cooled. The resulting film has a transparency of 1200 nm. The organic-inorganic composite film was high. Table 39 shows the film thickness and various characteristics of the glass plate with organic-inorganic composite film thus obtained.

 [0301] (Example B20)

 In Example B20, the organic dye concentration in the forming solution in Example B19 was increased.

 [0302] Ethyl alcohol (manufactured by Katayama Chemical) 48. 54g, tetraethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) 31. 25g, pure water 18.65g, concentrated hydrochloric acid (35% by mass, manufactured by Kanto Chemical Co., Ltd.) 0. 10 g, Polyester phosphate polymer (Solse Nose 41000 manufactured by Enomoto Lubrizol) 1. 26 g, cyanine-based organic dye having absorption in the near infrared region (NK-125, Hayashibara Biochemical Research Institute) 0.20 g Were added and stirred to obtain a forming solution. Table 38 shows the concentration of each component in this solution.

 [0303] Next, the forming solution was applied on the cleaned FL substrate by flow coating at 30% humidity and room temperature. As it was, it was dried at room temperature for about 30 minutes, put into an oven heated to 200 ° C in advance, heated for 15 minutes, and then cooled. The obtained film was a highly transparent organic-inorganic composite film having a thickness of 1300 nm. Table 39 shows the film thickness and various characteristics of the glass plate with organic-inorganic composite film thus obtained.

 [0304] (Example B21)

 In Example B21, the concentration of the organic dye in the forming solution in Example B20 was further increased.

 [0305] Ethyl alcohol (made by Katayama Chemical) 71. 94g, tetraethoxysilane (made by Shin-Etsu Chemical Co., Ltd.) 17.36g, pure water 10.15g, concentrated hydrochloric acid (35% by mass, manufactured by Kanto Chemical Co., Ltd.) 0.1 g, 0.1 g of polyether phosphate polymer (Solsperse 41000 manufactured by Nippon Lubrizol), 0.30 g of cyanine organic dye having absorption in the near infrared region (NK-125, Hayashibara Biochemical Laboratories) And stirred to obtain a forming solution. Table 38 shows the concentration of each component in this solution.

Next, the forming solution was applied on the cleaned FL substrate by a flow coating method at a humidity of 30% and at room temperature. As it was, it was dried at room temperature for about 30 minutes, then put into an oven heated to 200 ° C in advance, heated for 15 minutes, and then cooled. The obtained film was a highly transparent organic-inorganic composite film having a film thickness of 600 nm. Film thickness of the glass plate with organic-inorganic composite film thus obtained Table 39 shows the various characteristics.

[0307] (Example B22)

 In Example B22, the concentration of the hydrophilic organic polymer in the forming solution in Example B20 was increased.

[0308] Ethyl alcohol (made by Katayama Chemical) 24.65g, tetraethoxysilane (made by Shin-Etsu Chemical Co., Ltd.) 36. l lg, ethyl silicate 40 (made by Colcoat) 6. 50g, pure water 27. 14g, Concentrated hydrochloric acid (35 mass _^0/0, Kanto Ltd. I匕学) 0. 10 g, polyether phosphate ester-based polymer (Nippon Lou Burizoru made Sorusuno over scan 41000) 5. 20 g, Shianin based chromatic having absorption in the near-infrared region Machine dye (NK-125, Hayashibara Biochemical Laboratories) 0.30 g was added and stirred to obtain a forming solution. Table 38 shows the concentration of each component in this solution.

 [0309] Next, the forming solution was applied to the washed soda lime silicate glass substrate at a humidity of 30% at room temperature by a flow coating method. As it was, it was dried at room temperature for about 30 minutes, put in an oven preheated to 200 ° C., heated for 15 minutes, and then cooled. The obtained film was a highly transparent organic-inorganic composite film having a film thickness of 3400 nm. Table 39 shows the film thickness and various characteristics of the glass plate with organic-inorganic composite film thus obtained.

 [0310] As shown in Table 39, the organic-inorganic composite films obtained in Examples B19 to B22 were all excellent in the shielding ability of near-infrared rays (wavelength 700 to 1200 nm) on the short wavelength side.

 [0311] (Comparative Example B1)

 In Comparative Example B1, no hydrophilic organic polymer was added to the forming solution.

 [0312] Ethyl alcohol (made by Katayama Chemical) 31. 61g, tetraethoxysilane (made by Shin-Etsu Chemical Co., Ltd.) 36. l lg, ethyl silicate 40 (made by Colcoat) 6. 50g, pure water 25. 63g, concentrated hydrochloric acid (35% by mass, manufactured by Kanto Chemical Co., Ltd.) 0.10 g, azo-based organic dye (Tokyo Chemical Industry Alizarin Yellow GG) 0.05 g were added and stirred to obtain a forming solution. Table 40 shows the concentration of each component in this solution.

[0313] Next, the forming solution was applied on the cleaned UV cut glass substrate by a flow coat method at a humidity of 30% and at room temperature. After drying for about 30 minutes at room temperature, it was put in an oven preheated to 200 ° C and heated for 15 minutes, and then cooled. As a result, cracks accompanied with peeling occurred, and the film did not work. [0314] (Comparative Example B2)

 In Comparative Example B2, the water content in the forming solution was reduced.

[0315] Ethyl alcohol (made by Katayama Chemical) 45. 79g, tetraethoxysilane (made by Shin-Etsu Chemical Co., Ltd.) 36. l lg, ethyl silicate 40 (made by Colcoat) 6. 50g, pure water 7.55g, concentrated hydrochloric acid (35 mass _^0/0, Kanto Ltd. I匕学) 0. 10 g, polyether phosphate ester-based polymer (manufactured by Lubrizol SOLSPERSE 41000) 3. 90 g, § zone-based organic dye (manufactured by Tokyo Kasei Alizarin Yellow GG) 0 05 g was added and stirred to obtain a forming solution. Table 40 shows the concentration of each component in this solution.

 [0316] Next, the forming solution was applied on the UV-cut glass substrate that had been cleaned by the flow coating method at a humidity of 30% and at room temperature. After drying for about 30 minutes at room temperature, it was put in an oven preheated to 200 ° C and heated for 15 minutes, and then cooled. As a result, cracks accompanied with peeling occurred, and the film did not work.

 [0317] (Comparative Example B3)

 In Comparative Example B3, the proton concentration in the forming solution was extremely increased.

 [0318] Ethyl alcohol (made by Katayama Chemical) 57. 59g, tetraethoxysilane (made by Shin-Etsu Chemical Co., Ltd.) 20.83g, pure water 17.63g, concentrated hydrochloric acid (35% by mass, manufactured by Kanto Chemical Co., Ltd.) 3. 00 g, Polyether phosphate ester polymer (Solsperse 41000, manufactured by Nippon Lubrizol) 0.77 g, Polyethylene glycol 200 (manufactured by Kanto Igaku) 0.13 g, Azo-based organic dye (Alizarin Yellow GG, manufactured by Tokyo Chemical Industry) 0.05 g was added and stirred to obtain a forming solution. Table 40 shows the concentration of each component in this solution.

 [0319] Next, the forming solution was applied on the cleaned UV-cut glass substrate by a flow coating method at a humidity of 30% and at room temperature. After drying for about 30 minutes at room temperature, it was put in an oven preheated to 200 ° C and heated for 15 minutes, and then cooled. As a result, a film with a film thickness of 800 nm was obtained, but cracks accompanied with peeling occurred on almost the entire surface, and the characteristics of the film could not be evaluated.

[0320] [Table 1] silicon

 Proton water whole organic matter

 Alkoxyt '

; Exhibition degree (vs. SS; vs. Si0 total ₂ volume to liquid Taimaku entire Remark (Si0 ₂ in terms;

 (mol / kg) molar ratio) (mass%) C mass%) (mass%) mass%)

 Example A1 13. 0 0. 010 4. 3 30. 0 3. 9 23. 1

 32. 0 4. 2 24. 2

 Example A2 13. 0 0. 010 4.7 Addition of PEG

 (30.0) (3.9) (22.7)

 Example A3 13. 0 0. 014 4. 3 30. 0 3. 9 23.1 Addition of phosphoric acid Example A4 1 3. 0 0. 010 4. 3 5. 2

 * Yes ^! ! Overall = UV absorber + PEG

 * Value in parenthesis in Example A2 is the amount of UV absorber only

[0321] [Table 2]

 Size

 d

 o

03

0)

 * Units for numerical values other than film thickness are%

[0322] [Table 3]

Silicon alkoxide Proton Water Heating Whole organic matter

(Si0 ₂ in terms; concentration (to Si content; mode vs. Si0 total ₂ volume to liquid Taimaku total weight ⁰ 6) (mol / kg) Le ratio) CO (wt%) (wt%) (wt%)

 42. 7 5. 6

 Example A5 13. 0 0. 022 5. 0 200

 (7.7) (1.0)

 42. 7 5. 6 29.9 Example A6 13. 0 0. 022 5. 0 180

 (7.7) (1.0) (5.4)

42. 7 5. 6 29.9 Example A7 13. 0 0. 022 5. 0 160

 (7.7) (1.0) (5.4)

42. 7 5. 6 29.9 Example A8 13. 0 0. 022 5. 0 140

 (77) (1.0) (5.4)

* Whole organic matter = UV absorber + Polye "÷ Ruphosphate polymer

 * Figures in Katsuko are amounts of UV absorber only

[0323] [Table 4]

K

 * Units for numerical values other than film thickness are%

[0324] [Table 5]

Silicon alkoxy proton water organics entire ultraviolet absorber UV absorber (Si0 ₂ in terms; Dragon / (vs. Si content; (vs. Si0 ₂ weight: A (total to the liquid; the entire B (to the liquid; mass%) (mol / kg ) Molar ratio) Mass%) Mass ¹ ½) Mass << ½)

 31.4 4.0 0.08 Example A9 13.0 0.010 4.4

 (23.9) (23.4) (0.47)

32.0 3.0 0.20 Example A10 10.0 0.010 4.3

 (24.2) (22.7) (1.52)

33.0 3.0 0.30 Example A11 10.0 0.010 4.3

 (24.8) (22.6) (2.26)

29. 1 3.0 0.20 Example A12 11.0 0.010 4.3

 (22.5) (21.1) (1.41)

* Whole organic matter = UV absorber A (benzotriazole UV absorber) + UV absorber B (organic dye) * The value in Katsuko is the mass of the whole film "½

 [¾6]

* Units for values other than film thickness are% [Table 7]

Silicon Organic UV UV

 Propylene Water PEG Alkoxy® * Overall Absorbent A Absorbent B

; Concentration (vs. Si (vs. Si0 ₂ amount; (Si0 ₂ conversion: (vs. Si0 ₂ amount: (whole liquid; whole liquid;

 (mol / kg) molar ratio) mass%) mass%) mass%) mass%) mass%)

 35. 0 3. 0 0. 25 5.5 Example A13 1 1. 0 0. 010 4. 3

 (25.9) (20.2) (1.68) (4.04)

32. 1 3. 0 0. 25 5. 0 Example A14 1 2. 0 0. 010 4. 3

 (24.3) (18.9) (1.58) (3.79)

29. 6 3. 0 0. 25 4. 6 Example A15 13. 0 0. 010 4. 3

 (22.8) (17.8) (1.48) (3.56)

* Whole organic matter = UV absorber A (benzotriazole UV absorber) +

 UV absorber B (organic dye) + PEG (polyethylene glycol)

 * Figures in Katsuko are mass% of the entire membrane

 * The total amount of PEG with respect to the liquid was 0.6 mass 9% in any of Examples A13 to A15.

[0327] [Table 8]

 Unit of numerical values other than is%

[0328] [Table 9]

Silicon Organic matter overall

 Proton water

Alkoxide 'vs. Si0 ₂ vs. Si0 ₂ +

; 辰 f (vs. Si amount; solution vs. membrane)

(Si0 ₂ conversion;

 (mol / kg) Amount Molar ratio) Total Overall amount ΓΤΟ Mass%) (Mass%) (Quality *%) (Mass%) (Mass%) Example A16 8. 8 0. 01 1 5. 4 3. 9 25 9 44. 0 35. 0 Example A17 8. 8 0. 01 0 5. 4 3. 6 24. 4 40. 6 32. 3

 * Whole organic matter: UV absorber A (benzotriazole UV absorber) +

UV absorber B (organic dye) + Polyphosphate ester polymer 10] Film thickness Haze ratio After visible UV light transmittance (nm) Initial difficulty After film peeling Permeability Transmittance j65nm 1550nm Example A16 2100 0. 5 2. 9 None 2. 2 2. 4 34.6 Example A17 2100 0 5 3. 8 None 89. 1 1 .5 1. 3 34. 2 Glass plate ― 0. 0 1.5 .90 ― 90. 1 87. 1 86. 6

* Units for numerical values other than mil are%

[0330] [Table 11]

Note 1) Mass% is converted to RSiO ^ ₅ .

 ∞

 [0331] [Table 12]

0)

 [0332] [Table 13]

[0333] [Table 14]

* Units for numerical values other than film thickness are% [0334] [Table 15]

[0335] [Table 16]

 * Units for numerical values other than film thickness are%

 * ΰ ^ Α2 is not used as a film, and J ± ^ jA3 cannot be applied with a forming solution.

[0336] [Table 17]

* The value in Katsuko is the mass of the whole membrane ⁰ / ύ [0337] [Table 18]

 * Units for numerical values other than film thickness are%

[0338] [Table 19]

Silicon alkoxide proton water

(Si0 ₂ in terms; Tatsudo (vs. Si content; (vs. Si0 ₂ weight: (total versus solution; mass%) (mol / kg) molar ratio) mass%) mass%) Example A28 11.0 0.010 4.3 35.0 3.9 Embodiment Example A29 12.0 0.010 4.3 32. 1 3.9 Example A30 13.0 0.010 4.3 29.6 3.9 Example A31 11.0 0.005 4.3 32.3 3.6 Example A32 11.0 0.019 4.3 32.3 3.6 Example A33 11.0 0.029 4.3 32.3 3.6 Example A34 11.0 0.038 4.3 32.3 3.6 Example Example A35 11.0 0.010 4.3 27.3 3.0 Example A36 11.0 0.005 4.3 27.3 3.0 Example A37 11.0 0.005 4.3 27.3 3.0 Example A38 11.0 0.005 5.0 27.3 3.0

 * Whole organic matter = UV absorber A (benzotriazol UV absorber) +

 UV absorber B (organic dye) + PEG (polyethylene glycol)

* Figures in Katsuko are mass% of the total membrane 20]

 * Units for numerical values other than film thickness are%

[0340] [Table 21]

 [0341] [Table 22]

 * Units for numerical values other than film thickness are%

[0342] [表 23]*

[0342] [Table 23]

 * Whole organic matter = UV absorption »JA (benzotriazole UV absorber) + UV absorber B (organic dye) + Organic dye having absorption in the near infrared region

[0343] [Table 24]

Film thickness Haze rate After separation Visible light UV

 (nm) Initial After Delaminating Transmittance Transmittance

 Example A39 600 0.2 1.7 None 87. 1 15.2

 Example A40 600 0.3 3.2 None 84.6 17.8

 Example A41 600 0.3 3.4 None 16.0

 Glass plate

 One 0.0 1.5 ― 90. 1 66.6

00

 D C O C

 * Units for numerical values other than HIS and wavelength are%

* (Difference from glass plate) = (Light ¾jg rate at FL »¾ at the wavelength showing the minimum transmittance) 1 (Minimum transmittance) 25]

Silicon Organic matter Proton Water Heating

Alkoxyt 'vs. Si0 ₂ vs. Si0 ₂ +; JS degree (vs. Si amount; dish' vs. liquid vs. membrane)

(Si0 ₂ conversion;

 (mol / kg) (molar ratio) (° C) Total Overall volume Weight%) (Quality S%) (Mass ¾) (Quality *%) (Quality *%) Example A42 5.5 0.01 19 200 1.2 12.7 20.9 14.6 Example A43 5.5 0.005 19 200 1.2 12.7 20.9 14.6 Example A44 6.0 0.01 19 200 1.2 12.0 19.2 13.7 Example A45 5.5 0.01 19 200 1.2 15.0 20.9 17.7 Example A46 8.75 0.005 5.4 140 3.9 25.9 44.0 35.0

 * Whole organic matter = UV absorber A (benzoylazol UV absorber) + UV absorber B (organic dye) + polyether phosphate polymer

26] Film thickness Haze rate After separation Visible light UV

 (nm) Initial fiber after membrane peeling Permeability mrn

 Example A42 1000 0. 7 2. 9 None 18. 2

 Example A43 900 0. 6 3. 4 None 90. 1 19. 7

 Example A44 1000 0. 5 3. 9 None 1 6.0

 Example A45 800 0. 3 3. 2 None 90. 0 22.5

 Example A46 1900 0. 2 3. 1 None 89. 4 1. 9

 Glass plate ― 0. 0 1 .5 ― 90. 1

 (FL »1S)

∞ 00

 0 (

 * Units for numerical values other than film thickness and wavelength are%

 * (Difference from glass plate) = (Frequency of FL * plate at the wavelength indicating the ratio)-(Maximum MS ratio)

[Table 27]

* Figures in Katsuko are mass% of the entire membrane [Table 28] Film thickness Haze ratio After visible light UV wavelength 370nm

1 . 7 2. 1 実施例 B2 3100 0. 7 2. 8 なし 1 . 6 2. 2 実施例 B3 3100 0. 6 2. 8 なし 73. 9 1 . 6 2. 2 実施例 B4 3100 0. 8 2. 6 なし 73. 8 1 . 6 2. 2, Nm) After initial separation Membrane peeling Transmittance Transmittance in transmittance Example B1 3100 0. 8 3. 6 None

1.7 2.1 Example B2 3100 0. 7 2. 8 None 1.6 2 2.2 Example B3 3100 0. 6 2. 8 None 73. 9 1 .6 2. 2 Example B4 3100 0.8 2.6 None 73. 8 1 .6 2. 2

* Units for numerical values other than film thickness are%

[0348] [Table 29]

卜

 O C

 * Figures in Katsuko are mass% of the entire membrane

[0349] [Table 30]

 Units other than * are%

[0350] [Table 31] Silicon alkoxide Prone Water Organic polymer Organic dye

(Conversion to SiO ₂ ;; malleability (vs. Si amount; (whole liquid (whole liquid mass%) (mol / Kg molar ratio); mass%); mass%)) Example B10 1 3. 0 0. 024 4 3 5. 2 (28.4) 0. 1 (0.5) Example B11 13. 0 0. 022 4. 3 4. 6 (25.8) 0. 1 (0.6)

* Figures in Katsuko are mass% of the entire membrane

[0351] [Table 32]

[0352] [Table 33]

 * Figures in Katsuko are mass% of the entire membrane

[0353] [Table 34] Film thickness Haze rate (%)

, Nm) Initial post-fibrous membrane peeling Example B12 3100 0.7 2.8 None Example B13 1200 0.3 1.6 None Example B14 1200 0.2 2.6 None Example B15 1200 0.1 2.4 None Example B16 1200 0.1 2.1 None Example B17 1200 0.2 1.8 None

[0354] [Table 35]

Note 1) Mass% is calculated in terms of SiO ^ ₅ .

 [0355] [Table 36]

 * Figures in Katsuko are mass% of the entire membrane

[0356] [Table 37]

[0357] [Table 38] Silicon Organic matter overall

 Proton water

Arukokishito * to the liquid Taimaku vs. Si0 ₂ concentration (to Si content;

(Si0 ₂ conversion;

 (mol / kg) Mole ratio) Overall Total mass%) (mass ¾) (mass%) (mass%) Example B19 9.0 0.013 7.0 1.4 13.1 15.1 Example B20 9.0 0.013 7.0 1.5 14.0 16.2 Example B21 5.0 0.010 7.0 0.5 8.3 9.0 Example B22 13.0 0.024 7.0 5.5

0 (

* All Arisu = Organic polymer + Element ω 39]

Film thickness Haze rate After release Visible light

 (nm) Initial 鰣 After membrane peeling Permeability

 Example B19 1200 0. 4 3. 1 None 88. 1

 Example B20 1300 0. 6 3. 5 None

 Example B21 600 0. 4 3. 3 None

 Example B22 3400 0. 7 4. 0 None 76. 2

卜

0 0

0 0

 0)

 * Units for values other than film thickness and wavelength are% 0)

 * (Difference from glass plate) = (Light ^ g rate at FLS plate at wavelength showing S SSi rate)-(Maximum rate)

[Table 40]

 * Figures in Katsuko are mass% of total membrane Industrial applicability

 The present invention has a great utility value in each field using a transparent article as providing a transparent article having a silica-based film having excellent mechanical strength while containing a light absorber which is an organic substance.

Claims

The scope of the claims  [1] A transparent article comprising a transparent substrate, and an organic-inorganic composite film containing an organic material and an inorganic oxide formed on the surface of the transparent substrate,  The organic-inorganic composite film contains silica as the inorganic oxide,  The organic-inorganic composite film is mainly composed of the silica,  After the Taber one wear test specified in JIS R 3212 performed on the surface of the organic-inorganic composite film, the organic-inorganic composite film does not peel from the transparent substrate,  At least a part of the organic substance is an ultraviolet absorber;  Transparent article.  [2] The transparent article according to claim 1, wherein the ultraviolet absorber contains at least one compound selected from benzotriazole-based, benzophenone-based, hydroxyphenyltriazine-based and cyanoacrylate-based compounds.  [3] The transparent article according to [1], wherein the ultraviolet absorber contains an organic dye having ultraviolet absorbing ability.  [4] The organic dye having ultraviolet absorbing ability is at least one selected from polymethine series, imidazoline series, coumarin series, naphthalanolimide series, perylene series, azo series, isoindolinone series, quinophthalone series and quinolin series. The transparent article according to claim 3, comprising an organic dye. [5] The transparent according to claim 1, wherein the organic substance contains, in addition to the ultraviolet absorber, at least one selected from an organic dye having no ultraviolet absorbing ability and a hydrophilic organic polymer cartridge not having an ultraviolet absorbing ability. Goods. 6. The transparent article according to claim 1, wherein the organic substance contains a hydrophilic organic polymer having no ultraviolet absorbing ability in addition to the ultraviolet absorber. [7] The transparent article according to [1], wherein the organic substance contains an organic dye having absorption in the near-infrared region in addition to the ultraviolet absorber. 8. The transparent article according to claim 1, wherein the organic-inorganic composite film is a single layer. [9] The transparent article according to [1], wherein the thickness of the organic-inorganic composite film is more than 250 nm and not more than 5 μm. [10] The film thickness of the organic-inorganic composite film is more than 300 nm and not more than 5 μm. Transparent article.  11. The transparent article according to claim 10, wherein the thickness of the organic-inorganic composite film is 1 μm or more and 5 μm or less. [12] The transparent article according to [1], which is measured after the Taber abrasion test and has a haze ratio power S ₄ % or less of a portion to which the Taber abrasion test is applied.  13. The transparent article according to claim 1, wherein a mass of the ultraviolet absorber in the organic-inorganic composite film is 0.1 to 40% with respect to a total mass of the organic-inorganic composite film. 14. The transparent article according to claim 1, wherein the organic-inorganic composite film contains fine particles. 15. The transparent article according to claim 14, wherein the fine particles include at least one selected from indium tin oxide fine particles and antimony tin oxide fine particles. 16. The transparent article according to claim 1, wherein the transparent substrate is a glass plate or a resin plate. 17. The transparent article according to claim 1, wherein the visible light transmittance is 70% or more. 18. The transparent article according to claim 17, wherein the transparent substrate is a glass plate, has an ultraviolet transmittance of 1.1% or less and a light transmittance of 2.0% or less at a wavelength of 370 ηm. 19. The transparent article according to claim 1, wherein the transparent substrate is a glass plate tempered by a rapid cooling treatment.  20. The transparent article according to claim 1, wherein the transparent substrate is a glass plate having a glass composition containing at least one selected from acid-titanium and acid-cerium forces. [21] A glass plate having a glass composition in which the transparent substrate contains 0.2% by mass or more of Fe 2 O 3  twenty three  The transparent article according to claim 1. [22] When the transparent substrate is molded to a thickness of 3.1 mm, the ultraviolet transmittance is 5 to 40%, the light transmittance at a wavelength of 370 nm is 20 to 50%, and the visible light transmittance is 70% or more. 2. The transparent article according to claim 1, which is a glass plate having the following composition. 23. The transparent article according to claim 1, wherein the transparent substrate is a glass plate, and the transparent article is a window glass for vehicles or buildings. [24] A transparent substrate, and an organic-inorganic composite film containing an organic substance and an inorganic oxide formed on the surface of the transparent substrate, wherein the organic-inorganic composite film contains silica as the inorganic oxide, The composite film is mainly composed of the silica, and at least a part of the organic substance is A method for producing a transparent article, which is an ultraviolet absorber,  Applying the organic-inorganic composite film forming solution to the surface of the transparent substrate; removing at least a part of the liquid component contained in the forming solution from the forming solution applied to the transparent substrate; Including  The forming solution contains silicon alkoxide, strong acid, water, alcohol, and organic substance, and at least a part of the organic substance is an ultraviolet absorber,  Concentration power of the silicon alkoxide, exceeding 3 mass%, expressed by the SiO concentration when the silicon atom contained in the silicon alkoxide is converted to SiO,  twenty two  The concentration of the strong acid is in the range of 0.001 to 0.2 molZkg, expressed by the molar concentration of proton when assuming that the strong acid proton is completely dissociated,  More than 4 times the total number of moles of silicon atoms contained in the silicon alkoxide.  Removing at least a portion of the liquid component contained in the forming solution applied to the transparent substrate while maintaining the transparent substrate at a temperature of 400 ° C. or lower;  A method for producing a transparent article.  25. The method for producing a transparent article according to claim 24, wherein the forming solution is applied to the transparent substrate while maintaining the relative humidity of the atmosphere at 40% or less. [26] The concentration of the organic substance indicates the concentration of the silicon alkoxide by the SiO concentration.  2  25. The manufacture of a transparent article according to claim 24, wherein the content is 60% by mass or less based on the SiO when  2  Method.  27. The method for producing a transparent article according to claim 24, wherein the silicon alkoxide force includes at least one selected from tetraalkoxysilane and polymer force thereof. [28] The concentration of the silicon alkoxide is 30% by mass or less expressed by the SiO concentration.  2  The method for producing a transparent article according to claim 24. 29. The method for producing a transparent article according to claim 24, wherein the number of moles of water is 5 to 20 times the total number of moles of silicon atoms contained in the silicon alkoxide. [30] The film thickness is 25 by performing the step of applying the forming solution and the step of removing at least a part of the liquid component contained in the applied forming solution one time each. 25. The method for producing a transparent article according to claim 24, wherein the organic-inorganic composite film that is greater than Onm and not greater than 5 μm is formed.  [31] A transparent article comprising a transparent substrate and an organic-inorganic composite film containing an organic substance and an inorganic oxide formed on the surface of the transparent substrate,  The organic-inorganic composite film contains silica as the inorganic oxide,  The organic-inorganic composite film is mainly composed of the silica,  After the Taber one wear test specified in JIS R 3212 performed on the surface of the organic-inorganic composite film, the organic-inorganic composite film does not peel from the transparent substrate,  At least a part of the organic substance is an organic dye,  Transparent article.  32. The transparent article according to claim 31, wherein the organic dye contains an organic dye having ultraviolet absorbing ability.  [33] The organic dye having an ultraviolet absorbing ability is at least one selected from polymethine series, imidazoline series, coumarin series, naphthalanolimide series, perylene series, azo series, isoindolinone series, quinophthalone series and quinolin series. The transparent article according to claim 32, comprising an organic dye.  34. The transparent article according to claim 31, wherein the organic dye contains an organic dye having absorption in the near infrared region.  35. The transparent article according to claim 31, wherein the organic-inorganic composite film is a single layer. [36] The transparent article according to [31], wherein the thickness of the organic-inorganic composite film is more than 250 nm and not more than 250 nm.  [37] The transparent article according to [36], wherein the thickness of the organic-inorganic composite film is more than 300 nm and not more than 5 μm.  [38] The transparent article according to [37], wherein the thickness of the organic-inorganic composite film is 1 μm or more and 5 μm or less. [39] The transparent article according to [31], which has a haze ratio power S ₄ % or less of a portion to which the Taber abrasion test is applied, which is measured after the Taber abrasion test. [40] The transparent article according to [31], wherein the mass of the organic substance in the organic-inorganic composite film is 0.1 to 40% with respect to the total mass of the organic-inorganic composite film. The transparent article according to claim 31, wherein the organic-inorganic composite film contains a hydrophilic organic polymer in addition to the organic dye. [42] In addition to the organic dye, the organic-inorganic composite film includes at least one compound selected from a benzotriazole series, a benzophenone series, a hydroxyphenol triazine series, and a cyanoacrylate series as a part of the organic substance. 32. The transparent article of claim 31 comprising. [43] The transparent article according to [31], wherein the transparent substrate is a glass plate or a resin plate. 44. The transparent article according to claim 31, wherein the transparent substrate is a glass plate, and the transparent article is a window glass for vehicles or buildings. [45] The transparent article according to [31], wherein the thickness of the transparent substrate exceeds 0.1 mm. [46] A transparent substrate, and an organic-inorganic composite film containing an organic substance and an inorganic oxide formed on the surface of the transparent substrate, wherein the organic-inorganic composite film contains silica as the inorganic oxide, and the organic-inorganic A composite film comprising the silica as a main component, and at least a part of the organic substance is an organic dye,  Applying the organic-inorganic composite film forming solution to the surface of the transparent substrate; removing at least a part of the liquid component contained in the forming solution from the forming solution applied to the transparent substrate; Including  The forming solution contains silicon alkoxide, strong acid, water, alcohol, and organic matter, and contains an organic dye as the organic matter,  Concentration power of the silicon alkoxide, exceeding 3 mass%, expressed by the SiO concentration when the silicon atom contained in the silicon alkoxide is converted to SiO,  twenty two  The concentration of the strong acid is in the range of 0.001 to 0.2 molZkg, expressed by the molar concentration of proton when assuming that the strong acid proton is completely dissociated,  More than 4 times the total number of moles of silicon atoms contained in the silicon alkoxide.  Removing at least a portion of the liquid component contained in the forming solution applied to the transparent substrate while maintaining the transparent substrate at a temperature of 400 ° C. or lower;  A method for producing a transparent article. [47] The organic substance according to claim 46, wherein the organic substance contains a hydrophilic organic polymer in addition to the organic dye. A method for producing the transparent article described above.  48. The method for producing a transparent article according to claim 46, wherein the forming solution is applied to the transparent substrate while maintaining the relative humidity of the atmosphere at 40% or less. [49] The method for producing a transparent article according to [46], wherein the silicon alkoxide force includes tetraalkoxysilane and polymer force thereof. [50] The concentration of the silicon alkoxide is 30% by mass or less expressed by the SiO concentration.  2  47. The method for producing a transparent article according to claim 46. 51. The method for producing a transparent article according to claim 46, wherein the number of moles of water is 5 to 20 times the total number of moles of silicon atoms contained in the silicon alkoxide. [52] The step of applying the forming solution and the step of removing at least a part of the liquid component contained in the applied forming solution are each performed once, so that the film thickness becomes 25 47. The method for producing a transparent article according to claim 46, wherein the organic-inorganic composite film that exceeds Onm and is 5 μm or less is formed.  [53] a substrate having a light emitting surface; and an organic-inorganic composite film containing an organic substance and an inorganic oxide formed on the light emitting surface of the substrate;  The organic-inorganic composite film contains silica as the inorganic oxide,  The organic-inorganic composite film is mainly composed of the silica,  After the Taber one wear test specified in JIS R 3212 performed on the surface of the organic-inorganic composite film, the organic-inorganic composite film does not peel from the substrate,  At least a part of the organic substance is an ultraviolet absorber;  Backlight for liquid crystal display. [54] a liquid crystal panel having a light transmission surface, and an organic-inorganic composite film including an organic material and an inorganic oxide formed on the transmission surface of the liquid crystal panel,  The organic-inorganic composite film contains silica as the inorganic oxide,  The organic-inorganic composite film is mainly composed of the silica, After the Taber one wear test specified in JIS R 3212 performed on the surface of the organic-inorganic composite film, the organic-inorganic composite film does not peel from the liquid crystal panel, and at least a part of the organic matter is an ultraviolet absorber. Is, LCD display panel.