JP2015055715A - Anti-reflection film-forming composition and manufacturing method therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To form an anti-reflection film for preventing reflection of light rays irradiated from an eternal light source while maintaining light transmittance of a transparent conductive film or the like on which the anti-reflection film is formed.SOLUTION: An anti-reflection film-forming composition is coated on a transparent conductive film, glass, or light transmissive plastic having a refractive index in a range of 1.6-2.0 at a wavelength of 550 nm to form an anti-reflection film having a lower refractive index. The anti-reflection film-forming composition contains a hydrolysate of a metal alkoxide, and phosphoric acid. Defining A (mol/L) as molar concentration of metal of the metal alkoxide and B (mol/L) as molar concentration of the phosphoric acid, B/A shall be in a range of 0.002 to 0.1.

Description

  The present invention relates to an antireflection film-forming composition for forming an antireflection film that suppresses light reflection on the surface of a transparent conductive film or the like by applying it on a transparent conductive film, glass, or translucent plastic. And a manufacturing method thereof.

  A transparent conductive film is provided on a display surface of an image display device such as an LCD (Liquid Crystal Display), a PDP (Plasma Display Panel), an organic EL (ElectroLuminescence), or a touch panel. The transparent conductive film generally has a high refractive index of 2.0 or more. For example, when the transparent conductive film is placed in the air, light is reflected at the interface with the air. For this reason, in order to improve the visibility on the display surface of the image display device, it is required that the reflection of the light beam emitted from the external light source is small. In order to satisfy this requirement, an antireflection film is conventionally formed on a transparent conductive film (see, for example, Patent Document 1).

  The composition for forming the antireflection film of Patent Document 1 contains an inorganic material such as silica or magnesium fluoride, a fluorine resin, or the like for forming a low refractive index layer having a refractive index of 1.46 or less. In addition to the coating liquid to be used, the following (1) to (4) for forming a medium refractive index layer having a refractive index of 1.50 to 1.80 and a high refractive index layer having a refractive index of 1.65 or more. A coating composition containing is shown. (1) A rutile type having a primary particle diameter in the range of 0.01 to 0.1 μm, which is coated with an inorganic compound that reduces or eliminates photocatalytic activity and an organic compound and / or organometallic compound having an anionic polar group. Titanium oxide, (2) ionizing radiation-curable binder component, (3) a dispersant having an anionic polar group, and (4) an organic solvent.

JP 2002-277609 A (summary, paragraph [0123])

  The antireflection film composed of the medium refractive index layer and the high refractive index layer formed by the coating composition disclosed in Patent Document 1 has various performances such as transparency, film strength, adhesion to adjacent layers, and film thickness uniformity. Excellent. On the other hand, a transparent conductive film with an antireflection film is generally eroded when the dispersion medium of the composition for forming an antireflection film comes into contact with the surface of the transparent conductive film, which adversely affects performance such as transparency. Easy to receive. In particular, materials for transparent conductive films such as tin-doped indium oxide (ITO) and aluminum-doped zinc oxide (AZO) are generally easily dissolved by acids and alkaline substances, and in the dispersion medium of the antireflection film-forming composition. If these substances are mixed in, the light transmittance of the transparent conductive film simultaneously decreases due to the elution of some materials. As a result, there is a concern that the device performance may be adversely affected.

  An object of the present invention is to form an antireflection film that prevents reflection of light emitted from an external light source, and to maintain the light transmittance of a transparent conductive film or the like on which the antireflection film is formed. It is in providing a thing and its manufacturing method.

  The present inventors include phosphoric acid in the composition for forming an antireflective film, so that the constituent material of the transparent conductive film and the phosphoric acid eluted after application on the transparent conductive film are salted. This phosphorous layer protects the surface of a transparent conductive film, etc., and the phosphate has low solubility in acids, alkalis, organic solvents, etc. Focusing on suppressing elution of ITO, AZO, etc., which are constituent materials such as films, the present invention has been achieved.

  A first aspect of the present invention has a refractive index lower than the refractive index when coated on a transparent conductive film, glass or translucent plastic having a refractive index in the range of 1.6 to 2.0 at a wavelength of 550 nm. An antireflection film-forming composition used for forming an antireflection film, comprising a hydrolyzate of metal alkoxide and phosphoric acid, wherein the metal alkoxide has a metal molar concentration of A mol / L. When the molar concentration of phosphoric acid is B mol / L, B / A is in the range of 0.002 to 0.1.

  A second aspect of the present invention is the invention based on the first aspect, wherein transparent oxide particles are further dispersed in a dispersion medium containing the hydrolyzate of the metal alkoxide and the phosphoric acid, and the dispersion It is a composition for anti-reflective film formation which contains the said hydrolyzate in the ratio of 0.1-10 mass parts in conversion of an oxide with respect to 1 mass part of said transparent oxide particles in the said composition except a medium.

  A third aspect of the present invention is the composition for forming an antireflection film according to the first or second aspect, wherein the metal alkoxide is silicon alkoxide, aluminum alkoxide or titanium alkoxide.

  A fourth aspect of the present invention is the invention based on the second aspect, wherein the metal element constituting the transparent oxide particles is silicon, zirconium, niobium, indium, zinc, tin, tungsten, gallium, antimony, aluminum , An antireflection film-forming composition that is one or more elements selected from the group consisting of cerium and titanium.

  The 5th viewpoint of this invention is invention based on the 2nd or 4th viewpoint, Comprising: The said transparent oxide particle has the primary particle diameter in the range of 1-50 nm in a number average. In the present invention, the number average measurement of the primary particle diameter of the transparent oxide particles is performed by a direct observation method in which the particle diameter of 50 particles is arbitrarily measured from the TEM image to obtain the average value.

  According to a sixth aspect of the present invention, there is provided a method for producing the composition for forming an antireflection film according to the first aspect, wherein a step of preparing a first liquid by adding and mixing an organic solvent to a metal alkoxide, and the metal A step of preparing a second liquid by mixing water in an amount of 1 to 30 times mol with respect to 1 mol of alkoxide and phosphoric acid in an amount of 0.002 to 0.1 mol; The liquid is added to and mixed with the second liquid while maintaining the temperature at 25 to 85 ° C., and the hydrolyzate of the metal alkoxide and the phosphoric acid are added to a dispersion medium composed of the first liquid and the second liquid. Including the step of including.

  A seventh aspect of the present invention is the invention based on the sixth aspect, wherein the dispersion medium containing the hydrolyzate of the metal alkoxide and the phosphoric acid, and the transparent oxide particles are dispersed in alcohol, water or methyl ethyl ketone. The composition for forming an antireflection film further comprising a step of mixing the sol in a ratio of 10 to 9900 parts by mass of the transparent oxide particles in the sol with respect to 100 parts by mass of the oxide content of the hydrolyzate It is a manufacturing method.

  An eighth aspect of the present invention is a method for producing the composition for forming an antireflective film according to the second aspect, wherein a step of preparing a first liquid by adding and mixing an organic solvent to a metal alkoxide, 1 part by mass of 1 liquid, 1 to 30 parts by mass of water, 0.002 to 0.1 parts by mass of phosphoric acid, and 2 to 99 parts by mass of transparent oxide A step of preparing a third liquid by mixing a sol in which particles are dispersed; and adding and mixing the first liquid to the third liquid while maintaining the temperature at 25 to 85 ° C. A step of including a decomposition product, the phosphoric acid, and the transparent oxide particles in a dispersion medium composed of the first liquid and the third liquid.

  A ninth aspect of the present invention is produced by a transparent conductive film, the antireflection film-forming composition described in the first or third aspect on the transparent conductive film, or the method described in the sixth aspect. And a method for producing a composite film having an antireflection film formed by applying a composition for forming an antireflection film.

  A tenth aspect of the present invention is an invention based on the ninth aspect, and is a method for manufacturing a composite film in which a protective film is formed on the antireflection film.

  An eleventh aspect of the present invention is the invention based on the ninth or tenth aspect, wherein the transparent conductive film is tin-doped indium oxide (ITO) particles, aluminum-doped zinc oxide (AZO) particles, This is a method for producing a composite film including tin oxide (ATO) particles doped with antimony, zinc oxide (BZO) particles doped with boron, or titanium oxide (TNO) particles doped with niobium.

  In the composition for forming an antireflection film according to the first aspect of the present invention, since the composition contains phosphorus, the layer containing phosphorus has a transparent conductive film or the like on the surface of the transparent conductive film or the like on which the antireflection film is formed. , And ITO, AZO, etc., which are constituent materials such as a transparent conductive film, are prevented from eluting into the antireflection film. The technical reason that the presence of the layer containing phosphorus suppresses the elution of the constituent material such as the transparent conductive film has not been elucidated at this stage, but is presumed to be due to the formation of a hardly soluble phosphate. As a result, an antireflection film that prevents reflection of light rays emitted from an external light source is formed, and the light transmittance of a transparent conductive film or the like on which the antireflection film is formed is maintained.

The composition for forming an antireflection film according to the second aspect of the present invention includes transparent oxide particles having a high refractive index in addition to the hydrolyzate of metal alkoxide, so the ratio between the transparent oxide particles and the hydrolyzate is adjusted. By doing so, the refractive index of the antireflection film formed by this composition can be adjusted.
By adjusting the reflectance, it is possible to adjust the refractive index so that the performance as an antireflection film is most improved. This refractive index is determined by the refractive index (n) of the layers before and after the antireflection film. For example, the incident light side is air (n ₁ = 1), and the refractive index of the substrate on which the antireflection film is formed is glass. In the case of (n ₃ = 1.5), the optimum refractive index n ₂ = (n ₁ × n ₂ ) ^0.5 = 1.22.

  In the composition for forming an antireflection film according to the third aspect of the present invention, among many metal alkoxides, silicon alkoxide, aluminum alkoxide or titanium alkoxide is preferable as the metal alkoxide because of transparency and stability over time.

  In the composition for forming an antireflection film according to the fourth aspect of the present invention, among many transparent oxide particles, elements such as tin and indium are preferable as transparent oxide particles in terms of transparency.

  In the composition for forming an antireflective film according to the fifth aspect of the present invention, the transparent oxide particles have an effect of not reducing the light transmittance of the antireflective film itself by making the primary particle diameter within a predetermined range. There is.

  In the method for producing a composition for forming an antireflection film according to the sixth aspect of the present invention, hydrolysis of metal alkoxide is promoted by using phosphoric acid as an acid catalyst when metal alkoxide is decomposed with water. And a composition containing the characteristic phosphoric acid of the present invention can be prepared at the same time.

  In the manufacturing method of the 7th viewpoint of this invention, a transparent oxide particle can be included in a dispersion medium by mixing the dispersion medium of a 6th viewpoint, and the sol of transparent oxide particle.

  In the manufacturing method according to the eighth aspect of the present invention, by preparing a third liquid in which the sol of transparent oxide particles is mixed with water and phosphoric acid, the number of steps is more than that of the manufacturing method according to the sixth aspect of the present invention. Can be reduced.

  In the method for producing a composite film according to the ninth aspect of the present invention, the antireflection film-forming composition according to the first or third aspect or the antireflection film-forming composition according to the sixth aspect is applied onto the transparent conductive film. Since the antireflection film is formed, a composite film in which the light transmittance of the transparent conductive film is maintained even when the antireflection film is present can be produced.

  In the method for manufacturing a composite film according to the tenth aspect of the present invention, scratches and the like of the antireflection film can be prevented by forming a protective film on the antireflection film.

  In the manufacturing method of the composite film of the 11th viewpoint of this invention, ITO etc. are preferable as a transparent conductive particle for the reason of transparency among the transparent conductive particles contained in many transparent conductive films.

It is a block diagram of the composite film provided with the transparent conductive film and the antireflection film formed on this transparent conductive film by the composition for antireflection film formation of this invention. It is a block diagram of another composite film further provided with a protective film on the antireflection film shown in FIG.

Next, the form for implementing this invention is demonstrated.
<First Embodiment>
[Antireflection film-forming composition containing no transparent oxide particles]
The composition for forming an antireflection film according to the first embodiment is applied on a transparent conductive film having a refractive index in the range of 1.6 to 2.0 at a wavelength of 550 nm and has a refractive index lower than the refractive index. Used to form an antireflection film. The transparent conductive film is formed by applying a dispersion of conductive oxide particles using a wet coating method. For example, the transparent conductive film is formed on a photoelectric conversion layer of a solar cell, on a transparent plastic, or on glass. Examples of the conductive oxide particles include ITO, AZO, antimony-doped tin oxide (ATO), zinc-doped indium oxide (IZO), fluorine-doped tin oxide (FTO), and the like.

The composition for forming an antireflection film according to the first embodiment is constituted by containing a hydrolyzate of metal alkoxide and phosphoric acid in a dispersion medium. Examples of the metal of the metal alkoxide include aluminum, silicon, titanium, chromium, manganese, iron, cobalt, nickel, silver, copper, zinc, and molybdenum. Among these, silicon, aluminum, and titanium are preferable because they have few resource restrictions and high visible light transmittance. Examples of the silicon alkoxide include tetramethoxysilane, tetraethoxysilane, and tetrapropoxysilane. Examples of the aluminum alkoxide include aluminum isopropoxide, aluminum ethoxide, and aluminum methoxide. Examples of the titanium alkoxide include titanium methoxy. And titanium ethoxide, titanium isopropoxide and the like. Examples of phosphoric acid include orthophosphoric acid (H ₃ PO ₄ ) and pyrophosphoric acid (H ₄ P ₂ O ₇ ). Orthophosphoric acid is preferable from the viewpoint of promoting the reaction rate of hydrolysis of the metal alkoxide and availability. Phosphoric acid also acts as an acid catalyst for hydrolysis of the metal alkoxide described below.

  In the composition for forming an antireflection film of the first embodiment, when the molar concentration of metal in the metal alkoxide is A mol / L and the molar concentration of phosphoric acid is B mol / L, B / A is 0. It is in the range of 0.002 to 0.1, preferably in the range of 0.01 to 0.05. If it is less than the lower limit of this range, there is a problem that the protective film formation effect of the phosphate is small, and if it exceeds the upper limit, there is a problem that the visible light transmittance due to precipitation of excessive phosphate is lowered.

[Method for producing antireflection film-forming composition containing no transparent oxide particles]
First, an organic solvent is added to and mixed with the metal alkoxide described above to prepare a first liquid. Examples of the organic solvent include propylene glycol monomethyl ether acetate, isopropyl alcohol, and ethanol. An organic solvent is added in a range of 1 to 20 parts by mass with respect to 1 part by mass of the metal alkoxide, and mixed in a temperature range of 30 to 80 ° C. Next, water, preferably ion-exchanged water and the above-described phosphoric acid are mixed in a temperature range of 30 to 80 ° C. to prepare a second liquid. The amount of water is 1 to 30 times mol, preferably 5 to 20 times mol, per 1 mol of the metal alkoxide of the first liquid. If it is less than the lower limit, the metal alkoxide is difficult to hydrolyze, and if it exceeds the upper limit, there is a problem of gelation. The amount of phosphoric acid is 0.002 to 0.1 mol, preferably 0.01 to 0.05 mol, per 1 mol of the metal alkoxide of the first liquid. B / A mentioned above is satisfy | filled by making the quantity of phosphoric acid into the said range.

  Next, the second liquid is added and mixed in a state where the first liquid is maintained at a temperature of 25 to 85 ° C. with a water bath or the like. Thereby, a metal alkoxide is hydrolyzed with water, and a hydrolyzate is produced | generated. At the same time, the phosphoric acid of the second liquid is dispersed in the dispersion medium composed of the first liquid and the second liquid. Thereby, the composition for forming an antireflection film according to the first embodiment is manufactured.

<Second Embodiment>
[Antireflection film-forming composition containing transparent oxide particles]
The composition for forming an antireflection film according to the second embodiment is configured by further dispersing transparent oxide particles in a dispersion medium containing the hydrolyzate of metal alkoxide and phosphoric acid according to the first embodiment. .
In the composition excluding the dispersion medium, the hydrolyzate is contained in an amount of 0.1 to 10 parts by mass in terms of oxide with respect to 1 part by mass of the transparent oxide particles.
The oxide particles have a primary particle diameter in the range of 1 to 50 nm, preferably 10 to 30 nm in terms of number average. One or more elements selected from the group consisting of silicon, zirconium, niobium, indium, zinc, tin, tungsten, gallium, antimony, aluminum, cerium and titanium as the metal elements constituting the transparent oxide particles Is exemplified.

[Method for Producing Composition for Forming Antireflection Film Containing Transparent Oxide Particles (Part 1)]
In the first method for producing the composition for forming an antireflection film containing transparent oxide particles, the dispersion medium containing the hydrolyzate of metal alkoxide and phosphoric acid prepared in the first embodiment, and the above-mentioned A sol in which transparent oxide particles are dispersed in alcohol, water, methyl ethyl ketone or the like is mixed. The mixing ratio at this time is a ratio of 10 to 9900 parts by mass, preferably 50 to 900 parts by mass, of the transparent oxide particles in the sol with respect to 100 parts by mass of the oxide of the hydrolyzate. If it is less than the lower limit of this range, there is a problem that the refractive index is small and a sufficient antireflection effect cannot be obtained, and if it exceeds the upper limit, there is a problem that the adhesion of the film is lowered. Thereby, the composition for forming an antireflection film according to the second embodiment is produced.

[Method for Producing Composition for Forming Antireflection Film Containing Transparent Oxide Particles (Part 2)]
In the second method for producing a composition for forming an antireflection film containing transparent oxide particles, first, as in the first embodiment, an organic solvent is added to and mixed with a metal alkoxide to prepare a first liquid. . Next, water, preferably ion-exchanged water, the above-described phosphoric acid, and the above-described sol in which the transparent oxide particles are dispersed are mixed in a temperature range of 30 to 80 ° C. to prepare a third liquid. The amount of water is 1 to 30 parts by mass, preferably 5 to 20 times by mass with respect to 1 part by mass of the first liquid. If it is less than this lower limit, the metal alkoxide is difficult to hydrolyze, and if it exceeds the upper limit, there is a problem of gelation. The quantity of phosphoric acid is 0.002-0.1 mass part with respect to 1 mass part of 1st liquid, Preferably it is 0.01-0.05 mass part. B / A mentioned above is satisfy | filled by making the quantity of phosphoric acid into the said range. The amount of the transparent oxide particles is 0.1 to 99 parts by mass, preferably 5 to 90 parts by mass with respect to 1 part by mass of the first liquid. If it is less than this lower limit, the refractive index of the antireflection film itself cannot be adjusted, and if it exceeds the upper limit, there is a problem that the adhesion of the film is lowered.

  Next, the first liquid is added to and mixed with the third liquid in a state where the temperature is maintained at 25 to 85 ° C. Thereby, a metal alkoxide is hydrolyzed with water, and a hydrolyzate is produced | generated. At the same time, the phosphoric acid and the transparent oxide particles of the third liquid are dispersed in the dispersion medium composed of the first liquid and the third liquid. Thereby, the composition for forming an antireflection film according to the second embodiment is produced.

[Production method of composite membrane]
As shown in FIG. 1, the transparent conductive film 11 formed on the substrate 10 and the antireflection film 12 formed on the transparent conductive film and having a refractive index lower than the refractive index of the transparent conductive film, A composite membrane 20 is manufactured. Further, as shown in FIG. 2, the transparent conductive film 11 formed on the base material 10, the antireflection film 12, and the protection having a refractive index lower than the refractive index of the antireflection film formed on the antireflection film. A composite membrane 30 including the membrane 13 can also be manufactured. The antireflection film 12 formed by the composition of the present invention is manufactured by applying the antireflection film forming composition of the first or second embodiment on a transparent conductive film, drying it, and then baking it. Is done. For the application of the present invention, various wet coating methods such as spray coating, dispenser coating, spin coating, knife coating, slit coating, ink jet coating, screen printing, offset printing, and die coating can be employed.

  Next, examples of the present invention will be described in detail together with comparative examples.

<Example 1>
First, tetraethoxysilane (TEOS) is prepared as silicon alkoxide, propylene glycol monomethyl ether acetate (PGMEA) in an amount of 1 part by mass with respect to 1 part by mass of TEOS is added as an organic solvent, and 30 ° C. in a separable flask. The first liquid was prepared by stirring at a temperature of 15 minutes for 15 minutes. Next, separately from this first liquid, 1 mol of TEOS and 1 mol of ion-exchanged water and 0.002 mol of orthophosphoric acid are charged into a beaker and mixed at a temperature of 30 ° C. The second liquid was prepared by stirring for 15 minutes. Next, after maintaining the prepared first liquid at a temperature of 30 ° C. in a water bath, the second liquid was added to the first liquid and stirred for 300 minutes while maintaining the temperature of 30 ° C. As a result, a composition for forming an antireflection film containing the hydrolyzate of silicon alkoxide and phosphoric acid in a dispersion medium was obtained.

<Examples 2 and 3 and Comparative Examples 1 and 2>
An antireflection film-forming composition was prepared in the same manner as in Example 1 except that the amount of orthophosphoric acid was 0.01 mol, 0.10 mol, 0.001 mol, and 0.15 mol, respectively, with respect to 1 mol of TEOS. Obtained.

<Examples 4 and 5>
An antireflection film-forming composition was obtained in the same manner as in Example 1, except that aluminum isopropoxide was used as the aluminum alkoxide instead of silicon alkoxide and tetraisopropyl orthotitanate was used as the titanium alkoxide.

<Example 6 and Comparative Example 3>
An antireflection film-forming composition was obtained in the same manner as in Example 1 except that pyrophosphoric acid and hydrochloric acid were used in place of orthophosphoric acid.

<Example 7>
In the dispersion medium containing the hydrolyzate of silicon alkoxide obtained in Example 1 and orthophosphoric acid, zirconium oxide (ZrO ₂ ) nanoparticles having a primary average particle diameter of 30 nm as transparent oxide particles are isopropyl. By mixing the sol dispersed in alcohol with stirring at a ratio of ₂ parts by mass of ZrO ₂ in the sol to 1 part by mass of SiO ₂ in the hydrolyzate, an antireflection film is formed. A composition was obtained.

<Examples 8 to 12>
ZrO ₂ in the sol with respect to 1 part by mass of SiO ₂ in the hydrolyzate is 0.08 parts by mass, 0.1 parts by mass, 15.0 parts by mass, 30.0 parts by mass and 32.0 parts by mass, respectively. A composition for forming an antireflection film was obtained in the same manner as in Example 7 except that.

<Examples 13 to 23>
Instead of zirconium oxide (ZrO ₂ ) nanoparticles, silica (SiO ₂ ), niobium oxide (Nb ₂ O ₅ ), indium oxide (In ₂ O ₃ ), zinc oxide (ZnO), tin oxide (SnO ₂ ), tungsten oxide (WO ₃ ), gallium oxide (Ga ₂ O ₃ ), antimony oxide (Sb ₂ O ₃ ), alumina (Al ₂ O ₃ ), cerium oxide (CeO ₂ ) and titania (TiO ₂ ) nanoparticles are used respectively. A composition for forming an antireflection film was obtained in the same manner as in Example 7 except that.

<Comparison test>
(Measurement of reflectance and refractive index of antireflection film)
In order to measure the reflectance of the antireflection film 12 alone, it was obtained in Examples 1 to 23 and Comparative Examples 1 to 3 on soda glass on which an Al-doped zinc oxide film was formed with a thickness of 50 nm by a sputtering method. Each composition for forming an antireflection film was applied by spin coating, dried at 50 ° C. under atmospheric pressure, and baked at 150 ° C. to obtain 26 types of antireflection films 12 having a thickness of 100 nm. Black vinyl tape is pasted on the back side of the sample of the antireflection film in consideration of the effect of back side reflection, and the spectrophotometer (model U-4000, manufactured by Hitachi High-Tech) is used to reflect at the wavelength of 550 nm that humans feel most dazzling. The rate was measured. Further, the refractive index of a sample of the same antireflection film was measured using a spectroscopic ellipsometer (model M-2000, manufactured by JAWoolam Japan) at a wavelength of 550 nm of helium laser light.

[Measurement of haze on transparent conductive film surface]
Instead of measuring the light transmittance of the transparent conductive film, the haze at the interface between the transparent conductive film and the antireflection film was measured. A transparent conductive film 11 having a thickness of 100 nm containing ITO particles having an average particle diameter of 20 nm is formed on a base material 10 which is a glass substrate shown in FIG. 23 and the anti-reflective film-forming compositions obtained in Comparative Examples 1 to 3 were each applied by spin coating, dried at 50 ° C. under atmospheric pressure, baked at 150 ° C., and baked at 26 ° C. An antireflection film 12 was obtained. The haze (cloudiness) at the interface between the transparent conductive film 11 and the antireflection film 12, that is, the surface of the transparent conductive film, was measured using a turbidimeter (model HV-V3, manufactured by Suga Test Instruments Co., Ltd.).

  Table 1 shows the measurement results of the contents of Examples 1 to 23 and Comparative Examples 1 to 3, the reflectance and refractive index of the antireflection film, and the haze of the transparent conductive film surface.

<Evaluation>
When the refractive index takes a refractive index between air and the transparent conductive film (AZO), the reflectance increases as compared with the case where there is no antireflection film. In Comparative Example 1, the phosphoric acid content was small, and as a result of elution of AZO, haze increased. In Comparative Example 2, as a result of too much phosphoric acid, curing is still insufficient and film haze is deteriorated. In Comparative Example 3, when phosphoric acid was not used, the Al-doped ZnO film was easily eluted by this hydrochloric acid. On the other hand, in the transparent conductive film of Examples 1-23, haze was between 0.01-0.05, and was a small value.

Claims (11)

Used to form an antireflective film having a refractive index lower than the refractive index by coating on a transparent conductive film, glass or translucent plastic having a refractive index in the range of 1.6 to 2.0 at a wavelength of 550 nm. In the composition for forming an antireflection film,
When a metal alkoxide hydrolyzate and phosphoric acid are included, the metal alkoxide has a metal molar concentration of A mol / L, and the phosphoric acid molar concentration of B mol / L. An antireflection film-forming composition, wherein A is in the range of 0.002 to 0.1.   Transparent oxide particles are further dispersed in a dispersion medium containing the hydrolyzate of the metal alkoxide and the phosphoric acid, and with respect to 1 part by mass of the transparent oxide particles in the composition excluding the dispersion medium. The composition for forming an antireflection film according to claim 1, which contains a hydrolyzate in an amount of 0.1 to 10 parts by mass in terms of oxide.   The composition for forming an antireflection film according to claim 1 or 2, wherein the metal alkoxide is silicon alkoxide, aluminum alkoxide or titanium alkoxide.   The metal element constituting the transparent oxide particles is one or more elements selected from the group consisting of silicon, zirconium, niobium, indium, zinc, tin, tungsten, gallium, antimony, aluminum, cerium and titanium. The composition for forming an antireflection film according to claim 2.   The composition for forming an antireflection film according to claim 2 or 4, wherein the transparent oxide particles have a primary particle diameter in the range of 1 to 50 nm in terms of number average. A method for producing the composition for forming an antireflection film according to claim 1, comprising:
Adding an organic solvent to the metal alkoxide and mixing to prepare the first liquid;
A step of preparing a second liquid by mixing water in an amount of 1 to 30 moles with respect to 1 mole of the metal alkoxide and phosphoric acid in an amount of 0.002 to 0.1 moles;
The first liquid is added to and mixed with the second liquid while maintaining the temperature at 25 to 85 ° C., and the hydrolyzate of the metal alkoxide and the phosphoric acid are composed of the first liquid and the second liquid. A method for producing an antireflective film-forming composition comprising the steps of:   In the sol with respect to 100 parts by mass of the oxide content of the hydrolyzate, a dispersion medium containing the hydrolyzate of the metal alkoxide and the phosphoric acid, and a sol in which transparent oxide particles are dispersed in alcohol, water, or methyl ethyl ketone. The manufacturing method of Claim 6 which further includes the process of mixing in the ratio used as the said transparent oxide particle content of 10-9900 mass parts. A method for producing the composition for forming an antireflection film according to claim 2, comprising:
Adding an organic solvent to the metal alkoxide and mixing to prepare the first liquid;
With respect to 1 part by mass of the first liquid, 1-30 parts by mass of water, 0.002-0.1 parts by mass of phosphoric acid, and 2-99 parts by mass of transparent. Mixing a sol in which oxide particles are dispersed to prepare a third liquid;
The first liquid is added to and mixed with the third liquid while maintaining the temperature at 25 to 85 ° C., and the hydrolyzate of the metal alkoxide, the phosphoric acid, and the transparent oxide particles are mixed with the first liquid. And a step of adding the dispersion liquid comprising the third liquid to the dispersion medium.   It forms by apply | coating the composition for anti-reflective film formation of Claim 1 or 3 or the composition for anti-reflective film formation manufactured by the method of Claim 6 on the transparent conductive film and the said transparent conductive film. A method for producing a composite film having an antireflection film.   The method for producing a composite film according to claim 9, wherein a protective film is formed on the antireflection film.   The transparent conductive film is tin-doped indium oxide (ITO) particles, aluminum-doped zinc oxide (AZO) particles, antimony-doped tin oxide (ATO) particles, boron-doped zinc oxide (BZO) particles, or The manufacturing method of the composite film of Claim 9 or 10 containing the titanium oxide (TNO) particle | grains which doped niobium.

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