WO2007040257A1

WO2007040257A1 - Article provided with organic-inorganic composite film and method for producing same

Info

Publication number: WO2007040257A1
Application number: PCT/JP2006/319944
Authority: WO
Inventors: Kazuyuki Inoguchi; Teruyuki Sasaki; Kazutaka Kamitani
Original assignee: Nippon Sheet Glass Company, Limited
Priority date: 2005-10-05
Filing date: 2006-10-05
Publication date: 2007-04-12
Also published as: JPWO2007040257A1

Abstract

Disclosed is an article provided with an organic-inorganic composite film which is excellent in abrasion resistance while containing materials having antistatic properties and near infrared absorbing properties. This article comprises a base, and an organic-inorganic composite film formed on the base and containing an organic matter and an inorganic oxide. The organic-inorganic composite film mainly contains silica as at least a part of the inorganic oxide, while containing at least one selected from carbon nanotubes, fullerenes, antimony tin oxides and indium tin oxides and/or a conductive polymer as at least a part of the organic matter or the inorganic oxide. This organic-inorganic composite film does not separate from the base after Taber abrasion test performed on the surface of the organic-inorganic composite film in accordance with JIS R 3212.

Description

Specification

Article formed with organic-inorganic composite film and method for producing the same

Technical field

TECHNICAL FIELD [0001] The present invention relates to an article formed with an organic-inorganic composite film and a method for producing the same, and more specifically, wear resistance while including a material having a low heat resistance typified by a sol-gel method and typified by an organic substance. The present invention relates to an article on which an excellent film is formed and a method for producing the same. 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 (silica-based film) is to be obtained, a high temperature treatment is required in the melting method, so that the materials constituting the substrate and the film are limited.

[0003] In the sol-gel method, a solution of a metal organic or inorganic compound is used as a starting material, and the solution is converted into metal oxide or hydroxide fine particles by hydrolysis reaction and condensation polymerization reaction of the compound in the solution. This is a method in which a sol in which sol is dissolved, gelled and solidified, and this gel is heated 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 a sol-gel method is disclosed in, for example, Japanese Patent Application Laid-Open No. 11-269657.

[0005] In general, a silica-based film formed by a sol-gel method is inferior in mechanical strength, particularly the abrasion resistance of the film, as compared with a glassy film obtained by a melting method.

JP-A-11 269657 discloses that “at least one of silicon alkoxide and its hydrolyzate (including partial hydrolyzate) is 0.010 to 3 wt% in terms of silica, and acid 0.0 010 to 1 A method for forming a silica-based film by applying an alcohol solution containing 0N and 0 to 10% by weight of water as a coating liquid to a substrate 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, the film obtained by the sol-gel method has good wear resistance. Have sex. However, the 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 film thickness of 250 nm in order to ensure a practical appearance. The thickness of the silica-based film formed by the sol-gel method is usually 100-200n m.

[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 wear resistance 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] Incidentally, a substrate such as glass or resin may be provided with a node coat layer containing an antistatic material in order to prevent surface charging. In order for the hard coat layer to exhibit antistatic performance, it is required to control its surface resistivity within a range of 10 ¹⁴ Ω or less.

[0012] As the antistatic material, metal oxide fine particles such as indium stannate (ΙΤΟ) and antimony stannate (一般) are generally used. Recently, carbon nanotubes and fullerenes, which exhibit excellent conductivity and thermal stability, have attracted attention as materials. However, these antistatic materials have a problem that they have a tendency to agglomerate in the coating liquid and are not easily compatible.

[0013] Hard coat films containing soot and soot are attracting attention, particularly in the field of display panels, as a film that can exhibit a near-infrared absorbing effect.

[0014] In Japanese Patent Application Laid-Open No. 2005-15615, the addition of soot and soot to a polyethylene oxide aqueous solution together with hydrophilic silicon dioxide fine particles and a surfactant makes it possible to remove soot in the coating solution. Techniques that improve dispersibility such as these have been proposed. However, the abrasion resistance of the insulating film obtained by this technology is not always sufficient!

[0015] In order to improve the abrasion resistance of the silica-based film by the sol-gel method, the silica-based film is not less than 450 ° C. It is desirable to heat-treat above. However, if the organic-inorganic composite film is heat-treated at such a high temperature, the organic matter in the film is decomposed or the function of functional fine particles such as ITO is reduced.

Disclosure of the invention

[0016] An object of the present invention is to provide an article in which an organic-inorganic composite film excellent in wear resistance is formed while containing a material having antistatic ability and near infrared absorption ability.

[0017] The present invention is an article on which an organic-inorganic composite film is formed, including a base and an organic-inorganic composite film containing an organic substance and an inorganic oxide formed on the surface of the base, The organic / inorganic composite film contains silica as the inorganic oxide, and the organic / inorganic composite film contains silica as a main component and is applied to the surface of the organic / inorganic composite film. After the wear test, the organic-inorganic composite film does not peel off due to the substrate strength, and the organic-inorganic composite film is further added as at least part of the organic substance or as the inorganic oxide, and further, carbon nanotubes, fullerenes, antimony tins. Provided is an article formed with an organic-inorganic composite film comprising at least one selected from oxide and indium stannate properties, and Z or a conductive polymer.

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.

[0019] From another aspect, the present invention includes a base and an organic-inorganic composite film containing an organic substance and an inorganic oxide formed on the surface of the base, and the organic-inorganic composite film is the inorganic Silica is included as an oxide, the organic-inorganic composite film is mainly composed of the silica, and the organic-inorganic composite film is used as at least a part of the organic substance or as the inorganic oxide. A method for producing an article formed with an organic-inorganic composite film, comprising at least one selected from the group consisting of fullerene, antimony stannate and indium sulphate, and Z or a conductive polymer, A coating step of applying the organic-inorganic composite film forming solution to the surface of the substrate; and removing at least a part of the liquid component contained in the forming solution from the forming solution applied to the substrate. Including a removal step that, the The forming solution contains silicon alkoxide, strong acid, water and alcohol, at least one selected from carbon nanotubes, fullerene, antimony tin oxide and indium tin oxide, and Z or a conductive polymer, The forming solution further contains a hydrophilic organic polymer and Z or a surfactant as at least a part of the strong acid or as a component different from the strong acid, and the concentration force of the silicon alkoxide Silicon atoms contained in the silicon alkoxide SiO concentration when converted to SiO

2 Indicated by 2 degrees and exceeding 3% by mass, the concentration of the strong acid is 0.001-0. Lm olZkg expressed by the molar concentration of protons assuming that the proton is completely dissociated from the strong acid. The number of moles of water is at least four times the total number of moles of silicon atoms contained in the silicon alkoxide, and in the coating step, while maintaining the relative humidity of the atmosphere at less than 40%, The forming solution is applied to the substrate, and in the removing step, at least a part of the liquid component contained in the forming solution applied to the substrate is removed while maintaining the substrate at a temperature of 300 ° C. or lower. A method for producing an article on which an organic-inorganic composite film is formed is provided.

[0020] According to the present invention, an organic-inorganic composite film having excellent wear resistance and exhibiting antistatic ability and near infrared absorption ability can be formed by a sol-gel method even when the film thickness is thicker than 250 nm. wear. The organic-inorganic composite film according to the present invention includes at least one selected from carbon nanotubes, fullerenes, antimony stannates, and indium stannates, and contains Z or a conductive polymer. It can have excellent wear resistance comparable to a glass plate obtained by the melting method. The organic-inorganic composite film according to the present invention can have a high antistatic ability such that the film has a surface resistivity of 1.0 to 10 ”Ω or less. The organic-inorganic composite film according to the present invention has a wavelength of 1700 nm. It can have a high near-infrared absorption capacity with a near infrared transmittance of 30% or less.

[0021] According to the production method of the present invention, by applying the forming solution once, for example, the film thickness is more than 250 ηm and the wear resistance is excellent, and high antistatic ability and near infrared absorption ability are obtained. A possible film can be formed.

BEST MODE FOR CARRYING OUT THE INVENTION

[0022] Hereinafter, the sol-gel process will be described first. In the sol-gel method using silicon alkoxide as a starting material, silicon alkoxide contained in a film coating solution (hereinafter referred to as a forming solution) is hydrolyzed in the presence of water and a catalyst in the forming solution. Through a decomposition reaction and a dehydration condensation reaction, it becomes an oligomer via a siloxane bond, and the forming solution becomes a sol state along with this.

[0024] The forming solution in a sol state is applied to the substrate, and water or an organic solvent such as alcohol volatilizes from the applied forming solution. In this drying step, the oligomer is concentrated, the polycondensation reaction proceeds, the molecular weight increases, and the solution loses fluidity over time. Thus, a film having a semi-solid gel force is formed on the substrate. Immediately after gelling, the gap between the siloxane bond networks is filled with organic solvent and water. Gel force When water or solvent volatilizes, the siloxane polymer shrinks, the condensation polymerization reaction proceeds further, and the film is cured.

[0025] In the conventional sol-gel method, the gap filled with the organic solvent and water in the solidified gel remains as pores that cannot be completely filled even after heat treatment up to about 400 ° C. The abrasion resistance of the film should not be high enough. Therefore, conventionally, in order to obtain a hard film, a heat treatment at a higher temperature, for example, 500 ° C. or more has been 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 100-150 ° C evaporates the solvent and water contained in the forming solution. In the heat treatment at about 250-400 ° C, if the raw material contains organic material, the organic material decomposes and evaporates. When heat-treated at a temperature exceeding 400 ° C, usually no organic material remains in the film. Heat treatment above about 500 ° C causes the gel skeleton to shrink and the film to become dense.

[0027] As described above, in a normal sol-gel reaction, immediately after gelation, the gap between the formed networks is filled with an organic solvent or water. 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, the linear polymer is solidified in a folded state For this reason, the microstructure is not strong, and cracks easily occur when the solvent or water volatilizes 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] In the acidic region where a relatively dense film can be formed, the present inventors form a dense and crack-free film under certain conditions by adjusting the concentration of strong acid, the amount of water, etc. appropriately. The present invention has been completed by finding the knowledge that it can be done and further developing this knowledge.

[0031] It is known that the isoelectric point of silanol is 2. This indicates that when the pH of the forming solution is 2, silanol can exist most stably in the solution. 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, the hydrolyzed silicon alkoxide force monomer or low polymerization state tends to exist in the forming solution.

[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: If it is about 001-0.2molZkg, the pH of the solution will be about 3-1. By adjusting the pH to this range, the silicon alkoxide can be stably present as a monomer or a low polymerization silanol in the forming solution.

[0034] The forming solution contains a mixed solvent of water and alcohol, and can be added with another solvent as necessary. In the case of such a mixed solvent, a strong acid is used and the strong acid strength is also high. By setting the molar concentration of protons to 0.001 to 0.2 molZkg when it is assumed that protons are completely dissociated, a liquid having a pH of around 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 when acetic acid is included in the forming solution, the proton concentration of acetic acid is not included in the above proton concentration.

[0036] For example, phosphoric acid has three dissociation stages, and there is a possibility of dissociating three protons 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 on the premise of dissociation with strong acidity may be calculated assuming that only one proton is dissociated 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 dissociation of protons after the second stage. In the present specification, the strong acid specifically refers to an acid having protons having an acid dissociation exponential force in water.

[0037] As described above, the reason why the proton concentration is defined 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 determined in a mixture of an organic solvent and water. It is a force that is difficult to ask for.

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

[0039] This film is dense. Due to insufficient hydrolysis and polycondensation reaction of silicon alkoxide, heating in a low temperature range of 150 ° C or lower does not exceed a certain hardness. . In view of this, water was excessively added to the silicon alkoxide so that it proceeded easily after the application of the hydrolytic and polycondensation reaction force forming solution of the silicon alkoxide. Hydrolysis and polycondensation reactions are likely to proceed! In the soot state, the film becomes hard without heating to a high temperature. Specifically, the maximum number of moles required for hydrolysis, that is, four times or more of water, is added to the total number of moles of silicon atoms contained in the silicon alkoxide. The upper limit of the amount of water added can be, for example, 20 times, or even 40 times.

[0040] When the forming solution is dried, water evaporates in parallel with the volatilization of the solvent. Considering this, the number of moles of water is more than four times the total number of moles of silicon atoms, for example, 5 to 20 times. It is preferable that

[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 this, in the present invention, it is decided to add water having a mole number of 4 times or more, preferably more than 4 times, more preferably 5 times or more, 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 liquid fluctuates in the above range. This is another factor that promotes hydrolysis. Thus, when a dense film is formed and the hydrolysis and dehydration condensation reactions are sufficiently advanced, a hard film is formed. As a result, a film having excellent wear resistance can be obtained by a heat treatment at a lower temperature than conventional.

[0043] When this method is used, a silica-based film having excellent wear resistance 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 by the SiO concentration when converted to SiO so that the silicon alkoxide concentration is relatively high.

2 2 The formation solution should be prepared so that it exceeds 3% by weight. Specifically, it is desirable that the range be over 3% by mass and below 30% by mass.

[0044] A hydrophilic organic polymer and Z or a surfactant may be further added to the forming solution. Hydrophilic organic polymers and surfactants suppress the generation of cracks that may occur as the liquid components contained in the applied forming solution evaporate. Also hydrophilic organic Polymers and surfactants are interposed between the silica particles generated in the liquid, and alleviate the influence of film shrinkage caused by evaporation of the liquid component. Thus, it is considered that when a hydrophilic organic polymer or a surfactant is added, excessive curing shrinkage of the film can be suppressed, so that the stress in the film is relieved. The hydrophilic organic polymer and the surfactant serve to suppress the shrinkage of the film and maintain the abrasion resistance of the film.

[0045] In the method of the present invention, it is sufficient to heat the film at a lower temperature than in the prior art, so that the hydrophilic organic polymer and the surfactant remain in the film even after the heating. According to the present invention, it is possible to obtain a film having excellent abrasion resistance even when the film is thicker, in the state where the hydrophilic organic polymer and the surfactant are present in the film.

[0046] The hydrophilic organic polymer and Z or surfactant may be added to the forming solution in advance. In the organic-inorganic composite film in which the forming solution force is also formed, it is considered that the organic substance and the inorganic substance are combined at the molecular level.

[0047] Referring to various experimental results, it seems that the hydrophilic organic polymer and the surfactant suppress the growth of silica particles formed by the sol-gel reaction and suppress the porous property of the film. .

[0048] As the hydrophilic organic polymer, a polymer containing a polyoxyalkylene group (polyalkylene oxide structure), for example, polyethylene glycol, polypropylene glycol, polyether-based surfactant and the like can be used. Further, polyvinyl pyrrolidone type, polybule force prolatatam type surfactants and the like can also be used. Further, sodium polystyrene sulfonate can be used.

[0049] As the surfactant, a hydrophilic organic polymer that can function as the above-described surfactant may be used. For example, R NOH, RR 'NOH, RR' NOH, RR'R "R" 'NOH Structure of

4 3 2 2

A quaternary ammonium compound represented by the formula or represented by a structural formula having a chloride group (C1) in place of the hydroxyl group (OH) can also be used. When carbon nanotubes are dispersed in the film, it is particularly preferable to use a quaternary ammonium compound.

[0050] These hydrophilic organic polymers and surfactants may be used alone or in combination of two or more.

[0051] The organic-inorganic composite film according to the present invention comprises carbon nanotubes, fullerenes, antimony By including at least one selected from oxalates and indium stannates, and Z or conductive polymers, the surface resistivity can be less than 1. οχιο ¹⁴ Ω. Further, in the article in which the organic-inorganic composite film according to the present invention is formed, the organic-inorganic composite film further includes at least one selected from antimony stannate and indium stannate as the inorganic oxide. By including, the transmittance of near-infrared light having a wavelength of 1700 nm can be 30% or less, and the transmittance can be 20% or less. The organic-inorganic composite film according to the present invention may further contain carbon nanotubes and at least one selected from fullerene force and Z or a conductive polymer as at least a part of the organic substance. The article formed with the organic-inorganic composite film according to the present invention is suitable as a display substrate.

[0052] As the carbon nanotubes and fullerenes, for example, various ones described in S. Iijima, Nature, 354, 56 (1991) can be used.

[0053] As the conductive polymer, for example, polythiophene and derivatives thereof and polyisothianaphthene and derivatives thereof can be used. An example of the polythiophene derivative is polyethylene dioxythiophene (PEDOT). Thus, the conductive polymer may include PED OT. An example of a PEDOT dopant is p-toluenesulfonic acid. Since PEDOT is insoluble, it is desirable to coexist with, for example, polystyrene sulfonic acid when added to the forming solution. On the other hand, self-doped conductive polymers represented by the above polythiophenes and polyisothianaphthenes are water-soluble. Thus, the conductive polymer may be a polymer that can function as a hydrophilic organic polymer. The hydrophilic organic polymer that coexists with the conductive polymer is a non-conductive polymer.

[0054] Antimony tin oxide (ATO) and indium tin oxide (ITO) are preferably those having a volume average particle size of 1 to LOONm. When the particle size exceeds lOOnm, light is remarkably reflected by Rayleigh scattering, and the film may be whitened to reduce transparency. If the particle size is less than 1 nm, the conductivity may be lowered or the dispersibility of the particles may be lowered.

[0055] By the improvement of the sol-gel method as described above, even if the Taber abrasion test stipulated in JIS R 3212 is applied even though it includes a material having low heat resistance typified by organic matter, Provided is an article in which an organic-inorganic composite film that does not peel off its physical strength is formed without generation of cracks.

[0056] The thickness of the organic-inorganic composite film is more than 250 nm and not more than 5 μm, preferably more than 300 nm and not more than 5 μm, more preferably more than 800 nm and not more than 5 μm, and still more preferably It is more than 1 m and not more than 5 μm, particularly preferably more than 2 μm and not more than 5 μm. The thickness of the organic / inorganic composite film may be 4 μm or less.

[0057] 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 wear resistance equivalent to a glassy film obtained by the melting method.

[0058] In the organic-inorganic composite film according to the present invention, the organic substance content is 0.1 to 60%, preferably 2 to 60%, based on the total mass of the organic-inorganic composite film. The organic-inorganic composite film according to the present invention may contain phosphorus.

[0059] In a remote operation terminal such as an electronic device, a near infrared ray having a wavelength of 800 to 1200 nm is used as an optical signal. Electronic displays such as plasma display panels (PDP) may emit near-infrared rays of such a wavelength as well as display surface force. At this time, the reading of the optical signal from the remote operation terminal may be hindered and the electronic device may malfunction. In an article in which the organic-inorganic composite film according to the present invention is formed, the transmittance of near infrared rays having a wavelength of 波長 ηm can be 30% or less, and further the transmittance can be 20% or less. For this reason, when the article of the present invention is applied to a display substrate, for example, it is possible to prevent malfunction of the electronic device.

[0060] In order to impart abrasion resistance to the silica-based film, the addition of fluorine resin particles to the film is a force S. However, the organic-inorganic composite film according to the present invention has suitable wear resistance despite the fact that it does not contain fluorine resin fine particles, as shown in the examples described later. Thus, the organic-inorganic composite film according to the present invention may be in a state that does not contain the fluorocoagulant fine particles. The absence of fluorine resin fine particles does not mean that fluorine resin fine particles in an amount less than the addition amount necessary for imparting a function are mixed in the film.

[0061] The method of the present invention includes silicon alkoxide, strong acid, water, alcohol, a hydrophilic organic polymer, and Z or a surfactant. At least one selected from Len, antimony stannate and indium stannate

And a forming solution comprising Z or a conductive polymer. Hydrophilic organic polymers and surfactants are usually added as components separate from strong acids, but polymers that function as strong acids, such as polymers containing phosphate ester groups, are added as at least part of the strong acid. A little.

[0062] The silicon alkoxide is preferably at least one selected from tetraalkoxysilane and its polymer strength. Silicon alkoxides and polymers thereof may include those in which some or all of the alkoxyl groups are hydrolyzed. The force described later in detail In the present invention, silicon alcohol other than tetrafunctional silane such as trifunctional silane (R'Si (OR)) is used.

Three

An organic / inorganic composite film having excellent wear resistance can be formed to a thickness of more than 250 nm while suppressing the occurrence of cracks, without using coxide.

[0063] The concentration of silicon alkoxide is expressed as SiO concentration when silicon atoms contained in the silicon alkoxide are converted to SiO, and is more than 3 mass% and not more than 30 mass%.

twenty two

Desirably, it is in the range of more than 3% by mass and less than 13% by mass, more preferably in the range of more than 3% by mass and not more than 9% by mass. If the concentration of silicon alkoxide in the forming solution is too high, cracks may be generated in the film that cause the substrate force to peel off.

[0064] The total concentration of the hydrophilic organic polymer and the surfactant is the same as the concentration of silicon alkoxide.

2 When expressed by concentration, it is preferable to be 60% by mass or less based on the SiO 40

2

More preferably, it is not more than mass%. This is because if the remaining amount increases, the film strength after heat curing may decrease. On the other hand, if the concentration of the hydrophilic organic polymer or the surfactant is too low, the film stress due to shrinkage during curing cannot be relieved, and cracks may occur. Therefore, the total concentration of the hydrophilic organic polymer and the surfactant is preferably 0.1% by mass or more, particularly 5% by mass or more with respect to the SiO 2.

2

[0065] The hydrophilic organic polymer and the surfactant also function as a dispersant for suppressing aggregation of carbon nanotubes, ATO fine particles and the like with respect to acid. In particular, phosphate surfactants containing a phosphate ester group and a polyoxyalkylene group are excellent in dispersibility. To uniformly disperse these antistatic materials in the forming solution, carbon nanotubes Including a step of adding silicon alkoxide, water and alcohol to a mixed solution containing at least one selected from the group consisting of fullerene, ATO and ITO, and a hydrophilic organic polymer and cocoon or surfactant. Preferable to prepare the solution.

[0066] Examples of strong acids include hydrochloric acid, nitric acid, trichloroacetic acid, trifluoroacetic acid, sulfuric acid, phosphoric acid, methanesulfonic acid, paratoluenesulfonic acid, and oxalic acid. Among strong acids, volatile acids can be preferably used because they do not volatilize when heated and remain in the cured film. If an acid remains in the cured film, the inorganic component may be prevented from binding, and the film hardness may decrease.

[0067] Examples of the alcohol used in the production method of the present invention include methyl alcohol, ethyl alcohol, 1-propyl alcohol, isopropyl alcohol, and t-butyl alcohol.

[0068] In the coating step in the method of the present invention, the organic-inorganic composite film-forming solution is coated on the resin substrate while keeping the relative humidity of the atmosphere below 40%. If the relative humidity is too high, it may not be possible to obtain excellent wear resistance in which the silica-based film after film formation is difficult to become a dense structure due to excessive suction of moisture in the atmosphere. From the viewpoint of improving the wear resistance of the silica-based film, it is preferable to control the relative humidity to 30% or less. The lower limit of the relative humidity of the atmosphere in the coating process is not particularly limited, but from the viewpoint of improving the handleability (coating property) of the forming solution, the relative humidity is, for example, 15% or more, further 20% or more. It is preferable to control. Applying the forming solution under an atmosphere controlled so that the humidity is within the above range is important for achieving good wear resistance.

[0069] In the removing 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 removal step is performed at a temperature of 300 ° C or lower, preferably 250 ° C or lower, in view of the decomposition temperature of the organic matter. The lower limit temperature may be appropriately selected according to the required film hardness. The heat treatment temperature may be, for example, 100 ° C or higher, further 150 ° C or higher, and in some cases 180 ° C or higher.

[0071] The removing step is performed at room temperature (25 ° C) followed by an air drying step and an air drying step. It may be performed by a heat treatment step in an atmosphere of a higher temperature and 300 ° C or lower, for example, an atmosphere of 100 ° C or higher and 300 ° C or lower. The air drying step is preferably performed in an atmosphere controlled to a relative humidity of less than 0%, and further 30% or less. By controlling the relative humidity of the atmosphere within this range, the occurrence of film cracks can be more reliably prevented. The lower limit value of the relative humidity of the atmosphere in the air drying process is not particularly limited. For example, it may be 15% or even 20%.

[0072] In the method of the present invention, the hydrolysis or polycondensation state of silicon alkoxide in the organic-inorganic composite film forming solution is adjusted by adjusting the pH of the forming solution or by adding a hydrophilic organic polymer or a surfactant. I have control. In addition, a hydrophilic organic polymer and a surfactant are added in order to suppress excessive film shrinkage while adjusting the amount of water so that sufficient film shrinkage force can be obtained during drying and heating. Thus, the coating step of applying the organic-inorganic composite film forming solution and the removing step of removing at least a part of the liquid component contained in the applied forming solution are performed once, thereby reducing the By heat treatment in the temperature range, it has excellent wear resistance, and an organic / inorganic composite film with a thickness of more than 250 nm and below can be formed to some extent.

[0073] As described above, the organic-inorganic composite film according to the present invention has an abrasion resistance that is superior to a glass plate obtained by a melting method 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 is sufficiently practical. However, when a film having a thickness of 0.1 mm or less, particularly a resin film, is used for a substrate on which an organic-inorganic composite film is formed, the strength of the substrate itself is not sufficient, and the organic-inorganic composite is easily deformed. Abrasion resistance of the film decreases. Considering this, in the present invention, it is desirable to use a substrate having a thickness exceeding 0.1 mm. The thickness of the substrate is preferably 0.3 mm or more, more preferably 0.4 mm or more, and more preferably 0.5 mm or more, and may be 2 mm or more, and even 3 mm or more. The upper limit value of the substrate thickness is not particularly limited, but may be, for example, 20 mm, or 10 mm.

[0074] As the substrate, a glass substrate or a resin substrate can be used. When a glass substrate is used, the adhesion between the organic / inorganic composite film and the substrate can be easily improved. The materials for the resin substrate are: Polycarbonate, Polyethylene, Polypropylene, Polyethylene terephthalate, Polyethylene Examples of the resin include sulfone, polysulfone, cyclic polyolefin, polymethylpentene, and nylon.

[0075] The organic-inorganic composite film according to the present invention has a surface resistivity of 1. OX 10 ¹⁴ Ω / port or less, and in some cases 4. 以下 10 ¹³ Ω port or less, and is excellent in antistatic performance. Furthermore, since the organic-inorganic composite film can be formed with a thickness corresponding to the wavelength in the visible light region, that is, a thickness exceeding 800 nm, it is easy to prevent the occurrence of interference fringes in the film.

[0076] Functional materials such as organic dyes and ultraviolet absorbers can be further introduced using the organic-inorganic composite film that can be formed according to the present invention as a matrix. Many organic fine particles that can be used as these functional materials start to decompose at a temperature of 200 to 300 ° C. In the present invention, since the organic-inorganic composite film can be sufficiently cured even when heated to about 200 ° C., these thermally unstable materials can be obtained without impairing the function of the functional material. Organic fine particles can be introduced into the organic-inorganic composite film. Further, in the method of the present invention, since the forming solution contains a hydrophilic polymer or a surfactant, it is easy to uniformly disperse these organic fine particles in the film. The phosphate surfactant having a polyether group is particularly excellent in dispersibility. In the present invention, a dispersant may be further added to the organic-inorganic composite film forming solution.

[0077] In the solution for forming the organic-inorganic composite film, an organically modified metal alkoxide is used, and the number of moles of metal atoms of the metal alkoxide is 10% or less of the number of moles of silicon atoms of the silicon alkoxide. You may add so that it may become this quantity.

[0078] A metal oxide other than Si may be added within a range not exceeding the mass fraction of the silicon oxide to form a composite oxide. In that case, it is desirable to add in a way that does not affect the reactivity of silicon alkoxide.

[0079] Metal compounds that dissolve in water or alcohol, especially those that are simply ionized and dissolved, such as lithium, sodium, potassium, cesium, magnesium, calcium, cobalt, iron, nickel, copper, aluminum, gallium , Indium, scandium, yttrium

Necessary amounts of chlorides, oxides, nitrates, etc. of metals such as lanthanum, cerium, and zinc may be added.

[0080] Regarding boron, boric acid or boron alkoxides such as acetylacetone It can be added after chelating with β-diketone.

[0081] Regarding titanium and zirconium, it is possible to add oxychloride, oxynitrate or alkoxide after chelating with j8-diketone.

[0082] Also for aluminum, it is possible to add alkoxide after chelating with β-diketone.

Example

[0083] Hereinafter, the present invention will be described in more detail by way of examples.

[0084] (Example A1)

Polyether phosphate ester surfactant (Solsperse 41 000 made by Nippon Lubrizol) 0.17g, tetraethoxysilane (made by Shin-Etsu Chemical) 5.21g, ethyl alcohol (Katayama Chemical) 17.23g, pure 4.86 g of water, concentrated hydrochloric acid (35% by mass, manufactured by Kanto Chemical Co., Ltd.) 0.03 g, ATO fine particle dispersion (ethyl alcohol solution containing 30% by mass of ATO) 2.5 g, polyethylene dallicol 200 (manufactured by Katayama Chemical) 0 02g was added in order to obtain a forming solution.

Note that the above “polyethylene glycol 200” is a polyethylene glycol having a mass average molecular weight of 200. “Solsperse 41000” is a monoester type surfactant and hydrophilic organic polymer obtained by esterifying polyoxyethylene alkyl ether with phosphoric acid, and functions as an acid that dissociates two protons.

[0086] Table 1 shows the contents of silicon alkoxide (in terms of silica), proton concentration, water, and hydrophilic organic polymer and Z or surfactant in the forming solution. The water content in the forming solution is calculated by adding the water (0.35 mass%) contained in ethyl alcohol. The proton concentration was calculated assuming that all protons contained in the strong acid were dissociated. The calculation method of the water content and proton concentration is the same in all the following examples and comparative examples.

[0087] [Table 1] Silicon Al hydrophilic

Water Organic polymer, Coxide Proton concentration

(To total Si location; agent (Si0 ₂ in terms of: (mol / kg Roh antistatic materials surfactant

Molar ratio) (vs. Si0 ₂ position; quality position%)

(Mass%) Example A1 5.0 0.011 11 ATO 13

Example A2 2.0 0.01 1 1 3 Tube

Carbon nano

Example A3 5.0 0.01 1 1 1 Tube Example A4 2.0 0.01 1 1 Fullerene 3 Example A5 5.0 0.005 35 PEDOT 1 1 Comparative example A1 13.0 0.01 7 None 30 Comparative example A2 13.0 0.01 7 None 0

[0088] Next! On a cleaned soda-lime silicate glass substrate (300 x 300 mm, thickness: 3. lmm), 30% relative humidity (hereinafter simply referred to as “humidity”), room temperature (25 ° C) This forming solution was applied by flow coating. As it was, it was dried for about 10 minutes at room temperature, then put in an oven preheated to 200 ° C., heated for 12 minutes, and then cooled. The film obtained was a highly transparent film having a thickness of 1 OOOnm and no cracks. This organic-inorganic composite film contained 4% by mass of ATO fine particles.

[0089] The hardness of the film was evaluated by an abrasion test according to 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. The surface resistivity of the organic-inorganic composite film was measured using a commercially available surface resistivity meter (MCP-HT-260 HIRESTA IP manufactured by Mitsubishi Chemical Corporation). Film thickness, surface resistivity of organic / inorganic composite film, haze ratio before and after Taber test, presence or absence of film peeling after Taber test Table 2 shows the presence or absence of cracks. The haze rate was measured using HGM-2DP manufactured by Suga Test Instruments Co., Ltd.

[0090] [Table 2]

[0091] As shown in Table 2, the obtained organic-inorganic composite film had a hardness equivalent to that of a molten glass plate having a low haze ratio of 3.5% after the Taber test. In addition, there was no film peeling or cracking after the Taber test. Further, the surface resistivity of the organic-inorganic composite film was 9.2 × 10 ¹³ Ω, and the antistatic property was excellent.

[0092] (Example A2)

Example A2 is an example in which an organic-inorganic composite film was formed using a forming solution prepared in the same manner as in Example A1, except that carbon nanotubes were added instead of ATO fine particles.

[0093] Polyether phosphate ester surfactant (Solsperse 41 000 manufactured by Nippon Lubrizol Co., Ltd.) 0.02 g of carbon nanotubes was added to the mixture, and after mixing, 25.98 g of ethyl alcohol (Katayama Chemical Co., Ltd.) Add 1.86 g of pure water, and then add 2.08 g of tetraethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) and 0.03 g of concentrated nitric acid (60% by mass, manufactured by Kanto Chemical Co., Ltd.) Got. The various compositions in this solution are as shown in Table 1.

Next, on the washed soda-lime silicate glass substrate (305 X 305 mm, thickness: 3. lmm), this forming solution was applied by a flow coat method at a humidity of 30% at room temperature. As it was, it was dried at room temperature for about 10 minutes, put in an oven preheated to 200 ° C., heated for 12 minutes, and then cooled. The obtained film was a film having a thickness of 300 nm and having no cracks and a slightly high transparency. This organic-inorganic composite film contained 0.1% by mass of carbon nanotubes.

[0095] The hardness of the film was evaluated in the same manner as in Example A1. As shown in Table 2, the haze ratio after the Taber test was 2.5%, which was as low as a molten glass plate. Also, film peeling and cracking after the Taber test were strong. The surface resistivity of the organic-inorganic composite film was 3.Ο10 ¹³ Ω and was excellent in antistatic properties.

[0096] (Example A3)

Example A3 was the same as Example A1 except that carbon nanotubes were added instead of soot particles, and quaternary hydroxyammonium hydroxide was added instead of polyetherolate surfactant. This is an example in which an organic-inorganic composite film is formed using the forming solution prepared as described above.

[0097] quaternary hydroxide ammonium - as © beam, choline (Tama Chemicals Co., Ltd., trade name: Choline, chemical formula: [(CH) N + CH CH OH] OH-) an aqueous solution containing 4 mass ^_0/0 0.15g to carbon nano

3 3 2 2

Tube dispersion (ENA: ethanol solution containing 5% by mass of carbon nanotubes) Add 0.02 g, and after mixing, add 1.61 g of pure water and 6.47 g of ethyl alcohol (manufactured by Katayama Chemical). Concentrated hydrochloric acid (35% by mass, manufactured by Kanto Chemical Co., Ltd.), 0.01 g, and tetraethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) 1. 74 g were sequentially added to obtain a forming solution. Table 1 shows the various compositions in this solution.

Next, on the washed soda-lime silicate glass substrate (100 × 100 mm, thickness: 3. lmm), this forming solution was applied by flow coating at 30% humidity and room temperature. As it was, it was dried at room temperature for about 10 minutes, put in an oven preheated to 200 ° C., heated for 18 minutes, and then cooled. The film obtained was a highly transparent film with a thickness of 500 nm and no cracks. This organic-inorganic composite film contained 0.01% by mass of carbon nanotubes. [0099] The hardness of the film was evaluated in the same manner as in Example A1. As shown in Table 2, the haze ratio after the Taber test was 1.6%, which was as low as a molten glass sheet. Also, film peeling and cracking after the Taber test were strong. The organic / inorganic composite film had a surface resistivity of 1.3 to 10 ¹³ Ω and excellent antistatic properties.

[0100] (Example Α4)

Example IV4 is an example in which an organic-inorganic composite film was formed using a forming solution prepared in the same manner as Example A1, except that fullerene was added instead of the soot fine particles.

[0101] Polyether phosphate ester surfactant (Solsperse 41 000 made by Nippon Lubrizol) and 0.03g fullerene (MER C) were mixed with ethyl alcohol

60

25. 98g, pure water 1.86g added, then tetraethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) 2.0 g, concentrated nitric acid (60% by mass, manufactured by Kanto Chemical Co., Ltd.) 0.03g in order Addition gave a forming solution. Table 1 shows the various compositions in this solution.

Next, this forming solution was applied by flow coating on a soda-lime silicate glass substrate (305 X 305 mm, thickness: 3. lmm) washed at 30% humidity and room temperature. As it was, it was dried at room temperature for about 10 minutes, put in an oven preheated to 200 ° C., heated for 12 minutes, and then cooled. The film obtained was a highly transparent film having a thickness of 300 nm and no cracks. The organic-inorganic composite film contained 0.1 mass ^_0/0 fullerenes.

[0103] The hardness of the film was evaluated in the same manner as in Example A1. As shown in Table 2, the haze ratio after the Taber test was as low as 3.9%, a hardness comparable to a molten glass plate. Also, film peeling and cracking after the Taber test were strong. The surface resistivity of the organic / inorganic composite film was 2.3 Χ 10 ¹³ Ω and the antistatic property was excellent.

[0104] (Example Α5)

Example Α5 was formed in the same manner as in Example A1, except that instead of ΑΤΟfine particles, a mixture of polyethylene dioxythiophene (PEDOT) and polystyrene sulfonic acid (PSS) (PEDOTZPSS) was added. This is an example in which an organic-inorganic composite film is formed using a solution.

[0105] 0.06 g of polyethylene glycol and 2.87 g of ethyl alcohol (Katayama Chemical) 1.86 g of pure water were added, followed by tetraethoxysilane (Shin-Etsu Chemical Co., Ltd.) 1.74 g, concentrated hydrochloric acid (35 mass) %, Seki (Tohoku Chemical Co., Ltd.) 0. OOlg ゝ PEDOTZPSS (Bayer BaytronP HC V4) 3. 85 g was added in order to obtain a forming solution. The various compositions in this solution are shown in Table 1.

Next, on the washed soda-lime silicate glass substrate (100 × 100 mm, thickness: 3. lmm), this forming solution was applied by spin coating at a humidity of 30% at room temperature. The coated substrate is heated for 5 minutes on a hot plate heated to 70 ° C, then dried at room temperature for about 10 minutes, and then placed in an oven heated to 180 ° C in advance and heated for 30 minutes. And then cooled. The obtained film was a film with a thickness of 1200 nm and no cracks and a high transparency. This organic-inorganic composite film contained 0.5% by mass of PEDOT.

[0107] The hardness of the film was evaluated in the same manner as in Example A1. As shown in Table 2, the haze ratio after the Taber test was 3.1%, which was as low as a molten glass plate. Also, film peeling and cracking after the Taber test were strong. Further, the surface resistivity of the organic-inorganic composite film was 3.8 410 ⁴ Ω / mouth, and the antistatic property was excellent.

[0108] (Comparative Example A1)

In Comparative Example A1, an organic-inorganic composite film was formed using a forming solution prepared in the same manner as in Example A1, except that no soot particles were added and only polyethylene glycol was used as the hydrophilic organic polymer. It is an attempted example.

[0109] 23.70 g of ethyl alcohol (made by Katayama Chemical), 45.14 g of tetraethoxysilane (made by Shin-Etsu Chemical), 27.16 g of pure water, concentrated hydrochloric acid (35 mass%, manufactured by Kanto Chemical) 0. 10 g, polyethylene glycol 400 (manufactured by Kanto Chemical) 3. 90 g was added and stirred to obtain a forming solution. The various compositions in this solution are as shown in Table 1.

[0110] The above "polyethylene glycol 400" is a polyethylene glycol having a mass average molecular weight of 00.

[0111] Next, this forming solution was applied by a flow coating method on a cleaned soda-lime silicate glass substrate (100 X 100 mm, thickness: 3. lmm) 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 200 ° C., heated for 40 minutes, and then cooled.

[0112] The obtained film was a 2800 nm thick crack-free film with high transparency. As shown, part of the film peeled after the Taber test. Furthermore, when the surface resistivity of the film was measured, it showed a value exceeding 1Χ10 ¹⁴ Ω / mouth and was inferior in antistatic property.

[0113] (Comparative example Α2)

Comparative Example Α2 uses a forming solution prepared in the same manner as in Example A1 except that ΑΤΟfine particles are not added and phosphoric acid is used in place of the polyether phosphate ester surfactant. This is an example in which formation was attempted.

[0114] Ethyl alcohol (made by Katayama Chemical) 27. 49g, tetraethoxysilane (made by Shin-Etsu Chemical) 45

14g, pure water 27.16g, concentrated hydrochloric acid (35% by mass, manufactured by Kanto Sugaku) 0. lOg, phosphoric acid (85% by mass)

0. llg was added and stirred to obtain a forming solution. The various compositions in this solution are shown in Table 1.

[0115] Next, this forming solution was applied by flow coating on a cleaned soda lime silicate glass substrate (100 X 100 mm, thickness: 3. lmm) 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 200 ° C., heated for 40 minutes, and then cooled.

[0116] In this example, as shown in Table 2, cracks accompanied by peeling occurred and the film was not formed.

[0117] (Example B1)

ITO fine particle dispersion (Mitsubishi Materials: Ethyl alcohol solution containing 40% by mass of ITO) 7.5g, polyether phosphate ester surfactant (Disparon DA-375 manufactured by Enomoto Iseisei) 0.15g, Tetra Ethoxysilane (manufactured by Shin-Etsu Chemical) 20.8g, ethyl alcohol (manufactured by Katayama Chemical) 55.45g, pure water 15.8g, concentrated hydrochloric acid (35% by mass, manufactured by Kanto Chemical Co., Ltd.) 0.3g A forming solution was obtained. Table 3 shows the various compositions in this solution.

[0118] The above-mentioned "Dispalon DA-375" is a monoester surfactant obtained by esterifying polyoxyethylene alkyl ether with phosphoric acid, and functions as an acid that dissociates two protons. In this example and Examples B2 to B3 and Comparative Examples B1 to B2 to be described later, substrates having light transmittances of 21% and 46% for wavelengths lOOOnm and 1700 nm, respectively, were used. [0119] [Table 3]

Next, this forming solution was applied by flow coating on a soda-lime silicate glass substrate (100 × 100 mm, thickness: 2.5 mm) washed at 30% humidity and room temperature. Continue to air dry at room temperature for about 3 hours, then put into an oven heated to 90 ° C in advance and heated for 30 minutes, then into an oven heated to 200 ° C in advance and heated for 1 hour, Then it was cooled. The obtained film was a highly transparent film without cracks having a film thickness of lOOOnm.

[0121] The hardness of the film was evaluated in the same manner as in Example A1. Table 4 shows the film thickness, the haze ratio before and after the Taber test, the presence or absence of film peeling after the Taber test, the presence or absence of cracks, the content of fine particles, and the transmittance of near-infrared light with wavelengths lOOOnm and 1700 nm. Table 4 also shows the haze ratio before and after the Taber test on a molten glass plate as a blank.

[0122] [Table 4] Haze rate (%) Taper Fine particle Wavelength 1000nm Wavelength 1700nm Film thickness Crack

Permeability after test (Whole membrane: Permeability in

Initial film peeling (%) (%) (%) After test

Example B1 1000 0.0 2.8 None None 3 18 15 Example B2 1000 0.2 2.4 None None 3 18 14 Example B3 2000 0.4 3.5 None None 4.5 19 23 Example B4 2000 0.4 3.1 None None 4.5 75 10 Example B5 2200 0.4 3.5 No No 5 63 19 Comparative example B1 2800 0.2 2.3 Yes No ― 21> 30 Comparative example B2 ― ― ― ― Oh y

(Full surface) ― ― ― Comparative example B3 2800 0.2 2.4 Yes No ―> 30> 30 Gauff board-0.0 1.5 ― ― ― ― ―

[0123] As shown in Table 4, the haze ratio after the Taber test was as low as 2.8%, which was a hardness comparable to a molten glass plate. Also, there was no film peeling or cracking after the Taber test. Further, this film-coated article had transmittances of 18% and 15% of near-infrared transmittances of wavelengths lOOOnm and 1700 nm, respectively.

[0124] (Example B2)

Example B2 is an example in which a polyether phosphate ester surfactant different from Example B1 and polyethylene glycol were used as the hydrophilic organic polymer.

[0125] ITO fine particle dispersion (Mitsubishi Materials Co., Ltd., ethyl alcohol solution containing 40% by mass of ITO) 1. To 88 g, polyether phosphate ester surfactant (Sonores Nose 41000, Nippon Lubrizol) 0 23g, Polyethylene Glycol Nore 400 (Katayama Chemical) 0.04g, Tetraethoxysilane (Shin-Etsu Chemical) 6.25g, Ethyl Alcohol (Katayama Chemical) 15. 32g, Pure Water 5. 88g Concentrated hydrochloric acid (35% by mass, manufactured by Kanto Chemical Co., Ltd.) was added in order to obtain a forming solution. Various compositions in this solution are as shown in Table 3.

Next, this forming solution was applied by flow coating on a soda-lime silicate glass substrate (305 X 305 mm, thickness: 2.5 mm) washed at 30% humidity and room temperature. As it is, After drying at room temperature for about 30 minutes, it was put into an oven preheated to 200 ° C, heated for 14 minutes, and then cooled. The film obtained was a highly transparent film without cracks with a film thickness of lOOOnm.

[0127] The film hardness was evaluated in the same manner as in Example A1. As shown in Table 4, the haze ratio after the Taber test was 2.4%, which was as low as a molten glass plate. Also, film peeling and cracking after the Taber test were strong. In addition, this film-coated article had near infrared transmittances of 18% and 14% at wavelengths of 10 OOnm and 1700 nm, respectively.

[0128] When ITO fine particles are exposed to a temperature of 250 ° C or higher, oxidation may be accelerated and the near-infrared absorption ability may be reduced. However, in Examples B1 and B2, it was confirmed that the near-infrared absorption ability by the ITO fine particles was maintained because the heat treatment temperature was 200 ° C or lower.

[0129] (Example B3)

Example B3 is an example in which a polyether phosphate ester surfactant different from Example B1 and polyethylene glycol are used as the hydrophilic organic polymer, and ATO fine particles are used in place of the ITO fine particles.

[0130] Polyether phosphate surfactant (Nippon Lubrizol Solsperse 41 000) 0. 89g, Ethyl alcohol (Katayama Yigaku) 9. 48g, Pure water 5.62g, Polyethylene glycol 200 (Katayama Chemical) 0.12g, concentrated hydrochloric acid (35% by mass, manufactured by Kanto Chemical Co., Ltd.) 0.003g, tetraethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) 9.38g, ATO fine particle dispersion (ethyl containing 30% by mass of ATO) (Alcohol solution) 4.5 g was added in order to obtain a forming solution. Table 3 shows the various compositions in this solution.

Next, this forming solution was applied by flow coating on a soda-lime silicate glass substrate (300 × 300 mm, thickness: 2. lmm) washed at 30% humidity and room temperature. As it was, it was dried at room temperature for about 10 minutes, put in an oven preheated to 200 ° C., heated for 12 minutes, and then cooled. The obtained film was a highly transparent film having a thickness of 2000 nm and no cracks.

[0132] The hardness of the film was evaluated in the same manner as in Example A1. As shown in Table 4, the haze ratio after the Taber test was 3.5%, which was as low as a molten glass plate. The tape Film peeling and cracking after the bar test were strong. In addition, this film-coated article had near-infrared transmittances of 19% and 23% at wavelengths of 10 OOnm and 1700nm, respectively.

[0133] (Comparative Example B1)

Comparative Example B1 is an example in which an organic-inorganic composite film was attempted in the same manner as Comparative Example A1. As shown in Table 4, the obtained film peeled after the Taber test. In addition, this film-coated article had a transmittance of near infrared light having a wavelength of 1700 nm exceeding 30%.

[0134] (Comparative Example B2)

Comparative Example B2 is an example in which the formation of an organic-inorganic composite film was attempted in the same manner as Comparative Example A2. In this example, as shown in Table 4, cracks accompanied by peeling occurred and the film was not formed.

[0135] (Example B4)

Example B4 is an example in which an organic-inorganic composite film was formed on a substrate having transmittances of 82% and 87% of light with wavelengths lOOOnm and 1700 nm, respectively, using a forming solution prepared in the same manner as in Example B2. It is.

[0136] ITO fine particle dispersion (Mitsubishi Materials Co., Ltd., ethyl alcohol solution containing 40% by mass of ITO) 3. 38 g of polyether phosphate ester surfactant (Nihon Lubrizol Sonol Nose 41000) 0 49g, Polyethylene Glycol Nole 200 (Made by Katayama) 0.07g, Tetraethoxysilane (Made by Shin-Etsu Chemical) 7.29g, Ethyl Alcohol (Made by Katayama Chemical) 13.15g, Pure Water 5. 61g Then, 0.02 g of concentrated hydrochloric acid (35% by mass, manufactured by Kanto Chemical Co., Ltd.) was sequentially added to obtain a forming solution. Various compositions in this solution are as shown in Table 3.

[0137] Next, the washed soda-lime-silicate glass substrate (305

X 305 mm, thickness: 2.5 mm), this forming solution was applied by flow coating at a humidity of 30% and room temperature. As it was, it was dried at room temperature for about 20 minutes, put in an oven preheated to 200 ° C., heated for 18 minutes, and then cooled. The obtained film was a highly transparent film without a 2000 nm-thick crack.

[0138] The hardness of the film was evaluated in the same manner as in Example A1. As shown in Table 4, the haze ratio after the Taber test was 3.1%, which was as low as a molten glass plate. Also, film peeling and cracking after the Taber test were strong. This film-coated article has a wavelength of 17 The near-infrared transmittance of OOnm was 19%.

[0139] (Example B5)

Example B5 is an example in which an organic-inorganic composite film is formed on a substrate having transmittances of 82% and 87% of light with wavelengths lOOOnm and 1700 nm, respectively, using a forming solution prepared in the same manner as in Example B3. It is.

[0140] Polyether phosphate ester surfactant (Solsperse 41 000 made by Nippon Lubrizol) 1. 05g, Etenore Nore = 3—Nore (Katayama Igaku) 7.09g, pure water 6.26g, positive ethylene Glycol 200 (manufactured by Katayama Chemical) 0.18 g, concentrated hydrochloric acid (35% by mass, manufactured by Kanto Chemical Co., Ltd.) 0.003 g, tetraethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) 10. 42 g, ATO fine particle dispersion (30 ATO) (Ethal alcohol solution containing mass%) 5. OOg was added in order to obtain a forming solution. Table 3 shows the various yarns in this solution.

[0141] Next, a washed soda-lime-silicate glass substrate (300

X 300 mm, thickness: 2.5 mm), this forming solution was applied by flow coating at a humidity of 30% and room temperature. After drying for about 10 minutes at room temperature, it was put in an oven preheated to 200 ° C, heated for 18 minutes, and then cooled. The obtained film was a highly transparent film without cracks having a film thickness of 2200 nm.

[0142] The hardness of the film was evaluated in the same manner as in Example A1. As shown in Table 4, the haze ratio after the Taber test was 3.5%, which was as low as a molten glass plate. Also, film peeling and cracking after the Taber test were strong. In addition, this film-coated article had a near infrared transmittance of 19% at a wavelength of 17 OOnm.

[0143] (Comparative Example B3)

Comparative Example B3 is an example in which an organic-inorganic composite film was formed in the same manner as Comparative Example B1, except that the substrate in Comparative Example B1 was changed to the substrate used in Example B4. As shown in Table 4, the obtained film peeled after the Taber test. In addition, this film-coated article had a near-infrared transmittance of 1700 nm in wavelength exceeding 30%.

[0144] (Example C1)

Example C1 uses a forming solution prepared in the same manner as in Example A5 except that ATO fine particles were further added, and the transmittance of light with a wavelength of lOOOnm and 1700 nm was respectively obtained. This is an example in which an organic-inorganic composite film is formed on a substrate of 21% and 46%.

[0145] Polyether phosphate ester surfactant (Solsperse 41 000 manufactured by Nippon Lubrizol Co., Ltd.) 0.01 g, Polyethylene Glycolol 0.02 g, Ethino Reano Reconole (manufactured by Katayama Yi Gakuen) 1. After adding 68 g and 1.30 g of pure water, tetraethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) 0.87 g, paratoluene sulfonic acid (manufactured by Kanto Chemical) 0.001 g, PEDOTZPSS (Bayer BaytronP HC

V4) 0.63 g, ATO fine particle dispersion (manufactured by Mitsubishi Materials, ethyl alcohol solution containing 30% by mass of ITO) 0.5 g was added in order to obtain a forming solution. Table 5 shows the various compositions in this solution.

[0146] [Table 5]

[0147] Next, a washed soda-lime-silicate glass substrate (100

X 100 mm, thickness: 3.1 mm) was applied by spin coating at 30% humidity and room temperature. The coated substrate is heated on a hot plate heated to 70 ° C for 5 minutes, dried at room temperature for about 5 minutes, and then placed in an oven heated to 200 ° C in advance and heated for 20 minutes. And then cooled. The obtained film was a highly transparent film having a thickness of 1200 nm and no cracks. The organic-inorganic composite film contained PEDOT 0. 15 mass ^_0/0.

[0148] The hardness of the film was evaluated in the same manner as in Example A1. As shown in Table 6, the haze ratio after the Taber test was 3.4%, which was as low as a molten glass plate. Also, film peeling and cracking after the Taber test were strong. The surface resistivity of the organic / inorganic composite film was 3.4 X 10 ^1Q QZ port. Further, this film-coated article had transmittances of 18% and 25% of near-infrared rays having wavelengths of lOOOnm and 1700 nm, respectively.

[0149] [Table 6]

Industrial applicability

The present invention provides an article on which an organic-inorganic composite film excellent in wear resistance is formed while including a material having antistatic ability and near infrared absorption ability. It has great utility value in each field that uses the formed article.

Claims

The scope of the claims

[I] An article formed with an organic-inorganic composite film, including a base and an organic-inorganic composite film containing an organic substance and an inorganic oxide formed on the surface of the base,

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,

The organic-inorganic composite film is at least one selected from carbon nanotubes, fullerenes, antimony tin oxides and indium stannates as at least a part of the organic matter or as the inorganic oxide, and Z or Including conductive polymer,

Articles with an organic-inorganic composite film formed.

[2] The article according to claim 1, wherein the organic-inorganic composite film contains a hydrophilic organic polymer and Z or a surfactant as the organic substance.

[3] The article according to claim 1, wherein the organic-inorganic composite film further includes at least one selected from a carbon nanotube and a fullerene force, and Z or a conductive polymer as at least a part of the organic substance.

[4] The article according to claim 1, wherein the conductive polymer includes polyethylene dioxythiophene.

[5] The article according to claim 2, wherein the hydrophilic organic polymer contains a polyoxyalkylene group.

P

PPo

[6] The article according to claim 2, comprising a hydrophilic organic polymer force phosphate group and a polyoxyalkylene group.

7. The article according to claim 2, wherein the surfactant includes a quaternary ammonium compound.

8. The article according to claim 7, wherein the quaternary ammonia compound is a hydroxide.

[9] The article according to claim 1, wherein the thickness of the substrate is more than 0.1 mm.

10. The article according to claim 1, wherein the substrate is a glass substrate or a resin substrate.

[II] The organic-inorganic composite film contains the antimony stannate and has a film thickness exceeding 800 nm. The article of claim 1, comprising:

12. The article according to claim 1, wherein the surface resistivity of the organic-inorganic composite film is 1. OX 10 ¹⁴ Ω / mouth or less.

[13] The organic-inorganic composite film further includes at least one selected from antimony tin oxide and indium stannic acid oxide as the inorganic oxide, and has a near infrared wavelength of 1700 nm. The article according to claim 1, wherein the transmittance of the line is 30% or less.

14. The article according to claim 13, wherein the transmittance of near infrared rays having a wavelength of 1700 nm is 20% or less.

15. The article according to claim 1, wherein the thickness of the organic-inorganic composite film is more than 250 nm and 5 m or less.

[16] The article according to claim 15, wherein the thickness of the organic-inorganic composite film is more than 300 nm and not more than 5 μm.

17. The article according to claim 16, wherein the thickness of the organic-inorganic composite film is 1 m or more and 5 μm or less.

18. The article according to claim 1, which is a display substrate.

[19] The resin article according to claim 1, wherein the organic-inorganic composite film does not contain fine particles of fluorocoagulant!

[20] A base and an organic-inorganic composite film containing an organic substance and an inorganic oxide formed on the surface of the base, wherein the organic-inorganic composite film contains silica as the inorganic oxide, and the organic-inorganic The composite film is mainly composed of the silica, and the organic-inorganic composite film is further added as at least a part of the organic material, or as the inorganic oxide, and further includes carbon nanotubes, fullerene, antimony stannate, and indium tin. A method for producing an article formed with an organic-inorganic composite film, comprising at least one selected from acidity and / or a conductive polymer,

An application step of applying the organic-inorganic composite film forming solution to the surface of the substrate; and a removing step of removing at least a part of the liquid component contained in the forming solution from the forming solution applied to the substrate; Including

The forming solution is selected from silicon alkoxide, strong acid, water and alcohol, carbon nanotube, fullerene, antimony tin oxide and indium tin oxide. And at least one species, as well as Z or a conductive polymer,

The forming solution further comprises a hydrophilic organic polymer and Z or a surfactant as at least a part of the strong acid or as a component different from the strong acid,

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 0.1 ImolZkg, expressed by the molar concentration of proton when it is assumed that the strong acid proton is completely dissociated,

The number of moles of water is at least 4 times the total number of moles of silicon atoms contained in the silicon alkoxide. Apply to

In the removing step, at least a part of the liquid component contained in the forming solution applied to the substrate is removed while maintaining the substrate at a temperature of 300 ° C. or lower.

A method for producing an article on which an organic-inorganic composite film is formed.

21. The method for producing an article according to claim 20, wherein in the removing step, at least a part of the liquid component is removed while maintaining the substrate at a temperature of 250 ° C. or lower.

22. The method for producing an article according to claim 20, wherein the number of moles of water is 40 times or less the total number of moles of silicon atoms contained in the silicon alkoxide.

23. The method for producing an article according to claim 22, wherein the number of moles of water is 20 times or less the total number of moles of silicon atoms contained in the silicon alkoxide.

[24] The concentration of the silicon alkoxide is 30% by mass or less expressed by the SiO concentration.

2

21. A method for manufacturing an article according to claim 20.

[25] The carbon nanotube, the fullerene, the antimony tin oxide, and the indium tin oxide, at least one selected from the above, and Z or a conductive polymer, and the hydrophilic organic polymer and Z or a surfactant. 21. The method for producing an article according to claim 20, wherein the forming solution is prepared by adding a step of adding the silicon alkoxide, water, and alcohol to the mixed solution.

[26] The organic-inorganic composite film having a thickness of more than 250 nm and not more than 5 m is formed by performing the coating step and the removing step once each. Manufacturing method of the article.