JP5255270B2 - Inorganic oxide fine particles having a core-shell structure, dispersed sol containing the fine particles, and coating solution for optical substrate - Google Patents

Description

The present invention has a relatively high refractive index, and further, such as scratch resistance, abrasion resistance, impact resistance, weather resistance, light resistance, sweat resistance, hot water resistance, adhesion, transparency, dyeability, etc. Inorganic oxide fine particles having a core-shell structure used when preparing a coating liquid or paint for forming a curable coating film with excellent properties on a substrate, a dispersion sol containing the fine particles, and an optical substrate coating It is about liquid.

  In recent years, as a material for optical base materials such as eyeglass lenses, plastic base materials are increasingly used in place of inorganic glass base materials. This is because the plastic substrate has excellent characteristics in terms of lightness, impact resistance, processability, dyeability, and the like. However, the plastic substrate has a drawback that it is easily damaged compared to an inorganic glass substrate.

  Therefore, in order to avoid this drawback, a silicone-based curable coating film, that is, a hard coat layer is usually provided on the surface of an optical lens using a plastic substrate. Furthermore, when a plastic substrate having a relatively high refractive index is used as the material of the optical lens, in order to avoid light interference (appears as interference fringes) between the plastic substrate and the hard coat layer, The hard coat layer contains inorganic oxide fine particles, and the refractive index is adjusted to match the refractive index of the plastic substrate.

Various developments have been made and many applications have been made for coating liquids and paints for forming a silicone-based curable coating film having such characteristics, for example, a hard coat layer on a plastic substrate.
When manufacturing optical substrates (plastic lenses) such as eyeglass lenses, they are colorless and transparent, have a high refractive index, and are scratch resistant, abrasion resistant, impact resistant, weather resistant, light resistant, and sweat resistant. In addition, a coating liquid for forming a curable coating film excellent in properties such as hot water resistance, adhesion, and dyeability has been demanded, and many applications have been filed to date.

  For example, Patent Document 1 discloses oxide fine particles containing at least one of silica, iron oxide, titanium oxide, cerium oxide, zirconium oxide, antimony oxide, zinc oxide and tin oxide, or a mixture thereof or a composite oxide thereof. A high refractive index coating composition containing fine particles and an organosilicon compound is disclosed. However, a curable coating film formed using a coating solution containing these fine particles has a relatively high refractive index, but cannot be said to have excellent weather resistance.

  As the background, in optical base materials such as eyeglass lenses, the thickness of plastic lenses and so on has been reduced in order to reduce weight, and as a result, the higher refractive index of coating films has been promoted. However, the weather resistance of the coating film was impaired by the titanium oxide having photocatalytic activity.

Therefore, the present applicants have applied a coating film-forming coating containing fine particles formed by coating a composite oxide of silicon, zirconium and / or aluminum on the surface of a core particle containing a titanium-based oxide and an organosilicon compound. A liquid has been developed and applied for. That is, the photocatalytic activity of the titanium oxide contained in the core particles is suppressed by coating the core particles containing the titanium-based oxide with the composite oxide.

For example, in Patent Document 2, (1) fine particles having titanium oxide fine particles as nuclei and surfaces thereof coated with zirconium oxide and silicon oxide, and (2) complex oxide fine particles made of a solid solution of titanium oxide and zirconium oxide are used as nuclei. Fine particles whose surfaces are coated with silicon oxide, (3) fine particles whose surface is coated with silicon oxide and zirconium oxide and / or aluminum oxide, using fine oxide fine particles of titanium and silicon as a nucleus, and (4) titanium. A coating liquid for forming a film is disclosed, which comprises fine particles of silicon and zirconium composite oxide as a core and the surface of which is coated with at least one of silicon oxide, zirconium oxide and aluminum oxide, and an organosilicon compound. . That is, in the invention according to Patent Document 2, a core-shell structure obtained by coating the surface of titanium-containing core particles having an anatase type crystal structure with at least one selected from silicon oxide, zirconium oxide, and aluminum oxide. Inorganic oxide fine particles are used.

Patent Document 3 discloses composite oxide fine particles in which a composite solid solution oxide of titanium and tin is used as a core particle, and the surface thereof is coated with a composite oxide of silicon oxide and zirconium and / or aluminum oxide; A coating forming coating solution containing an organosilicon compound is disclosed. That is, in the invention according to Patent Document 3, a core-shell obtained by coating the surface of titanium-containing core particles having a rutile crystal structure with a composite oxide of silicon oxide and zirconium and / or aluminum oxide. Inorganic oxide fine particles having a structure are used.

According to the invention described in these Patent Documents 2 and 3, in the range of refractive index 1.52 to 1.67, not only has excellent weather resistance, but also other properties such as A curable coating film having excellent properties in properties such as scratch resistance, abrasion resistance, impact resistance, light resistance, sweat resistance, hot water resistance, adhesion, transparency, and dyeability can be obtained.
However, recently, an optical substrate (plastic lens) having a refractive index of 1.70 or more, more specifically, 1.71 to 1.76 has been developed, and coating for forming a curable coating film corresponding to this has been developed. Although a liquid is required, in order to increase the refractive index of the coating film, it is necessary to further increase the titanium content contained in the core particles or to further reduce the thickness of the coating layer. . As a result, although a curable coating film having a high refractive index was obtained, its weather resistance tended to be impaired.

On the other hand, an optical lens such as a spectacle lens in which the hard coat layer is formed on the surface of a plastic substrate and an antireflection film is further provided thereon has a disadvantage that it is inferior in impact resistance.
As means for solving this drawback, (1) a method of forming a primer layer containing a thermosetting urethane resin and colloidal metal oxide fine particles containing titanium oxide (for example, Patent Document 4), (2) A method for forming a primer layer containing polyurethane resin and fine metal oxide particles such as zinc oxide, silicon dioxide, aluminum oxide, titanium oxide, zirconium oxide, tin oxide, beryllium oxide, antimony oxide, tungsten oxide, cerium oxide (for example, Patent Document 5) is known. Here, the metal oxide fine particles are added to adjust the refractive index of the coating film (inhibition of light interference) and improve the strength of the coating film. As in the case of the hard coat layer, an optical lens is used. When the titanium content in the fine particles is increased for the purpose of adapting to a higher refractive index, the weather resistance of the coating film is deteriorated.

JP 7-325201 A JP-A-8-048940 JP 2000-204301 A JP-A-6-118203 JP-A-6-337376

As a result of intensive studies as to whether or not a coating solution for forming a curable coating film having a high refractive index and weather resistance by solving the above-mentioned problems can be obtained, It has been found that the inorganic oxide fine particles having the core-shell structure may contain a potassium compound (excluding K ₂ O as an oxide for the reasons described below), and the present invention has been completed. .
That is, an object of the present invention is to provide inorganic oxide fine particles having a core-shell structure containing a potassium compound (excluding K ₂ O as an oxide, the same shall apply hereinafter) in a specific range. Furthermore, the present invention provides a dispersion such as an aqueous dispersion sol or an organic solvent dispersion sol containing the inorganic oxide fine particles, a hard coat forming coating solution or a primer layer forming coating solution prepared using the dispersion, and the like. It aims at providing the coating liquid for optical base materials of this.

The inorganic oxide fine particles having a core-shell structure according to the present invention are:
The surface of a core particle composed of titanium oxide fine particles and / or composite oxide fine particles containing titanium and one or more metal elements selected from zirconium, tin, tungsten, niobium, cerium and silicon, Inorganic oxide fine particles coated with silicon and an oxide and / or composite oxide of one or more metal elements selected from zirconium, aluminum and antimony,
The fine particles contain a potassium compound (excluding K ₂ O as an oxide) in an amount of 1.0 to 8.0% by weight in terms of K ₂ O.
Here, it is preferable that the inorganic oxide fine particles contain a solid acid composed of an oxide of the metal element.
Moreover, it is preferable that at least a part of the potassium compound contained in the inorganic oxide fine particles is present in a form combined with a solid acid.

The potassium compound is contained in the core particles in an amount of 0.0 to 5.0% by weight in terms of K ₂ O, and in the coating layer in an amount of 1.0 to 7.0% by weight in terms of K ₂ O. preferable.
The core particles are preferably titanium-based composite oxide fine particles having an anatase type crystal structure.
Further, the core particles are preferably titanium-based composite oxide fine particles having a rutile crystal structure.

The coating on the core particles is expressed by the weight ratio (S / C) of 7/100 to 150 on the oxide basis when the weight of the core particles is represented by C and the weight of the coating layer is represented by S. / 100 is preferable to be performed.
The average particle size of the fine particles is preferably in the range of 4 to 40 nm when measured by a dynamic light scattering method.
Further, the specific surface area of the fine particles is preferably in the range of 70 to 450 m ² / g.

The dispersion sol according to the present invention is preferably a water dispersion sol obtained by dispersing the inorganic oxide fine particles having the core-shell structure in water.
Furthermore, the dispersion sol according to the present invention is preferably an organic solvent dispersion sol obtained by dispersing the inorganic oxide fine particles having the core-shell structure in an organic solvent soluble in water.

The coating liquid for optical substrates according to the present invention is
(1) Titanium oxide fine particles and / or core particles composed of composite oxide fine particles containing titanium and one or more metal elements selected from zirconium, tin, tungsten, niobium, cerium and silicon Potassium compounds (as oxides) are formed in inorganic oxide fine particles whose surface is coated with silicon and an oxide and / or composite oxide of one or more metal elements selected from zirconium, aluminum and antimony. Inorganic oxide fine particles having a core-shell structure containing 1.0 to 8.0% by weight (excluding K ₂ O) in terms of K ₂ O, and (2) organosilicon represented by the following general formula (I) It is characterized by containing a compound and / or a hydrolyzate thereof.
R ¹ _a R ² _b Si (OR ³ ) _{4- (a + b)} (I)
(In the formula, R ¹ is an alkyl group having 1 to 6 carbon atoms, an organic group having 8 or less carbon atoms containing a vinyl group, an organic group having 8 or less carbon atoms containing an epoxy group, and 8 carbon atoms containing a methacryloxy group. The following organic group, an organic group having 1 to 5 carbon atoms containing a mercapto group or an organic group having 1 to 5 carbon atoms containing an amino group, R ² is an alkyl group having 1 to 3 carbon atoms, an alkylene group, A cycloalkyl group, a halogenated alkyl group or an allyl group, R ³ is an alkyl group having 1 to ³ carbon atoms, an alkylene group or a cycloalkyl group, a is an integer of 0 or 1, b is 0, 1 Or an integer of 2.)

It is preferable that the inorganic oxide fine particles are surface-treated with an organosilicon compound or an amine compound.
Moreover, it is preferable that the coating liquid for optical substrates further contains an uncrosslinked epoxy compound.
Furthermore, it is preferable that the coating liquid for an optical substrate is a coating liquid for forming a hard coat layer.

The coating liquid for optical substrates according to the present invention is
(1) Titanium oxide fine particles and / or core particles composed of composite oxide fine particles containing titanium and one or more metal elements selected from zirconium, tin, tungsten, niobium, cerium and silicon Potassium compounds (as oxides) are formed in inorganic oxide fine particles whose surface is coated with silicon and an oxide and / or composite oxide of one or more metal elements selected from zirconium, aluminum and antimony. inorganic oxide particles having a K ₂ except O) of K ₂ O equivalent value at 1.0 to 8.0 wt% included so-shell structure, and (2) include a thermosetting resin or a thermoplastic resin It is a feature.

It is preferable that the inorganic oxide fine particles are surface-treated with an organosilicon compound or an amine compound.
Moreover, it is preferable that the said thermosetting resin is 1 type, or 2 or more types of thermosetting resins chosen from urethane type resin, epoxy resin, melamine type resin, and silicone type resin.
Further, the thermoplastic resin is preferably one or more thermoplastic resins selected from acrylic resins, urethane resins and ester resins.
The optical substrate coating solution is preferably a primer layer forming coating solution.
In addition, it is preferable that the optical base material for apply | coating said coating liquid for optical base materials is a plastic lens.

According to the inorganic oxide fine particles having the core-shell structure according to the present invention, the photocatalytic activity of the titanium oxide can be suppressed by the potassium compound contained in the fine particles, so that the content of the titanium oxide can be increased. it can. Thereby, inorganic oxide fine particles having a relatively low photocatalytic activity and a high refractive index characteristic can be obtained.
Further, when a coating liquid containing the inorganic oxide fine particles according to the present invention, for example, a coating liquid for forming a hard coat layer is used, it has a relatively high refractive index of 1.52 or more, particularly 1.70 or more, and weather resistance. A curable coating film having excellent properties can be easily formed on a substrate. Furthermore, a colorless and transparent curable coating film excellent in properties such as scratch resistance, abrasion resistance, impact resistance, light resistance, sweat resistance, hot water resistance, adhesion, and dyeability can be formed.
Therefore, the coating liquid for optical substrates according to the present invention can be suitably used when forming a hard coat layer or a primer layer on an optical substrate such as a plastic lens.

  Hereinafter, the inorganic oxide fine particles having a core-shell structure according to the present invention, the dispersion sol containing the fine particles, and the coating liquid for optical substrates will be specifically described.

[Inorganic oxide fine particles]
The inorganic oxide fine particles having a core-shell structure according to the present invention are:
The surface of a core particle composed of titanium oxide fine particles and / or composite oxide fine particles containing titanium and one or more metal elements selected from zirconium, tin, tungsten, niobium, cerium and silicon, Inorganic oxide fine particles coated with silicon and an oxide and / or composite oxide of one or more metal elements selected from zirconium, aluminum and antimony,
The fine particles contain a potassium compound (excluding K ₂ O as an oxide) in an amount of 1.0 to 8.0% by weight on a K ₂ O conversion basis.

In the present invention, the inorganic oxide fine particles having a core-shell structure are obtained by coating the surface of core particles composed of metal element oxide fine particles and / or composite oxide fine particles with metal element oxide and / or composite oxide. Meaning inorganic oxide fine particles, these components will be described in more detail as follows.
The titanium oxide fine particles as the core particles are fine particles of a compound represented by the chemical formula TiO ₂ . However, the titanium-based composite oxide fine particles include fine particles of various compounds obtained by combining titanium and the element. If some of these compounds are schematically represented by chemical formulas, [Chemical Formula 1] and As shown in [Chemical Formula 2].
The crystal structure is mainly classified into anatase type, rutile type or a mixed type thereof, although it varies depending on the preparation conditions of the compound (including elements used and the content of each element). However, in the present invention, fine particles of a titanium-based composite oxide having an anatase type crystal structure or fine particles of a titanium-based composite oxide having a rutile type crystal structure are preferable.

In addition, the composite oxide as a coating includes a plurality of compounds obtained by combining silicon and the element. If a part of these compounds is schematically represented by a chemical formula, [Chemical Formula 3] Street.

  In the inorganic oxide fine particles, the coating of the composite oxide on the core particles is expressed by weight ratio (S / C) when the weight of the core particles is represented by C and the weight of the coating layer is represented by S. However, it is desirable to carry out in a range of 7/100 to 150/100, preferably 12/100 to 40/100 on the oxide basis. Here, when the weight ratio is less than 7/100, it is difficult to suppress the photocatalytic activity due to the titanium oxide, and as a result, the weather resistance of the coating film is deteriorated, or the coating film is discolored during ultraviolet irradiation (for example, , Change to blue-gray) is not preferable. Further, when the weight ratio exceeds 150/100, when the aqueous dispersion sol containing the core particles and the aqueous solution for forming the coating layer are mixed, not only the stability of the aqueous dispersion sol is deteriorated, Since the degree of shielding the titanium-based oxide contained in the core particles is increased by increasing the thickness of the coating layer, the refractive index of the coating film is lowered as a result.

In the present invention, it is necessary that the inorganic oxide fine particles contain a potassium compound in an amount of 1.0 to 8.0% by weight, preferably 1.5 to 6.5% by weight in terms of K ₂ O. . Here, when the content is less than 1.0% by weight, it is difficult to improve the weather resistance of the coating film, or it is difficult to suppress discoloration of the coating film, which is not preferable. On the other hand, when the content exceeds 8.0% by weight, the potassium compound is eluted and the pH of the water-dispersed sol is increased. As a result, the stability of the water-dispersed sol is deteriorated, which is not preferable.
However, in the present invention, K ₂ O as a potassium oxide is excluded from the potassium compounds. This is because K ₂ O itself is relatively stable and therefore has little effect on improving the “weather resistance of the coating film” in the present invention. In addition, in the preparation process of the inorganic oxide fine particles according to the present invention, the K ₂ O is not formed in the fine particles.

Further, the potassium compound, the 0.0 to 5.0 wt% in the nucleus particles in K ₂ O equivalent value preferably comprises 1.0 to 4.5 wt%, K ₂ O converted to the coating layer It is desirable to contain 1.0 to 7.0% by weight, preferably 1.5 to 6.5% by weight on the basis. Here, the core particles do not necessarily contain a potassium compound, but in order to suppress the photocatalytic activity of a titanium-based oxide (including a titanium-based composite oxide in addition to titanium oxide) It is preferable to appropriately select from the range of 5.0% by weight or less in terms of K ₂ O conversion. However, when the content exceeds 5.0% by weight, the stability of the water-dispersed sol is deteriorated, which is not preferable.
On the other hand, the potassium content contained in the coating layer varies depending on the potassium content contained in the core particles, but is preferably 1.0% by weight or more on a K ₂ O conversion basis. Here, if the content is less than 1.0% by weight, particle growth may be promoted more than necessary, and if the content exceeds 7.0% by weight, the stability of the particles may be increased. Since it gets worse, it is not preferable.

In the inorganic oxide fine particles, a solid acid composed of an oxide of the metal element by-produced when the fine particles are prepared, that is, ZrO ₂ · TiO ₂ , ZrO ₂ · SiO ₂ , SiO ₂ · TiO ₂ , SnO _{2. · TiO 2, SnO 2 · SiO} 2, SiO 2 · Al 2 O 3, SiO 2 · Sb 2 O 5, Sb 2 O 5 · ZrO 2 may contain a solid acid, such as preferred. This is because when these solid acids are contained in the presence of the potassium compound, not only the weather resistance of the coating film is improved, but also the coating film is discolored during ultraviolet irradiation (for example, discoloration to blue-gray). This is because it can be suppressed. The reason is not necessarily clear, but it is considered that various reactions (for example, Ti ⁴⁺ + e ⁻ → Ti ³⁺ ) that occur when irradiated with ultraviolet rays are suppressed by the action of the solid acid.
In addition, it is said that there are OH groups that act as bases and O.H groups that act as acids on the surface of titanium-based oxides (including titanium-based composite oxides in addition to titanium oxides). Yes. Therefore, the solid acid acts on the former active group (namely, OH group), and the potassium ion acts on the latter active group (namely, O.H group). It is considered that the surface activity of the titanium-based oxide is suppressed. Furthermore, it is considered that these interactions inhibit the reaction with various organic substances (for example, plastic lenses, primer compositions, etc.) by suppressing free radicalization (.OH) of OH groups.

Furthermore, it is preferable that at least a part of the potassium compound contained in the inorganic oxide fine particles is present in a form combined with the solid acid contained in the fine particles. That is, when the solid acid as described above is formed in the fine particles, potassium ions derived from the potassium compound added at the time of preparing the inorganic oxide fine particles are easily reacted with these solid acids and immobilized. This is because even if the amount of potassium ions is increased, the pH variation in the dispersion is small and the sol stability is not significantly affected.
Examples of compounds obtained by reacting potassium ions with solid acids in this way include xSiO ₂ .yK.zZrO ₂ , xSiO ₂ .yK.zTiO ₂ , xSiO ₂ .yK.zSnO _{2 and the} like. It is done.
Thus, it is thought that the potassium compound added in the preparation process of the inorganic oxide fine particles is ionized to bring about the above-described effects, thereby improving the weather resistance of the coating film. In addition, in the case of K ₂ O as a potassium oxide, it is also crystalline, and not only can not provide the above-mentioned effects but also difficult to fix in the fine particles. It will have a great impact on the stability of the product.

The average particle diameter of the inorganic oxide fine particles is preferably in the range of 4 to 40 nm when measured by the dynamic light scattering method described below. Here, when the average particle diameter is less than 4 nm, when the sol containing the inorganic oxide fine particles is concentrated to a desired concentration, the stability of the sol is deteriorated, and when the average particle diameter exceeds 40 nm. Since the transmittance of the coating film is deteriorated, it is not preferable.
The specific surface area of the inorganic oxide fine particles is preferably in the range of 70 to 450 m ² / g. Here, when the specific surface area is less than 70 m ² / g, the transmittance of the coating film is deteriorated, and when the specific surface area exceeds 450 m ² / g, a sol containing the inorganic oxide fine particles is obtained at a desired concentration. When the solution is concentrated to a low concentration, the stability of the sol is deteriorated.

[Dispersed sol]
Water-dispersed sol A water-dispersed sol containing inorganic oxide fine particles having a core-shell structure according to the present invention is obtained by uniformly dispersing the inorganic oxide fine particles in water such as pure water. It is preferable that the content is in the range of 5 to 30% by weight. Here, when the solid content is less than 5% by weight, not only the reactivity with the surface treatment agent is deteriorated, but also the amount of the solvent used for solvent substitution is increased, which is not economical. On the other hand, when the solid content exceeds 30% by weight, the stability of the water-dispersed sol is deteriorated, which is not preferable.

Organic solvent dispersion sol An organic solvent dispersion sol containing inorganic oxide fine particles having a core-shell structure according to the present invention is obtained by uniformly dispersing the inorganic oxide fine particles in an organic solvent soluble in water, The solid content of the inorganic oxide fine particles is preferably in the range of 20 to 40% by weight.
Examples of such water-soluble organic solvents include alcohols such as methanol, ethanol, butanol, propanol, isopropyl alcohol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether. It is preferable to use selected from ethers such as The reason is that the drying speed of the coating film is relatively fast and it is easy to form a film. However, as a matter of course, a part or all of the organic solvent soluble in water may be used by substituting with an organic solvent hardly soluble in water as necessary. Here, when the solid content is less than 20% by weight, the solid content of the coating liquid for an optical substrate is reduced, so the film thickness of the coating film is reduced, and the film hardness is reduced. It is not preferable. On the other hand, if the solid content exceeds 40% by weight, the stability of the organic solvent-dispersed sol is deteriorated, which is not preferable.

[Preparation method]
The preparation method of inorganic oxide fine particles having a core-shell structure and a dispersed sol containing the fine particles according to the present invention is generally as follows. However, the present invention is characterized in that the inorganic oxide fine particles contain a potassium compound (excluding K ₂ O as an oxide) in a specific range, and thus is limited to these preparation methods. It is not something.

Titanium-based composite oxide particles (1) of titanium tetrachloride containing about 1-3 wt% Preparation Example of titanium tetrachloride aqueous dispersion sol containing inorganic oxide particles as core particles in terms of TiO ₂ basis having an anatase type crystal structure An aqueous solution and aqueous ammonia containing about 10 to 20% by weight of ammonia (NH ₃ ) are mixed to obtain a white slurry having a pH of about 8 to 9. The slurry is then filtered and washed with pure water to obtain a hydrous titanate cake having a solid content of about 8 to 10% by weight.
Next, hydrogen peroxide containing about 30 to 40% by weight of hydrogen peroxide and pure water were added to the cake, and then stirred at a temperature of about 70 to 90 ° C. for about 0.5 to 5 hours. By heating, an aqueous solution of titanate peroxide containing about 1 to 3% by weight of titanate peroxide based on TiO ₂ is obtained. This aqueous solution of titanic acid peroxide is transparent yellowish brown and has a pH of about 7.5 to 8.5.

Then, the peroxide titanate solution, the average particle diameter comprising silica particulates about 4～12Nm, by mixing a silica sol and pure water containing about 10 to 20 wt% of silicon oxide (SiO _2), in an autoclave At about 160-170 ° C. for about 15-40 hours.
Next, the obtained sol is cooled to room temperature and then concentrated using an ultrafiltration membrane device to obtain an aqueous dispersion sol having a solid content of about 5 to 30% by weight. The inorganic oxide fine particles contained in the water-dispersed sol are composite oxide fine particles containing titanium and silicon having an anatase type crystal structure, and are used as “nuclear particles” in the present invention.

However, since the inorganic oxide fine particles obtained from this method do not contain a potassium compound, in order to contain the potassium compound in the fine particles, silica sol and pure water are added to the aqueous peroxide titanate solution. At the time of addition, a desired amount of an aqueous potassium hydroxide solution may be added and heat-treated in an autoclave, or a desired amount of an aqueous potassium hydroxide solution may be added to the obtained water-dispersed sol. However, since the inorganic oxide fine particles used as the core particles do not necessarily contain a potassium compound, such an addition operation may not be performed.

In addition, when the amount of the potassium compound contained in the inorganic oxide fine particles exceeds 5.0% by weight on a K ₂ O conversion basis, or when it contains a desired amount or more of the potassium compound, the added hydroxide is added. The amount of potassium compound is adjusted by adjusting the amount of potassium or by adding a cation exchange resin to the sol obtained from the autoclave and stirring, and then separating the cation exchange resin incorporating potassium ions. It is preferable to reduce.
In this manner, an aqueous dispersion sol containing inorganic oxide fine particles (core particles) containing 0.0 to 5.0% by weight of a potassium compound in terms of K ₂ O can be obtained.
Furthermore, when other inorganic components such as zirconium and cerium are included in the inorganic oxide fine particles, these metals are included when silica sol and pure water are added to the aqueous solution of titanic peroxide. What is necessary is just to heat-process in an autoclave after adding desired amount of aqueous solution. As a result, an aqueous dispersion sol containing composite oxide fine particles containing titanium and these metals is obtained.

(2) Preparation Example of Aqueous Dispersion Sol Containing Coated Inorganic Oxide Fine Particles Aqueous zirconium oxychloride containing about 1 to 3% by weight of zirconyl oxychloride in terms of ZrO ₂ , and about 10 to 20% of ammonia (NH ₃ ) % Aqueous ammonia is gradually added under stirring to obtain a slurry liquid having a pH of about 8 to 9 containing zirconium-containing gel. The slurry is then filtered and then washed with pure water to obtain a cake containing about 9 to 11% by weight of the zirconium component on a ZrO ₂ conversion basis.
Next, after adding potassium hydroxide aqueous solution and pure water to the cake to make it alkaline, hydrogen peroxide containing about 30 to 40% by weight of hydrogen peroxide (H ₂ O ₂ ) is added, and about 30 to Heat at a temperature of 50 ° C. As a result, an aqueous zirconate peroxide solution containing about 0.3 to 1% by weight of zirconate peroxide in terms of ZrO ₂ is obtained. The pH of this aqueous zirconate peroxide solution is about 11-13.

On the other hand, after diluting a commercially available water glass with pure water, it is dealkalized using a cation exchange resin to obtain a silicic acid aqueous solution containing about 1 to 3% by weight of a silicon component on a SiO ₂ conversion basis. The pH of this aqueous silicic acid solution is about 2-3.
Next, pure water is added to the aqueous dispersion sol containing the inorganic oxide fine particles (nuclear particles) obtained above and stirred to obtain an aqueous dispersion sol having a solid content of about 1 to 3% by weight. Next, the aqueous dispersion sol is heated to a temperature of about 80 to 95 ° C., and then the zirconic acid aqueous solution and the silicic acid aqueous solution are gradually added thereto, followed by aging for about 0.5 to 2 hours after the addition.
Subsequently, after adjusting the pH of the obtained liquid mixture to 7-10 as needed, this liquid mixture is put into an autoclave and it heats at the temperature of about 160-170 degreeC for about 16-20 hours.

Next, the obtained sol is cooled to room temperature and then concentrated using an ultrafiltration membrane device to obtain an aqueous dispersion sol having a solid content of about 10 to 30% by weight. The inorganic oxide fine particles contained in the water-dispersed sol are complex oxides containing zirconium and silicon on the surface of the composite oxide fine particles (core particles) containing titanium and silicon having an anatase type crystal structure. It is inorganic oxide fine particles formed by coating. The appearance of the water-dispersed sol containing the inorganic oxide fine particles is usually transparent and light milky white.

It is added when the amount of the potassium compound contained in the coating layer of the inorganic oxide fine particles exceeds 7.0% by weight on the K ₂ O conversion basis, or when the potassium compound contains a desired amount or more. After adjusting the amount of potassium hydroxide or adding a cation exchange resin to the sol obtained from the autoclave and stirring, the cation exchange resin incorporating the potassium ions is separated to thereby remove the potassium compound. It is preferable to reduce the content.
On the other hand, when the content of the potassium compound is less than 1.0% by weight in terms of K ₂ O, it is preferable to adjust the amount of potassium hydroxide added.

In this manner, an aqueous dispersion sol containing inorganic oxide fine particles formed by coating a composite oxide (coating layer) containing 1.0 to 7.0% by weight of a potassium compound in terms of K ₂ O can be obtained. .
Furthermore, when other metal components such as aluminum and antimony are included in the coating layer of the inorganic oxide fine particles, the aqueous solution containing these metals prepared in advance and the silicic acid in the aqueous zirconate peroxide solution What is necessary is just to heat-process in an autoclave by adding aqueous solution. As a result, an aqueous dispersion sol containing composite oxide fine particles containing silicon and these metals can be obtained.

(3) Preparation Example of Methanol Dispersion Sol Containing Coated Inorganic Oxide Fine Particles The aqueous dispersion sol containing inorganic oxide fine particles obtained above was stirred in a methanol solution in which tetraethoxysilane as a surface treatment agent was dissolved. Followed by heating at a temperature of about 40-60 ° C. for about 1-20 hours.
Next, after cooling this mixed solution to room temperature, the dispersion medium is replaced from water to methanol using an ultrafiltration membrane device.

Further, the obtained methanol dispersion is concentrated by an ultrafiltration membrane device to prepare a methanol dispersion sol containing inorganic oxide fine particles having a solid content of 10 to 30% by weight.
Inorganic oxide fine particles thus obtained (that is, fine particles obtained by coating the surface of a composite oxide fine particle containing titanium and silicon having an anatase type crystal structure with a composite oxide containing zirconium and silicon. The appearance of the methanol-dispersed sol containing) is a transparent light blue white. The average particle diameter of the inorganic oxide fine particles is in the range of about 4 to 40 nm when measured by a dynamic light scattering method.

Titanium-based composite oxide fine particles having a rutile crystal structure (1) Preparation example of water-dispersed sol containing inorganic oxide fine particles as core particles Titanium tetrachloride containing about 7-8 wt% of titanium tetrachloride on a TiO ₂ basis An aqueous solution and aqueous ammonia containing about 10 to 20% by weight of ammonia (NH ₃ ) are mixed to obtain a white slurry having a pH of about 9 to 10. The slurry is then filtered and washed with pure water to obtain a hydrous titanate cake having a solid content of about 8 to 14% by weight.
Next, after adding hydrogen peroxide water containing about 30 to 40% by weight of hydrogen peroxide (H ₂ O ₂ ) and pure water to this cake, the temperature is about 70 to 90 ° C. By heating with stirring for 5 hours, an aqueous solution of titanic acid peroxide containing about 1 to 3% by weight of titanic acid peroxide in terms of TiO ₂ is obtained. This aqueous solution of titanic acid peroxide is transparent yellowish brown and has a pH of about 7.5 to 8.5.

Next, a cation exchange resin is mixed with the aqueous solution of titanic acid titanate, and an aqueous potassium stannate solution containing about 0.5 to 2% by weight of potassium stannate in terms of SnO ₂ is gradually added thereto with stirring. To do.
Next, after separating the cation exchange resin incorporating potassium ions and the like, silica sol containing silica fine particles having an average particle diameter of about 4 to 12 nm and containing about 10 to 20% by weight of silicon oxide (SiO ₂ ) and pure water. And heated in an autoclave at a temperature of about 160-170 ° C. for about 15-20 hours.
Next, the obtained sol is cooled to room temperature and then concentrated by an ultrafiltration membrane device to obtain an aqueous dispersion sol having a solid content of about 5 to 30% by weight. The inorganic oxide fine particles contained in the water-dispersed sol are composite oxide fine particles containing titanium, tin and silicon having a rutile crystal structure, and are used as “nuclear particles” in the present invention.

The inorganic oxide fine particles (nuclear particles) obtained from this method contain a potassium compound. However, since this potassium compound has been conventionally considered as an impurity that adversely affects the refractive index of the coating film, it is positively charged. The ion exchange resin was removed as much as possible so that its content was about 0.5% by weight or less in terms of K ₂ O. However, in the present invention, the content of the potassium compound is as long 5 wt% or less K ₂ O equivalent value is preferably in the range of 1.0 to 4.5% by weight if possible. That is, if the content does not exceed 5% by weight in terms of K ₂ O, it is not always necessary to remove this using an expensive cation exchange resin. However, when the content is less than 1.0% by weight in terms of K ₂ O, it is preferable to adjust by increasing the content of the potassium compound contained in the coating layer described below.

The method for increasing or decreasing the content of the potassium compound contained in the inorganic oxide fine particles (nuclear particles) is the same as the method described in the explanation regarding the “titanium composite oxide fine particles having anatase type crystal structure” above. It is the same.
In this manner, an aqueous dispersion sol containing inorganic oxide fine particles (core particles) containing 0.0 to 5.0% by weight of a potassium compound in terms of K ₂ O can be obtained.
Furthermore, when other inorganic components such as zirconium and cerium are included in the inorganic oxide fine particles, these metals are included when silica sol and pure water are added to the aqueous solution of titanic peroxide. What is necessary is just to heat-process in an autoclave after adding desired amount of aqueous solution. As a result, an aqueous dispersion sol containing composite oxide fine particles containing titanium and these metals is obtained.

(2) Preparation Example of Aqueous Dispersion Sol Containing Coated Inorganic Oxide Fine Particles Zirconic acid peroxide is produced in the same manner as described in the above explanation regarding “titanium-based composite oxide fine particles having anatase type crystal structure”. An aqueous solution and an aqueous silicic acid solution are obtained.
On the other hand, an aqueous dispersion sol having a solid content of about 1 to 3% by weight is obtained by adding pure water to the aqueous dispersion sol containing the inorganic oxide fine particles (core particles) obtained above and stirring. Next, the aqueous dispersion sol is heated to a temperature of about 80 to 95 ° C., and then the zirconic acid aqueous solution and the silicic acid aqueous solution are gradually added thereto, followed by aging for about 0.5 to 2 hours after the addition is completed. .
Subsequently, after adjusting the pH of the obtained liquid mixture to 7-10 as needed, this liquid mixture is put into an autoclave and it heats at the temperature of about 160-170 degreeC for about 16-20 hours.

Next, the obtained sol is cooled to room temperature and then concentrated by an ultrafiltration membrane device to obtain an aqueous dispersion sol having a solid content of about 10 to 30% by weight. The inorganic oxide fine particles contained in this water-dispersed sol are composed of a complex oxide containing zirconium and silicon on the surface of a composite oxide fine particle (core particle) containing titanium, tin and silicon having a rutile crystal structure. Inorganic oxide fine particles formed by coating with The appearance of the water-dispersed sol containing the inorganic oxide fine particles is usually transparent and light milky white.

The method for increasing or decreasing the content of the potassium compound contained in the coating layer of the inorganic oxide fine particles is the same as the method described in the explanation regarding the “titanium composite oxide fine particles having an anatase type crystal structure” above. It is the same.
In this manner, an aqueous dispersion sol containing inorganic oxide fine particles formed by coating a composite oxide (coating layer) containing 1.0 to 7.0% by weight of a potassium compound in terms of K ₂ O can be obtained. .
Furthermore, when other metal components such as aluminum and antimony are included in the coating layer of the inorganic oxide fine particles, the aqueous solution containing these metals prepared in advance and the silicic acid in the aqueous zirconate peroxide solution What is necessary is just to heat-process in an autoclave by adding aqueous solution. As a result, an aqueous dispersion sol containing composite oxide fine particles containing silicon and these metals can be obtained.

(3) Preparation Example of Methanol Dispersion Sol Containing Coated Inorganic Oxide Fine Particles The aqueous dispersion sol containing inorganic oxide fine particles obtained above was stirred in a methanol solution in which tetraethoxysilane as a surface treatment agent was dissolved. Followed by heating at a temperature of about 40-60 ° C. for about 1-20 hours.
Next, after cooling this mixed solution to room temperature, the dispersion medium is replaced from water to methanol using an ultrafiltration membrane device.

Further, the obtained methanol dispersion is concentrated by an ultrafiltration membrane device to prepare a methanol dispersion sol containing inorganic oxide fine particles having a solid content of 10 to 30% by weight.
Inorganic oxide fine particles obtained in this way (that is, the surface of a composite oxide fine particle containing titanium, tin and silicon having a rutile-type crystal structure is coated with a composite oxide containing zirconium and silicon. The appearance of the methanol-dispersed sol containing fine particles is a transparent light blue white. The average particle diameter of the inorganic oxide fine particles is in the range of about 4 to 40 nm when measured by a dynamic light scattering method.

[Coating liquid for optical substrate]
Coating liquid A for optical substrates
The coating liquid A for an optical substrate according to the present invention is:
(1) Nuclear particles composed of titanium oxide fine particles and / or composite oxide fine particles containing titanium and one or more metal elements selected from zirconium, tin, tungsten, niobium, cerium and silicon Potassium compounds (as oxides) are formed in inorganic oxide fine particles whose surface is coated with silicon and an oxide and / or composite oxide of one or more metal elements selected from zirconium, aluminum and antimony. inorganic oxide particles having a K except ₂ O) K ₂ O equivalent value at 1.0 to 8.0 wt% included so-shell structure, and (2) an organosilicon represented by the following general formula (I) It contains a compound and / or a hydrolyzate thereof.
R ¹ _a R ² _b Si (OR ³ ) _{4- (a + b)} (I)
(In the formula, R ¹ is an alkyl group having 1 to 6 carbon atoms, an organic group having 8 or less carbon atoms containing a vinyl group, an organic group having 8 or less carbon atoms containing an epoxy group, and 8 carbon atoms containing a methacryloxy group. The following organic group, an organic group having 1 to 5 carbon atoms containing a mercapto group or an organic group having 1 to 5 carbon atoms containing an amino group, R ² is an alkyl group having 1 to 3 carbon atoms, an alkylene group, A cycloalkyl group, a halogenated alkyl group or an allyl group, R ³ is an alkyl group having 1 to ³ carbon atoms, an alkylene group or a cycloalkyl group, a is an integer of 0 or 1, b is 0, 1 Or an integer of 2.)

It is preferable that the inorganic oxide fine particles have been surface-treated with an organosilicon compound (hereinafter referred to as “organosilicon compound (1)”) or an amine compound.
As the organosilicon compound used for the surface treatment, a conventionally known silane coupling agent having a hydrolyzable group can be used, and the type thereof is appropriately selected according to the use, the type of solvent, and the like. . These silane coupling agents may be used alone or in combination of two or more. Specific examples of the organosilicon compound (1) include the following compounds (a) to (d).

(A) a monofunctional silane represented by the general formula R ₃ SiX (wherein R represents an organic group having an alkyl group, a phenyl group, a vinyl group, a methacryloxy group, a mercapto group, an amino group or an epoxy group; X represents a hydrolyzable group such as an alkoxy group or a chloro group.)
Typical examples include trimethylethoxysilane, dimethylphenylethoxysilane, dimethylvinylethoxysilane, and the like.
(B) Bifunctional silane represented by the general formula R ₂ SiX ₂ (wherein R and X are as defined above).
Representative examples include dimethyldiethoxysilane, diphenyldiethoxysilane, and the like.

(C) Trifunctional silane represented by the general formula RSiX ₃ (wherein R and X are as defined above).
Typical examples include methyltriethoxysilane and phenyltriethoxysilane.
(D) Tetrafunctional silane represented by the general formula SiX ₄ (wherein X is as defined above).
Typical examples include tetraalkoxysilanes such as tetramethoxysilane and tetraethoxysilane.

In this surface treatment, the organosilicon compound (1) may be hydrolyzed with a hydrolyzable group after mixing with the inorganic oxide fine particles, or may be partially hydrolyzed or hydrolyzed with the hydrolyzable group. Then, it may be mixed with the inorganic oxide fine particles and further hydrolyzed as necessary.
Further, at the stage where the surface treatment operation is completed, it is preferable that all of the hydrolyzable groups are in a state of reacting with —OH groups present on the surface of the coating layer of the inorganic oxide fine particles. , A part of which may remain unreacted. When performing this surface treatment, it is desirable to use inorganic oxide fine particles having —OH groups on the surface of the coating layer as the inorganic oxide fine particles.

  Examples of the amine compounds include ammonia; alkylamines such as ethylamine, triethylamine, isopropylamine and n-propylamine; aralkylamines such as benzylamine; alicyclic amines such as piperidine; alkanols such as monoethanolamine and triethanolamine. Amines; quaternary ammonium salts such as tetramethylammonium salt and tetramethylammonium hydroxide, or quaternary ammonium hydroxide.

  A typical example of the organosilicon compound represented by the above general formula (I) (hereinafter referred to as “organosilicon compound (2)”) used by mixing with the inorganic oxide fine particles is an alkoxysilane compound. Specifically, tetraethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, trimethylchlorosilane, α-glucidoxymethyltrimethoxysilane, α-glycidoxyethyl Trimethoxysilane, β-glycidoxyethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyl Methyldiethoxysilane, β- (3,4-epoxy Cyclohexyl) -ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) -ethyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β (aminoethyl) -γ- Examples include aminopropylmethyldimethoxysilane, N-β (aminoethyl) -γ-aminopropylmethyldiethoxysilane. Among these, tetraethoxysilane, methyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) -ethyltrimethoxysilane, etc. Is preferably used. Moreover, these organosilicon compounds (2) may use not only one type but also two or more types.

  In preparing the coating liquid A for an optical substrate according to the present invention, the organosilicon compound (2) is partially hydrolyzed in the absence of a solvent or in a polar organic solvent such as alcohol in the presence of an acid and water. It is preferable to mix with the inorganic oxide fine particles after decomposition or hydrolysis. However, the organosilicon compound (2) may be partially hydrolyzed or hydrolyzed after being mixed with the inorganic oxide fine particles.

Thus, the coating liquid A for an optical substrate according to the present invention is prepared by mixing the organosilicon compound (2) and / or a hydrolyzate thereof and the inorganic oxide fine particles. As for the ratio, when the weight of the organosilicon compound (2) converted to SiO ₂ is represented by X and the weight of the inorganic oxide fine particles is represented by Y, the weight ratio (X / Y) is 30/70 to It is preferable to be in the range of 90/10. Here, when the weight ratio is less than 30/70, the adhesiveness with the optical substrate is lowered, and when the weight ratio exceeds 90/10, the refractive index of the coating film is lowered. It is not preferable.

In addition to the above components, the coating liquid A for an optical substrate according to the present invention improves the dyeability of the hard coat layer and the adhesion to a plastic lens substrate, and further prevents the occurrence of cracks. In addition, an uncrosslinked epoxy compound may be contained.
Examples of the uncrosslinked epoxy compound include 1,6-hexanediol diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, and the like. Among these, it is preferable to use 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, or the like. Moreover, these uncrosslinked epoxy compounds may use not only one type but also two or more types.

Furthermore, the coating liquid A for an optical substrate according to the present invention contains components other than those described above, for example, a surfactant, a leveling agent, or an ultraviolet absorber, as well as Patent Document 2, Patent Document 3, JP-A-11-310755, It may contain an organic compound or an inorganic compound described in a conventionally known document such as International Application Publication WO2007 / 046357.
Moreover, the coating liquid A for optical substrates prepared in this way can be suitably used as a coating liquid for forming a hard coat layer.

Coating liquid B for optical substrates
The coating liquid B for an optical substrate according to the present invention is
(1) Nuclear particles composed of titanium oxide fine particles and / or composite oxide fine particles containing titanium and one or more metal elements selected from zirconium, tin, tungsten, niobium, cerium and silicon Potassium compounds (as oxides) are formed in inorganic oxide fine particles whose surface is coated with silicon and an oxide and / or composite oxide of one or more metal elements selected from zirconium, aluminum and antimony. Inorganic oxide fine particles having a core-shell structure containing 1.0 to 8.0% by weight (excluding K ₂ O) in terms of K ₂ O, and (2) a thermosetting resin or a thermoplastic resin.

It is preferable that the inorganic oxide fine particles are surface-treated with an organosilicon compound or an amine compound.
The organosilicon compound and amine compound used for the surface treatment can be appropriately selected from the above and used, and thus the description thereof is omitted here.

  Examples of the thermosetting resin used by mixing with the inorganic oxide fine particles include urethane resin, epoxy resin, melamine resin, and silicone resin. Among these, it is preferable to use a urethane resin, an epoxy resin, or the like. Further, these thermosetting resins may be used not only in one type but also in two or more types.

  Examples of the thermoplastic resin used by mixing with the inorganic oxide fine particles include acrylic resins, urethane resins and ester resins. Among these, it is preferable to use urethane resin, ester resin, or the like. Moreover, these thermoplastic resins may use not only one type but also two or more types.

Furthermore, the coating liquid B for optical substrates according to the present invention is described in components other than those described above, for example, neutralizers, surfactants or ultraviolet absorbers, and further known literatures such as International Application Publication WO2007 / 026529. It may contain an organic compound or an inorganic compound.
Moreover, the coating liquid B for optical substrates prepared in this way can be used suitably as a coating liquid for primer layer formation.

[Optical substrate]
As the optical substrate used in the present invention, there are various plastic substrates. When this is used as an optical lens, polystyrene resin, allyl resin (especially aromatic allyl resin), polycarbonate resin, There is a plastic lens substrate made of thiourethane resin, polythioepoxy resin or the like. Moreover, as a plastic base material used other than an optical lens, there is a plastic base material made of PMMA resin, ABS resin, epoxy resin, polysulfone resin, or the like.
In addition, the optical base material used in this invention can be suitably selected from these plastic base materials currently marketed or test-supplied.

[Measuring method]
Next, the measurement methods and evaluation test methods used in the examples and others of the present invention will be specifically described as follows.
(1) Average particle diameter of particles 7.0 g of water-dispersed sol of inorganic oxide fine particles (solid content 20% by weight) is placed in a cylindrical stainless steel cell with a transmission window having a length of 3 cm, a width of 2 cm, and a height of 2 cm. The particle size distribution is measured using an ultrafine particle size analyzer (Model 9340-UPA150, manufactured by Honeywell) using a dynamic light scattering method, and the average particle size is calculated therefrom.

(2) Specific surface area of particles About 30 ml of a dry powder of inorganic oxide fine particles is collected in a magnetic crucible (B-2 type), dried at a temperature of 300 ° C. for 2 hours, then placed in a desiccator and cooled to room temperature. Next, 1 g of a sample is taken, and the specific surface area (m ² / g) is measured by the BET method using a fully automatic surface area measuring device (manufactured by Yuasa Ionics Co., Ltd., Multisorb 12 type).

(3) Presence / absence of solid acid contained in particles Collect about 30 ml of water-dispersed sol of inorganic oxide fine particles in a magnetic crucible (Type B-2), dry at 200 ° C. for 3 hours, place in a desiccator and cool to room temperature To do. Next, 1.5 g of a sample is taken, and the amount of free solid acid (that is, solid acid remaining amount) is measured as the amount of adsorption of ammonia using MULTI MICRO CALORIMETER (manufactured by Tokyo Riko Co., Ltd., MMC-511SV). . Thereby, the presence or absence of a solid acid present in the inorganic oxide fine particles is confirmed.
However, the amount of solid acid obtained from this measurement method does not indicate the total amount of solid acid contained in the inorganic oxide fine particles. That is, since the solid acid combined with the potassium compound or the like in the process of preparing the fine particles does not adsorb ammonia, it cannot be measured.

(4) Crystal form of core particle About 30 ml of water-dispersed sol of inorganic oxide fine particles is collected in a magnetic crucible (B-2 type), dried at 110 ° C. for 12 hours, then placed in a desiccator and cooled to room temperature. Next, after pulverizing for 15 minutes in a mortar, the crystal form is measured using an X-ray diffractometer (RINT1400, manufactured by Rigaku Corporation).

(5) Content of metal oxide contained in particles Aqueous dispersion sol (sample) of inorganic oxide fine particles is collected in zirconia balls, dried and fired, and then Na ₂ O ₂ and NaOH are added and melted. Furthermore, after dissolving with H ₂ SO ₄ and HCl and diluting with pure water, the content of titanium, tin, and silica is converted to oxide using an ICP device (Shimadzu Corporation, ICPS-8100). Measured with (TiO ₂ , SnO ₂ and SiO ₂ ).
Next, the sample is collected in a platinum dish, HF and H ₂ SO ₄ are added, heated, and dissolved with HCl. Furthermore, after diluting this with pure water, the content of zirconium is measured by an oxide conversion standard (ZrO ₂ ) using an ICP device (manufactured by Shimadzu Corporation, ICPS-8100).
Then, the sample was taken in a platinum dish and heated by adding HF and H ₂ SO _4, dissolved in HCl. Furthermore, after diluting this with pure water, the content of potassium is measured by an oxide conversion standard (K ₂ O) using an atomic absorption device (manufactured by Hitachi, Ltd., Z-5300).

(6) Appearance (interference fringes)
A fluorescent lamp “trade name: Mellow 5N” (manufactured by Toshiba Lighting & Technology Co., Ltd., three-wavelength daylight white fluorescent lamp) is mounted in a box whose inner wall is black, and the substrate of the example shown below and the comparison of the fluorescent light Example Reflection is performed on the surface of the antireflection film of the substrate, and the occurrence of rainbow patterns (interference fringes) due to light interference is visually confirmed, and evaluated according to the following criteria.
S: There is almost no interference fringe. A: The interference fringe is not conspicuous. B: Although the interference fringe is recognized, it is within an allowable range. C: The interference fringe is conspicuous. D: There is an interference fringe with glare.

(7) Appearance (cloudy)
A fluorescent lamp "trade name: Mellow 5N" (manufactured by Toshiba Lighting & Technology Co., Ltd., three-wavelength daylight white fluorescent lamp) is mounted in a box whose inner wall is black, and the following example substrate and comparative example substrate are fluorescent lamps. The transparency (degree of cloudiness) is visually confirmed and evaluated according to the following criteria.
A: No haze B: Slight haze C: Clear haze D: Significant haze

(8) Scratch resistance test The surface of the substrate on which the hard coat layer was formed was manually rubbed with Bonstar Steel Wool # 0000 (manufactured by Nippon Steel Wool Co., Ltd.), and the degree of damage was visually determined. Evaluate with.
A: Almost no flaws B: Some flaws enter C: Some flaws enter D: Most flawed areas are scratched.

(9) Adhesion test The lens surface of the substrate on which the hard coat layer is formed is cut with a knife at intervals of 1 mm to form 100 squares of 1 mm square, and after strongly pressing the cellophane adhesive tape, the plastic Abruptly pulling in the 90 degree direction with respect to the in-plane direction of the lens substrate, this operation is performed a total of 5 times, the number of squares that do not peel off is counted, and the following criteria are evaluated.
Good: The number of cells not peeled is 95 or more. Bad: The number of cells not peeled is less than 95.

(10) Weather resistance test The substrate on which the hard coat layer was formed was subjected to an exposure test using a xenon weather meter (X-75 type manufactured by Suga Test Instruments Co., Ltd.), and then the same test as the confirmation of appearance and the above-mentioned adhesion test And evaluate according to the following criteria. The exposure time is 200 hours for a substrate having an antireflection film and 50 hours for a substrate not having an antireflection film.
Good: The number of cells not peeled is 95 or more. Bad: The number of cells not peeled is less than 95.

(11) Light resistance test UV light is irradiated for 50 hours with a mercury lamp for fading test (H400-E manufactured by Toshiba Corporation), the lens color before and after the test is visually confirmed, and evaluated according to the following criteria. The irradiation distance between the lamp and the test piece is 70 mm, and the output of the lamp is adjusted so that the surface temperature of the test piece is 45 ± 5 ° C. This test was conducted on a plastic lens having an antireflection film applied to the surface of the hard coat layer.
○: Not much discoloration is observed Δ: Some discoloration is recognized ×: Clear discoloration is observed

Hereinafter, the present invention will be specifically described based on examples. However, the present invention is not limited to the scope described in these examples.

[Example 1]
Preparation of water-dispersed sol containing titanium-based composite oxide fine particles (1) having anatase type crystal structure and inorganic oxide fine particles as sol (1) core particles Titanium tetrachloride (manufactured by Osaka Titanium Technologies Co., Ltd.) A white slurry liquid having a pH of 8.5 was prepared by mixing 100 kg of titanium tetrachloride aqueous solution containing 2.0% by weight in terms of TiO ₂ and ammonia water containing 15% by weight of ammonia (manufactured by Ube Industries). . Next, the slurry was filtered and then washed with pure water (manufactured by Catalyst Chemical Industry Co., Ltd.) to obtain 20 kg of a hydrous titanate cake having a solid content of 10% by weight.
Next, to this cake 20 kg, hydrogen peroxide containing 35% by weight of hydrogen peroxide (manufactured by Mitsubishi Gas Chemical Co., Inc.) 22.84 kg and pure water 57.16 kg were added, and then at a temperature of 80 ° C. The mixture was heated with stirring for a period of time to obtain 100 kg of an aqueous solution of titanic acid peroxide containing 2% by weight of titanic acid peroxide in terms of TiO ₂ . This aqueous solution of titanic acid peroxide was transparent yellowish brown and had a pH of 8.1.

Next, 496.5 g of a silica sol (catalyst chemical industry Co., Ltd.) containing 15% by weight of silica fine particles having an average particle diameter of 7 nm and 29.5 kg of pure water were mixed with 22.5 kg of the aqueous solution of titanic acid peroxide. And heated in an autoclave (pressure-resistant glass industry, 120 L) at a temperature of 165 ° C. for 18 hours.
Next, after the obtained sol was cooled to room temperature, it was concentrated using an ultrafiltration membrane device (ACV-3010, manufactured by Asahi Kasei Co., Ltd.), and a water-dispersed sol 5 having a solid content of 10% by weight. Obtained 245 kg.
The inorganic oxide fine particles contained in the water-dispersed sol thus obtained were measured by the above-mentioned method. As a result, composite oxide fine particles containing titanium and silicon having an anatase type crystal structure (hereinafter referred to as “inorganic oxide”). Referred to as “fine particles 1Ac”). Furthermore, when the content of the metal component contained in the inorganic oxide fine particle 1Ac was measured, it was 88.0% by weight of TiO ₂ and 12.0% by weight of SiO _{2 on} the oxide conversion standard of each metal component. .

(2) Preparation of water-dispersed sol containing coated inorganic oxide fine particles 26.3% of zirconium oxychloride aqueous solution containing 2% by weight of zirconium oxychloride (manufactured by Taiyo Mining Co., Ltd.) in terms of ZrO ₂ , and 15% of ammonia. Aqueous ammonia containing wt% was gradually added with stirring to obtain a slurry solution having a pH of 8.5 containing zirconium hydrate. Subsequently, this slurry was filtered and then washed with pure water to obtain 5.26 kg of a cake having a zirconium component of 10% by weight in terms of ZrO ₂ .
Next, 1.80 kg of pure water was added to 200 g of this cake, and 120 g of an aqueous potassium hydroxide solution containing 10% by weight of potassium hydroxide (manufactured by Kanto Chemical Co., Ltd.) was added to make it alkaline. 400 g of hydrogen peroxide containing wt% was added and heated to a temperature of 50 ° C. to dissolve this cake. Further, 1.48 kg of pure water was added to obtain 4.0 kg of an aqueous solution of zirconate peroxide containing 0.5 wt% of zirconate peroxide in terms of ZrO ₂ on a conversion basis. The pH of the aqueous zirconate peroxide solution was 12.

On the other hand, after diluting commercially available water glass (manufactured by AGC S-Tech Co., Ltd.) with pure water, it is dealkalized using a cation exchange resin (manufactured by Mitsubishi Chemical Corporation), and the silicon component is converted into SiO ₂ An aqueous silicic acid solution containing 2% by weight was obtained. The silicic acid aqueous solution had a pH of 2.3.
Next, 12.0 kg of pure water is added to 3.0 kg of the water-dispersed sol containing the inorganic oxide fine particles 1Ac obtained in the step (1), and the mixture is stirred to obtain an aqueous dispersion having a solid content of 2% by weight. A sol was obtained. Next, after heating this water-dispersed sol to a temperature of 90 ° C., 1020 g of the zirconic acid aqueous solution and 795 g of the silicic acid aqueous solution were gradually added thereto. Further, after the addition was completed, the mixture was stirred while maintaining the temperature at 90 ° C. Aged for 1 hour.
Next, this mixed solution was put in an autoclave (manufactured by Pressure Glass Industrial Co., Ltd., 50 L) and subjected to heat treatment at a temperature of 165 ° C. for 18 hours.
Next, after cooling the obtained liquid mixture to room temperature, it concentrates with an ultrafiltration membrane apparatus (Asahi Kasei Co., Ltd. make, SIP-1013), and the water dispersion sol 1A whose solid content is 20 weight% is obtained. Obtained.

When the inorganic oxide fine particles contained in the water-dispersed sol thus obtained were measured by the above method, the surface of the composite oxide fine particles (nuclear particles) containing titanium and silicon having an anatase type crystal structure. Was an inorganic oxide fine particle (hereinafter, referred to as “inorganic oxide fine particle 1Aw”) coated with a composite oxide containing zirconium and silicon. The appearance of the water-dispersed sol containing the inorganic oxide fine particles 1Aw was transparent and light milky white.

Furthermore, when the metal component contained in the inorganic oxide fine particles 1Aw was measured, TiO _{2 was} 82.2% by weight, SiO _{2 was} 14.6% by weight, and ZrO ₂ 1.5 was 1.5 based on the oxide conversion standard of each metal component. Wt% and K ₂ O 1.7 wt%. The measurement result of the whole particles, when the from the measurement results of the inorganic oxide fine particles 1Ac (core particles) was calculated content ratio of the metal component contained in the coating layer, ZrO ₂ 1.5 to the particle total amount Wt%, SiO ₂ 3.4 wt% and K ₂ O 1.7 wt%.
The measured solid acid remaining contained in the inorganic oxide fine particles adsorbed NH ₃ amount was 0.06 mmol / g.
Further, the average particle size of the inorganic oxide fine particles 1Aw was 10 nm as measured by the ultrafine particle size analyzer, and the specific surface area of the dry powder was 223 m ² / g.
Further, whether or not K ₂ 0 is contained in the inorganic oxide fine particles was measured using an X-ray diffractometer (RINT 1400, manufactured by Rigaku Corporation), the peak of K ₂ 0 as a crystalline substance was measured. Was not detected.

(3) Preparation of methanol-dispersed sol containing coated inorganic oxide fine particles Water-dispersed sol containing inorganic oxide fine particles 1Aw obtained in the step (2) was treated with tetraethoxysilane (Tama Chemical Industry ( The product was added to a methanol solution in which the product was dissolved under stirring, and then heated at a temperature of 50 ° C. for 6 hours.
Next, after cooling this mixed solution to room temperature, the dispersion medium was replaced with methanol (manufactured by China Essential Oil Co., Ltd.) using an ultrafiltration membrane.
Further, the obtained methanol dispersion was concentrated with an ultrafiltration membrane (SIP-1013, manufactured by Asahi Kasei Co., Ltd.). Prepared.
The appearance of the methanol-dispersed sol containing the inorganic oxide fine particles thus obtained was a transparent light blue white.

[Example 2]
Preparation of water-dispersed sol containing titanium-based composite oxide fine particles (2) having anatase type crystal structure and inorganic oxide fine particles as sol (1) core particles Titanium tetrachloride (manufactured by Osaka Titanium Technologies Co., Ltd.) A white slurry liquid having a pH of 8.5 was prepared by mixing 100 kg of titanium tetrachloride aqueous solution containing 2.0% by weight in terms of TiO ₂ and ammonia water containing 15% by weight of ammonia (manufactured by Ube Industries). . Next, this slurry was filtered and then washed with pure water to obtain 20 kg of a hydrous titanate cake having a solid content of 10% by weight.

Next, after adding 5.71 kg of hydrogen peroxide containing 35 wt% hydrogen peroxide (Mitsubishi Gas Chemical Co., Ltd.) and 14.29 kg of pure water to 5.0 kg of this cake, a temperature of 80 ° C. And heated for 1 hour with stirring to obtain 25 kg of a titanic acid aqueous solution containing 2% by weight of titanic acid peroxide on a TiO ₂ basis. Further, 25.0 kg of pure water was added to obtain an aqueous solution of titanic acid peroxide containing 1% by weight of titanic acid peroxide on a TiO ₂ basis. This aqueous solution of titanic acid peroxide was transparent yellowish brown and had a pH of 8.3.

Next, after adding 3.0 kg of an anion exchange resin (manufactured by Mitsubishi Chemical Corporation) to 50.0 kg of the aqueous solution of titanic acid peroxide, an aqueous zirconium oxychloride solution containing 1% by weight of zirconium oxychloride on a ZrO ₂ conversion basis ( 5.0 kg of Taiyo Mining Co., Ltd.) was gradually added and mixed. Thereafter, the anion exchange resin was separated and removed. Further, after adding and mixing 607 g of silica sol (catalyst chemical industry Co., Ltd.) containing 15% by weight of silica fine particles having an average particle diameter of 7 nm and pure water (catalyst chemical industry Co., Ltd.) 8.5 kg, hydroxylation was performed. 1.67 kg of potassium hydroxide aqueous solution containing 1% by weight of potassium (manufactured by Kanto Chemical Co., Inc.) was added and heated in an autoclave at a temperature of 165 ° C. for 18 hours.

Next, after the obtained sol was cooled to room temperature, it was concentrated with an ultrafiltration membrane device (ACV-3010, manufactured by Asahi Kasei Co., Ltd.), and 6.4 kg of an aqueous dispersion sol having a solid content of 10% by weight. Got.
The inorganic oxide fine particles contained in the water-dispersed sol thus obtained were measured by the above method. As a result, composite oxide fine particles containing titanium, silicon, and zirconium having an anatase type crystal structure (hereinafter referred to as “ Inorganic oxide fine particles 2Ac ”). Furthermore, when the content of the metal component contained in the inorganic oxide fine particle 2Ac was measured, it was 78.4% by weight of TiO ₂ , 11.8% by weight of SiO ₂ , ZrO _{2 based on} the oxide conversion standard of each metal component. 7.8 and the weight percent and K ₂ O2.0% by weight.

(2) Preparation of water-dispersed sol containing coated inorganic oxide fine particles Under the same conditions as in Example 1, the surface of the inorganic oxide fine particles 2Ac obtained in the step (1) was treated with zirconium, silicon. Then, an aqueous dispersion sol 2A containing fine inorganic oxide particles coated with a complex oxide containing potassium was obtained.
The inorganic oxide fine particles contained in the water-dispersed sol thus obtained were measured by the above method. As a result, composite oxide fine particles (nuclear particles) containing titanium, silicon, and zirconium having an anatase type crystal structure. These were inorganic oxide fine particles (hereinafter referred to as “inorganic oxide fine particles 2Aw”) obtained by coating the surface of the composite oxide with a complex oxide containing zirconium and silicon. The appearance of the water-dispersed sol containing the inorganic oxide fine particles 2Aw was transparent and light milky white.

Further, when the metal components contained in the inorganic oxide fine particles 2Aw were measured, TiO _{2 was} 73.5% by weight, SiO _{2 was} 14.4% by weight, ZrO ₂ 8.8 based on the oxide conversion standard of each metal component. Wt% and K ₂ O 3.3 wt%. The measurement result of the whole particles, when the from the measurement results of the inorganic oxide fine particles 2Ac (core particles) was calculated content ratio of the metal component contained in the coating layer, ZrO ₂ 1.5 to the particle total amount wt%, it was SiO ₂ 3.3 wt% and K ₂ O1.4% by weight.
Furthermore, when the amount of solid acid contained in the inorganic oxide fine particles was measured as the NH ₃ adsorption amount, it was 0.05 mmol / g.
Furthermore, the average particle diameter of the inorganic oxide fine particles 2Aw was 15 nm as measured by a dynamic light scattering method, and the specific surface area of the dry powder was 206 m ² / g.

(3) Preparation of methanol-dispersed sol containing coated inorganic oxide fine particles Water-dispersed sol containing inorganic oxide fine particles 2Aw obtained in the step (2) was treated with tetraethoxysilane (Tama Chemical Industry ( The product was added to a methanol solution in which the product was dissolved under stirring, and then heated at a temperature of 50 ° C. for 6 hours.
Subsequently, solvent substitution was performed under the same conditions as in the method shown in Example 1 to prepare methanol-dispersed sol 2A containing inorganic oxide fine particles 2Aw having a solid content of 20% by weight.

[Example 3 and Comparative Example 1]
Preparation of water-dispersed sol containing titanium-based composite oxide fine particles (3) to (8) having anatase type crystal structure and inorganic oxide fine particles as sol (1) core particles The same conditions as the method shown in Example 1 Thus, 100 kg of an aqueous solution of titanic acid peroxide containing 2% by weight of titanic acid peroxide in terms of TiO ₂ was obtained.
Next, 287 g of silica sol (catalyst chemical industry Co., Ltd.) containing 12.87 kg of the titanic acid peroxide aqueous solution and 15% by weight of silica fine particles having an average particle diameter of 7 nm and pure water (catalyst chemical industry Co., Ltd.) )) 16.846 kg is mixed, and an aqueous solution of potassium hydroxide containing 1% by weight of potassium hydroxide (manufactured by Kanto Chemical Co., Ltd.) is added in the ratio shown in Table 1, and then an autoclave (manufactured by Pressure Glass Industrial Co., Ltd.) is added. 50 L) at a temperature of 165 ° C. for 18 hours.
Further, the silica sol and the potassium hydroxide aqueous solution were added to the titanate aqueous solution at the ratio shown in Table 1, and heat treatment was performed in an autoclave under the same conditions as described above.

Next, after cooling the obtained sol to room temperature, it was concentrated with an ultrafiltration membrane device (Asahi Kasei Co., Ltd., SIP-1013) to obtain an aqueous dispersion sol having a solid content of 10 wt%. .
The inorganic oxide fine particles contained in each water-dispersed sol thus obtained were measured by the above method. As a result, composite oxide fine particles containing titanium and silicon having an anatase type crystal structure (hereinafter referred to as “ Inorganic oxide fine particles 3Ac to 8Ac ”). Furthermore, the content of the metal component contained in these inorganic oxide fine particles 3Ac to 8Ac was measured in the same manner as in Example 1. The results are shown in Table 1.

(2) Preparation of water-dispersed sol containing coated inorganic oxide fine particles Under the same conditions as in Example 1, 5.26 kg of a cake containing 10% by weight of the zirconium component on a ZrO ₂ conversion basis was obtained.
Next, after adding 461 g of pure water to 51 g of this cake to prepare a slurry liquid containing 1% by weight of the zirconium component in terms of ZrO _2, water containing 10% by weight of potassium hydroxide (manufactured by Kanto Chemical Co., Inc.). After adding 102 g of an aqueous potassium oxide solution to make it alkaline, 102 g of hydrogen peroxide containing 35% by weight of hydrogen peroxide (manufactured by Mitsubishi Gas Chemical Co., Ltd.) is added, and 306 g of pure water is further added to a temperature of 50 ° C. The cake was dissolved by heating. As a result, 1020 g of an aqueous zirconate peroxide solution containing 0.5% by weight of zirconate peroxide in terms of ZrO ₂ was obtained.
Further, the potassium hydroxide aqueous solution and the hydrogen peroxide solution were added to the cake in the ratio shown in Table 1, and under the same conditions as described above, the zirconium zirconate was added at 0.5% by weight in terms of ZrO _2. An aqueous zirconate peroxide solution containing was obtained.

Subsequently, after diluting a commercially available water glass (manufactured by AGC S-Tech Co., Ltd.) with pure water under the same conditions as in the method shown in Example 1, a cation exchange resin (manufactured by Mitsubishi Chemical Corporation) was used. The resulting solution was dealkalized to obtain a silicic acid aqueous solution containing 2% by weight of a silicon component on a SiO ₂ conversion basis.
Next, 12.0 kg of pure water is added to 3.0 kg of the water-dispersed sol containing the inorganic oxide fine particles 3Ac to 8Ac obtained in the step (1) and stirred, so that the solid content is 2% by weight. An aqueous dispersion sol was obtained.

Next, after heating the water-dispersed sol of the inorganic oxide fine particles 3Ac to a temperature of 90 ° C., 1020 g of the zirconate aqueous solution and 795 g of the silicic acid aqueous solution are gradually added thereto. The mixture was aged for 1 hour under stirring while maintaining the temperature.
Further, the aqueous dispersion sol containing the inorganic oxide fine particles 4Ac to 8Ac is also subjected to aging under the same conditions as above by adding the aqueous zirconate peroxide solution and the aqueous silicic acid solution at the ratio shown in Table 1. It was.
Next, each of these liquid mixtures was put in an autoclave and subjected to heat treatment at a temperature of 165 ° C. for 18 hours.
Next, after cooling the obtained mixed liquid to room temperature, it is concentrated using an ultrafiltration membrane device (Asahi Kasei Co., Ltd., SIP-1013), and an aqueous dispersion sol having a solid content of 20% by weight. 3A-8A were obtained.

When the inorganic oxide fine particles contained in the water-dispersed sol thus obtained were measured by the above method, the surface of the composite oxide fine particles (nuclear particles) containing titanium and silicon having an anatase type crystal structure. Were inorganic oxide fine particles (hereinafter referred to as “inorganic oxide fine particles 3Aw to 8Aw”) formed by coating with a composite oxide containing zirconium and silicon.
Further, the content of the metal component contained in these inorganic oxide fine particles 3Aw to 8Aw was measured in the same manner as in Example 1. Further, in the same manner as in Example 1, the amount of solid acid contained in the fine particles was measured as the NH ₃ adsorption amount. The results are shown in Table 1.

(3) Preparation of methanol-dispersed sol containing coated inorganic oxide fine particles Tetraethoxysilane as a surface treatment agent for each water-dispersed sol containing inorganic oxide fine particles 3Aw to 8Aw obtained in the step (2). After adding to the methanol solution in which (Tama Chemical Co., Ltd. product) was dissolved, it heated at the temperature of 50 degreeC for 6 hours.
Subsequently, solvent substitution was performed under the same conditions as in the method shown in Example 1, and methanol dispersed sols 3A to 8A containing inorganic oxide fine particles 3Aw to 8Aw having a solid content of 20% by weight were prepared.

[Comparative Example 2]
Adjustment of the potassium content contained in the titanium-based composite oxide fine particles (9) having an anatase type crystal structure and the sol (1) coated inorganic oxide fine particles Inorganic oxidation obtained in the step (2) of Example 1 50 g of a cation exchange resin (manufactured by Mitsubishi Chemical Corporation) was added to 2000 g of an aqueous dispersion sol 1Aw containing 1 Aw of the material fine particles, and the mixture was stirred at room temperature for 1 hour.
As a result, an aqueous dispersion sol 9A containing inorganic oxide fine particles 9Aw in which the content of the potassium compound contained in the inorganic oxide fine particles was reduced was obtained.
When the metal components contained in the inorganic oxide fine particles 9Aw obtained in this way were measured, the oxide conversion standard of each metal component was 82.8% by weight of TiO ₂ , 15.1% by weight of SiO ₂ , ZrO. It was ₂ 1.6 wt% and K ₂ O0.5% by weight. The measurement result of the entire particle, the more measurements of the inorganic oxide fine particles 1Ac (core particles) was calculated the content ratio of the metal component contained in the coating layer, ZrO ₂ 1.6 to the particle total amount wt%, it was SiO ₂ 3.8 wt% and K ₂ O0.5% by weight.
Furthermore, when the amount of solid acid contained in the inorganic oxide fine particles was measured as the NH ₃ adsorption amount, it was 0.09 mmol / g.

(2) Preparation of methanol-dispersed sol containing coated inorganic oxide fine particles Tetraethoxysilane (manufactured by Tama Chemical Industry Co., Ltd.) as a surface treating agent was used for the aqueous dispersion sol containing inorganic oxide fine particles 9Aw obtained above. After being added to a methanol solution in which was dissolved, the mixture was heated at a temperature of 50 ° C. for 6 hours.
Subsequently, solvent substitution was performed under the same conditions as in the method shown in Example 1, and a methanol-dispersed sol 9A containing inorganic oxide fine particles 9Aw having a solid content of 20% by weight was prepared.

[Example 4]
Adjustment of the potassium content contained in the titanium-based composite oxide fine particles (10) having an anatase type crystal structure and the sol (1) coated inorganic oxide fine particles Inorganic oxidation obtained in the step (2) of Comparative Example 1 100 g of a cation exchange resin (manufactured by Mitsubishi Chemical Corporation) was added to 2000 g of an aqueous dispersion sol 8Aw containing product fine particles 8Aw, and the mixture was stirred at room temperature for 1 hour.

As a result, an aqueous dispersion sol 10A containing inorganic oxide fine particles 10Aw in which the content of the potassium compound contained in the inorganic oxide fine particles was reduced was obtained.
When the metal component contained in the thus obtained inorganic oxide fine particles 10Aw was measured, it was 37.1% by weight of TiO ₂ , 36.7% by weight of SiO ₂ , ZrO in terms of oxide conversion standard of each metal component. It was ₂ 19.2 wt% and K ₂ O7.0 wt%. From the measurement result of the whole particle and the measurement result of the inorganic oxide fine particle 8Ac (nuclear particle), the content ratio of the metal component contained in the coating layer was calculated, and ZrO ₂ 19.2 with respect to the total amount of the particle. Wt%, SiO ₂ 31.6 wt% and K ₂ O 6.6 wt%. However, in calculating the potassium compound contained in the coating layer, it was considered that potassium ions or the like did not elute from the core particles of the inorganic oxide fine particles 8Ac during the treatment with the cation exchange resin.
Furthermore, when the amount of solid acid contained in the inorganic oxide fine particles was measured as the NH ₃ adsorption amount, it was 0.28 mmol / g.

(2) Preparation of methanol-dispersed sol containing coated inorganic oxide fine particles Tetraethoxysilane (manufactured by Tama Chemical Industry Co., Ltd.) as a surface treating agent was used for the water-dispersed sol containing inorganic oxide fine particles 10Aw obtained above. After being added to a methanol solution in which was dissolved, the mixture was heated at a temperature of 50 ° C. for 6 hours.
Subsequently, solvent substitution was performed under the same conditions as in the method shown in Example 1, and methanol-dispersed sols 10A containing inorganic oxide fine particles 10Aw having a solid content of 20% by weight were prepared.

[Example 5]
Adjustment of content of potassium contained in titanium-based composite oxide fine particles (11) and sol (1) core particles having anatase type crystal structure Inorganic oxide fine particles 3Ac obtained in the step (1) of Example 3 Water dispersion sol 3A containing
To 3.0 kg, 290 g of a potassium hydroxide aqueous solution containing 1% by weight of potassium hydroxide (manufactured by Kanto Chemical Co., Inc.) was added and stirred at room temperature for 1 hour.
As a result, an aqueous dispersion sol 11A containing inorganic oxide fine particles 11Ac in which the content of the potassium compound contained in the inorganic oxide fine particles (core particles) was increased was obtained. In addition, it was found that the potassium compound added from the outside in this way also adheres to the surface of the inorganic oxide fine particles and is taken into the fine particles. This is considered to be due to the reaction between the O · H groups present on the surface of the fine particles and potassium ions.
When the metal component contained in the thus obtained inorganic oxide fine particles 11Ac was measured, TiO _{2 was} 86.9% by weight, SiO _{2 was} 11.8% by weight, and K based on the oxide conversion standard of each metal component. It was ₂ O1.3% by weight.

(2) Preparation of water-dispersed sol containing coated inorganic oxide fine particles Under the same conditions as in Example 1, the surface of the inorganic oxide fine particles 11Ac obtained in the step (1) was treated with zirconium and silicon. A water-dispersed sol 11A containing inorganic oxide fine particles (hereinafter referred to as “inorganic oxide fine particles 11Aw”) formed by coating with a composite oxide containing selenium was obtained.
When the metal component contained in the thus obtained inorganic oxide fine particles 11Aw was measured, 81.1% by weight of TiO ₂ , 14.5% by weight of SiO ₂ , ZrO on the basis of oxide conversion of each metal component. ₂ 1.4% by weight and K ₂ O 3.0% by weight. From the measurement result of the whole particle and the measurement result of the inorganic oxide fine particle 11Ac (nuclear particle), the content ratio of the metal component contained in the coating layer was calculated, and ZrO ₂ 1.4 was calculated based on the total amount of the particle. % By weight, 3.5% by weight of SiO ₂ and 1.8% by weight of K ₂ O.
Furthermore, when the amount of solid acid contained in the inorganic oxide fine particles was measured as the NH ₃ adsorption amount, it was 0.05 mmol / g.

(3) Preparation of methanol-dispersed sol containing coated inorganic oxide fine particles Tetraethoxysilane (manufactured by Tama Chemical Industry Co., Ltd.) as a surface treatment agent was used for the water-dispersed sol containing inorganic oxide fine particles 11Aw obtained above. After being added to a methanol solution in which was dissolved, the mixture was heated at a temperature of 50 ° C. for 6 hours.
Next, solvent replacement was performed under the same conditions as in the method shown in Example 1 to prepare a methanol-dispersed sol 11A containing inorganic oxide fine particles 11Aw having a solid content of 20% by weight.

[Comparative Example 3]
Titanium-based composite oxide fine particles (12) having anatase-type crystal structure and sol Anatase-type under the same conditions as in the method shown in step (1) of Example 1 (i.e., preparation of core particle 1Ac) An aqueous dispersion sol having composite oxide fine particles containing titanium and silicon (hereinafter referred to as “inorganic oxide fine particles 12Ac”) having a crystal structure was prepared.
In addition, when the content of the metal component contained in the fine particles was measured, it was 88.0% by weight of TiO ₂ and 12.0% by weight of SiO _{2 on the} basis of oxide conversion of each metal component.
Furthermore, when the amount of solid acid contained in the inorganic oxide fine particles was measured as the NH ₃ adsorption amount, it was 0.02 mmol / g.
Next, water dispersion containing the fine particles is performed under the same conditions as in the step (3) of Example 1 without applying the means shown in Step (2) of Example 1 (that is, coating of the fine particles). The sol was added with stirring to a methanol solution in which tetraethoxysilane (manufactured by Tama Chemical Co., Ltd.) as a surface treating agent was dissolved, and then heated at a temperature of 50 ° C. for 3 hours.
Furthermore, solvent substitution was performed under the same conditions as in the method shown in Example 1 to prepare a methanol-dispersed sol 12A containing inorganic oxide fine particles 12Aw having a solid content of 20% by weight.

[Example 6]
Preparation of water-dispersed sol containing titanium-based composite oxide fine particles (1) having a rutile-type crystal structure and inorganic oxide fine particles as sol (1) core particles Titanium tetrachloride (manufactured by Osaka Titanium Technologies Co., Ltd.) A white slurry having a pH of 9.5 is mixed with 93.665 kg of an aqueous titanium tetrachloride solution containing 7.75% by weight in terms of TiO ₂ and 36.295 kg of aqueous ammonia containing 15% by weight of ammonia (manufactured by Ube Industries). A liquid was prepared. Next, this slurry was filtered and then washed with pure water (manufactured by Catalyst Chemical Industry Co., Ltd.) to obtain 72.6 kg of a hydrous titanate cake having a solid content of 10% by weight.
Next, 83.0 kg of hydrogen peroxide containing 35% by weight of hydrogen peroxide (manufactured by Mitsubishi Gas Chemical Co., Ltd.) and 411.4 kg of pure water are added to the cake, and then at a temperature of 80 ° C. for 1 hour. The mixture was heated under stirring, and 159 kg of pure water was further added to obtain 726 kg of an aqueous solution of titanic acid peroxide containing 1% by weight of titanic acid peroxide on a TiO ₂ basis. This aqueous solution of titanic acid peroxide was transparent yellowish brown and had a pH of 8.5.

Next, 3.5 kg of a cation exchange resin was mixed with 72.9 kg of the aqueous solution of titanic acid peroxide, and stannic acid containing 1% by weight of potassium stannate (manufactured by Showa Kako Co., Ltd.) in terms of SnO _2. 9.11 kg of aqueous potassium solution was gradually added under stirring.
Next, after separating a cation exchange resin (manufactured by Mitsubishi Chemical Corporation) incorporating potassium ions and the like, silica sol (catalyst chemical industry Co., Ltd.) 1 containing 15% by weight of silica fine particles having an average particle diameter of 7 nm is obtained. 0.2 kg and 18.0 kg of pure water were mixed and heated in an autoclave (pressure-resistant glass industry, 120 L) at a temperature of 165 ° C. for 18 hours.

Next, after cooling the obtained sol to room temperature, it was concentrated with an ultrafiltration membrane device (ACV-3010, manufactured by Asahi Kasei Co., Ltd.), and 10.0 kg of an aqueous dispersion sol having a solid content of 10% by weight. Got.
The inorganic oxide fine particles contained in the water-dispersed sol thus obtained were measured by the above method. As a result, composite oxide fine particles containing a rutile crystal structure and containing titanium, tin and silicon (hereinafter referred to as “inorganic Oxide fine particles 1Bc). Furthermore, when the content of the metal component contained in the inorganic oxide fine particle 1Bc was measured, it was 73.7% by weight of TiO ₂ , 9.3% by weight of SnO ₂ , SiO _{2 based on} the oxide conversion standard of each metal component. It was 15.7 wt% and K ₂ O1.3% by weight.

(2) Preparation of water-dispersed sol containing coated inorganic oxide fine particles 26.3 kg of zirconium oxychloride aqueous solution containing 2% by weight of zirconium oxychloride (manufactured by Taiyo Mining Co., Ltd.) in terms of ZrO ₂ , and 15% of ammonia. Aqueous ammonia containing wt% was gradually added with stirring to obtain a slurry solution having a pH of 8.5. Next, this slurry was filtered and then washed with pure water to obtain 5.26 kg of a cake containing 10% by weight of a zirconium component in terms of ZrO ₂ in terms of conversion.
Next, 1.80 kg of pure water was added to 200 g of this cake, and 120 g of an aqueous potassium hydroxide solution containing 10% by weight of potassium hydroxide (manufactured by Kanto Chemical Co., Ltd.) was added to make it alkaline. 400 g of hydrogen peroxide containing wt% was added and heated to a temperature of 50 ° C. to dissolve this cake. Further, 1.48 kg of pure water was added to obtain 4.0 kg of an aqueous zirconate peroxide solution containing 0.5 wt% of zirconate peroxide in terms of ZrO ₂ . The aqueous zirconate peroxide solution had a pH of 12.2.

On the other hand, after diluting commercially available water glass (manufactured by AGC S-Tech Co., Ltd.) with pure water, it is dealkalized using a cation exchange resin (manufactured by Mitsubishi Chemical Corporation), and the silicon component is converted into SiO ₂ An aqueous silicic acid solution containing 2% by weight was obtained. The pH of the aqueous silicic acid solution was 2.3.
Next, 12.0 kg of pure water is added to 3.0 kg of the water-dispersed sol containing the inorganic oxide fine particles 1Bc obtained in the step (1), and the mixture is stirred to obtain an aqueous dispersion having a solid content of 2% by weight. A sol was obtained. Next, after heating this water-dispersed sol to a temperature of 90 ° C., 1020 g of the zirconic acid aqueous solution and 795 g of the silicic acid aqueous solution were gradually added thereto. Further, after the addition was completed, the mixture was stirred while maintaining the temperature at 90 ° C. Aged for 1 hour.
Next, this mixed solution was put in an autoclave (manufactured by Pressure Glass Industrial Co., Ltd., 50 L) and subjected to heat treatment at a temperature of 165 ° C. for 18 hours.
Next, after cooling the obtained mixed liquid to room temperature, it is concentrated using an ultrafiltration membrane device (Asahi Kasei Co., Ltd., SIP-1013), and an aqueous dispersion sol having a solid content of 20% by weight. 1B was obtained.

The inorganic oxide fine particles contained in the water-dispersed sol thus obtained were measured by the above method. As a result, the composite oxide fine particles (nuclear particles) having a rutile crystal structure and containing titanium, tin and silicon. The surface was inorganic oxide fine particles (hereinafter referred to as “inorganic oxide fine particles 1Bw”) formed by coating a complex oxide containing zirconium and silicon. The appearance of the water-dispersed sol containing the inorganic oxide fine particles 1Bw was transparent and light milky white.
Furthermore, when the metal component contained in the inorganic oxide fine particles 1Bw was measured, it was 68.7% by weight of TiO ₂ , 8.8% by weight of SnO ₂ , 17.9% of SiO _{2 on the} basis of oxide conversion of each metal component. wt%, and ZrO ₂ 1.5 wt% and K ₂ O3.1% by weight. From the measurement result of the whole particle and the measurement result of the inorganic oxide fine particle 1Bc (nuclear particle), the content ratio of the metal component contained in the coating layer was calculated, and ZrO ₂ 1.5 with respect to the total amount of the particle was calculated. wt%, it was SiO ₂ 3.3 wt% and K ₂ O1.9% by weight.
Further, the residual amount of the solid acid contained in the inorganic oxide fine particles was measured as the NH ₃ adsorption amount, which was 0.05 mmol / g.
Furthermore, the average particle diameter of the inorganic oxide fine particles 1Bw was 15 nm as measured by a dynamic light scattering method, and the specific surface area of the dry powder was 224 m ² / g.

(3) Preparation of methanol-dispersed sol containing coated inorganic oxide fine particles Water-dispersed sol containing inorganic oxide fine particles 1Bw obtained in the step (2) was treated with tetraethoxysilane (Tama Chemical Industry ( The product was added to a methanol solution in which the product was dissolved under stirring, and then heated at a temperature of 50 ° C. for 6 hours.
Next, after cooling this mixed solution to room temperature, the dispersion medium was replaced with water (manufactured by China Essential Oil Co., Ltd.) using water as an ultrafiltration membrane device.
Further, the obtained methanol dispersion was concentrated with an ultrafiltration membrane device (SIP-1013, manufactured by Asahi Kasei Co., Ltd.), and a methanol dispersion sol 1B containing inorganic oxide fine particles 1Bw having a solid content of 20% by weight. Was prepared.
The appearance of the methanol-dispersed sol containing the inorganic oxide fine particles thus obtained was a transparent light blue white.

[Example 7 and Comparative Example 4]
Preparation of water-dispersed sol containing titanium-based composite oxide fine particles (2) to (7) having a rutile-type crystal structure and inorganic oxide fine particles as sol (1) core particles Conditions similar to the method shown in Example 6 Thus, 726 kg of a titanic acid aqueous solution containing 1% by weight of titanic acid peroxide in terms of TiO ₂ was obtained.
Subsequently, 3.5 kg of cation exchange resin was mixed with 72.9 kg of the aqueous solution of titanic acid peroxide, and stannic acid containing 1% by weight of potassium stannate (manufactured by Showa Kako Co., Ltd.) on the basis of SnO ₂ conversion. 9.11 kg of aqueous potassium solution was gradually added under stirring.

Next, 1.20 kg of silica sol (catalyst chemical industry Co., Ltd.) 1.20 kg and pure water containing 15% by weight of silica fine particles having an average particle diameter of 7 nm in a mixed solution of the aqueous solution of titanic peroxide and the potassium stannate 18.0 kg (manufactured by Catalytic Chemical Industry Co., Ltd.) is mixed, and 1435 g of a potassium hydroxide aqueous solution (manufactured by Kanto Chemical Co., Ltd.) containing 1% by weight of potassium hydroxide is added. Manufactured, 120 L) at a temperature of 165 ° C. for 18 hours.
Further, the silica sol and the potassium hydroxide aqueous solution were added to the titanic acid aqueous solution at the ratio shown in Table 2, and heat treatment was performed in an autoclave under the same conditions as described above.

Next, the obtained sol was cooled to room temperature, and then concentrated with an ultrafiltration membrane device (ACV-3010, manufactured by Asahi Kasei Corporation) to obtain an aqueous dispersion sol having a solid content of 10% by weight. .
The inorganic oxide fine particles contained in each water-dispersed sol thus obtained were measured by the above method. As a result, composite oxide fine particles containing a rutile crystal structure and containing titanium, tin, and silicon (hereinafter referred to as “fine oxide fine particles”) And “inorganic oxide fine particles 2Bc to 7Bc”. Furthermore, the content of the metal component contained in these inorganic oxide fine particles 2Bc to 7Bc was measured in the same manner as in Example 6. The results are shown in Table 2.

(2) Preparation of water-dispersed sol containing coated inorganic oxide fine particles Under the same conditions as in Example 6, 5.26 kg of a cake containing 10% by weight of zirconium component in terms of ZrO ₂ on a conversion basis was obtained.
Next, 459 g of pure water was added to 51 g of this cake, and 102 g of an aqueous potassium hydroxide solution containing 10% by weight of potassium hydroxide (manufactured by Kanto Chemical Co., Ltd.) was added to make it alkaline, and then 35% by weight of hydrogen peroxide. 102 g of hydrogen peroxide solution (manufactured by Mitsubishi Gas Chemical Co., Inc.) was added, 306 g of pure water was further added, and the cake was dissolved by heating to a temperature of 45 ° C. As a result, 1020 g of an aqueous zirconate peroxide solution containing 0.5% by weight of zirconate peroxide in terms of ZrO ₂ was obtained.
Further, the potassium hydroxide aqueous solution and the hydrogen peroxide solution were added to the cake at the ratio shown in Table 2, and under the same conditions as described above, zirconic peroxide was added at 0.5% by weight in terms of ZrO _2. An aqueous zirconate peroxide solution containing was obtained.

Furthermore, after diluting a commercially available water glass (manufactured by AGC S-Tech Co., Ltd.) with pure water under the same conditions as in the method shown in Example 6, a cation exchange resin (manufactured by Mitsubishi Chemical Corporation) was used. The resulting solution was dealkalized to obtain a silicic acid aqueous solution containing 2% by weight of a silicon component on a SiO ₂ conversion basis.
Next, 12.0 kg of pure water is added to 3.0 kg of the water-dispersed sol containing the inorganic oxide fine particles 2Bc to 7Bc obtained in the step (1) and stirred, so that the solid content is 2% by weight. An aqueous dispersion sol was obtained.

Next, after heating the water-dispersed sol of the inorganic oxide fine particles 2Bc to a temperature of 90 ° C., 1020 g of the zirconate aqueous solution and 795 g of the silicic acid aqueous solution were gradually added thereto. The mixture was aged for 1 hour under stirring while maintaining the temperature.
Further, the aqueous dispersion sol containing the inorganic oxide fine particles 3Bc to 7Bc is also subjected to aging under the same conditions as above by adding the aqueous zirconate peroxide solution and the aqueous silicic acid solution at the ratio shown in Table 2. It was.
Next, each of these liquid mixtures was put in an autoclave and subjected to heat treatment at a temperature of 165 ° C. for 18 hours.
Next, after cooling the obtained liquid mixture to room temperature, it concentrates with an ultrafiltration membrane apparatus (Asahi Kasei Co., Ltd. make, SIP-1013), and water-dispersed sol 2B whose solid content is 20 weight%- 7B was obtained.

The inorganic oxide fine particles contained in the water-dispersed sol thus obtained were measured by the above method. As a result, the composite oxide fine particles (nuclear particles) having a rutile crystal structure and containing titanium, tin and silicon. The surface was inorganic oxide fine particles (hereinafter referred to as “inorganic oxide fine particles 2Bw to 7Bw”) formed by coating a composite oxide containing zirconium and silicon.
Further, the content of the metal component contained in these inorganic oxide fine particles 2Bw to 7Bw was measured in the same manner as in Example 6. Further, in the same manner as in Example 6, the residual amount of solid acid contained in the fine particles was measured as the NH ₃ adsorption amount. The results are shown in Table 2.

(3) Preparation of methanol-dispersed sol containing coated inorganic oxide fine particles Tetraethoxysilane as a surface treatment agent for each water-dispersed sol containing inorganic oxide fine particles 2Bw to 7Bw obtained in the step (2). After adding to the methanol solution in which (Tama Chemical Co., Ltd. product) was dissolved, it heated at the temperature of 50 degreeC for 6 hours.
Subsequently, solvent substitution was performed under the same conditions as in the method shown in Example 6 to prepare methanol dispersion sols 2B to 7B containing inorganic oxide fine particles 2Bw to 7Bw having a solid content of 20% by weight.

[Comparative Example 5]
Adjustment of the potassium content contained in the titanium-based composite oxide fine particles (8) having a rutile-type crystal structure and the inorganic oxide fine particles as sol (1) core particles Inorganic obtained in the step (1) of Example 6 80 g of a cation exchange resin (Mitsubishi Chemical Corporation) was added to 3000 g of an aqueous dispersion sol containing oxide fine particles 1Bc, and the mixture was stirred at room temperature for 1 hour.
As a result, an aqueous dispersion sol containing inorganic oxide fine particles 8Bc in which the content of the potassium compound contained in the inorganic oxide fine particles was reduced was obtained.
When the metal components contained in the inorganic oxide fine particles 8Bc (nuclear particles) thus obtained were measured, 74.8% by weight of TiO ₂ and SnO ₂ 9.3 based on oxide conversion standards of the respective metal components. Wt%, SiO ₂ 15.6 wt% and K ₂ O 0.3 wt%.

(2) Preparation of methanol-dispersed sol containing coated inorganic oxide fine particles Using the water-dispersed sol containing inorganic oxide fine particles 8Bc (nuclear particles) obtained in the step (1), the above-mentioned step (Example 6) Under the same conditions as in 2), an aqueous dispersion sol containing inorganic oxide fine particles 8Bw formed by coating the surface of the core particles with a composite oxide containing zirconium and silicon was prepared.
Next, 200 g of a cation exchange resin (manufactured by Mitsubishi Chemical Corporation) was added to 3000 g of the aqueous dispersion sol containing the obtained inorganic oxide fine particles 8Bw, and the mixture was stirred at room temperature for 1 hour.

As a result, an aqueous dispersion sol 8B containing inorganic oxide fine particles 8Bw in which the content of the potassium compound contained in the inorganic oxide fine particles was reduced was obtained.
When the metal component contained in the thus obtained inorganic oxide fine particles 8Bw was measured, it was 70.6% by weight of TiO ₂ , 8.9% by weight of SnO ₂ , SiO _{2 based on} the oxide conversion standard of each metal component. ₂ 18.3% by weight, 1.6% by weight of ZrO ₂ and 0.6% by weight of K ₂ O. The measurement result of the entire particle, the more measurements of the inorganic oxide fine particles 8Bc (core particles) was calculated the content ratio of the metal component contained in the coating layer, ZrO ₂ 1.6 to the particle total amount Wt%, SiO ₂ 3.6 wt% and K ₂ O 0.3 wt%.
Furthermore, when the amount of solid acid contained in the inorganic oxide fine particles was measured as the NH ₃ adsorption amount, it was 0.08 mmol / g.

(3) Preparation of methanol-dispersed sol containing coated inorganic oxide fine particles Tetraethoxysilane (manufactured by Tama Chemical Industry Co., Ltd.) as a surface treating agent was used for the water-dispersed sol containing inorganic oxide fine particles 8Bw obtained above. After being added to a methanol solution in which was dissolved, the mixture was heated at a temperature of 50 ° C. for 3 hours.
Next, solvent replacement was performed under the same conditions as in the method shown in Example 6 to prepare methanol-dispersed sol 8B containing inorganic oxide fine particles 8Bw having a solid content of 20% by weight.

[Example 8]
Adjustment of the potassium content contained in the titanium-based composite oxide fine particles (9) having a rutile-type crystal structure and the sol (1) coated inorganic oxide fine particles Inorganic oxidation obtained in the step (2) of Comparative Example 4 150 g of a cation exchange resin (manufactured by Mitsubishi Chemical Corporation) was added to 3000 g of water-dispersed sol 6B containing fine particles 6Bw, and the mixture was stirred at room temperature for 1 hour.
As a result, an aqueous dispersion sol 9B containing inorganic oxide fine particles 9Bw in which the content of the potassium compound contained in the inorganic oxide fine particles was reduced was obtained.
When the metal components contained in the inorganic oxide fine particles 9Bw thus obtained were measured, TiO ₂ 44.1% by weight, SnO ₂ 5.5% by weight, SiO _{2 on the} basis of oxide conversion of each metal component. ₂ 31.1 wt%, ZrO ₂ 13.8 wt% and K ₂ O 5.5 wt%. When the content ratio of the metal component contained in the coating layer was calculated from the measurement result of the whole particle and the measurement result of the inorganic oxide fine particle 6Bc (nuclear particle), ZrO ₂ 13.8 was calculated based on the total amount of the particle. % By weight, 23.9% by weight of SiO ₂ and 2.9% by weight of K ₂ O. However, in calculating the potassium compound contained in the coating layer, it was considered that potassium ions or the like were not eluted from the core particles of the inorganic oxide fine particles 6Bc during the treatment with the cation exchange resin.
Furthermore, when the amount of solid acid contained in the inorganic oxide fine particles was measured as the NH ₃ adsorption amount, it was 0.29 mmol / g.

(2) Preparation of methanol-dispersed sol containing coated inorganic oxide fine particles Tetraethoxysilane (manufactured by Tama Chemical Industry Co., Ltd.) as a surface treatment agent was used for the water-dispersed sol containing inorganic oxide fine particles 9Bw obtained above. After being added to a methanol solution in which was dissolved, the mixture was heated at a temperature of 50 ° C. for 6 hours.
Next, solvent replacement was performed under the same conditions as in the method shown in Example 6 to prepare methanol-dispersed sols 9B containing inorganic oxide fine particles 9Bw having a solid content of 20% by weight.

[Example 9]
Preparation of water-dispersed sol containing titanium-based composite oxide fine particles (10) having a rutile-type crystal structure and inorganic oxide fine particles as sol (1) core particles Under the same conditions as in step (1) of Example 6, An aqueous dispersion sol containing inorganic oxide fine particles 10Bc (nuclear particles) made of composite oxide fine particles having a rutile crystal structure was prepared. In addition, the content of the metal component contained in the inorganic oxide fine particle 10Bc is 73.7% by weight of TiO ₂ and SnO ₂ 9. 3 wt% and SiO ₂ 15.7 wt% and K ₂ O 1.3 wt%.

(2) Preparation of water-dispersed sol containing coated inorganic oxide fine particles Under the same conditions as in Example 6, 5.26 kg of a cake containing 10% by weight of the zirconium component on a ZrO ₂ conversion basis was obtained.
Next, 1.80 kg of pure water was added to 200 g of this cake, and 1.20 kg of a potassium hydroxide aqueous solution containing 1% by weight of potassium hydroxide (manufactured by Kanto Chemical Co., Ltd.) was added to make it alkaline. 400 g of hydrogen peroxide containing 35% by weight (Mitsubishi Gas Chemical Co., Ltd.) was added and heated at a temperature of 45 ° C. As a result, 4.0 kg of a zirconium peroxide solution containing 0.5% by weight of zirconium peroxide in terms of ZrO ₂ was obtained.

Furthermore, 555 g of antimony trioxide (manufactured by Nippon Seiko Co., Ltd.) was added to 9.29 kg of an aqueous potassium hydroxide solution containing 2.6% by weight of potassium hydroxide (manufactured by Kanto Chemical Co., Ltd.) with stirring. A suspension of antimony oxide was obtained. Next, the suspension was heated to a temperature of 98 ° C., and 1110 g of hydrogen peroxide containing 35% by weight of hydrogen peroxide (Mitsubishi Gas Chemical Co., Ltd.) was added to the suspension over 14 hours with stirring. . As a result, an antimony peroxide aqueous solution containing 5.6% by weight of antimony peroxide per Sb ₂ O ₅ was obtained. This was diluted with pure water to obtain an aqueous antimonic acid solution containing 1% by weight of antimony peroxide on the basis of Sb ₂ O ₅ conversion.
Next, after diluting a commercially available water glass (manufactured by AGC S-Tech Co., Ltd.) with pure water under the same conditions as in the method shown in Example 6, a cation exchange resin (manufactured by Mitsubishi Chemical Corporation) Was used to obtain a silicic acid aqueous solution containing 2% by weight of a silicon component on a SiO ₂ conversion basis.

Next, 27.0 kg of pure water is added to 3.0 kg of the water-dispersed sol containing the inorganic oxide fine particles 10Bc obtained in the step (1) and stirred, whereby water having a solid content of 1 wt% is added. A dispersed sol was obtained. Next, after heating the aqueous dispersion sol to a temperature of 90 ° C., 3.66 kg of the aqueous zirconate peroxide solution, 1.83 kg of the antimonic peroxide aqueous solution and 2.84 kg of the silicic acid aqueous solution were gradually added thereto, Further, after completion of the addition, the mixture was aged with stirring for 1 hour while maintaining the temperature at 90 ° C.
Subsequently, this liquid mixture was put into the autoclave and heat-processed at the temperature of 165 degreeC for 18 hours.
Next, after cooling the obtained mixed liquid to room temperature, it is concentrated with an ultrafiltration membrane device (Asahi Kasei Co., Ltd., SIP-1013) to obtain an aqueous dispersion sol 10B having a solid content of 20% by weight. Obtained.

The inorganic oxide fine particles contained in the water-dispersed sol thus obtained were measured by the above method. As a result, the composite oxide fine particles (nuclear particles) having a rutile crystal structure and containing titanium, tin and silicon. These were inorganic oxide fine particles (hereinafter referred to as “inorganic oxide fine particles 10Bw”) formed by coating the surface with a composite oxide containing zirconium, antimony and silicon.
Moreover, when the content of the metal component contained in these inorganic oxide fine particles 10Bw was measured, it was 56.8% by weight of TiO ₂ , 22.9% by weight of SiO ₂ , SnO, based on the oxide conversion standard of each metal component. ₂ 7.1 wt%, ZrO ₂ 4.7 wt%, Sb ₂ O ₅ 4.7 wt% and K ₂ O 3.8 wt%. From the measurement result of the whole particle and the measurement result of the inorganic oxide fine particle 10Bc (core particle), the content ratio of the metal component contained in the coating layer was calculated, and ZrO ₂ 4.7 with respect to the total amount of the particle. Wt%, SiO ₂ 10.8 wt%, Sb ₂ O ₅ 4.7 wt% and K ₂ O 2.8 wt%.
Furthermore, when the amount of solid acid contained in the inorganic oxide fine particles was measured as the NH ₃ adsorption amount, it was 0.18 mmol / g.

(3) Preparation of methanol-dispersed sol containing coated inorganic oxide fine particles Each water-dispersed sol containing inorganic oxide fine particles 10Bw obtained in the step (2) was treated with tetraethoxysilane (Tama After being added to a methanol solution in which Chemical Industry Co., Ltd. was dissolved under stirring, it was heated at a temperature of 50 ° C. for 3 hours.
Subsequently, solvent substitution was performed under the same conditions as the method shown in Example 6 to prepare methanol-dispersed sols 10B containing inorganic oxide fine particles 10Bw having a solid content of 20% by weight.

[Example 10]
Adjustment of content of potassium contained in titanium-based composite oxide fine particles (11) having a rutile-type crystal structure and sol (1) core particles Inorganic oxide fine particles 1Bc obtained in the step (1) of Example 6 were used. 290 g of a potassium hydroxide aqueous solution containing 1% by weight of potassium hydroxide (manufactured by Kanto Chemical Co., Inc.) was added to 3000 g of the aqueous dispersion sol containing 1B, followed by stirring at room temperature for 1 hour.
As a result, an aqueous dispersion sol 11B containing the inorganic oxide fine particles 11Bc in which the content of the potassium compound contained in the inorganic oxide fine particles (nuclear particles) was increased was obtained. In addition, it was found that the potassium compound added from the outside in this way also adheres to the surface of the inorganic oxide fine particles and is taken into the fine particles. This is considered to be due to the reaction between the O · H groups present on the surface of the fine particles and potassium ions.
When the metal component contained in the thus obtained inorganic oxide fine particles 11Bc was measured, it was 73.0% by weight of TiO ₂ , 9.2% by weight of SnO ₂ , SiO _{2 based on} the oxide conversion standard of each metal component. It was ₂ 15.5 wt% and K ₂ O2.3% by weight.

(2) Preparation of water-dispersed sol containing coated inorganic oxide fine particles Under the same conditions as in Example 6, the surface of the inorganic oxide fine particles 11Bc obtained in the step (1) was coated with zirconium, tin. Then, an aqueous dispersion sol 11B containing inorganic oxide fine particles (hereinafter referred to as “inorganic oxide fine particles 11Bw”) coated with a composite oxide containing silicon and silicon was obtained.
When the metal component contained in the thus obtained inorganic oxide fine particles 11Bw was measured, it was 68.6% by weight of TiO ₂ , 8.6% by weight of SnO ₂ , SiO _{2 based on} the oxide conversion standard of each metal component. ₂ 17.6 wt%, was ZrO ₂ 1.4 wt% and K ₂ O3.8% by weight. From the measurement result of the whole particle and the measurement result of the inorganic oxide fine particle 11Bc (core particle), the content ratio of the metal component contained in the coating layer was calculated, and ZrO ₂ 1.4 was calculated based on the total amount of the particle. % By weight, 3.0% by weight of SiO ₂ and 1.6% by weight of K ₂ O.
Furthermore, when the amount of solid acid contained in the inorganic oxide fine particles was measured as the NH ₃ adsorption amount, it was 0.04 mmol / g.

(3) Preparation of methanol-dispersed sol containing coated inorganic oxide fine particles Tetraethoxysilane (manufactured by Tama Chemical Industry Co., Ltd.) as a surface treating agent was used for the water-dispersed sol containing inorganic oxide fine particles 11Bw obtained above. After being added to a methanol solution in which was dissolved, the mixture was heated at a temperature of 50 ° C. for 3 hours.
Next, solvent replacement was performed under the same conditions as in the method shown in Example 6 to prepare methanol-dispersed sol 11B containing inorganic oxide fine particles 11Bw having a solid content of 20% by weight.

[Comparative Example 6]
Titanium-based composite oxide fine particles (12) having a rutile-type crystal structure and sol The rutile type under the same conditions as in the method (ie, preparation of core particle 1Bc) shown in step (1) of Example 6 An aqueous dispersion sol having composite oxide fine particles containing titanium and silicon (hereinafter referred to as “inorganic oxide fine particles 12Bc”) having a crystal structure was prepared.
In addition, when the content of the metal component contained in the fine particles was measured, TiO _{2 was} 73.7% by weight, SnO _{2 was} 9.3% by weight, and SiO _{2 was} 15.7% by weight in terms of oxide of each metal component. % And K ₂ O 1.3% by weight.
Furthermore, when the amount of solid acid contained in the inorganic oxide fine particles was measured as the NH ₃ adsorption amount, it was 0.03 mmol / g.
Next, water dispersion containing the fine particles is performed under the same conditions as in the step (3) of Example 6 without applying the means shown in Step (2) of Example 6 (that is, coating of the fine particles). The sol was added to a methanol solution in which tetraethoxysilane (manufactured by Tama Chemical Industry Co., Ltd.) as a surface treatment agent was dissolved, and then heated at a temperature of 50 ° C. for 6 hours.
Furthermore, solvent substitution was performed under the same conditions as the method shown in Example 6 to prepare a methanol-dispersed sol 12B containing inorganic oxide fine particles 12Bw having a solid content of 20% by weight.

[Example 11]
Preparation of optical substrate coating solution (hard coating layer forming coating solution) (1)
80 g of γ-glycidoxypropyltrimethoxysilane (Z-6040 manufactured by Toray Dow Corning Co., Ltd.), 20 g of γ-glycidoxypropylmethyldiethoxysilane (Z-6042 manufactured by Toray Dow Corning Co., Ltd.) and methanol A plurality of containers containing 50 g of the mixed solution were prepared, and 25 g of 0.01N hydrochloric acid aqueous solution was dropped into these mixed solutions while stirring. Furthermore, this liquid mixture was stirred at room temperature all day and night to hydrolyze the silane compound.
Next, 350 g of methanol dispersion sols 1A to 5A, 10A and 11A obtained in Examples 1 to 5, 50 g of pure water and Tris (2,4-pentanedionato, respectively) were placed in a container containing these hydrolysis solutions. ) Aluminum III (manufactured by Tokyo Chemical Industry Co., Ltd.) 2 g, glycerol polyglycidyl ether (manufactured by Nagase Kasei Kogyo Co., Ltd., Denacol EX-314, epoxy equivalent 145) 5 g and a silicone surfactant (Toray 0.5 g of Dow Corning Co., Ltd., L-7001) was added, and the mixture was stirred overnight at room temperature to form a coating composition for forming a hard coat layer (hereinafter referred to as “Hard” Coating paints 1A (1) to 5A (1), 10A (1), 11A (1) ”) were prepared.

[Comparative Example 7]
Preparation of optical substrate coating solution (hard coating layer forming coating solution) (2)
γ-glycidoxypropyltrimethoxysilane (Toray Dow Corning Co., Ltd., Z-6040) 80 g, γ-glycidoxypropylmethyldiethoxysilane (Toray Dow Corning Co., Ltd., Z-6042) 20 g A plurality of containers containing a mixture of methanol and 50 g of methanol were prepared, and 25 g of 0.01N hydrochloric acid aqueous solution was dropped into the mixture while stirring. Furthermore, this liquid mixture was stirred at room temperature all day and night to hydrolyze the silane compound.
Next, 350 g of methanol-dispersed sols 6A to 9A and 12A obtained in Comparative Examples 1 to 3, respectively, 50 g of pure water, and tris (2,4-pentanedionato) aluminum were placed in a container containing these hydrolyzed solutions. III (manufactured by Tokyo Chemical Industry Co., Ltd.), 5 g of glycerol polyglycidyl ether (manufactured by Nagase Kasei Kogyo Co., Ltd., Denacol EX-314, epoxy equivalent 145) and a silicone surfactant (Toray Dow Corning as leveling agent) Co., Ltd., L-7001) 0.5 g was added and stirred at room temperature for a whole day and night to form a coating composition for forming a hard coat layer (hereinafter referred to as “for hard coat” as a coating solution for an optical substrate). Paints 6A (1) to 9A (1), 12A (1) ”) were prepared.

[Example 12]
Preparation of optical substrate coating solution (hard coating layer forming coating solution) (3)
A plurality of containers containing a mixed solution of 100 g of γ-glycidoxypropyltrimethoxysilane (Z-6040, manufactured by Toray Dow Corning Co., Ltd.) and 50 g of methanol were prepared, and the mixture was stirred in the mixed solution to give a solution of 0. 25 g of a 01N hydrochloric acid aqueous solution was added dropwise. Furthermore, these mixed liquids were stirred at room temperature for a whole day and night to hydrolyze the silane compound.
Subsequently, 350 g of the methanol dispersion sols 1A to 5A, 10A, and 11A obtained in Examples 1 to 5, respectively, tris (2,4-pentanedionato) iron III ( 3 g of Tokyo Chemical Industry Co., Ltd.) and 0.5 g of a silicone surfactant (L-7001 made by Toray Dow Corning Co., Ltd.) as a leveling agent are added and stirred overnight at room temperature. A coating composition for forming a hard coat layer (hereinafter referred to as “hard coat coating 1A (2) to 5A (2), 10A (2), 11A (2)”) as a coating liquid for an optical substrate was prepared. .

[Comparative Example 8]
Preparation of optical substrate coating solution (hard coating layer forming coating solution) (4)
A plurality of containers containing a mixed solution of 100 g of γ-glycidoxypropyltrimethoxysilane (Z-6040, manufactured by Toray Dow Corning Co., Ltd.) and 50 g of methanol were prepared, and the mixture was stirred in the mixed solution to give a solution of 0. 25 g of a 01N hydrochloric acid aqueous solution was added dropwise. Furthermore, these mixed liquids were stirred at room temperature for a whole day and night to hydrolyze the silane compound.
Next, 350 g of each of the methanol-dispersed sols 6A to 9A and 12A obtained in Comparative Examples 1 to 3 were placed in a container containing these hydrolyzed liquids, tris (2,4-pentanedionato) iron III (Tokyo Kasei). 3 g of Kogyo Co., Ltd.) and 0.5 g of a silicone surfactant (manufactured by Toray Dow Corning Co., Ltd., L-7001) as a leveling agent were added and stirred overnight at room temperature. A coating composition for forming a hard coat layer (hereinafter referred to as “hard coat coatings 6A (2) to 9A (2), 12A (2)”) as a coating liquid for materials was prepared.

[Example 13]
Preparation of optical substrate coating solution (hard coating layer forming coating solution) (5)
γ-glycidoxypropyltrimethoxysilane (Toray Dow Corning Co., Ltd., Z-6040) 80 g, γ-glycidoxypropylmethyldiethoxysilane (Toray Dow Corning Co., Ltd., Z-6042) 20 g A plurality of containers containing a mixture of methanol and 50 g of methanol were prepared, and 25 g of 0.01N hydrochloric acid aqueous solution was dropped into the mixture while stirring. Furthermore, this liquid mixture was stirred at room temperature all day and night to hydrolyze the silane compound.
Next, 350 g of methanol dispersion sols 1B to 4B and 9B to 11B obtained in Examples 6 to 10, 350 g of pure water, and tris (2,4-pentanedionato, respectively) were put in a container containing these hydrolysis solutions. ) Aluminum III (manufactured by Tokyo Chemical Industry Co., Ltd.) 2 g, glycerol polyglycidyl ether (manufactured by Nagase Kasei Kogyo Co., Ltd., Denacol EX-314, epoxy equivalent 145) 5 g and a silicone surfactant (Toray 0.5 g of Dow Corning Co., Ltd., L-7001) was added, and the mixture was stirred overnight at room temperature to form a coating composition for forming a hard coat layer (hereinafter referred to as “Hard” Coating paints 1B (3) to 4B (3), 9B (3) to 11B (3) ”were prepared.

[Comparative Example 9]
Preparation of optical substrate coating solution (hard coating layer forming coating solution) (6)
γ-glycidoxypropyltrimethoxysilane (Toray Dow Corning Co., Ltd., Z-6040) 80 g, γ-glycidoxypropylmethyldiethoxysilane (Toray Dow Corning Co., Ltd., Z-6042) 20 g A plurality of containers containing a mixture of methanol and 50 g of methanol were prepared, and 25 g of 0.01N hydrochloric acid aqueous solution was dropped into the mixture while stirring. Furthermore, this liquid mixture was stirred at room temperature all day and night to hydrolyze the silane compound.
Subsequently, 350 g of methanol-dispersed sols 5B to 8B and 12B obtained in Comparative Examples 4 to 6, 350 g of pure water, and tris (2,4-pentanedionato) aluminum were obtained in containers containing these hydrolyzed liquids. III (manufactured by Tokyo Chemical Industry Co., Ltd.), 5 g of glycerol polyglycidyl ether (manufactured by Nagase Kasei Kogyo Co., Ltd., Denacol EX-314, epoxy equivalent 145) and a silicone surfactant (Toray Dow Corning as leveling agent) Co., Ltd., L-7001) 0.5 g was added and stirred at room temperature for a whole day and night to form a coating composition for forming a hard coat layer (hereinafter referred to as “for hard coat” as a coating solution for an optical substrate). Paints 5B (3) to 8B (3), 12B (3) ”were prepared.

[Example 14]
Preparation of optical substrate coating solution (hard coating layer forming coating solution) (7)
Prepare a plurality of containers containing a mixture of 100 g of γ-glycidoxypropyltrimethoxysilane (manufactured by Toray Dow Corning Co., Ltd., Z-6040) and 50 g of methanol. 25 g of a 01N hydrochloric acid aqueous solution was added dropwise. Furthermore, these mixed liquids were stirred at room temperature for a whole day and night to hydrolyze the silane compound.
Next, 350 g of the methanol dispersion sols 1B to 4B and 9B to 11B obtained in Examples 6 to 10, and Tris (2,4-pentandionato) iron III ( 3 g of Tokyo Chemical Industry Co., Ltd.) and 0.5 g of a silicone surfactant (L-7001 made by Toray Dow Corning Co., Ltd.) as a leveling agent are added and stirred overnight at room temperature. A coating composition for forming a hard coat layer (hereinafter referred to as “hard coat coatings 1B (4) to 4B (4), 9B (4) to 11B (4)”) as a coating liquid for an optical substrate was prepared. .

[Comparative Example 10]
Preparation of optical substrate coating solution (hard coating layer forming coating solution) (8)
Prepare a plurality of containers containing a mixture of 100 g of γ-glycidoxypropyltrimethoxysilane (manufactured by Toray Dow Corning Co., Ltd., Z-6040) and 50 g of methanol. 25 g of a 01N hydrochloric acid aqueous solution was added dropwise. Furthermore, these mixed liquids were stirred at room temperature for a whole day and night to hydrolyze the silane compound.
Next, 350 g of each of the methanol dispersion sols 5B to 8B and 12B obtained in Comparative Examples 4 to 6, and Tris (2,4-pentanedionato) iron III (Tokyo Kasei) were placed in a container containing these hydrolyzed solutions. 3 g of Kogyo Co., Ltd.) and 0.5 g of a silicone surfactant (manufactured by Toray Dow Corning Co., Ltd., L-7001) as a leveling agent were added and stirred overnight at room temperature. A coating composition for forming a hard coat layer (hereinafter referred to as “hard coat coatings 5B (4) to 8B (4), 12B (4)”) as a coating solution for the material was prepared.

[Example 15]
Preparation of optical substrate coating solution (primer layer forming coating solution) (9)
A plurality of containers containing 122 g of commercially available polyurethane emulsion “Superflex 150” (Daiichi Kogyo Seiyaku Co., Ltd., water-dispersed urethane elastomer solid content: 30%) were prepared, and these were obtained in Examples 1 to 5. 240 g of methanol dispersion sols 1A to 5A, 10A, and 11A and 480 g of methanol were added and stirred for 1 hour.
Next, 0.5 g of a silicone surfactant (manufactured by Toray Dow Corning Co., Ltd., L-7604) is added to these mixed solutions as a leveling agent, and the mixture is stirred at room temperature for a whole day and night. A coating composition for forming a primer layer (hereinafter referred to as “primer coating 1A (5) to 5A (5), 10A (5), 11A (5)”) was prepared as a coating solution for the material.

[Comparative Example 11]
Preparation of optical substrate coating solution (primer layer forming coating solution) (10)
A plurality of containers containing 122 g of a commercially available polyurethane emulsion “Superflex 150” (Daiichi Kogyo Seiyaku Co., Ltd., water-dispersed urethane elastomer solid content: 30%) were prepared, and these were obtained in Comparative Examples 1 to 3. 240 g of methanol dispersion sols 6A to 9A and 12A and 480 g of methanol were added and stirred for 1 hour.
Next, 0.5 g of a silicone surfactant (manufactured by Toray Dow Corning Co., Ltd., L-7604) is added to these mixed solutions as a leveling agent, and the mixture is stirred at room temperature for a whole day and night. A coating composition for forming a primer layer (hereinafter referred to as “primer coatings 6A (5) to 9A (5), 12A (5)”) as a coating solution for the material was prepared.

[Example 16]
Preparation of optical substrate coating solution (primer layer forming coating solution) (11)
17.5 g of a commercially available melamine compound aqueous solution (Milben SM-850 manufactured by Showa Polymer Co., Ltd.), 682 g of propylene glycol monomethyl ether (manufactured by Dow Chemical Japan Co., Ltd.), a commercially available polyol compound (Nippon Polyurethane Co., Ltd.) A plurality of containers containing 44.9 g of Nipponporan 131) and 0.5 g of p-toluenesulfonic acid (manufactured by Kishida Chemical Co., Ltd.) as a curing catalyst were prepared, and the methanol dispersion obtained in Examples 6 to 10 315 g of sols 1B to 4B and 9B to 11B were added and stirred for 1 hour.
Next, 0.5 g of a silicone surfactant (manufactured by Toray Dow Corning Co., Ltd., L-7001) as a leveling agent is added to these mixed solutions, and the mixture is stirred overnight at room temperature. A coating composition for forming a primer layer (hereinafter referred to as “primer coatings 1B (6) to 4B (6), 9B (6) to 11B (6)”) was prepared as a coating liquid for materials.

[Comparative Example 12]
Preparation of optical substrate coating solution (primer layer forming coating solution) (12)
17.5 g of a commercially available melamine compound aqueous solution (Milben SM-850 manufactured by Showa Polymer Co., Ltd.), 682 g of propylene glycol monomethyl ether (manufactured by Dow Chemical Japan Co., Ltd.), a commercially available polyol compound (Nippon Polyurethane Co., Ltd.) A plurality of containers containing 44.9 g of Nipponporan 131) and 0.5 g of p-toluenesulfonic acid (manufactured by Kishida Chemical Co., Ltd.) as a curing catalyst were prepared. 240 g of sols 5B to 8B and 12B were added and stirred for 1 hour.
Next, 0.5 g of a silicone surfactant (manufactured by Toray Dow Corning Co., Ltd., L-7001) as a leveling agent is added to these mixed solutions, and the mixture is stirred overnight at room temperature. A coating composition for forming a primer layer (hereinafter referred to as “primer coatings 5B (6) to 8B (6), 12B (6)”) as a coating solution for the material was prepared.

[Preparation Example 1]
<Creation of plastic lens substrate for test (1)>
(1) Pretreatment of plastic lens substrate The following number of commercially available plastic lens substrates required for the following tests and evaluations were prepared.
(a) “Monomer name: MR-8” (plastic lens base material having a refractive index of 1.60) manufactured by Mitsui Chemicals, Inc.
(b) "Monomer name: MR-7" (plastic lens base material with a refractive index of 1.67) manufactured by Mitsui Chemicals, Inc.
(c) “Monomer name: MR-174” (plastic lens base material having a refractive index of 1.74) manufactured by Mitsui Chemicals, Inc.
Subsequently, these plastic lens base materials were immersed in a 10 wt% KOH aqueous solution kept at 40 ° C. for 2 minutes for etching treatment. Further, these were taken out, washed with water, and then sufficiently dried.

(2) Formation of hard coat layer The coating composition for forming a hard coat layer (hard coat paint) obtained above was applied to the surface of the plastic lens substrate to form a coating film. In addition, application | coating of this coating composition was performed using the dipping method (drawing speed 250mm / min).
Next, after drying the said coating film for 10 minutes at 90 degreeC, it heat-processed for 2 hours at 110 degreeC, and hardened | cured the coating film (hard-coat layer).
In addition, the film thickness after hardening of the said hard-coat layer formed in this way was 2.0-2.6 micrometers in general.

(3) Formation of antireflection film layer An inorganic oxide component having the following constitution was deposited on the surface of the hard coat layer by a vacuum deposition method. Here, the order of SiO ₂ : 0.06λ, ZrO ₂ : 0.15λ, SiO ₂ : 0.04λ, ZrO ₂ : 0.25λ, and SiO ₂ : 0.25λ from the hard coat layer side toward the atmosphere side. The layers of the antireflection film laminated with each other were formed. The design wavelength λ was 520 nm.
In Examples and Comparative Examples of the present invention, an antireflection film layer was formed on the surface of the hard coat layer using a conventionally known vapor deposition method, but a wet process described in International Application Publication WO 2006/095469 and the like. The antireflection film layer may be formed using a method (that is, a method of applying a coating composition containing a conventionally known vehicle component and low refractive index hollow silica fine particles to the surface of the hard coat layer). Of course.

[Preparation Example 2]
<Creation of plastic lens substrate for test (2)>
(1) Pretreatment of plastic lens substrate Pretreatment of a plastic substrate was performed under the same conditions as in Preparation Example 1.
(2) Formation of primer layer The primer layer-forming coating composition (primer coating) obtained above was applied to the surface of the plastic lens substrate to form a coating film. In addition, application | coating of this coating composition uses a dipping method, the primer coating material prepared in Example 15 and Comparative Example 11 is the primer coating material prepared in Example 16 and Comparative Example 12 at a pulling-up speed of 120 mm / min. Application was performed on a plastic lens substrate at 200 mm / min.
Next, the said coating film was heat-processed at 100 degreeC for 10 minute (s), and the coating film (primer layer) was pre-hardened.
In addition, the film thickness after preliminary curing of the primer layer formed in this manner is approximately 0.5 to 0.7 μm when pulled up at 120 mm / min, and approximately about 30 mm when pulled up at 200 mm / min. It was 0.8 to 1.0 μm.

(3) Formation of hard coat layer Under the same conditions as in Preparation Example 1, on the surface of the plastic lens substrate formed with the primer layer, the coating composition for forming the hard coat layer obtained above (hard A coating film was applied to form a coating film, and the coating was cured. At this time, the main curing of the primer layer was also performed at the same time.
In addition, the film thickness of the hard coat layer thus formed was approximately 2.0 to 2.6 μm.
(4) Formation of antireflection film layer Under the same conditions as in Preparation Example 1, an antireflection film layer was formed on the surface of the hard coat layer.

[Example 17]
A hard coat layer was formed on a plastic lens substrate by the method shown in Preparation Example 1 using the hard coat paints 1A (1) to 5A (1), 10A (1) and 11A (1) obtained in Example 11. And an antireflection film layer were formed.
For the example substrates 1A (1) to 5A (1), 10A (1), and 11A (1) obtained in this way, the appearance (interference fringes) and the appearance (cloudy) were evaluated using the evaluation test method described above. Scratch resistance, adhesion, weather resistance and light resistance were tested and evaluated. The results are shown in Table 3.

[Comparative Example 13]
Using the hard coat paints 6A (1) to 9A (1) and 12A (1) obtained in Comparative Example 7, the hard coat layer and the antireflection film layer were formed on the plastic lens substrate by the method shown in Preparation Example 1. Formed respectively.
For the comparative substrates 6A (1) to 9A (1) and 12A (1) thus obtained, using the above evaluation test method, the appearance (interference fringes), appearance (cloudiness), scratch resistance, The adhesion, weather resistance and light resistance were tested and evaluated. The results are shown in Table 4.

[Example 18]
A hard coat layer was formed on a plastic lens substrate by the method shown in Preparation Example 1 using the hard coat paints 1A (2) to 5A (2), 10A (2) and 11A (2) obtained in Example 12. And an antireflection film layer were formed.
For the example substrates 1A (2) to 5A (2), 10A (2), and 11A (2) obtained in this way, the appearance (interference fringes) and the appearance (cloudy) were evaluated using the evaluation test method described above. Scratch resistance, adhesion, weather resistance and light resistance were tested and evaluated. The results are shown in Table 5.

[Comparative Example 14]
Using the hard coat paints 6A (2) to 9A (2) and 12A (2) obtained in Comparative Example 8, the hard coat layer and the antireflection film layer were formed on the plastic lens substrate by the method shown in Preparation Example 1. Formed respectively.
With respect to the comparative substrates 6A (2) to 9A (2) and 12A (2) thus obtained, the above-described evaluation test method was used to determine the appearance (interference fringes), appearance (cloudiness), scratch resistance, The adhesion, weather resistance and light resistance were tested and evaluated. The results are shown in Table 6.

[Example 19]
Using the hard coat paints 1B (3) to 4B (3) and 9B (3) to 11B (3) obtained in Example 13, the hard coat layer was formed on the plastic lens substrate by the method shown in Preparation Example 1. And an antireflection film layer were formed.
For the example substrates 1B (3) to 4B (3) and 9B (3) to 11B (3) thus obtained, the appearance (interference fringes) and the appearance (cloudy) were evaluated using the evaluation test method described above. Scratch resistance, adhesion, weather resistance and light resistance were tested and evaluated. The results are shown in Table 7.

[Comparative Example 15]
Using the hard coat paints 5B (3) to 8B (3) and 12B (3) obtained in Comparative Example 9, the hard coat layer and the antireflection film layer were formed on the plastic lens substrate by the method shown in Preparation Example 1. Formed respectively.
With respect to the comparative substrates 5B (3) to 8B (3) and 12B (3) thus obtained, the above-described evaluation test method was used to determine the appearance (interference fringes), appearance (cloudiness), scratch resistance, The adhesion, weather resistance and light resistance were tested and evaluated. The results are shown in Table 8.

[Example 20]
Using the coating materials 1B (4) to 4B (4) and 9B (4) to 11B (4) for hard coat obtained in Example 14, the hard coat layer was formed on the plastic lens substrate by the method shown in Preparation Example 1. Formed respectively.
With respect to the example substrates 1B (4) to 4B (4) and 9B (4) to 11B (4) thus obtained, the appearance (interference fringes) and the appearance (cloudy) were evaluated using the above evaluation test method. The scratch resistance, adhesion and weather resistance were tested and evaluated. The results are shown in Table 9. Here, since the antireflection film layer was not provided on the hard coat layer, the light resistance test was not performed.

[Comparative Example 16]
Using the hard coat paints 5B (4) to 8B (4) and 12B (4) obtained in Comparative Example 10, a hard coat layer was formed on the plastic lens substrate by the method shown in Preparation Example 1, respectively.
For the comparative substrates 5B (4) to 8B (4) and 12B (4) thus obtained, using the above evaluation test method, the appearance (interference fringes), the appearance (cloudiness), the scratch resistance, Adhesion and weather resistance were tested and evaluated. The results are shown in Table 10. Here, since the antireflection film layer was not provided on the hard coat layer, the light resistance test was not performed.

[Example 21]
Using the primer coating materials 1A (5) to 5A (5), 10A (5), 11A (5) obtained in Example 15 and the hard coat coating material shown in Table 11 obtained in Example 11, A primer layer, a hard coat layer, and an antireflection film layer were formed on the plastic lens substrate by the method shown in Preparation Example 2, respectively.
For the example substrates 1A (5) to 5A (5), 10A (5), and 11A (5) obtained in this way, the above-described evaluation test method was used for appearance (interference fringes) and appearance (cloudy). Scratch resistance, adhesion, weather resistance and light resistance were tested and evaluated. The results are shown in Table 11.

[Comparative Example 17]
Using the primer coating materials 6A (5) to 9A (5) and 12A (5) obtained in Comparative Example 11 and the hard coat coating materials shown in Table 12 obtained in Comparative Example 7, it is shown in Preparation Example 2. By the method, a primer layer, a hard coat layer and an antireflection film layer were formed on the plastic lens substrate.
For the comparative substrates 6A (5) to 9A (5) and 12A (5) thus obtained, the above-described evaluation test method was used to determine the appearance (interference fringes), appearance (cloudiness), scratch resistance, The adhesion, weather resistance and light resistance were tested and evaluated. The results are shown in Table 12.

[Example 22]
Using the primer coating materials 1B (6) to 4B (6) and 9B (6) to 11B (6) obtained in Example 16 and the hard coating materials shown in Table 13 obtained in Example 13, A primer layer, a hard coat layer, and an antireflection film layer were formed on the plastic lens substrate by the method shown in Preparation Example 2, respectively.
With respect to the example substrates 1B (6) to 4B (6) and 9B (6) to 11B (6) thus obtained, the appearance (interference fringes) and the appearance (cloudiness) were evaluated using the above evaluation test method. Scratch resistance, adhesion, weather resistance and light resistance were tested and evaluated. The results are shown in Table 13.

[Comparative Example 18]
Using the primer coating materials 5B (6) to 8B (6) and 12B (6) obtained in Comparative Example 12 and the hard coat coating materials shown in Table 14 obtained in Comparative Example 9, the results are shown in Preparation Example 2. By the method, a primer layer, a hard coat layer and an antireflection film layer were formed on the plastic lens substrate.
For the comparative substrates 5B (6) to 8B (6) and 12B (6) thus obtained, using the above evaluation test method, the appearance (interference fringes), the appearance (cloudiness), the scratch resistance, The adhesion, weather resistance and light resistance were tested and evaluated. The results are shown in Table 14.

Claims (21)

The surface of a core particle composed of titanium oxide fine particles and / or composite oxide fine particles containing titanium and one or more metal elements selected from zirconium, tin, tungsten, niobium, cerium and silicon,
Inorganic oxide fine particles coated with an element containing silicon element as an essential component, and other oxides and / or composite oxides of one or more metal elements selected from zirconium, aluminum and antimony There,
An inorganic oxide fine particle having a core-shell structure, wherein the fine particle contains a potassium compound (excluding K ₂ O as an oxide) in an amount of 1.0 to 8.0% by weight in terms of K ₂ O.   The inorganic oxide fine particle having a core-shell structure according to claim 1, wherein the inorganic oxide fine particle contains a solid acid composed of an oxide of the metal element.   The inorganic oxide fine particle having a core-shell structure according to claim 2, wherein at least a part of the potassium compound contained in the inorganic oxide fine particle is present in a form combined with the solid acid. The potassium compound, said comprising 0.0 to 5.0 wt% in the nucleus particles in K ₂ O equivalent value, that it contains 1.0 to 7.0% by weight K ₂ O equivalent value in the coating layer The inorganic oxide fine particles having a core-shell structure according to any one of claims 1 to 3.   The inorganic oxide fine particle having a core-shell structure according to any one of claims 1 to 4, wherein the core particle is a titanium-based composite oxide fine particle having an anatase type crystal structure.   The inorganic oxide fine particles having a core-shell structure according to any one of claims 1 to 4, wherein the core particles are titanium-based composite oxide fine particles having a rutile-type crystal structure.   When the weight of the core particles is represented by C and the weight of the coating layer is represented by S, the weight ratio (S / C) is 7/100 to 150 on the oxide basis. The inorganic oxide fine particles having a core-shell structure according to any one of claims 1 to 6, wherein the inorganic oxide fine particles have a core / shell structure.   The inorganic oxide having a core-shell structure according to any one of claims 1 to 7, wherein an average particle size of the inorganic oxide fine particles is in a range of 4 to 40 nm when measured by a dynamic light scattering method. Fine particles. The inorganic oxide fine particles having a core-shell structure according to any one of claims 1 to 8, wherein a specific surface area of the inorganic oxide fine particles is in a range of 70 to 450 m ² / g.   A water-dispersed sol obtained by dispersing inorganic oxide fine particles having a core-shell structure according to any one of claims 1 to 9 in water.   An organic solvent-dispersed sol obtained by dispersing the inorganic oxide fine particles having the core-shell structure according to any one of claims 1 to 9 in an organic solvent soluble in water. (1) Titanium oxide fine particles and / or core particles composed of composite oxide fine particles containing titanium and one or more metal elements selected from zirconium, tin, tungsten, niobium, cerium and silicon Inorganic oxidation in which the surface is covered with an element containing silicon element as an essential component and other oxides and / or composite oxides of one or more metal elements selected from zirconium, aluminum and antimony Inorganic oxide fine particles having a core-shell structure in which a potassium compound (excluding K ₂ O as an oxide) is contained in an amount of 1.0 to 8.0% by weight in terms of K ₂ O, and (2) An organosilicon compound represented by the following general formula (I) and / or a hydrolyzate thereof;
R ¹ _a R ² _b Si (OR ³ ) _{4- (a + b)} (I)
(In the formula, R ¹ is an alkyl group having 1 to 6 carbon atoms, an organic group having 8 or less carbon atoms containing a vinyl group, an organic group having 8 or less carbon atoms containing an epoxy group, and 8 carbon atoms containing a methacryloxy group. The following organic group, an organic group having 1 to 5 carbon atoms containing a mercapto group or an organic group having 1 to 5 carbon atoms containing an amino group, R ² is an alkyl group having 1 to 3 carbon atoms, an alkylene group, A cycloalkyl group, a halogenated alkyl group or an allyl group, R ³ is an alkyl group having 1 to ³ carbon atoms, an alkylene group or a cycloalkyl group, a is an integer of 0 or 1, b is 0, 1 Or an integer of 2.)
The coating liquid for optical base materials characterized by including.   The coating liquid for an optical substrate according to claim 12, wherein the inorganic oxide fine particles are surface-treated with an organosilicon compound or an amine compound.   The coating liquid for optical substrates according to any one of claims 12 to 13, further comprising an uncrosslinked epoxy compound in the coating liquid for optical substrates.   The optical substrate coating solution according to any one of claims 12 to 14, wherein the optical substrate coating solution is a hard coat layer forming coating solution. (1) Titanium oxide fine particles and / or core particles composed of composite oxide fine particles containing titanium and one or more metal elements selected from zirconium, tin, tungsten, niobium, cerium and silicon Inorganic oxidation in which the surface is covered with an element containing silicon element as an essential component and other oxides and / or composite oxides of one or more metal elements selected from zirconium, aluminum and antimony Inorganic oxide fine particles having a core-shell structure in which a potassium compound (excluding K ₂ O as an oxide) is contained in an amount of 1.0 to 8.0% by weight in terms of K ₂ O, and (2) A coating liquid for an optical substrate comprising a thermosetting resin or a thermoplastic resin.   The coating liquid for an optical substrate according to claim 16, wherein the inorganic oxide fine particles have been surface-treated with an organosilicon compound or an amine compound.   18. The thermosetting resin according to claim 16, wherein the thermosetting resin is one or more thermosetting resins selected from urethane resins, epoxy resins, melamine resins, and silicone resins. The coating liquid for optical base materials in any one.   The optical material according to any one of claims 16 to 17, wherein the thermoplastic resin is one or more thermoplastic resins selected from acrylic resins, urethane resins and ester resins. Substrate coating solution.   The optical substrate coating solution according to any one of claims 16 to 19, wherein the optical substrate coating solution is a primer layer forming coating solution.   The optical substrate coating liquid according to any one of claims 12 to 20, wherein the optical substrate is a plastic lens.