JP5116285B2 - Base material with transparent coating - Google Patents

Description

The present invention relates to a substrate with a transparent coating comprising a substrate and a transparent coating formed on the substrate, the transparent coating comprising a matrix component and niobium oxide fine particles.
More specifically, since the transparent film contains niobium-based oxide fine particles, it has a high refractive index, excellent weather resistance, light resistance, adhesion to a substrate, scratch resistance, scratch strength, pencil hardness, etc. Relates to a substrate with a transparent coating in which no interference fringes are generated. Furthermore, it is related with the base material with a transparent film which was excellent in the antireflection performance, when a transparent film with a low refractive index was provided on the transparent film.

  In order to improve the scratch resistance of the substrate surface such as glass, plastic sheet, plastic lens, etc., it is known to form a transparent film (hereinafter sometimes referred to as a hard coat film) on the substrate surface. As a hard coat film, an organic resin film or an inorganic film is formed on the surface of glass, plastic or the like. Furthermore, it is practiced to further improve the scratch resistance by blending resin particles or inorganic particles such as silica and titanium oxide in an organic resin film or an inorganic film.

  At this time, a transparent film having a high refractive index is formed on a substrate having a high refractive index, and inorganic particles having a high refractive index such as titanium oxide are blended and used in such a transparent film having a high refractive index. Yes. However, particles such as titanium oxide may have insufficient weather resistance or inferior dispersibility.

In addition, in order to prevent reflection of the surface of a substrate such as glass, plastic sheet, plastic lens, etc., it is known to form an antireflection film on the surface. For example, by a coating method, a vapor deposition method, a CVD method, A film of a low refractive index substance such as fluororesin or magnesium fluoride is formed on the surface of a glass or plastic substrate, or a coating liquid containing low refractive index fine particles such as silica fine particles is applied to the substrate surface. A method for forming an antireflection coating is known (see, for example, JP-A-7-133105). Further, in order to impart antistatic performance and electromagnetic wave shielding performance to the base material, a conductive film containing metal fine particles and conductive oxide fine particles is also formed.

  Thus, even when an antireflection film and / or a conductive film is provided, a hard coat film may be formed between the substrate and the antireflection film and / or the conductive film in order to improve the scratch resistance. Has been done.

However, in the conventional hard coat film, particularly when the substrate is a resin-made substrate, the adhesion to the substrate and the scratch resistance of the film itself may be insufficient.
Further, even when an antireflection film and / or a conductive film is provided on the hard coat film, the conventional hard coat film may be scratched after the hard coat film is formed or dust may adhere due to static electricity. In addition, there is a problem that the yield of the product is lowered due to a decrease in transparency and haze of the substrate with conductive film finally produced.

  In addition, when the substrate is a resin film substrate having a refractive index of 1.6 or more such as PET, it is necessary to match the refractive index of the hard coat film to be formed with the refractive index of the substrate in order to prevent interference fringes. Therefore, it is necessary to add particles with a high refractive index, such as titanium oxide. However, in the case of titanium oxide, there is an ultraviolet absorbing ability, and when the matrix component of the hard coat film is an ultraviolet curable resin, insufficient curing occurs and the hard coat The strength as a film may not be obtained. Furthermore, the weather resistance and light resistance of the hard coat film may be lowered due to the photocatalytic ability of titanium oxide.

  Under such circumstances, the present inventor has intensively studied to solve the above problems, and as a result, if niobium-based oxide fine particles are blended in the transparent film, the hard coat film does not hinder the curability and weather resistance. It was found that a transparent film having excellent interference and no interference fringes can be obtained.

  That is, in the present invention, a transparent film-coated base having a transparent film excellent in weather resistance, light resistance, ultraviolet shielding performance and the like while being excellent in adhesion to the substrate, scratch resistance, hardness and the like and suppressing generation of interference fringes. The purpose is to provide materials.

The summary of the substrate with a transparent coating according to the present invention is as follows.
[1] A substrate and a transparent film formed on the substrate,
A substrate with a transparent coating, wherein the transparent coating comprises a matrix component and niobium oxide fine particles mainly composed of niobium oxide.
[2] The niobium-based oxide fine particles are mixed with niobium oxide, Fe, Ce, Si, Zr, Al, Ti, S
The substrate with a transparent coating according to [1], which is a composite oxide fine particle containing at least one oxide selected from oxides of n, Sb, W, and Zn.
[3] The niobium-based oxide fine particles are composed of niobium-based oxide core particles mainly composed of niobium oxide or core particles made of other inorganic oxides. Nb, Fe, Ce, Si, Zr, Al, Ti , Sn, Sb
The substrate with a transparent coating according to [1] or [2], which has a core-shell structure coated with one or more oxides selected from oxides of W, Zn.
[4] The substrate with a transparent coating according to [1] to [3], wherein the niobium-based oxide fine particles have an average particle diameter in the range of 1 to 200 nm.
[5] The base material with a hard coat film according to [1] to [4], wherein the matrix component is a thermosetting resin, a thermoplastic resin, or an ultraviolet curable resin.
[6] The substrate with a transparent coating according to [1] to [5], wherein an antireflection film is further formed on the transparent coating.
[7] The substrate with a transparent coating according to [1] to [6], wherein the substrate has a refractive index of 1.55 or more.
[8] The substrate with a transparent coating according to [1] to [7], wherein the substrate is a polyethylene terephthalate (PET) film substrate.

In the present invention, since the transparent coating provided on the substrate surface contains niobium-based oxide fine particles, weather resistance, light resistance, curability, ultraviolet shielding performance, adhesion to the substrate, scratch resistance, It is possible to provide a substrate with a transparent coating that is excellent in scratch strength, pencil hardness, and the like and that does not generate interference fringes.
Furthermore, when a transparent film having a low refractive index is provided on the transparent film, a substrate with a transparent film excellent in antireflection performance can be provided.

Hereinafter, the substrate with a transparent coating according to the present invention will be described.
[Base material with transparent coating]
The substrate with a transparent coating of the present invention comprises a substrate and a transparent coating formed on the substrate.

Substrate As the substrate used in the present invention, a known substrate can be used without particular limitation, and glass, in particular, a resin film substrate such as a plastic sheet, a plastic film, a plastic panel made of polyethylene terephthalate (PET). The material can be preferably used.

Transparent coating The transparent coating is characterized by comprising a matrix component and niobium oxide fine particles.
Niobium-based oxide fine particles The niobium-based oxide fine particles used in the transparent film of the present invention are fine particles mainly composed of niobium oxide (Nb ₂ O ₅ ), and include Nb ₂ O ₅ or Nb ₂ O ₅ and Fe. , Ce, Si, Zr, Al, Ti, Sn, Sb, W, and complex oxide fine particles containing one or more oxides selected from oxides of Zn. Among these, composite oxide fine particles containing one or more oxides selected from oxides of Fe, Ce, Si, Zr, Al, Ti, and Sn can be suitably used.

  When these oxides are included, the resulting coating solution for forming a transparent film is excellent in stability. Further, the obtained transparent film has a high refractive index and is transparent, and can suppress interference fringes even when the refractive index of the base material is 1.60 or more, particularly 1.66 or more, hot water resistance, weather resistance, It excels in light resistance, ultraviolet absorption performance, scratch resistance, abrasion resistance, flexibility and dyeability, and also has excellent adhesion to the substrate.

In addition, when any of Si, Al, Zr, and Sn oxides is included, the stability of the coating liquid for forming a transparent film is further excellent, and the obtained transparent film has a high refractive index and is transparent. The interference fringes can be suppressed even when the refractive index of the glass is 1.55 or more, particularly 1.60 or more, hot water resistance, weather resistance, light resistance, ultraviolet absorption performance, scratch resistance, abrasion resistance, flexibility Excellent in dyeability and dyeability, and also in excellent adhesion to the substrate.

The niobium oxide content in the niobium-based oxide fine particles is 50% by weight or more as Nb ₂ O ₅ ,
Furthermore, it is preferable that it exists in the range of 60 to 95 weight%. If the content of niobium oxide is small, it may vary depending on the refractive index of other oxides, but interference fringes may not be sufficiently suppressed. Also, depending on the type of other oxides, Weather resistance, light resistance, and ultraviolet absorption performance may be insufficient.

  The average particle diameter of the niobium-based oxide fine particles is preferably in the range of 1 to 200 nm, more preferably 2 to 100 nm, and particularly preferably 2 to 50 nm. When the average particle size is large, the obtained transparent film may become cloudy, and when the average particle size is small, it is difficult to obtain. Even if it is obtained, the adhesion between the transparent film and the substrate is transparent. Insufficient hardness of the coating may result in inferior scratch resistance and abrasion resistance and at the same time the refractive index may not be sufficiently high.

Alternatively, as the niobium-based oxide fine particles used in the present invention, the niobium-based oxide fine particles as described above are used as the core particles, or other inorganic oxide fine particles are used as the core particles, and the core particles are used as Nb, Fe, Ce. Particles having a core-shell structure coated with one or more oxides selected from oxides of Si, Zr, Al, Ti, Sn, Sb, W, and Zn can also be suitably used.

  When other inorganic oxide fine particles are used as the core particles, the other inorganic oxides are composed of oxides of Ti, Zr, Sn, Ce and complex oxides thereof, and the refractive index is approximately 1.6 or more. Any inorganic oxide can be suitably used.

Further, when niobium-based oxide fine particles are used as core particles, the shell does not necessarily contain niobium oxide, but when other inorganic oxide fine particles are used as the core particles, the shell may contain niobium oxide. In any case, the content of niobium oxide in the niobium-based oxide fine particles finally used is preferably 50% by weight or more as Nb ₂ O ₅ , and more preferably 70% by weight or more. Is preferred. If the content of Nb ₂ O ₅ is small, the resulting niobium-based oxide fine particles may have insufficient semiconductor, optical properties, dielectric properties, ultraviolet shielding properties, light resistance, weather resistance, and the like.

Also in the case of niobium-based oxide fine particles having a core-shell structure, the average particle diameter is preferably in the range of 1 to 200 nm, more preferably 2 to 100 nm, particularly 2 to 50 nm.
The content of niobium-based oxide fine particles in the transparent film is preferably in the range of 5 to 90% by weight, more preferably 10 to 80% by weight.

  When the content of niobium oxide fine particles in the transparent film is small, a hard coat film having excellent adhesion to the base material, scratch resistance, scratch strength, pencil hardness, etc., and excellent film curability and weather resistance. It may be difficult to obtain.

  If the content of niobium oxide fine particles in the transparent film is large, the matrix component will decrease, making it difficult to obtain a transparent film with excellent adhesion to the substrate, scratch resistance, scratch strength, pencil hardness, etc. It is.

  As described above, there are three forms of the niobium-based oxide fine particles used in the present invention. The first form is niobium-based oxide fine particles composed only of niobium oxide, the second form is niobium-based oxide fine particles composed of a complex oxide composed of niobium oxide and another oxide, The form is niobium oxide fine particles having a core-shell structure.

The niobium-based oxide fine particles used in the present invention are produced, for example, by the following production method. The niobium-based oxide fine particles thus obtained have a uniform particle size and excellent transparency and stability, and are low in the content of impurities such as alkalis and anions and stabilizers, and thus are suitable for the transparent coating of the present invention. Can be used.
[Production Method of Niobium Oxide Fine Particle Dispersion]
The niobium-based oxide fine particles used in the present invention require a solution obtained by dissolving and / or peptizing a niobic acid dispersion by adding hydrogen peroxide when the main component of the fine particles is a niobium oxide. According to the above, it is produced by hydrothermal treatment at 80 to 300 ° C. in the presence of a compound other than the niobium compound.

Niobic acid is not particularly limited as long as it can be dissolved and / or peptized in hydrogen peroxide, and conventionally known niobic acid can be used. Here, niobic acid refers to a hydroxide of niobium (or a hydrate of niobium oxide), which can be represented by Nb ₂ O ₅ .nH ₂ O, where n is approximately in the range of 1 to 5. .

Such niobic acid can be obtained, for example, by the following method.
(1) Using niobium pentachloride and / or niobium oxychloride as a starting material, hydrolyzing and then washing.
(2) A solution obtained by dissolving niobium metal or niobium oxide with an acid or an aqueous solution of niobium pentafluoride is neutralized and / or hydrolyzed and then washed.
(3) The solution of orthoniobate or metaniobate is neutralized and / or hydrolyzed and then washed.

In the above, acid or alkali can be added to neutralization or hydrolysis as necessary. As the alkali, ammonia water is suitable.
The washing can be performed by an ion exchange resin method, a filter method, an ultrafiltration method, or the like. The alkali and the acid radical in the niobic acid after washing are 0.5% by weight with respect to Nb ₂ O ₅ of niobic acid. % Or less is preferable. If it exceeds 0.5% by weight, there will be too much alkali and / or acid radicals in the finally obtained niobium oxide fine particle dispersed sol, and the stability and transparency of the sol will decrease, and there will be no stability. Therefore, there is a problem that the use is limited.

  When producing composite oxide particles composed of niobium oxide and another oxide, a mixed dispersion or mixed solution of compounds of elements other than niobium is used together with the niobic acid dispersion. Elements other than niobium are as described above, and nitrates, sulfates, chloride salts, organic acid salts, oxides, and the like of these elements are used. Specifically, ferrous chloride, ferric chloride, ferric nitrate, cerium nitrate, aluminum chloride, aluminum sulfate, titanium tetrachloride, titanyl sulfate, tin nitrate, antimony pentachloride, ammonium tungstate, zinc nitrate, Examples thereof include iron oxide, cerium oxide, silica, aluminum oxide, titanium oxide, tin oxide, antimony oxide, tungsten oxide, and zinc oxide. Here, the oxide includes hydroxide and hydrate, and these sols are preferably used.

Hydrogen peroxide is added to a mixed dispersion or solution of compounds of elements other than niobic acid and niobium, or to a dispersion or solution of compounds of elements other than niobium (hereinafter referred to as niobic acid, etc.). Is converted from niobic acid or the like to an oxide, and hydrogen peroxide having a concentration of approximately 5 to 40% by weight to 1 part by weight of the total oxide is converted to H ₂ O ₂ by 1.5 to 6 parts by weight. Preferably 2
Add ~ 4 parts by weight. The concentration of niobic acid, etc. at this time is 0.5 to 10 in terms of oxide.
It adjusts so that it may become weight%, Preferably 1-5 weight%.

Hydrogen peroxide is added to the niobic acid dispersion or solution prepared as described above and a dispersion or solution with a compound of an element other than niobium (hereinafter collectively referred to as niobic acid or the like). The amount used is 1.5 to 6 weights by converting niobic acid or the like into an oxide, and converting hydrogen peroxide having a concentration of approximately 5 to 40% by weight into H ₂ O ₂ with respect to 1 part by weight of the total oxide. Parts, preferably 2-4 parts by weight. The concentration of niobic acid, etc. at this time is 0.5 to 0.5 in terms of oxide.
It is adjusted to 10 wt%, preferably 1 to 5 wt%.

When the amount of H ₂ O ₂ used is small, niobic acid and compounds of elements other than niobium are not completely dissolved and / or peptized and unreacted niobic acid and the like remain, which is not preferable. When the number of moles of H ₂ O ₂ with respect to niobic acid or the like is too large, the dissolution and / or peptization rate is high, and the reaction is completed at a low temperature or in a short time, but excess hydrogen peroxide remains in the system. In other words, it is not economical, and there is a risk that oxygen gas is generated during the hydrothermal treatment or that the pressure increases.

If the amount of H ₂ O ₂ used for niobic acid or the like is within the above range, niobic acid can be completely dissolved and / or peptized in 0.5 to 5 hours, depending on the heating and melting temperature.
Also, when the concentration of niobic acid or the like is low, the production efficiency is low because the concentration is too low, and the viscosity of the niobium-based oxide fine particle dispersion obtained even if the concentration of niobic acid or the like is too high becomes too stable or stable. It may be lacking.

  In addition, it can heat as needed when melt | dissolving and / or peptizing. The heating temperature is preferably in the range of approximately 30 to 100 ° C. If the heating temperature is low, dissolution and peptization may be insufficient, and the particle size distribution of the niobium oxide fine particle dispersion obtained by hydrothermal treatment may become non-uniform, and dissolution and / or dissolution may occur. The glue time may become too long and the production efficiency may be lowered. Further, when the heating temperature exceeds 100 ° C., the dissolution and / or peptization time is shortened, but the particle size distribution of the fine particles of the niobium oxide fine particle dispersion obtained by hydrothermal treatment tends to be non-uniform. is there.

As described above, the first method for producing niobium-based oxide fine particles used in the present invention comprises adding hydrogen peroxide to a niobic acid dispersion liquid / solution or a mixed dispersion liquid or mixture of compounds of elements other than niobic acid and niobium. In addition, the solution obtained by dissolution and / or peptization is hydrothermally treated at 80 to 300 ° C. In the second production method, hydrogen peroxide is added to a niobic acid dispersion and dissolved and / or peptized, and hydrogen peroxide is added to and dissolved in a dispersion or solution of a compound of an element other than niobium. And / or the solution obtained by peptization is mixed and hydrothermally treated at 80 to 300 ° C. In the third production method, a dispersion or solution of a compound of an element other than niobium is mixed with a solution obtained by dissolving and / or peptizing hydrogen peroxide in a niobic acid dispersion, Hydrothermally treat with.

  The niobium-based oxide fine particles used in the present invention can be prepared by any of these methods. If the hydrothermal treatment temperature is low, niobic acid is not sufficiently oxidized by dehydration. Further, the obtained niobium-based oxide fine particle dispersion may lack stability, and if the hydrothermal treatment temperature is in the range of 80 to 300 ° C., not only niobium-based oxide fine particles having a uniform particle diameter can be obtained, A niobium oxide fine particle dispersion having excellent stability can be obtained. A preferable hydrothermal treatment temperature is in the range of 100 to 250 ° C.

The hydrothermal treatment described above is preferably performed in the presence of the following particle growth regulator.
Particle Growth Modifier As the particle growth regulator used in the present invention, carboxylic acid or carboxylate, hydroxycarboxylic acid (having a carboxyl group and an alcoholic hydroxyl group in one molecule), and hydroxycarboxylate are used.

  Specifically, monocarboxylic acids and monocarboxylic acid salts such as formic acid, acetic acid, succinic acid, acrylic acid (unsaturated carboxylic acid), gluconic acid, malic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid And polyvalent carboxylic acids such as sebacic acid, maleic acid, fumaric acid, and phthalic acid, and polyvalent carboxylic acid salts.

  Further, α-lactic acid, β-lactic acid, γ-hydroxyvaleric acid, glyceric acid, tartaric acid, citric acid, tropic acid, hydroxycarboxylic acid and hydroxycarboxylate of benzylic acid can be mentioned.

  Such a particle growth regulator may be hydrolyzed in addition to the niobium compound when preparing niobic acid, or may be added to the prepared niobic acid or the like, or dissolved or peptized by adding hydrogen peroxide. It may be added after.

The amount of the particle growth regulator used is the molar ratio (Pm) / (Nm) of the total number of moles (Nm) of niobium compounds, niobic acid, and compounds of elements other than niobium and the number of moles of grain growth regulator (Pm). Is 0.0
It is preferably in the range of 1-1, more preferably 0.1-0.5.

  When the molar ratio is small, the particle growth regulator is insufficient, and the niobium oxide fine particles obtained by hydrothermal treatment may have nonuniform particle sizes or coarse particles. Even if the molar ratio is too high, the effect of suppressing the generation of coarse particles evenly and making the particle diameter more uniform, and in addition, there are many particle growth regulators and the yield may be reduced. There is a problem that the economy is reduced.

In the present invention, the hydrothermal treatment is preferably performed in the presence of seed particles.
Seed particles include group III of the periodic table such as Al, group IV such as Ti, Zr, Si, and Sn, group V such as V, Nb, and Sb, group VI such as W, and group VIII such as Fe. An inorganic compound of one or more elements selected from the group is used.

  As the form of the inorganic compound, salts, oxides, hydroxides, oxyacids or oxyacid salts are used. Preferably, a gel or sol such as oxide, hydroxide or oxyacid is used. Among them, the sol has high dispersibility, stability, and uniform particle size, and niobium-based oxide fine particles having a uniform particle size can be obtained.

  The average particle size of the seed particles is preferably less than 5 nm, and particularly preferably in the range of 0.5 to 3 nm. Moreover, it is preferable that the usage-amount of a seed particle exists in the range of 1-30 weight% of the total weight as an oxide of the compound of niobium compound, niobic acid, and elements other than niobium, Furthermore, it is 2-20 weight%. If the amount of seed particles used is small, the effect of making the particle diameter uniform may be insufficient, and if the seed particles are other than niobium compounds even if the amount of seed particles used is excessive, the inclusion of niobium-based oxides Insufficient amounts may reduce the semiconductor, optical properties, dielectric properties, ultraviolet shielding properties, light resistance, weather resistance, and the like of the resulting niobium-based oxide fine particles, thereby limiting the application.

Furthermore, in the present invention, hydrothermal treatment can be performed in the presence of core particles instead of the seed particles.
As the core particles, oxide or hydroxide particles having the same kind as the seed particles and having an average particle diameter of 5 to 50 nm, preferably 10 to 30 nm are used.
The amount of the core particles used is preferably in the range of 5 to 50% by weight, more preferably 10 to 30% by weight, based on the total weight of oxides of niobium compounds, niobic acid, and compounds of elements other than niobium. In particular, the content of Nb ₂ O _{5 in} the finally obtained niobium-based oxide fine particles is preferably 50% by weight or more. When the content of Nb ₂ O ₅ in the niobium-based oxide fine particles is small, the semiconductor, optical properties, dielectric properties, ultraviolet shielding properties, light resistance, weather resistance, etc. of the obtained niobium-based oxide fine particles are insufficient. There is.

Particles having a core-shell structure can be prepared by the following method.
The niobium-based oxide fine particles obtained as described above are used as core particles, and (1) a niobic acid dispersion / solution, (2) a dispersion or solution of a compound of elements other than niobic acid and niobium. (3) A solution obtained by adding hydrogen peroxide to a dispersion or solution of a compound of an element other than niobium and dissolving and / or peptizing is mixed, and hydrothermally treated at 80 to 300 ° C. A niobium oxide fine particle dispersion can also be prepared.

  In this case, niobium-based oxide particles having a core-shell structure in which the niobium-based oxide fine particles are the core and the core particles are coated with an oxide derived from a solution in which niobic acid or the like is dissolved and / or peptized. A fine particle dispersion is obtained. For example, in the case of (1), niobium-based oxide fine particles obtained by coating niobium-based oxide fine particles as core particles with niobium oxide are obtained. In the case of (2), niobium-based oxide fine particles as core particles are converted to niobium. Niobium-based oxide fine particles coated with a complex oxide of an element other than acid and niobium can be obtained. In the case of (3), the niobium-based oxide fine particles as core particles are converted to oxides or complex oxides that do not contain niobium oxide. Niobium-based oxide fine particles coated with can be obtained.

  Furthermore, inorganic oxide fine particles composed of oxides other than niobium are used as the core particles, and (1) niobic acid dispersion / solution or (2) compounds of elements other than niobic acid and niobium are used in the fine particle dispersion. It is also possible to prepare a niobium oxide fine particle dispersion by mixing a solution obtained by adding hydrogen peroxide to a dispersion or solution of the above and dissolving and / or peptizing the solution and hydrothermally treating at 80 to 300 ° C.

  The elements other than niobium in the above are preferably at least one selected from Fe, Ce, Si, Zr, Al, Ti, Sn, Sb, W, and Zn. The compounds of elements other than niobium are the same as described above. A compound is used. The hydrothermal treatment temperature is preferably in the range of 80 to 300 ° C, more preferably 100 to 250 ° C, as described above.

The niobium-based oxide fine particle dispersion obtained as described above can be used after removing remaining ions with an ion exchange resin or the like, if necessary. However, the niobium oxide fine particle dispersion obtained in the present invention is not necessarily required because impurities and ions are reduced in advance in the washing step.

  Moreover, it can also be used by substituting with a desired solvent such as alcohols such as methanol and ethanol, glycols such as 1.3-butylene glycol, and glycerin with a rotary evaporator. The niobium oxide fine particle dispersion obtained by the above method is very stable even when the dispersion medium is an organic solvent, and does not aggregate, gel, or precipitate.

The average particle size of the fine particles of the niobium-based oxide fine particle dispersion obtained by the production method of the present invention is generally in the range of 1 to 100 nm, preferably 2 to 60 nm.
If the average particle size is small, the stability may be insufficient and a fine particle dispersed sol may not be obtained.If the average particle size is large, the particles are too large to settle or have poor transparency. May be sufficient.

Moreover, the niobium oxide fine particle dispersion obtained as described above can be used for various purposes as it is, or can be diluted or concentrated as necessary.
The concentration of such a niobium-based oxide fine particle dispersion is preferably in the range of 5 to 40% by weight, more preferably 10 to 30% by weight as an oxide. Within this range, there is no practical problem and the dispersibility of the dispersion is excellent.

In the present invention, the obtained niobium-based oxide fine particle dispersion can be dried and calcined as necessary to be used as niobium-based oxide fine particles.
The drying temperature is not particularly limited as long as niobium oxide fine particle powder can be obtained, and it is usually dried at room temperature to 120 ° C.

  The firing temperature may be in the range of 300 to 700 ° C. When firing in such a temperature range, oxidization or crystallization sufficiently proceeds depending on the component, and niobium excellent in optical properties, ultraviolet shielding properties, weather resistance, etc. Systemic oxide fine particles can be obtained. When firing at a high temperature, depending on the particle size, the particles may aggregate or be fused together.

  In the present invention, the niobium-based oxide fine particle dispersion obtained by the above method may be dried in advance and used in the form of fine powder. The dispersion medium composed of water and / or an organic solvent may be colloidal. When used in the state of a dispersion dispersed in, an excellent substrate with a transparent film can be obtained.

  The niobium-based oxide fine particles can be used by treating the surface with silicone, a fluorine compound or the like in order to impart water repellency and oil repellency when blended in the coating liquid for forming a transparent film.

  Furthermore, the niobium-based oxide fine particles can be used by surface treatment or surface coating with a hydrolyzable organosilicon compound such as a silane coupling agent. The surface treatment method or the surface coating method is not particularly limited, and for example, the surface is coated with an organosilane compound by adding a hydrolyzable organosilicon compound to the dispersion and reacting for a predetermined time at a predetermined temperature.

The kind of the hydrolyzable organosilicon compound used here is appropriately selected according to the application.
Specific examples of hydrolyzable organosilicon compounds for surface modification include tetraalkoxysilanes such as tetramethoxysilane and tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriacetoxysilane, and methyltripropoxy. Silane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropyltripropoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ- (β- Trialkoxy or triacyloxysilanes such as lysidoxyethoxy) propyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, and dimethyldimethoxysilane, Dimethyldiethoxysilane, phenylmethyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylphenyldiethoxysilane, γ-chloropropylmethyldimethoxysilane, dimethyldiacetoxysilane, γ-methacryloxypropyl Dialkoxysilanes or diacyloxysilanes such as methyldimethoxysilane, γ-mercaptoprovirmethyldimethoxysilane, γ-aminopropylmethyldimethoxysilane Or trimethylchlorosilane, and the like can be used alone or in combination of two or more.

  In order to improve the surface of the niobium oxide fine particles, the alcohol solution of the hydrolyzable organosilicon compound and the niobium oxide fine particle dispersion are mixed, and an acid or alkali is used as a hydrolysis catalyst as necessary. And reacting at a constant temperature for a certain period of time, and then separating the water in the mixed solution to produce niobium oxide fine particles dispersed in an organic solvent. If it does in this way, the dispersion stability in an organic solvent will improve.

As a matrix component contained in the matrix component transparent film, a resin matrix is suitable.
As such a resin matrix, specifically, any of known thermosetting resins, thermoplastic resins, ultraviolet curable resins and the like can be employed as coating resins.

  Examples of such resins include conventionally used thermoplastic resins such as polyester resins, polycarbonate resins, polyamide resins, polyphenylene oxide resins, thermoplastic acrylic resins, vinyl chloride resins, fluororesins, vinyl acetate resins, and silicone rubbers. , Urethane resins, melamine resins, silicon resins, butyral resins, reactive silicone resins, phenol resins, epoxy resins, unsaturated polyester resins, thermosetting resins such as thermosetting acrylic resins, and the like. Further, it may be a copolymer or modified body of two or more of these resins.

  These resins may be emulsion resins, water-soluble resins, and hydrophilic resins. Further, in the case of a thermosetting resin, it may be an ultraviolet curable type or an electron beam curable type, and in the case of a thermosetting resin, a curing catalyst may be included.

Transparent coating In the present invention, a transparent coating comprising the above-described matrix component and niobium-based oxide fine particles mainly composed of niobium oxide is formed on the substrate surface.

The thickness of the transparent film is preferably in the range of 0.1 to 20 μm, more preferably 0.2 to 10 μm, and particularly preferably 0.2 to 5 μm.
When the thickness of the transparent film is less than the lower limit of the above range, the transparent film is thin and the stress applied to the surface of the transparent film cannot be sufficiently absorbed, resulting in an insufficient pencil hardness.

  When the thickness of the transparent film exceeds the upper limit of the above range, it becomes difficult to apply the film so that the film thickness is uniform or to dry uniformly. Therefore, the transparent film obtained by generation of cracks and voids is difficult. The strength and transparency may be insufficient.

Such a transparent film can be formed by applying a coating solution containing a matrix-forming component that forms the matrix component and the niobium-based oxide fine particles.
In preparing the coating liquid, it is preferable to use it as a dispersion liquid in which niobium-based oxide fine particles are dispersed in a dispersion medium in order to prepare a coating liquid having a uniform dispersion and excellent stability.

The niobium oxide fine particle dispersion may be either an aqueous dispersion sol or an organic solvent dispersion sol dispersed in an organic solvent such as alcohol.
Furthermore, the niobium-based oxide fine particles may have a surface treated with a known silane coupling agent.

  The niobium oxide fine particle dispersion and the matrix-forming component thus prepared can be diluted with an appropriate solvent to form a coating solution for forming a transparent film. Further, a surfactant or the like can be added to the coating solution in order to improve dispersibility and stability.

  In addition, the coating solution may contain a solvent that dissolves the matrix-forming component and can easily volatilize. If the matrix-forming component is a thermosetting resin, a curing agent is blended as necessary. It may be.

  In the case of a thermoplastic resin, such a coating solution is applied to a substrate by a known method such as a dip method, a spray method, a spinner method, or a roll coating method, dried, and cured in the case of a thermosetting resin. If necessary, a transparent film can be formed by heat treatment at a temperature lower than the softening point of the substrate.

The base material with a transparent coating of the present invention may be provided with an antireflection film on the transparent coating.
Antireflection Film The antireflection film used in the present invention is not particularly limited as long as it has antireflection performance, and a conventionally known antireflection film can be used. Specifically, if the refractive index is lower than that of the transparent coating, antireflection performance is provided.

Such an antireflection film comprises an antireflection film forming matrix and, if necessary, a low refractive index component.
The matrix for forming an antireflection film is a component that can form an antireflection film, and can be selected and used from the viewpoints of adhesion to a substrate, hardness, coatability, and the like.

Specifically, the same matrix component as the transparent film forming component can be used.
It is also possible to use a hydrolyzable organosilicon compound as the matrix. Specifically, for example, a partial hydrolyzate of alkoxysilane is suitably used by adding water and an acid or alkali as a catalyst to a mixture of alkoxysilane and alcohol.

Examples of hydrolyzable organosilicon compounds include those represented by the general formula RnSi (OR ') 4-n [R, R': hydrocarbon groups such as alkyl groups, aryl groups, vinyl groups, acrylic groups, n = 0, 1, 2, Alternatively, alkoxysilane represented by 3] can be used. In particular, tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, and tetraisopropoxysilane are preferably used.

Low refractive index components that may be optionally included include CaF2, NaF, NaAlF6, and MgF.
In addition to low refractive index substances such as silica, silica particles (silica particles, silica hollow particles, silica / alumina composite oxide particles), porous silica particles, and the like can be given.

  For example, composite oxide fine particles in which the surface of porous inorganic oxide fine particles disclosed in Japanese Patent Application Laid-Open No. 7-133105 filed by the applicant of the present application is coated with silica, Japanese Patent Application Laid-Open No. 2001-233611, and Japanese Patent Application Laid-Open No. 2003-192994. By using the hollow silica fine particles disclosed in Japanese Patent Publication No. JP-A No. 2000-184, an antireflection film having a low refractive index and excellent antireflection performance can be obtained.

  The content of the low refractive index component in the antireflection film is preferably 90% by weight or less, more preferably 50% by weight or less. If the content of the low refractive index component is too large, the strength of the coating is reduced, or a transparent coating (intermediate film when another transparent coating (also referred to as an intermediate film) described later) is formed, etc. Adhesion with the substrate may be insufficient.

The thickness of the antireflection film is preferably 50 to 300 nm, more preferably 80 to 200 nm.
When the thickness of the antireflection film is less than the above range, the film strength, antireflection performance, and the like may be inferior. If the thickness of the antireflection film exceeds the above range, cracks may occur in the film, which may increase the strength of the film, and the film may be too thick, resulting in insufficient antireflection performance.

The refractive index of such an antireflective film varies depending on the mixing ratio of the low refractive index component and the resin matrix and the refractive index of the resin used, but is usually in the range of 1.28 to 1.50. preferable. When the refractive index of the antireflection film exceeds 1.50, although depending on the refractive index of the substrate, the antireflection performance may be insufficient, and it is difficult to obtain a film having a refractive index of less than 1.28. is there.

The antireflection film is formed by applying an antireflection film forming coating liquid containing the above-described antireflection film forming matrix and, if necessary, a low refractive index component and a solvent.
Any solvent can be used as long as it easily evaporates and does not adversely affect the resulting antireflection film.

  The coating solution for forming the antireflection film is not particularly limited, and is applied to the substrate by a known method such as a dipping method, a spray method, a spinner method, or a roll coating method, as in the case of forming the transparent film. In particular, when the forming component is a thermosetting resin, curing of the antireflection film may be promoted by heat treatment, ultraviolet irradiation treatment, electron beam irradiation treatment, etc. When a functional organosilicon compound is contained, hydrolysis and polycondensation of the hydrolyzable organosilicon compound may be promoted.

The substrate with a transparent coating according to the present invention as described above contains niobium-based oxide fine particles in the transparent coating, so there is no interference fringe, adhesion to the substrate, scratch resistance, film hardness, etc. Is excellent.
[Example]
EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited by these Examples.
[Example 1]
Nb based oxide particles (A1) were mixed to prepare a concentration 35.3% by weight of the KNbO ₃ solution 1917g of water 23083g of the dispersion, the concentration of 2.71 wt% of KNbO ₃ solution, to which the 1 mol / L acetic acid Added and neutralized. The pH at this time was 5.5. This was filtered and washed with distilled water to obtain 1990 g of niobic acid gel. The solid content concentration of this gel was 24.01% by weight in terms of Nb ₂ O ₅ .

After adding 33540 g of water to 1460 g of the resulting niobic acid gel and stirring sufficiently, 4000 g of 35% by weight hydrogen peroxide was added and dissolved by heating at 80 ° C. for 2 hours. Water was added to the resulting solution to adjust the concentration to 0.5% by weight in terms of Nb ₂ O ₅ , and then hydrothermal treatment was performed at 150 ° C. for 18 hours in an autoclave.

Next, this was concentrated to obtain 3500 g of an aqueous dispersion of niobium oxide fine particles (A1) having a concentration of 10% by weight in terms of Nb ₂ O ₅ .
Next, a portion of the niobium oxide fine particle (A1) dispersion is substituted with methanol for the dispersion medium, further substituted with isopropyl alcohol (IPA), and concentrated to give a niobium oxide having a solid content of 20% by weight. A fine particle (A1) IPA dispersion was obtained.

For each particle, the average particle size was measured by a laser method (manufactured by PARTICS SIZING SYSTEM: NICOM 380), the uniformity of the particle size was observed, and the acid radicals in the particles were measured, and the results are shown in the table. Moreover, stability, transparency, and the refractive index of particle | grains are evaluated about each dispersion liquid, and a result is shown in a table | surface.
Uniformity of particle diameter Niobium oxide fine particles (A1) Transmission electron micrographs of niobium oxide fine particles (A1) collected from the IPA dispersion were taken and evaluated according to the following criteria.
Almost no particles smaller than 1/2 of the average particle diameter or particles larger than 2 times are recognized: ○
Slightly less than 1/2 the average particle size or more than twice the average particle size: Δ
Particles with an average particle size of ½ or less or twice or more are clearly recognized: X
Measurement of IPA dispersion stability Viscosity of niobium oxide fine particle dispersion immediately after adjusting to a concentration of 20% by weight in terms of Nb ₂ O ₅ ,
The viscosity after heating at 50 ° C. for 10 days was measured and evaluated according to the following criteria.
Viscosity increase rate is less than 10%: ◎
Viscosity increase rate less than 10-20%: ○
Viscosity increase rate 20 to less than 50%: Δ
Viscosity increase rate 50% or more: ×
Transparency Measurement A niobium oxide fine particle dispersion liquid adjusted to a concentration of 0.1% by weight in terms of Nb ₂ O ₅ was put into a 10 mm thick quartz cell, and a transmittance measuring device (manufactured by JASCO Corporation: V- The transmittance was measured at 550 and a wavelength of 550 nm, and evaluated according to the following criteria.

Transmission 90% or more: ○
Transmittance less than 90%: ×
Preparation of coating liquid for forming transparent coating (H-1) 83.58 g of isopropyl alcohol dispersion of niobium-based oxide fine particles (A1) and UV curable resin (Unidic 17-824-9, manufactured by Dainippon Ink, Inc.) 7.66 g (solid content concentration 78.9%), UV curable resin (Nippon Kayaku Co., Ltd. Kayrad KS-HDDA, solid content concentration 100%) 0.67 g, isopropyl alcohol 4.56 g, butyl cellosolve 2.62 g, light A coating liquid (H-1) for forming a transparent film was prepared by sufficiently mixing 0.91 g of an initiator (Irgacure 184 manufactured by Ciba Specialty Co., Ltd., dissolved in IPA and having a solid content of 50%).

Production of substrate with transparent coating (F-1) Coating solution for forming transparent coating (H-1) was applied to a PET film (thickness: 100 μm, refractive index: 1.65) by a bar coater method at 70 ° C. After drying for 1 minute, it was cured by irradiation with 600 mJ / cm ² with a high-pressure mercury lamp (80 W / cm) to prepare a substrate with transparent coating (F-1). The thickness of the transparent film at this time was 5 μm.

The total light transmittance and haze were measured with a haze meter (Nippon Denshoku Co., Ltd .: NDH2000), and the results are shown in Table 1.
Furthermore, pencil hardness, scratch resistance, adhesion and weather resistance were evaluated by the following methods and evaluation criteria, and the results are shown in Table 1.

Measurement of pencil hardness It measured with the pencil hardness tester according to JIS-K-5400.
Measurement of scratch resistance: Using # 0000 steel wool, sliding 50 times at a load of 500 g / cm 2, visually observing the surface of the film, evaluating according to the following criteria, and the results are shown in the table.

Evaluation criteria:
No streak injury is found: ◎
Slightly scratched streak: ○
Many scratches are found in the streak: △
The surface has been cut entirely: ×
Adhesive transparent coated substrate (F-1) surface with 11 parallel scratches with a knife at 1mm vertical and horizontal intervals to make 100 squares, and cellophane tape (registered trademark) is adhered to it, Adhesiveness was evaluated by classifying the number of squares remaining after the cellophane tape (registered trademark) was peeled off into the following four stages. The results are shown in Table 1.

Number of remaining cells: 95 or more: ◎
Number of remaining squares 90-94: ○
Number of remaining squares: 85-89:
Number of remaining squares: 84 or less: ×
After exposure for 200 hours using a weather meter with a weather-resistant carbon arc (manufactured by Suga Test Instruments Co., Ltd.), the total light transmittance was measured, compared with the total light transmittance before exposure, and evaluated according to the following criteria: .

Reduction in total light transmittance is less than 0.5%: ◎
Reduction in total light transmittance is 0.5 to less than 1.0%: ○
Reduction in total light transmittance is 1.0 to less than 2.0%: Δ
Reduction of total light transmittance is 2.0% or more: ×
[Example 2]
Preparation of Niobium Oxide Fine Particles (A2) Dispersion Niobium Oxide Fine Particles in the same manner as in Example 1 except that 1 mol / L oxalic acid was used instead of the 1 mol / L acetic acid solution of Example 1. (A2) An IPA dispersion was obtained.

  The niobium oxide fine particles (A2) were measured for average particle size, uniformity of particle size, and acid radicals in the particles, and the results are shown in the table. Moreover, stability, transparency, and the refractive index of particle | grains are evaluated about a dispersion liquid, and a result is shown in a table | surface.

Preparation of coating liquid for forming transparent film (H-2) 83.58 g of niobium oxide fine particles (A2) IPA dispersion, UV curable resin (Unidic 17-824-9, manufactured by Dainippon Ink Co., Ltd., solid content) 7.66 g (concentration 78.9%), UV curable resin (Nippon Kayaku Co., Ltd. Kayrad KS-HDDA, solid content concentration 100%) 0.67 g, isopropyl alcohol 4.56 g, butyl cellosolve 2.62 g, photoinitiator A transparent coating film forming coating solution (H-2) was prepared by sufficiently mixing 0.91 g (Irgacure 184 manufactured by Ciba Specialty Co., Ltd., dissolved in IPA and having a solid content of 50%).

Production of base material with hard coat film (F-2) In Example 1, the base material with transparent coating (F-2) was prepared in the same manner except that the coating liquid for forming a transparent coating (H-2) was used. . The thickness of the transparent film at this time was 5 μm.

The obtained hard coat film was evaluated for total light transmittance, haze, pencil hardness, scratch resistance, adhesion and weather resistance, and the results are shown in Table 1.
[Example 3]
Preparation of Niobium Oxide Fine Particles (A3) Dispersion Niobium oxide fine particles (A3) in the same manner as in Example 1 except that 1 mol / L hydrochloric acid was used instead of the 1 mol / L acetic acid solution of Example 1. ) An IPA dispersion was obtained.

  The niobium oxide fine particles (A3) were measured for average particle size, uniformity of particle size, and acid radicals in the particles, and the results are shown in the table. Moreover, stability, transparency, and the refractive index of particle | grains are evaluated about a dispersion liquid, and a result is shown in a table | surface.

Preparation of coating liquid for forming transparent film (H-3) Niobium oxide fine particles (A3) 83.58 g of IPA dispersion, UV curable resin (Unidic 17-824-9, manufactured by Dainippon Ink Co., Ltd., solid content) 7.66 g (concentration 78.9%), UV curable resin (Nippon Kayaku Co., Ltd. Kayrad KS-HDDA, solid content concentration 100%) 0.67 g, isopropyl alcohol 4.56 g, butyl cellosolve 2.62 g, photoinitiator A transparent coating film forming coating solution (H-3) was prepared by sufficiently mixing 0.91 g (Irgacure 184 manufactured by Ciba Specialty Co., Ltd., dissolved in IPA and having a solid content of 50%).

Production of substrate with transparent film (F-3) In Example 1, a substrate with transparent film (F-3) was prepared in the same manner except that the coating liquid for forming a transparent film (H-3) was used. The thickness of the transparent film at this time was 5 μm.

The obtained hard coat film was evaluated for total light transmittance, haze, pencil hardness, scratch resistance, adhesion and weather resistance, and the results are shown in Table 1.
[Example 4]
Preparation of Niobium Oxide Fine Particle (A4) Dispersion 1000 g of the niobium oxide fine particle (A1) methanol dispersion obtained in Example 1 and 1000 g of pure water were placed in a reaction vessel, heated to 63 ° C., and then stirred with tetraethoxy 2 liters of a mixed solution of silane and methanol (weight ratio 153/1000) was gradually added. After completion of the addition, the solution was further aged by maintaining the temperature at 63 ° C., then substituted with IPA and concentrated, and niobium oxide fine particles surface-modified with tetraethoxysilane having a solid concentration of 20% by weight ( A4) An IPA dispersion was obtained.

The stability, transparency, and refractive index of the niobium oxide fine particles (A4) IPA dispersion were evaluated, and the results are shown in the table.
Preparation of coating liquid for forming transparent film (H-4) Niobium oxide fine particles (A4) 83.58 g of IPA dispersion, UV curable resin (Unidic 17-824-9, manufactured by Dainippon Ink Co., Ltd., solid content) 7.66 g (concentration 78.9%), UV curable resin (Nippon Kayaku Co., Ltd. Kayrad KS-HDDA, solid content concentration 100%) 0.67 g, isopropyl alcohol 4.56 g, butyl cellosolve 2.62 g, photoinitiator A transparent coating-forming coating solution (H-4) was prepared by thoroughly mixing 0.91 g (Irgacure 184 manufactured by Ciba Specialty Co., Ltd., dissolved in IPA and having a solid content of 50%).

Production of substrate with transparent film (F-4) In Example 1, a substrate with transparent film (F-4) was prepared in the same manner except that the coating liquid for forming a transparent film (H-4) was used. The thickness of the transparent film at this time was 5 μm.

The obtained transparent film was evaluated for total light transmittance, haze, pencil hardness, scratch resistance, adhesion and weather resistance, and the results are shown in Table 1.
[Example 5]
Preparation of Niobium Oxide Fine Particle (A5) Dispersion Niobium Oxidation Surface-Modified with Methyltrimethoxysilane as in Example 4 except that tetraethoxysilane in Example 4 was replaced with methyltrimethoxysilane Fine particles (A5)
An IPA dispersion was obtained.

The stability, transparency, and refractive index of the niobium oxide fine particles (A5) IPA dispersion were evaluated, and the results are shown in the table.
Preparation of coating liquid for forming transparent film (H-5) 83.58 g of niobium oxide fine particles (A5) IPA dispersion, UV curable resin (Unidic 17-824-9, manufactured by Dainippon Ink Co., Ltd., solid content) 7.66 g (concentration 78.9%), UV curable resin (Nippon Kayaku Co., Ltd. Kayrad KS-HDDA, solid content concentration 100%) 0.67 g, isopropyl alcohol 4.56 g, butyl cellosolve 2.62 g, photoinitiator A transparent coating-forming coating solution (H-5) was prepared by sufficiently mixing 0.91 g (Irgacure 184 manufactured by Ciba Specialty Co., Ltd., dissolved in IPA and having a solid content of 50%).

Production of substrate with transparent film (F-5) A substrate with transparent film (F-5) was prepared in the same manner as in Production Example 1 except that the coating liquid for forming a transparent film (H-5) was used. The thickness of the transparent film at this time was 5 μm.

The obtained transparent film was evaluated for total light transmittance, haze, pencil hardness, scratch resistance, adhesion and weather resistance, and the results are shown in Table 1.
[Example 6]
Preparation of Niobium Oxide Fine Particle (A6) Dispersion γ-Glycidoxypropyltriethoxy in the same manner as in Example 4 except that tetraethoxysilane in Example 4 was replaced with γ-glycidoxypropyltriethoxysilane. A niobium-based oxide fine particle (A6) IPA dispersion surface-modified with silane was obtained.

The stability, transparency, and refractive index of the niobium-based oxide fine particles (A6) IPA dispersion were evaluated, and the results are shown in the table.
Preparation of coating liquid for forming transparent film (H-6) Niobium oxide fine particles (A6) 83.58 g of IPA dispersion, UV curable resin (Unidic 17-824-9, manufactured by Dainippon Ink Co., Ltd., solid content) 7.66 g (concentration 78.9%), UV curable resin (Nippon Kayaku Co., Ltd. Kayrad KS-HDDA, solid content concentration 100%) 0.67 g, isopropyl alcohol 4.56 g, butyl cellosolve 2.62 g, photoinitiator A transparent coating film forming coating solution (H-6) was prepared by sufficiently mixing 0.91 g (Irgacure 184 manufactured by Ciba Specialty Co., Ltd., dissolved in IPA and having a solid content of 50%).

Production of substrate with transparent coating (F-6) A coating solution for forming a transparent coating (H-6) was applied to a PET film (thickness: 100 μm, refractive index: 1.65) by a bar coater method at 120 ° C. Dried for 1 minute.
The thickness of the transparent film at this time was 5 μm.

The obtained transparent film was evaluated for total light transmittance, haze, pencil hardness, scratch resistance, adhesion and weather resistance, and the results are shown in Table 1.
[Example 7]
Preparation of Niobium Oxide Fine Particle (A7) Dispersion 706.91 g of niobium pentafluoride was dissolved in water, and ammonia water having a concentration of 15 wt% was added thereto.
69 L was added over 40 minutes. This was filtered and washed to obtain 2000 g of niobic acid gel. The solid content concentration of this gel was 25.0% by weight in terms of Nb ₂ O ₅ .

After adding 33540 g of water to 1300 g of the resulting niobic acid gel and stirring sufficiently, 3000 g of 35% by weight hydrogen peroxide solution was added and dissolved by heating at 80 ° C. for 2 hours. Water was added to the obtained solution to adjust the concentration to 0.5% by weight in terms of Nb ₂ O ₅ , and then hydrothermal treatment was performed at 200 ° C. for 18 hours in an autoclave.

Next, this was concentrated to obtain 3500 g of an aqueous dispersion of niobium oxide fine particles (A7) having a concentration of 10% by weight in terms of Nb ₂ O ₅ .
Next, for a part of the aqueous dispersion of niobium oxide fine particles (A7), the water in the dispersion medium is replaced with methanol and further replaced with isopropyl alcohol (IPA), and the niobium oxide fine particles with a concentrated solid content concentration of 20% by weight ( A7) An IPA dispersion was obtained.

  The niobium oxide fine particles (A7) were measured for average particle size, uniformity of particle size, and acid radicals in the particles, and the results are shown in the table. Moreover, stability, transparency, and the refractive index of particle | grains are evaluated about a dispersion liquid, and a result is shown in a table | surface.

Preparation of coating liquid for transparent film formation (H-7)

83.58 g of an isopropyl alcohol dispersion of niobium-based oxide fine particles (A7), 7.66 g of an ultraviolet curable resin (Unidic 17-824-9, manufactured by Dainippon Ink Co., Ltd., solid content concentration 78.9%), ultraviolet rays Cured resin (Nippon Kayaku Co., Ltd. Kayrad KS-HDDA, solid content concentration 100%) 0.67 g, isopropyl alcohol 4.56 g, butyl cellosolve 2.62 g, photoinitiator (Irgacure 184 manufactured by Ciba Specialty Co., Ltd.) A transparent coating film forming coating solution (H-7) was prepared by sufficiently mixing 0.91 g dissolved in IPA and having a solid concentration of 50%).
Production of substrate with transparent coating (F-7) A coating solution for forming a transparent coating (H-7) was applied to a PET film (thickness: 100 μm, refractive index: 1.65) by a bar coater method at 70 ° C. After drying for 1 minute, it was cured by irradiation with 600 mJ / cm ² with a high-pressure mercury lamp (80 W / cm) to prepare a substrate with transparent coating (F-7). The thickness of the transparent film at this time was 5 μm.

About the obtained substrate with transparent coating (F-7), total light transmittance, haze, pencil hardness, scratch resistance,
The adhesion and weather resistance were evaluated, and the results are shown in Table 1.
[Example 8]
Preparation of Niobium Oxide Fine Particle (A8) Dispersion The surface was modified with tetraethoxysilane in the same manner as in Example 4 except that the methanol-dispersed niobium oxide fine particle (A7) dispersion obtained in Example 7 was used. A niobium-based oxide fine particle (A8) IPA dispersion was obtained.

The stability, transparency, and refractive index of the niobium oxide fine particles (A8) IPA dispersion were evaluated, and the results are shown in the table.
Preparation of coating liquid for forming transparent film (H-8) 83.58 g of isopropyl alcohol dispersion of niobium oxide fine particles (A8) and UV curable resin (Unidic 17-produced by Dainippon Ink Co., Ltd.) 824-9, solid content concentration 78.9%) 7.66 g, UV curable resin (Kayarad KS-HDDA, Nippon Kayaku Co., Ltd., solid content concentration 100%) 0.67 g, isopropyl alcohol 4.56 g, butyl cellosolve 2 .62 g and 0.91 g of photoinitiator (Irgacure 184 manufactured by Ciba Specialty Co., Ltd., dissolved in IPA and having a solid content of 50%) were sufficiently mixed to prepare a coating solution for forming a transparent film (H-8). .

Production of substrate with transparent coating (F-8) A substrate with transparent coating (F-8) was prepared in the same manner as in Example 1 except that the coating solution for forming a transparent coating (H-8) was used. The thickness of the transparent film at this time was 5 μm.

The obtained hard coat film was evaluated for total light transmittance, haze, pencil hardness, scratch resistance, adhesion and weather resistance, and the results are shown in Table 1.
[Example 9]
Preparation of Niobium Oxide Fine Particle (A9) Dispersion Niobium pentachloride was hydrolyzed with water, filtered and washed to obtain 2780 g of a niobic acid gel. The solid content concentration of this gel was 22.7% by weight in terms of Nb ₂ O ₅ . This niobic acid gel is weighed to 500 g in terms of Nb ₂ O ₅ , placed in a 10 L beaker, further charged with 1800 g of 35% by weight hydrogen peroxide, heated with stirring, and heated at 70 ° C. for 2 Dissolved for hours. Next, 2000 g of water was added thereto, heated at 70 ° C. for 1 hour, water was added again to obtain a 1% by weight solution in terms of Nb ₂ O ₅ concentration, and this was placed in an autoclave and subjected to hydrothermal treatment at 220 ° C. for 15 hours. .

Next, this was concentrated to obtain 500 g of an aqueous dispersion of niobium oxide fine particles (A9) having a concentration of 10% by weight in terms of Nb ₂ O ₅ .
Next, a part of the aqueous dispersion of niobium-based oxide fine particles (A9) is replaced with methanol, further replaced with isopropyl alcohol (IPA), concentrated, and concentrated to give a niobium-based oxide having a solid content concentration of 20% by weight. Fine particle (A9) IPA dispersion was obtained.

  The niobium-based oxide fine particles (A9) were measured for average particle size, uniformity of particle size, and acid radicals in the particles, and the results are shown in the table. Moreover, stability, transparency, and the refractive index of particle | grains are evaluated about a dispersion liquid, and a result is shown in a table | surface.

Preparation of coating liquid for forming transparent film (H-9) 83.58 g of isopropyl alcohol dispersion of niobium-based oxide fine particles (A9) and UV curable resin (Unidic 17-824-9 manufactured by Dainippon Ink Co., Ltd.) 7.66 g (solid content concentration 78.9%), UV curable resin (Nippon Kayaku Co., Ltd. Kayrad KS-HDDA, solid content concentration 100%) 0.67 g, isopropyl alcohol 4.56 g, butyl cellosolve 2.62 g, light A coating solution (H-9) for forming a transparent film was prepared by thoroughly mixing 0.91 g of an initiator (Irgacure 184 manufactured by Ciba Specialty Co., Ltd., dissolved in IPA and having a solid content of 50%).

Production of substrate with transparent coating (F-9) A substrate with transparent coating (F-9) was prepared in the same manner as in Example 1 except that the coating solution for forming a transparent coating (H-9) was used. The thickness of the transparent film at this time was 5 μm.

The obtained hard coat film was evaluated for total light transmittance, haze, pencil hardness, scratch resistance, adhesion and weather resistance, and the results are shown in Table 1.
[Example 10]
Preparation of Niobium Oxide Fine Particle (A10) Dispersion Niobium pentachloride was hydrolyzed with water, filtered and washed to obtain 2780 g of a niobic acid gel.
The solid content concentration of this gel was 22.7% by weight in terms of Nb ₂ O ₅ . This niobic acid gel is weighed to 500 g in terms of Nb ₂ O ₅ , placed in a 50 L container containing 22797 g of water, further charged with 5714 g of 35% by weight hydrogen peroxide, and heated with stirring. It melt | dissolved at 70 degreeC for 2 hours. Subsequently, 19286 g of water was added thereto to make a 1% by weight solution in terms of Nb ₂ O ₅ concentration. Subsequently, 333 g of silica sol having an average particle diameter of 7 nm as core particles and a SiO ₂ concentration of 15% by weight and 4662 g of water were mixed, placed in an autoclave, and hydrothermally treated at 220 ° C. for 15 hours.

Next, this was concentrated to obtain 5500 g of a niobium oxide fine particle (A10) aqueous dispersion having a concentration of 10% by weight in terms of (Nb ₂ O ₅ + SiO ₂ ).
Next, a portion of the aqueous dispersion of niobium-based oxide fine particles (A10) is replaced with methanol, further replaced with isopropyl alcohol (IPA), and concentrated to concentrate a niobium-based oxide having a solid content of 20% by weight. A fine particle (A10) IPA dispersion was obtained.

The niobium oxide fine particles (A10) were measured for average particle size, uniformity of particle size, and acid radicals in the particles, and the results are shown in the table. Moreover, stability, transparency, and the refractive index of particle | grains are evaluated about a dispersion liquid, and a result is shown in a table | surface.

Preparation of coating liquid for forming a transparent film (H-10) A coating liquid for forming a transparent film (H-10) was prepared in the same manner as in Example 1 except that the niobium oxide fine particles (A10) IPA dispersion was used. .

Production of substrate with transparent coating (F-10) A substrate with transparent coating (F-10) was prepared in the same manner as in Example 1 except that the coating solution for forming a transparent coating (H-10) was used. The thickness of the transparent film at this time was 5 μm.

The obtained hard coat film was evaluated for total light transmittance, haze, pencil hardness, scratch resistance, adhesion and weather resistance, and the results are shown in Table 1.
[Example 11]
Preparation of Niobium Oxide Fine Particle (A11) Dispersion Niobium pentachloride and ferric chloride were hydrolyzed with water, washed by filtration, and 2780 g of a mixed gel of niobic acid and iron hydroxide was obtained. The solid content concentration of this gel was 23.5% by weight in terms of (Nb ₂ O ₅ + Fe ₂ O ₃ ). This mixed gel of niobic acid and iron hydroxide was weighed so as to be 500 g in terms of (Nb ₂ O ₅ + Fe ₂ O ₃ ), put into a 50 L container containing 22872 g of water, and an excess of 35% by weight concentration. 5714 g of hydrogen oxide water was added, heated with stirring, dissolved at 70 ° C. for 2 hours, and then 19286 g of water was added thereto to give a 1% by weight solution in terms of (Nb ₂ O ₅ + Fe ₂ O ₃ ). Subsequently, 333 g of silica sol having an average particle diameter of 7 nm as core particles and a SiO ₂ concentration of 15% by weight and 4662 g of water were mixed, and this was placed in an autoclave and hydrothermally treated at 220 ° C. for 15 hours.

Next, this was concentrated to obtain 5238 g of an aqueous dispersion of niobium oxide fine particles (A11) having a concentration of 10% by weight in terms of (Nb ₂ O ₅ + Fe ₂ O ₃ + SiO ₂ ).
Next, a part of the aqueous dispersion of niobium-based oxide fine particles (A11) is replaced with methanol and further replaced with isopropyl alcohol (IPA) and concentrated to concentrate a niobium-based oxide having a solid concentration of 20% by weight. A fine particle (A11) IPA dispersion was obtained.

The average particle diameter, the uniformity of the particle diameter, and the acid radical in the particles were measured for the niobium oxide fine particles (A11), and the results are shown in Table 1. Moreover, stability, transparency, and the refractive index of particle | grains are evaluated about a dispersion liquid, and a result is shown in a table | surface.

Preparation of coating liquid for forming transparent film (H-11) A coating liquid for forming transparent film (H-11) was prepared in the same manner as in Example 1 except that the niobium oxide fine particles (A11) IPA dispersion was used. .

Production of substrate with transparent film (F-11) A substrate with transparent film (F-11) was prepared in the same manner as in Example 1 except that the coating liquid for forming a transparent film (H-11) was used. The thickness of the transparent film at this time was 5 μm.

The obtained hard coat film was evaluated for total light transmittance, haze, pencil hardness, scratch resistance, adhesion and weather resistance, and the results are shown in Table 1.
[Example 12]
Preparation of niobium oxide fine particle (A12) dispersion
Preparation of core particles In the same manner as in Example 3, niobium-based oxide fine particles (A3) in water dispersion for core particles were obtained. The average particle diameter of the niobium-based oxide fine particles was 20 nm.
Preparation of Zirconium Compound Solution A 15% aqueous ammonia solution was added to an aqueous solution having a ZrO ₂ concentration of 2 wt. The slurry was washed and filtered to give 10% by weight of the cake as ZrO _2. After adding 3.08 kg of water to 60 g of this cake and adding KOH aqueous solution to make it alkaline, 120 g of hydrogen peroxide was added thereto and heated to give 299 g of 2 wt% zirconium hydrogen peroxide-dissolved aqueous solution as ZrO _2. Prepared.
Preparation of Silicic Acid Solution A commercially available water glass was diluted with water and then dealkalized with a cation exchange resin to prepare 926 g of a silicic acid solution having a SiO ₂ concentration of 2% by weight. 14 kg of water was added to 3500 g of the niobium oxide fine particle (A3) dispersion for core particles prepared above to obtain a solid concentration of 2% by weight, and then heated to 90 ° C., and 299 g of a hydrogen peroxide-dissolved aqueous solution of zirconium and silica. 926 g of acid solution was mixed. Next, the mixed solution was hydrothermally treated at 200 ° C. for 18 hours in an autoclave, and then concentrated to form a pale milky white transparent niobium oxide particle having a solid content concentration of 10% by weight. An aqueous dispersion of niobium oxide fine particles (A12) coated with a product was obtained.

Next, a part of the aqueous dispersion of niobium-based oxide fine particles (A12) was replaced with methanol, further substituted with isopropyl alcohol (IPA), and concentrated to obtain a niobium-based oxide having a solid content of 20% by weight. Fine particle (A12) IPA dispersion was obtained.

The niobium-based oxide fine particles (A12) were measured for average particle size, uniformity of particle size, and acid radicals in the particles, and the results are shown in the table. Moreover, stability, transparency, and the refractive index of particle | grains are evaluated about a dispersion liquid, and a result is shown in a table | surface.

Preparation of coating liquid for forming a transparent film (H-12) A coating liquid for forming a transparent film (H-12) was prepared in the same manner as in Example 1 except that the niobium oxide fine particles (A12) IPA dispersion was used. .

Production of substrate with transparent film (F-12) In Example 1, a substrate with transparent film (F-12) was prepared in the same manner except that the coating liquid for forming a transparent film (H-12) was used. The thickness of the transparent film at this time was 5 μm.

The obtained hard coat film was evaluated for total light transmittance, haze, pencil hardness, scratch resistance, adhesion and weather resistance, and the results are shown in Table 1.
[Example 13]
Preparation of niobium oxide fine particle (A13) dispersion
Preparation of core particles Titanium tetrachloride was hydrolyzed with water, filtered and washed to obtain 2780 g of titanic acid gel. The solid content concentration of this gel was 9.4% by weight in terms of TiO ₂ . This titanic acid gel is weighed to 500 g in terms of TiO 2, placed in a 50 L container containing 22882 g of water, and further 5714 g of hydrogen peroxide solution having a concentration of 35% by weight, and heated with stirring at 90 ° C. Dissolved for 2 hours. Subsequently, 19286 g of water was added thereto to obtain a 0.5% by weight solution in terms of TiO ₂ concentration. This was put into an autoclave and hydrothermally treated at 150 ° C. for 15 hours. Subsequently, this was concentrated to obtain 5238 g of a titanium oxide fine particle dispersion having a concentration of 1.5% by weight in terms of TiO ₂ and an average particle diameter of 12 nm.

Preparation of niobium compound solution Niobium pentachloride was hydrolyzed with water, filtered and washed to obtain 2780 g of a gel of niobic acid. The solid content concentration of this gel was 22.7% by weight in terms of Nb ₂ O ₅ . This niobic acid gel is weighed to 500 g in terms of Nb ₂ O ₅ , placed in a 50 L container containing 22797 g of water, further charged with 5714 g of 35% by weight hydrogen peroxide, and heated with stirring. It melt | dissolved at 70 degreeC for 2 hours. Next, 19286 g of water was added thereto to obtain a 1% by weight niobium hydrogen peroxide-dissolved aqueous solution in terms of Nb ₂ O ₅ concentration.
Preparation of Zirconium Compound Solution A 15% aqueous ammonia solution was added to an aqueous solution having a ZrO ₂ concentration of 2% by weight with 1710 g of zirconium oxychloride added to 1280 g of water to obtain a slurry having a pH of 8.5. The slurry was washed and filtered to give 10% by weight of the cake as ZrO _2. After adding 30.8 kg of water to 600 g of this cake and adding KOH aqueous solution to make it alkaline, 1200 g of hydrogen peroxide was added and heated, and 2990 g of hydrogen peroxide-dissolved aqueous solution of 2 wt% zirconium as ZrO ₂ was added. Prepared.

5238 g of the titanium oxide fine particle dispersion for core particles prepared above is heated to 90 ° C. and mixed with a hydrogen peroxide-dissolved aqueous solution of niobium and 2990 g of a hydrogen peroxide-dissolved aqueous solution of zirconium, and this mixture is then placed in an autoclave. After hydrothermal treatment at 180 ° C. for 18 hours, niobium-based oxidation in which transparent titanium oxide fine particles with a concentration of 10% by weight and solid milk concentration are coated with a composite oxide composed of niobium oxide and zirconium oxide. Fine particle (A13) aqueous dispersion was obtained.

Next, a portion of the aqueous dispersion of niobium-based oxide fine particles (A13) is replaced with methanol, further replaced with isopropyl alcohol (IPA), concentrated, and concentrated to obtain a niobium-based oxide having a solid content of 20% by weight. Fine particle (A13) IPA dispersion was obtained.

The niobium-based oxide fine particles (A13) were measured for average particle size, uniformity of particle size, and acid radicals in the particles, and the results are shown in the table. Moreover, stability, transparency, and the refractive index of particle | grains are evaluated about a dispersion liquid, and a result is shown in a table | surface.
Preparation of coating liquid for forming transparent film (H-13) A coating liquid for forming transparent film (H-13) was prepared in the same manner as in Example 1 except that the niobium oxide fine particles (A13) IPA dispersion was used. .

Production of substrate with transparent film (F-13) In Example 7 except that the transparent film forming coating solution (H-13) was used, a substrate with a transparent film was formed, and then an antireflection film was formed. A substrate with transparent coating (F-13) was prepared.

The obtained substrate with a transparent coating (F-13) was evaluated for total light transmittance, haze, pencil hardness, scratch resistance, adhesion and weather resistance, and Table 1 shows the results.
[Example 14]
Nb based oxide particles (A14) were mixed to prepare a concentration 35.3% by weight of the KNbO ₃ solution 1917g of water 23083g of the dispersion, the concentration of 2.71 wt% of KNbO ₃ solution, to which the 1 mol / L acetic acid Added and neutralized. The pH at this time was 5.5. This was filtered and washed with distilled water to obtain 1990 g of niobic acid gel. The solid content concentration of this gel was 24.01% by weight in terms of Nb ₂ O ₅ .

Preparation of seed particle dispersion Water was added to a portion of 498 g of niobic acid gel to give a niobic acid gel dispersion having a concentration of 2% by weight in terms of Nb ₂ O ₅ , and this was irradiated with ultrasonic waves for 20 minutes. 5978 g of a seed particle dispersion was prepared. The average particle size of the seed particles was about 1 nm.

35823 g of water was added to 1492 g of the remaining niobic acid gel, and after sufficient stirring, 6000 g of 35% by weight hydrogen peroxide water was added and dissolved by heating at 80 ° C. for 2 hours. Water was added to the resulting solution to adjust the concentration to 0.5% by weight in terms of Nb ₂ O ₅ , 5978 g of seed particle dispersion was added thereto, and hydrothermal treatment was performed at 180 ° C. for 18 hours in an autoclave.

Subsequently, this was concentrated to obtain 3500 g of an aqueous dispersion of niobium oxide fine particles (A14) having a concentration of 10% by weight in terms of Nb ₂ O ₅ .
Next, a part of the aqueous dispersion of niobium-based oxide fine particles (A14) is replaced with methanol, further substituted with isopropyl alcohol (IPA), and concentrated to obtain a niobium-based oxide having a solid content of 20% by weight. Fine particle (A14) IPA dispersion was obtained.

The niobium oxide fine particles (A14) were measured for average particle size, uniformity of particle size, and acid radicals in the particles. The results are shown in Table 1. Moreover, stability, transparency, and the refractive index of particle | grains are evaluated about each dispersion liquid, and a result is shown in a table | surface.

Preparation of Transparent Film Forming Coating Liquid (H-14) A transparent film forming coating liquid (H-14) was prepared in the same manner as in Example 1 except that the niobium oxide fine particles (A14) IPA dispersion was used.

Production of substrate with transparent film (F-14) A substrate with transparent film (F-14) was prepared in the same manner as in Example 1 except that the coating liquid for forming a transparent film (H-14) was used. The thickness of the transparent film at this time was 5 μm.

The obtained hard coat film was evaluated for total light transmittance, haze, pencil hardness, scratch resistance, adhesion and weather resistance, and the results are shown in Table 1.
[Example 15]
Preparation of coating solution (D-1) for antireflection film formation
As a low refractive index component, silica-based hollow fine particle dispersion sol (manufactured by Catalyst Kasei Kogyo Co., Ltd .: Thruria, concentration 20.5% by weight, dispersion medium: isopropyl alcohol) was used.
33 g of a dispersion obtained by diluting this sol with isopropyl alcohol to a solid content concentration of 5% by weight and an ultraviolet curable resin (Dainippon Ink Co., Ltd .: Unidic 17-824-9, solid content concentration of 78.9%) 1.54 g , Photoinitiator (Irgacure 184, IPA, manufactured by Ciba Specialty Co., Ltd.)
(1) (Solid content concentration: 10%) 0.42 g and isopropanol and butyl rosolve 1/1 (weight ratio) mixed solvent 65.46 g were mixed thoroughly to obtain a coating solution for forming an antireflection film (D-1)
Was prepared.
Production of substrate with transparent film (F-15) A coating liquid for forming a transparent film (H-4) prepared in the same manner as in Example 4 was placed on a PET film (thickness: 100 μm, refractive index: 1.65). After coating by a coater method and drying at 70 ° C. for 1 minute, the substrate was cured by irradiation with 600 mJ / cm ² with a high-pressure mercury lamp (80 W / cm) to prepare a substrate with transparent coating (F-15). The thickness of the transparent film at this time was 5 μm.

Next, an antireflection film-forming coating solution (D-1) was applied onto the transparent film by a bar coater method, and the temperature was 70 ° C
After drying for 1 minute, after drying at 70 ° C. for 1 minute, the substrate with a transparent coating (F-15) provided with an antireflection film was cured by irradiation with 600 mJ / cm ² with a high-pressure mercury lamp (80 W / cm). ) Was prepared.
At this time, the thickness of the antireflection film was 80 nm.

The obtained transparent film-coated substrate (F-15) was evaluated for total light transmittance, haze, bottom reflectance, luminous reflectance, pencil hardness, scratch resistance, adhesion and weather resistance, and the results are shown in Table 1. Shown in
[Example 16]
Production of substrate with transparent coating (F-16) A coating solution for forming a transparent coating (H-13) prepared in the same manner as in Example 13 was placed on a PET film (thickness: 100 μm, refractive index: 1.65). After coating with a coater method and drying at 70 ° C. for 1 minute, the substrate was cured by irradiation with 600 mJ / cm ² with a high-pressure mercury lamp (80 W / cm) to prepare a substrate with transparent coating (F-16). The thickness of the transparent film at this time was 5 μm.

Next, an antireflection film-forming coating solution (D-1) prepared in the same manner as in Example 15 was applied onto the transparent film by a bar coater method, dried at 70 ° C. for 1 minute, and then dried at 70 ° C. for 1 minute. After that, it was cured by irradiation with 600 mJ / cm ² with a high-pressure mercury lamp (80 W / cm) to prepare a substrate with transparent coating (F-16) provided with an antireflection film.

At this time, the thickness of the antireflection film was 80 nm.
Evaluation of total light transmittance, haze, bottom reflectance, luminous reflectance, pencil hardness, scratch resistance, adhesion and weather resistance of the obtained substrate with transparent coating (F-16) provided with an antireflection film The results are shown in Table 1.
[Example 17]
Preparation of coating liquid for forming transparent film (H-17) 89.55 g of isopropyl alcohol dispersion of niobium-based oxide fine particles (A1) prepared in the same manner as in Example 1 and an ultraviolet curable resin (Dainippon Ink Co., Ltd.) Unidic 17-824-9, solid content concentration 78.9%) 6.38 g, UV curable resin (Nippon Kayaku Kayrad KS-HDDA, solid content concentration 100%) 0.57 g, and isopropyl alcohol 0.14 g, 2.62 g of butyl cellosolve, and photoinitiator (Irgacure 184 manufactured by Ciba Specialty Co., Ltd., dissolved in IPA and solid content concentration of 50%) 0.61 g are sufficiently mixed to form a transparent film forming solution paint (H- 17) was prepared.

Production of substrate with transparent coating (F-17) A substrate with transparent coating (F-17) was prepared in the same manner as in Example 1 except that the coating solution for forming a transparent coating (H-17) was used. The thickness of the transparent film at this time was 5 μm.

The obtained hard coat film was evaluated for total light transmittance, haze, pencil hardness, scratch resistance and adhesion, and the results are shown in Table 1.
[Example 18]
Preparation of coating liquid for forming transparent film (H-18) 35.82 g of isopropyl alcohol dispersion of niobium-based oxide fine particles (A1) prepared in the same manner as in Example 1 and an ultraviolet curable resin (Dainippon Ink Co., Ltd.) Unidic 17-824-9, solid concentration 78.9%) 17.86 g, UV curable resin (Kayarad KS-HDDA, Nippon Kayaku Co., Ltd., solid concentration 100%) 1.56 g and isopropyl alcohol 40 .01 g, 2.62 g of butyl cellosolve, 2.13 g of photoinitiator (Irgacure 184 manufactured by Ciba Specialty Co., Ltd., dissolved in IPA and solid content concentration of 50%) and 2.13 g were sufficiently mixed to form a transparent film forming solution paint (H-18 ) Was prepared.

Production of substrate with transparent coating (F-18) A substrate with transparent coating (F-18) was prepared in the same manner as in Example 1 except that the coating solution for forming a transparent coating (H-18) was used. The thickness of the transparent film at this time was 5 μm.

The obtained hard coat film was evaluated for total light transmittance, haze, pencil hardness, scratch resistance, adhesion and weather resistance, and the results are shown in Table 1.
[Comparative Example 1]
Preparation of oxide fine particle (R1) dispersion
Preparation of titanium oxide-containing core particle dispersion
While stirring 25 kg of titanium sulfate aqueous solution having a concentration of 0.4% by weight converted to TiO ₂ , ammonia water having a concentration of 15% by weight was gradually added thereto for hydrolysis to obtain a white slurry liquid having a pH of 8.5. It was. The slurry was filtered and then washed to obtain 11.11 kg of a hydrous titanate gel cake having a solid content concentration of 9% by weight.

After adding 12.12 kg of hydrogen peroxide water having a concentration of 33% by weight and 26.8 kg of water to 11.11 kg of the cake, the cake was heated at 80 ° C. for 5 hours to obtain 2.0% by weight of titanium peroxide as TiO _2. The acid aqueous solution was transparent yellowish brown and had a pH of 8.1. Next, 666.6 g of silica sol having an average particle diameter of 7 nm and a SiO ₂ concentration of 15% by weight, 50.03 kg of the above titanic acid aqueous solution, and 49.34 kg of pure water were mixed, and the mixture was autoclaved at 200 ° C., 96 ° C. Heated for hours. The colloidal solution obtained after heating was concentrated to obtain 11.0 kg of a titanium oxide-containing core particle dispersion having a solid content of 10% by weight.
Zirconium peroxide solution 526 g of zirconium oxychloride dissolved in 947 g of water was hydrolyzed by adding 15% ammonia water to an aqueous solution of zirconium oxychloride having a concentration of 2% by weight of ZrO ₂ to obtain a slurry of pH 8.5. It was. This slurry was filtered and washed to prepare 610 g of a hydrogen peroxide solution of zirconium having a concentration of 2% by weight as ZrO ₂ .
Preparation of Silicic Acid Solution A commercially available water glass was diluted with water and then dealkalized with a cation exchange resin to prepare 1890 g of a silicic acid solution having a SiO ₂ concentration of 2% by weight.

  28.56 kg of water was added to 7.14 kg of the titanium oxide-containing core particle-dispersed sol prepared above to obtain a solid concentration of 2% by weight, and then heated to 90 ° C., followed by 610 g of zirconium hydrogen peroxide solution and silicic acid solution. 1890 g was mixed. The mixture was then heat-treated at 200 ° C. for 18 hours in an autoclave, and then concentrated by an ultrafiltration membrane method, and transparent titanium oxide-containing core particles having a solid milk concentration of 10% by weight were formed into silicon oxide. An oxide fine particle (R1) aqueous dispersion composed of titanium oxide, silica and zirconium oxide having a coating layer composed of and zirconium oxide was obtained.

  Next, for one minute of the oxide fine particle (R1) aqueous dispersion, the water of the dispersion medium is replaced with methanol, and further replaced with isopropyl alcohol (IPA), and concentrated until the solid content concentration becomes 20% by weight, and the oxide fine particles are concentrated. (R1) An IPA dispersion was prepared.

  For the oxide fine particles (R1), the average particle size, the uniformity of the particle size, and the acid radical in the particles were measured, and the results are shown in the table. Moreover, stability, transparency, and the refractive index of particle | grains are evaluated about a dispersion liquid, and a result is shown in a table | surface.

Preparation of Transparent Film Forming Coating Liquid (RH-1) A transparent film forming coating liquid (RH-1) was prepared in the same manner as in Example 1 except that the oxide fine particle (R1) IPA dispersion was used.

Production of substrate with transparent coating (RF-1) A substrate with transparent coating (RF-1) was prepared in the same manner as in Example 1 except that the coating solution for forming a transparent coating (RH-1) was used. The thickness of the transparent film at this time was 5 μm.

The obtained hard coat film was evaluated for total light transmittance, haze, pencil hardness, scratch resistance, adhesion and weather resistance, and the results are shown in Table 1.
[Comparative Example 2]
Preparation of oxide fine particle (R2) dispersion A titanium oxide-containing core particle dispersion having a solid content of 10% by weight was prepared in the same manner as in Comparative Example 1.
Next, for one minute of the titanium oxide-containing core particle dispersion, water in the dispersion medium is replaced with methanol and further replaced with isopropyl alcohol (IPA), and concentrated until the solid content concentration becomes 20% by weight to form oxide fine particles (R2). An IPA dispersion was prepared.

  For the oxide fine particles (R2), the average particle size, the uniformity of the particle size, and the acid radicals in the particles were measured, and the results are shown in the table. Moreover, stability, transparency, and the refractive index of particle | grains are evaluated about a dispersion liquid, and a result is shown in a table | surface.

Preparation of Transparent Film Forming Coating Liquid (RH-2) A transparent film forming coating liquid (RH-2) was prepared in the same manner as in Example 1 except that the oxide fine particle (R2) IPA dispersion was used.

Production of substrate with transparent film (RF-2) A substrate with transparent film (RF-2) was prepared in the same manner as in Example 1 except that the coating liquid for forming a transparent film (RH-2) was used. The thickness of the transparent film at this time was 5 μm.

The obtained hard coat film was evaluated for total light transmittance, haze, pencil hardness, scratch resistance, adhesion and weather resistance, and the results are shown in Table 1.
[Comparative Example 3]
Preparation of oxide fine particle (R3) dispersion 1000 g of oxide fine particle (R1) methanol dispersion obtained in the same manner as in Comparative Example 1 and 1000 g of pure water were placed in a reaction vessel and heated to 63 ° C. 2 liters of a mixture of methoxysilane and methanol (weight ratio 153/1000) was gradually added. After completion of the addition, the solution was further aged by maintaining the temperature at 63 ° C., substituted with methanol, further substituted with isopropyl alcohol (IPA), concentrated, and γ-glycidoxypropyltriethoxysilane having a solid content of 20% by weight. A surface-modified oxide fine particle (R3) IPA dispersion was obtained.

The oxide fine particle (R3) IPA dispersion stability, transparency, and refractive index of the particles were evaluated, and the results are shown in the table.
Preparation of Transparent Film Forming Coating Liquid (RH-3) A transparent film forming coating liquid (RH-3) was prepared in the same manner as in Example 1 except that the oxide fine particle (R3) IPA dispersion was used.

Production of substrate with transparent coating (RF-3) A substrate with transparent coating (RF-3) was prepared in the same manner as in Example 1 except that the coating solution for forming a transparent coating (RH-3) was used. The thickness of the transparent film at this time was 5 μm.

The obtained hard coat film was evaluated for total light transmittance, haze, pencil hardness, scratch resistance, adhesion and weather resistance, and the results are shown in Table 1.
[Comparative Example 4]
Preparation of Oxide Fine Particle (R4) Dispersion 1000 g of Oxide Fine Particle (R2) Methanol Dispersion obtained in the same manner as Comparative Example 2 and 1000 g of pure water were placed in a reaction vessel and heated to 63 ° C. 2 liters of a mixture of glycidoxypropyltriethoxysilane and methanol (weight ratio 153/1000) was gradually added. After completion of the addition, the solution was further aged by maintaining the temperature at 63 ° C., then substituted with methanol, further substituted with isopropyl alcohol (IPA), concentrated, and γ-glycidoxypropyltriethoxy having a solid concentration of 20% by weight. Oxide fine particles (R4) IPA dispersion surface-modified with silane was obtained.

The oxide fine particle (R4) IPA dispersion stability, transparency, and refractive index of the particles were evaluated, and the results are shown in the table.
Preparation of Transparent Film Forming Coating Liquid (RH-4) A transparent film forming coating liquid (RH-4) was prepared in the same manner as in Example 1 except that the oxide fine particle (R4) methanol dispersion was used.

Production of substrate with transparent coating (RF-4) A substrate with transparent coating (RF-4) was prepared in the same manner as in Example 1 except that the coating solution for forming a transparent coating (RH-4) was used. The thickness of the transparent film at this time was 5 μm.

The obtained hard coat film was evaluated for total light transmittance, haze, pencil hardness, scratch resistance and adhesion, and the results are shown in Table 1.
[Comparative Example 5]
Production of substrate with transparent coating (RF-5) A coating solution for forming a transparent coating (RH-1) prepared in the same manner as in Comparative Example 1 was placed on a PET film (thickness: 100 μm, refractive index: 1.65). After coating by a coater method and drying at 70 ° C. for 1 minute, the substrate was cured by irradiation with 600 mJ / cm ² with a high-pressure mercury lamp (80 W / cm) to prepare a substrate with a transparent coating (RF-5). The thickness of the transparent film at this time was 5 μm.

Next, an antireflection film-forming coating solution (D-1) prepared in the same manner as in Example 15 was applied onto the transparent film by a bar coater method, dried at 70 ° C. for 1 minute, and then dried at 70 ° C. for 1 minute. Then, it was cured by irradiation with 600 mJ / cm ² with a high-pressure mercury lamp (80 W / cm) to prepare a substrate with a transparent coating (RF-5) provided with an antireflection film.

At this time, the thickness of the antireflection film was 80 nm.
Evaluation of total light transmittance, haze, bottom reflectance, luminous reflectance, pencil hardness, scratch resistance, adhesion and weather resistance of the obtained substrate with transparent coating (RF-5) provided with an antireflection film The results are shown in Table 1.
[Comparative Example 6]
Production of substrate with transparent coating (RF-6) Transparent coating coating solution (RH-2) prepared in the same manner as in Comparative Example 2 was applied to a PET film (thickness: 100 μm, refractive index: 1.65). After applying by a coater method and drying at 70 ° C. for 1 minute, the substrate was cured by irradiation with 600 mJ / cm ² with a high-pressure mercury lamp (80 W / cm) to prepare a substrate with a transparent coating (RF-6). The thickness of the transparent film at this time was 5 μm.

Next, an antireflection film-forming coating solution (D-1) prepared in the same manner as in Example 15 was applied onto the transparent film by a bar coater method, dried at 70 ° C. for 1 minute, and then dried at 70 ° C. for 1 minute. Then, it was cured by irradiation with 600 mJ / cm ² with a high-pressure mercury lamp (80 W / cm) to prepare a transparent coated substrate (RF-6) provided with an antireflection film.
At this time, the thickness of the antireflection film was 80 nm.

Evaluation of total light transmittance, haze, bottom reflectance, luminous reflectance, pencil hardness, scratch resistance, adhesion and weather resistance of the obtained substrate with transparent coating (RF-6) provided with an antireflection film The results are shown in Table 1.
[Comparative Example 7]
Production of transparent film-coated substrate (RF-7) A transparent film-forming coating solution (RH-3) prepared in the same manner as in Comparative Example 3 was applied to a PET film (thickness: 100 μm, refractive index: 1.65). After coating by a coater method and drying at 70 ° C. for 1 minute, the substrate was cured by irradiation with 600 mJ / cm ² with a high-pressure mercury lamp (80 W / cm) to prepare a substrate with a transparent coating (RF-7). The thickness of the transparent film at this time was 5 μm.

Next, an antireflection film-forming coating solution (D-1) prepared in the same manner as in Example 15 was applied onto the transparent film by a bar coater method, dried at 70 ° C. for 1 minute, and then dried at 70 ° C. for 1 minute. Then, it was cured by irradiation with 600 mJ / cm ² with a high-pressure mercury lamp (80 W / cm) to prepare a substrate with a transparent coating (RF-7) provided with an antireflection film.

At this time, the thickness of the antireflection film was 80 nm.
Evaluation of total light transmittance, haze, bottom reflectance, luminous reflectance, pencil hardness, scratch resistance, adhesion and weather resistance of the obtained substrate with transparent coating (RF-7) provided with an antireflection film The results are shown in Table 1.
[Comparative Example 8]
Production of transparent film-coated substrate (RF-8) Transparent film-forming coating solution (RH-4) prepared in the same manner as in Comparative Example 4 was applied to a PET film (thickness: 100 μm, refractive index: 1.65). After coating by a coater method and drying at 70 ° C. for 1 minute, the substrate was cured by irradiation with 600 mJ / cm ² with a high-pressure mercury lamp (80 W / cm) to prepare a substrate with a transparent coating (RF-8). The thickness of the transparent film at this time was 5 μm.

Next, an antireflection film-forming coating solution (D-1) prepared in the same manner as in Example 15 was applied onto the transparent film by a bar coater method, dried at 70 ° C. for 1 minute, and then dried at 70 ° C. for 1 minute. Then, it was cured by irradiation with 600 mJ / cm ² with a high-pressure mercury lamp (80 W / cm) to prepare a substrate with a transparent coating (RF-8) provided with an antireflection film.

At this time, the thickness of the antireflection film was 80 nm.
Evaluation of total light transmittance, haze, bottom reflectance, luminous reflectance, pencil hardness, scratch resistance, adhesion and weather resistance of the obtained substrate with transparent coating (RF-8) provided with an antireflection film The results are shown in Table 1.

Claims (7)

It consists of a base material and a transparent film formed on the base material,
Transparent coating, Ri Na and a niobium based oxide fine particle mainly comprising matrix component and niobium oxide containing UV-curable resin,
A composite oxide in which the niobium-based oxide fine particles include niobium oxide and one or more oxides selected from oxides of Fe, Ce, Si, Zr, Al, Ti, Sn, Sb, W, and Zn. A substrate with a transparent coating, which is a fine particle .   The niobium-based oxide fine particles are niobium-based oxide core particles mainly composed of niobium oxide or core particles made of other inorganic oxides. Nb, Fe, Ce, Si, Zr, Al, Ti, Sn, It has a core-shell structure coated with one or more oxides selected from oxides of Sb, W, and Zn (when the core particles do not contain niobium oxide, the shell contains niobium oxide) The substrate with a transparent film according to claim 1.   The substrate with a transparent coating according to claim 1 or 2, wherein the niobium-based oxide fine particles have an average particle diameter in the range of 1 to 200 nm. A solution obtained by dissolving and / or peptizing the niobium-based oxide fine particles by adding hydrogen peroxide to a mixed dispersion or mixed solution of compounds of elements other than niobic acid and niobium is added at 80 to 300 ° C. with water. Whether it was obtained by heat treatment,
The niobium-based oxide fine particles obtained above are used as core particles, and (1) a niobic acid dispersion / solution, (2) a dispersion or solution of a compound of elements other than niobic acid and niobium, (3 ) Obtained by hydrothermal treatment at 80-300 ° C by mixing a solution obtained by adding hydrogen peroxide to any dispersion or solution of an elemental compound other than niobium and dissolving and / or peptizing. Or
As the core particles, inorganic oxide fine particles composed of oxides other than niobium are used, and (1) niobic acid dispersion solution / solution or (2) compound of elements other than niobic acid and niobium is dispersed in the fine particle dispersion. A solution obtained by adding hydrogen peroxide to a solution or solution and mixing and dissolving and / or peptizing the solution, and hydrothermally treating at 80 to 300 ° C. A substrate with a transparent coating according to 1.   The base material with a transparent film according to any one of claims 1 to 4, wherein an antireflection film is further formed on the transparent film.   The base material with a transparent film according to any one of claims 1 to 5, wherein the base material has a refractive index of 1.55 or more.   The substrate with a transparent coating according to claim 1, wherein the substrate is a film substrate made of polyethylene terephthalate (PET).