JP6049368B2 - Al-modified inorganic oxide fine particles, production method thereof, dispersion, and coating composition - Google Patents

Description

  The present invention relates to Al-modified gold flat sugar-like fine particles whose surface is modified with aluminum, a method for producing the same, a dispersion containing the fine particles, and a coating composition.

In order to adjust the refractive index of a coating film or resin, it is well known to blend fine oxide particles such as zirconium and titanium.
Such oxide fine particles are required to have high stability and high dispersibility when blended in a film or resin.

As one of means for improving the stability of oxide fine particles, a method of treating the particle surface with a silane coupling agent is known, but a more effective treatment method has been demanded.
As one of such methods, Patent Document 1 describes a method of coating the surface of zirconia fine particles with antimony pentoxide and / or silica.

  Patent Document 2 describes a titanium oxide sol in which titanium oxide sol particles are coated with a layer made of a hydrated oxide of silicon and aluminum.

JP 2009-107872 A JP 2007-246351 A

  The modified zirconia fine particles described in Patent Document 1 are improved in dispersibility by covering the surface of the zirconia fine particles with antimony pentoxide and / or silica, and the stability in the acidic region is increased. There was a need for further improvement.

  Further, the titanium oxide sol particles described in Patent Document 2 are coated with silicon oxide and aluminum oxide to improve stability, but further development of such an effect has been demanded. .

  In addition, when blending oxide fine particles into a coating film, etc., it is required to improve the strength of the resulting coating film, and in particular, for applications such as hard coat films and primer films for optical lenses such as eyeglasses. However, there is a background that improvement in film adhesion is required.

  In the present invention, in view of such a background, the dispersion stability is high, and stable oxide fine particles can be obtained even in an acidic pH region. Furthermore, the oxide particles are transparent and excellent in film hardness and adhesion. It aims at obtaining the coating composition for forming a coating film.

  As a result of intensive studies, the present inventors have found that oxide fine particles obtained by modifying gold-peeled inorganic oxide fine particles with a specific amount of aluminum can solve the above problems, and have completed the present invention.

The present invention relates to the following [1] to [9], for example.
[1] It is an inorganic oxide fine particle in the form of confetti, in which aluminum is modified in a range of 0.1 × 10 ^{−6 to} 1.5 × 10 ⁻⁶ mol / m ² per unit surface area. Al-modified confetti fine particles.
[2] The Al-modified gold flat sugar-like fine particles according to [1], wherein the inorganic oxide fine particles include one or more metal elements selected from zirconium, tin, titanium, niobium, tungsten, antimony, and indium. .
[3] The Al-modified gold flat sugar-like fine particles according to [1] or [2], wherein the inorganic oxide fine particles have a core-shell structure.

[4] The Al-modified confetti fine particles according to [3], wherein the shell of the core-shell structure contains silicon.
[5] The negative surface charge amount (μeq / g) obtained as a measured value of the cation potential when measured by adjusting the pH of the aqueous solution for measurement to 6 with a streaming potential measuring device is in the range of 15 to 35 μeq / g. The Al-modified gold flat sugar-like fine particles according to any one of [1] to [4], wherein

[6] The surface roughness (μeq / m ² ) obtained by dividing the surface negative charge amount (μeq / g) by the specific surface area (m ² / g) of the Al-modified confetti fine particles is 0.07 to The Al-modified octopus sugar-like fine particles according to any one of [1] to [4], which are in the range of 0.2 μeq / m ² .

  [7] The average particle diameter measured using a transmission electron microscope (TEM) of the Al-modified gold flat sugar-like fine particles is in the range of 8 to 60 nm, according to any one of [1] to [6] Al modified confetti fine particles.

[8] A dispersion containing the Al-modified confetti fine particles according to any one of [1] to [7].
[9] A coating composition comprising the Al-modified confetti fine particles according to any one of [1] to [7] and a binder component.

[10] The method for producing Al-modified confetti fine particles according to any one of [1] to [7], wherein the following step (1) includes confetti-like inorganic oxide fine particles containing silicon at least on the surface. Producing an aqueous dispersion in the range of pH 9.0 to 11.5;
(2) When silicon contained in the aqueous dispersion is represented by SiO ₂ and aluminum contained in the aluminum source is represented by Al ₂ O ₃ , the molar ratio (Al ₂ O ₃ / SiO ₂ ) is 0.0005. Mixing the aluminum source at a rate such that 0.050;
(3) heating the obtained mixed liquid to a temperature of 60 to 200 ° C. and stirring for 0.5 to 20 hours;
A method for producing Al-modified gold flat sugar-like fine particles, comprising:

  The Al-modified octopus sugar-like fine particles according to the present invention have a confetti-like shape having a plurality of protrusions on the surface, and a predetermined amount of aluminum is modified on the surface of the fine particles. In addition, the coating film obtained from the paint containing the fine particles has excellent film hardness and adhesion.

In particular, it shows an excellent effect in terms of weathering adhesion, that is, improvement in adhesion maintained when exposed to the outdoors for a long time.
Furthermore, since the Al-modified gold flat sugar-like fine particles according to the present invention can easily adjust the refractive index and are excellent in weather resistance, scratch resistance, and transparency, they are incorporated into coating films such as hard coats and primers on optical substrates. Suitable as a filling material.

Hereinafter, the Al-modified gold flat sugar-like fine particles according to the present invention will be specifically described.
Al-modified confetti particles The Al-modified confetti particles in the present invention can be obtained by modifying aluminum on the surface of the confetti-like inorganic oxide particles having protrusions.

  As the gold-peeled inorganic oxide fine particles, commercially available gold-peeled inorganic oxide fine particles containing one or more metal elements selected from zirconium, tin, titanium, niobium, tungsten, antimony, and indium, or zirconium, tin, What was obtained by forming protrusions on inorganic oxide particles having a core-shell structure composed of a core particle and a shell containing one or more metal elements selected from titanium, niobium, tungsten, antimony, and indium can be used.

Al-modified gold flat sugar-like fine particles obtained using such inorganic oxide fine particles are more preferred because of their high refractive index.
In the case of using commercially available confetti-like inorganic oxide fine particles, it is necessary to perform Al modification after forming a silicon-containing layer on the surface.

In the case where protrusions are grown on the inorganic oxide fine particles to form a confetti-like shape, the inorganic oxide particles must have a core-shell structure having a silicon-containing layer as the outermost layer.
In the case of using the core-shell type inorganic oxide fine particles, there is an effect that the coating film is excellent in weather resistance and film hardness.

  The Al-modified gold flat sugar-like fine particles in which the inorganic oxide fine particles have a core-shell structure are composed of core particles, one or more shells covering the surface, a plurality of protrusions formed on the shell surface, and the surfaces of the shell and the protrusions. It is preferable that it is comprised with the aluminum modified.

As described above, the core particle preferably contains one or more metal elements selected from zirconium, tin, titanium, niobium, tungsten, antimony, and indium.
More preferably, the core particle preferably contains one or more metal elements selected from zirconium, tin, titanium, niobium, tungsten, antimony, and indium as a main component. Al-modified confetti fine particles containing such core particles are preferred because of their high refractive index.

Specifically, the main component means that the total amount of one or more metal elements selected from zirconium, tin, titanium, niobium, tungsten, antimony, and indium is an oxide conversion standard (ZrO ₂ , SnO ₂ , TiO ₂ , Nb ₂ O ₅ , WO ₃ , Sb ₂ O ₅ , In ₂ O ₃ ), which means more than 70% by weight of the core particles.

The core particles may contain elements such as silicon, barium, strontium, lithium, inlanthanium, potassium, and sodium as subcomponents.
Moreover, the said core particle may contain trace amount aluminum in the range which does not impair this invention.
In addition, about the particle diameter of a core particle, the average particle diameter of Al modification gold flat sugar-like microparticles | fine-particles will finally be in the range of 8-60 nm.

The surface of the core particle is preferably covered with a shell containing an oxide or composite oxide of a metal element. In addition, it is preferable that the shell of the inorganic oxide fine particles contains silicon because the coating film is excellent in weather resistance and hardness.
The shell may have two or more layers, and the outermost shell preferably contains silicon.

  Such a shell is provided for the purpose of improving the stability and light resistance of the inorganic oxide fine particles and adjusting the refractive index, and the composition thereof is not particularly limited, but silicon, zirconium, An oxide or composite oxide containing one or more metal elements such as antimony is preferable. The shell may contain an oxide of aluminum or a composite oxide.

Regarding the coating amount of the shell, it is preferable that the outermost shell containing at least silicon is coated in the range of 5 to 60 parts by weight with respect to 100 parts by weight of the core particles.
When the coating amount is less than 5 parts by weight, the weather resistance adhesion and film hardness of the coating film may decrease, which is not preferable.

If the coating amount exceeds 60 parts by weight, the refractive index may decrease, which is not preferable.
Further, when an optional shell is further included between the core particle and the outermost shell, these optional shells may be coated in the range of 0 to 100 parts by weight with respect to 100 parts by weight of the core particle. preferable.

If the coating amount of the arbitrary shell exceeds 100 parts by weight, the refractive index may decrease, which is not preferable.
In the case of producing confetti-like inorganic oxide fine particles having protrusions without using a commercially available product, the method disclosed in JP 2008-169102 A is used. That is, it is obtained by growing silica particles on the surface of the core-shell type inorganic oxide particles.

  The inorganic oxide fine particles used in the present invention are in the shape of confetti that has a large number of protrusions on the surface, as long as the shape has a large number of protrusions on the surface of the base particles, and the shape of the base particles is spherical. For example, it may be substantially spherical, rice-grained, or needle-shaped. That is, no matter what the shape of the base particles is, there is no problem as long as the particles obtained by forming the protrusions have a spherical or substantially spherical shape.

  That is, the confetti of the confetti of the present invention is a particle having a convex part on the surface of a spherical or substantially spherical particle, the shape of the convex part is a wavy irregularity or a protrusion, but there is no particular limitation. Absent. In addition, it is preferable that the number of protrusions in the case of wavy and the number of protrusions in the case of protrusions are large.

The protrusion formed on the surface of the shell is preferably an oxide or composite oxide containing silicon. The protrusion may further be a complex oxide containing aluminum.
An example of a method for producing the confetti-like inorganic oxide fine particles having protrusions is shown below.

  First, an aqueous dispersion of arbitrarily shaped oxide fine particles or composite oxide fine particles containing one or more metal elements selected from zirconium, tin, titanium, niobium, tungsten, antimony, and indium is produced by a known method. . The shape of the oxide fine particles or composite oxide fine particles is not particularly limited and may be spherical, rice-grained, or needle-shaped.

  Such an aqueous dispersion includes a neutralization hydrolysis method using a metal salt or metal alkoxide as a raw material, a hydrolysis method, and a neutralization coagulating agent that peptizes a metal hydroxide obtained by adding an alkali to an aqueous metal salt solution. It can be produced by a known liquid phase method such as a precipitation method or a hydrothermal synthesis method, or a commercially available product may be used.

  Moreover, the oxide particles or composite oxide particles obtained by drying the aqueous dispersion of oxide particles or composite oxide particles obtained by the liquid phase method once or by drying and then firing, After pulverization, re-dispersed in water and deionized or classified as necessary may be used as an aqueous dispersion of core particles.

  Furthermore, the powder of oxide particles or composite oxide particles obtained by a gas phase method such as a gas phase oxidation method, a gas phase decomposition method or a physical vapor synthesis (PVS) method is pulverized and redispersed in water. May be used as an aqueous dispersion of core particles.

  For example, a dispersion liquid of high-refractive-index fine particles obtained by once pulverizing and pulverizing like titanium-based fine particles described in JP 2010-168266 A can be used particularly preferably.

  Further, a dispersion obtained by firing, pulverizing, and redispersing a dispersion of zirconia fine particles instead of titanium fine particles may be used in accordance with such a method. Such particles are preferred because of their high refractive index and high light resistance and weather resistance. These fine particles may contain silicon, potassium, sodium and the like as accessory components.

If necessary, these oxide fine particles or composite oxide fine particles may be used as a core, and the surface thereof may be covered with a shell of any metal oxide or composite metal oxide.
Such a shell is coated for the purpose of improving light resistance, weather resistance, stability, etc., and its composition is not particularly limited. For example, an oxide or composite oxide containing silicon, zirconium, antimony, aluminum, etc. Things.

  Such core-shell structured particles can be produced by, for example, the production method of inorganic oxide fine particles described in JP-A-2009-155296, or water dispersion of high-refractive-index metal oxide fine particles described in JP-A 2010-168266. It can be produced by a known method such as a sol production method or a method analogous thereto.

Next, the surface of such oxide fine particles, composite oxide fine particles, or core-shell type fine particles is covered with a shell made of silicon-containing oxide or composite oxide.
When the surface of the fine particles is covered with a shell containing silicon, protrusions can be uniformly formed on the surface of the shell.

Next, a plurality of protrusions are formed on the surface of the shell containing silicon to produce confetti-like inorganic oxide fine particles.
As an example of the method for forming the protrusions, for example, a method according to the method for producing the gold flat sugar-like silica sol or the gold flat sugar-like silica-alumina sol described in JP-A-2008-169102 can be used.

  That is, an aqueous dispersion of coated fine particles in which core particles or core-shell type particles are coated with an oxide or composite oxide containing silicon is used as liquid A, and in the presence of an electrolyte composed of a strong acid salt, liquid B (alkaline silicate) is used. When the core particles are grown by adding an aqueous solution), 50 to 2500 parts by mass of silica contained in the B liquid is added to 100 parts by mass of the silica contained in the A liquid. In this method, the ratio (EA / EE) of EA) to the number of equivalents (EE) of the electrolyte is in the range of 0.4 to 8.

  Alternatively, 0.1 to 2.5 parts by mass of sodium aluminate is added to 100 parts by mass of the coated fine particle dispersion (liquid A) coated with a silicon-containing oxide or composite oxide. Alumina-coated fine particles (fine particles in which alumina is present in the form of spots on the surface of the coated fine particles, which are partially agglomerated in the present application with an aluminum-containing shell, are added continuously or intermittently and then aged. (Corresponding to the coated fine particles), and then adding alkali metal silicate corresponding to 0.1 to 100 parts by mass to 100 parts by mass of the alumina-coated fine particles and aging, In this method, particles are grown by adding a silicic acid solution continuously or intermittently.

However, in Japanese Patent Laid-Open No. 2008-169102, sodium aluminate added to prepare alumina-coated fine particles corresponding to fine particles partially coated with an aluminum-containing shell of the present invention is a dispersion of coated fine particles (A Liquid) 0.1 to 2.5 parts by mass based on 100 parts by mass of NaAlO ₂ , but in the present invention, a dispersion of coated fine particles partially coated with a shell containing aluminum (A liquid) it may be added sodium aluminate so that 0.005 to 0.05 wt% in terms of Al ₂ O ₃ basis relative weight solids contained.

By such a method, a plurality of protrusions can be formed on the surface of the inorganic oxide fine particles coated with an oxide or composite oxide containing silicon, and can be made into a confetti shape.
In addition, the pH of the aqueous dispersion of the coated fine particles (A liquid) is preferably 8 to 13, and sodium hydroxide, potassium hydroxide, aqueous ammonia, amines, various inorganic acids, An organic acid or the like may be added.

  As an example of a preferable method for producing Al-modified octopus sugar particles according to the present invention, an aluminum source in a predetermined range is added to an aqueous dispersion of octopus sugar-like inorganic oxide particles containing at least silicon on the surface under alkaline conditions. And reacting them.

  In this case, before the formation of the silicon-containing layer on the surface of the commercially available gold-peeled inorganic oxide fine particles, the gold-peeled inorganic oxide fine particles having protrusions grown on the surface of the core-shell type inorganic oxide fine particles are used. It is necessary to use after processing.

The method of modifying with Al is preferably a production method including the following steps (1) to (3).
(1) A step of producing an aqueous dispersion having a pH of 9.0 to 11.5 and containing at least the surface of gold-containing sugar-like inorganic oxide fine particles.
(2) When silicon contained in the aqueous dispersion is represented by SiO ₂ and aluminum contained in the aluminum source is represented by Al ₂ O ₃ , the molar ratio (Al ₂ O ₃ / SiO ₂ ) is 0.0005. A step of mixing the aluminum source at a ratio of 0.050.
Although it does not specifically limit as this aluminum source, An aluminate, aluminum alkoxide, etc. can be used.
(3) The obtained mixed liquid is heated to a temperature of 60 to 200 ° C. and stirred for 0.5 to 20 hours to modify aluminum on the surface of the confetti-like inorganic oxide fine particles, thereby modifying Al. A process of obtaining confetti fine particles.

Each step will be described more specifically.
Process (1)
In this step, an alkaline aqueous dispersion having a pH of 9.0 to 11.5 and containing at least a gold-plated sugar-like inorganic oxide fine particle containing silicon on the surface is produced.

  As such an alkaline aqueous dispersion, protrusions are grown on the aqueous dispersion obtained by dispersing the pre-treated commercially available confetti-like inorganic oxide fine particles in water, or the core-shell inorganic oxide fine particles described above. If necessary, the pH of the aqueous dispersion of the confetti-like inorganic oxide fine particles obtained by the method is adjusted to 9.0-11.5 by dealkalizing treatment with an ion exchange resin, addition of alkali hydroxide or the like. Obtained by adjusting to the range.

  Further, as the alkaline aqueous dispersion, for example, a well-known confetti sugar silica sol or a confetti sugar alumina sol as described in JP-A-2008-169102 may be used.

(Process 2)
In this step, an aluminum source is added to the aqueous dispersion of the confetti-like inorganic oxide fine particles prepared in the above step to prepare a mixed solution.
As the aluminum source, aluminate or aluminum alkoxide can be used.
The amount of the aluminum source added is expressed by the molar ratio (Al ₂ ) when silicon contained in the aqueous dispersion of gold oxide-like inorganic oxide fine particles is represented by SiO ₂ and the aluminum contained in the aluminum source is represented by Al ₂ O _3. The aluminum source may be mixed at such a ratio that O ₃ / SiO ₂ ) is 0.0005 to 0.050.

(Process 3)
In this step, the liquid mixture obtained in the above step is heated to a temperature of 60 to 200 ° C. and stirred for 0.5 to 20 hours. By this step, aluminum is modified on the surface of the confetti-like inorganic oxide fine particles to obtain Al-modified confetti-like fine particles.

Under alkaline conditions where the pH is in the range of 9.0 to 11.5, the silica has high solubility, the silicon present on the surface of the inorganic oxide fine particles prepared in the step (1), the aluminum added in the step (2), Therefore, a large amount of aluminum is modified on the surface of the gold flat sugar-like inorganic oxide fine particles. The aluminum is modified in the form of a composite oxide of silicon and aluminum on the surface of the inorganic oxide fine particles to form a high negative charge density. Therefore, a very stable dispersion with high dispersibility and transparency can be obtained.
In addition, the final shape of the Al-modified confetti fine particles having aluminum modified on the surface is confetti.
If necessary, this dispersion may be subjected to treatment such as pH adjustment, concentration adjustment, solvent substitution and the like.

Further, the confetti fine particles contained in this dispersion may be treated with a known surface treating agent such as a silane coupling agent or amines.
This dispersion is stable even in an acidic pH range, and is suitable for mixing with an acidic binder component and blending it into a coating composition or a resin composition.

  The aluminum is preferably modified in such a manner that a negative charge is generated on the surface of the inorganic oxide fine particles. More preferably, the aluminum is preferably modified in the form of a complex oxide with silicon. The composite oxide preferably includes at least a Si—O—Al bond.

The Al-modified confetti fine particles according to the present invention have a range in which aluminum is 0.1 × 10 ^{−6 to} 1.5 × 10 ⁻⁶ mol / m ² per unit surface area of the confetti-like inorganic oxide fine particles. It is characterized by being modified.

  Since the Al-modified octopus sugar fine particles according to the present invention have a confetti-like shape and the amount of aluminum modification per unit surface area is in the above range, the surface negative charge amount of the Al-modified octopus sugar fine particles increases, and the solvent And dispersion stability in the binder is improved. Therefore, it is excellent in the effect of improving the weather adhesion and film hardness and scratch resistance of the coating film containing the fine particles.

When the modification amount of the aluminum is less than 0.1 × 10 ⁻⁶ mol / m ² , it is not preferable because the scratch resistance and transparency of the coating film are lowered, and 1.5 × 10 ⁻⁶ mol / m ² is not preferable. Exceeding this is not preferable because the stability of the Al-modified gold flat sugar-like fine particles is lowered and the hardness and scratch resistance of the coating film are lowered.

  In addition, when the Al-modified octopus sugar-like fine particles according to the present invention have a core-shell type structure and aluminum is contained in the protrusions on the shell and / or the shell surface, the Al-modified octopus sugar-like fine particles are modified per unit surface area. The amount of aluminum shall include the aluminum contained in the shell and protrusion.

  The cation streaming potential titration value was measured using Poly-Dadmac (polydiallyldimethyl-ammonium chloride solution) as a cation standard titration solution with a streaming potential measuring device (PCD-T3, manufactured by MUTEK). The streaming potential titration value thus obtained was defined as the surface negative charge amount. The value obtained by the above measurement is the surface negative charge amount (μeq / g) per 1 g of the solid content of the Al-modified confetti fine particles.

It is preferable that the surface negative charge amount of the Al-modified octopus sugar fine particles according to the present invention is in the range of 15 to 35 μeq / g, more preferably 18 to 30 μeq / g, when measured in a pH 6 solvent.
Since the amount of surface negative charge is proportional to the amount of Al modification per unit weight, if the amount of modification is large, the amount of solid acid (silica alumina) having a negative charge increases and the amount of surface negative charge increases. Although the amount of Al charged during production can be increased, the amount of Al that can produce Si and solid acid is limited, and if too much Al is formed, positively charged alumina is formed, so the surface negative charge amount Will go down.

  A large amount of aluminum is modified in a form having a negative charge on the surface of the Al-modified gold flat sugar-like fine particles related to the present invention, and the negative charge density is in the above range, so that the dispersion stability in a dispersion solvent or a binder is improved. Excellent in strength and stable even in acidity, it has excellent film strength, scratch resistance and transparency when blended into a coating film.

The average particle diameter of the Al-modified gold flat sugar-like fine particles according to the present invention is preferably 8 to 60 nm, more preferably 10 to 50 nm. When the average particle diameter is less than 8 nm, it is not preferable because the film tends to increase in viscosity when concentrated to a high concentration, and it becomes difficult to obtain a desired film hardness.
Moreover, when the said average particle diameter exceeds 60 nm, since transparency of the coating film obtained may deteriorate, it is unpreferable. The average particle diameter of the Al-modified gold flat sugar-like fine particles can be controlled by the particle diameter of the core particles, the silica coating film thickness (amount), and the protrusion height (amount).

The surface of the Al-modified gold flat sugar particles according to the present invention can be further treated with a known surface treating agent such as an organosilicon compound such as a silane coupling agent or amines.
The refractive index of the Al-modified gold plain sugar particles is 1.7 to 2.7, more preferably 1.85 to 2.5 when the core particles are titanium oxide particles or composite oxide particles. It is preferable that it exists in. Such Al-modified gold flat sugar fine particles can be suitably used as high refractive index particles.

  The refractive index of the Al-modified gold flat sugar-like fine particles is 1.6 to 2.2 when the core particles are zirconium or niobium oxide fine particles, or complex oxide fine particles mainly containing zirconium or niobium. Preferably it is in the range of 1.7 to 2.1. Such Al-modified gold flat sugar particles can be suitably used as medium to high refractive index particles.

  The refractive index of the Al-modified gold flat sugar-like fine particles is 1.5-2. When the core particles are tin or tungsten oxide fine particles or complex oxide fine particles mainly composed of tin, tungsten, antimony or indium. It is preferably 0, more preferably in the range of 1.6 to 1.9. Such Al-modified confetti fine particles can be suitably used as medium refractive index particles.

Dispersion The dispersion according to the present invention is characterized in that it contains Al-modified confetti fine particles according to the present invention.
The dispersion solvent of the dispersion may be water or an organic solvent, or a mixture of water and an organic solvent.
Examples of the organic solvent include alcohols such as methanol, ethanol, butanol, propanol and isopropyl alcohol, ethers such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether and propylene glycol monoethyl ether, and ketones such as methyl ethyl ketone and γ-butyrolactone. Etc.

  The solid content concentration of the dispersion is preferably 5 to 60% by weight, more preferably 10 to 50% by weight. When the solid content concentration is less than 5% by weight, the effect of the fine particles may not be sufficiently obtained, which is not economical. On the other hand, if the solid content concentration exceeds 60% by weight, the dispersion may be thickened or storage stability may be lowered, which is not preferable.

  The dispersion containing Al-modified octopus sugar particles according to the present invention has high dispersion stability, for example, is stable even in acidity, can be concentrated at a high concentration, has high transparency, and is refracted by Al-modified octopus sugar particles. It can be used for various applications by controlling the rate, catalytic activity, ultraviolet absorbing ability and the like.

  This dispersion is very stable, can be easily mixed with a binder component, and has excellent stability in an acidic pH range, and therefore can be used particularly suitably for blending into a coating composition or a resin composition.

Coating Composition The coating composition according to the present invention is characterized by containing Al-modified confetti fine particles according to the present invention and a binder component.
Since the coating composition contains the Al-modified confetti fine particles, the refractive index can be easily adjusted, and since the familiarity between the fine particles and the binder component is good, the coating composition has excellent coating film hardness and scratch resistance and is transparent. A film can be formed.

  Moreover, since the surface negative charge density of the Al-modified gold flat sugar particles is high and the shape thereof is gold flat sugar, the coating film obtained from the coating composition has adhesion to a substrate and other coating films, Particularly excellent in weather resistance.

Such a coating composition can be used for any coating film.
Since the coating film obtained from this coating composition has a high refractive index and excellent weather resistance and light resistance, it is particularly preferably used for a hard coat layer coating film or primer layer coating film for optical substrates such as lenses. Suitable for

Examples of the binder component include an organosilicon compound, a thermosetting organic resin, a thermoplastic organic resin, or an ultraviolet curable organic resin.
Examples of the organosilicon compound include alkoxysilane compounds, and specifically include tetraethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, α-glucidoxy. Methyltrimethoxysilane, α-glycidoxyethyltrimethoxysilane, β-glycidoxyethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxy Propylmethyldimethoxysilane, γ-γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) -ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) -ethyltriethoxysilane, γ-aminopropylto Silane, .gamma.-aminopropyltriethoxysilane, N-beta (aminoethyl)-.gamma.-aminopropyl methyl dimethoxy silane, N-beta and the like (aminoethyl)-.gamma.-aminopropyl methyl diethoxy silane.
These may be used alone or in combination of two or more.

  These organosilicon compounds may be used in a state where at least a part thereof is hydrolyzed. Such an organosilicon compound is particularly suitable as a binder component of a coating composition for forming a hard coat film.

The thermosetting organic resin is preferably at least one selected from urethane resins, epoxy resins and melamine resins.
More specifically, examples of the urethane resin include a reaction product of a block-type polyisocyanate such as hexamethylene diisocyanate and an active hydrogen-containing compound such as polyester polyol and polyether polyol, and the epoxy resin. Examples of the resin include a polyalkylene ether-modified epoxy resin and an epoxy group-containing compound in which a flexible skeleton (soft segment) is introduced into a molecular chain.

  Furthermore, examples of the melamine-based resin include cured products of etherified methylol melamine, polyester polyol, and polyether polyol. Among these, it is preferable to use a urethane-based resin that is a cured product of a block type isocyanate and a polyol. Moreover, these thermosetting organic resins may use not only one type but also two or more types.

  The thermoplastic organic resin is preferably at least one selected from an acrylic resin, a urethane resin, and an ester resin, and more preferably a self-emulsifying aqueous emulsion resin. Such a resin is particularly suitable as a binder component of the primer layer-forming coating composition.

Preparation method of coating composition As an example of the preparation method of the coating composition according to the present invention, when an organosilicon compound is used as a binder component, the organosilicon compound is used without a solvent or in a polar organic solvent such as alcohol. It is preferable to partially hydrolyze or hydrolyze in the presence of acid, water, etc., and then mix with a dispersion of Al-modified confetti fine particles. Or, after mixing the dispersion of the organosilicon compound and Al-modified confetti fine particles, these may be partially hydrolyzed or hydrolyzed.

The mixing ratio is expressed by X when the weight of the organosilicon compound is converted to SiO ₂ , and when the weight of the Al-modified octopus saccharide fine particles contained in the dispersion of the Al-modified octopus saccharide fine particles is expressed by Y. The ratio (X / Y) is preferably 30/70 to 90/10, preferably 35/65 to 80/20.

  In addition, a coating composition using a thermosetting organic resin and the thermoplastic resin as a binder component is prepared by mixing the resin and a dispersion of Al-modified gold flat sugar particles, and the mixing ratio is the weight of the resin. The weight ratio (R / S) is 90/10 to 30/70, more preferably 80, when the weight of the Al-modified confetti particles contained in the dispersion of Al-modified confetti particles is represented by S. It is preferable to carry out so that it becomes / 20-35 / 65.

The coating composition preferably further contains an ultraviolet absorber.
As the ultraviolet absorber, a conventionally known ultraviolet absorber or a currently developed ultraviolet absorber can be used. Typical ultraviolet absorbers such as benzophenone series, cinnamic acid series, and p-aminobenzoic acid are used. And organic compounds having optical stability such as a system and salicylic acid, and perovskite structure composite oxides such as calcium titanate, barium titanate, and strontium titanate can be used.

[Measurement method and evaluation test 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) Measuring method of average particle diameter The average particle diameter of Al-modified confetti fine particles and the like according to the present invention is measured under the condition of an acceleration voltage of 150 kV using a transmission electron microscope (TEM) (Hitachi H-800). A TEM photograph was taken at a magnification of 500,000 times, and the primary particle diameters of any 100 or more fine particles photographed in this photograph were observed visually, and the average was obtained.

(2) Specific surface area measuring method About 30 ml of powder obtained by drying a dispersion containing Al-modified gold flat sugar-like fine particles is collected in a magnetic crucible (type B-2) and dried at a temperature of 300 ° C. for 2 hours. Place in a desiccator and cool to room temperature. Next, 1 g of a sample was taken, and the specific surface area (m ² / g) of the particles was measured by a BET method using a fully automatic surface area measuring device (manufactured by Yuasa Ionics Co., Ltd., Multisorb 12 type).

(3) Composition analysis method of Al-modified confetti fine particles <contents of titanium, silicon and tin>
After collecting 1 g of an aqueous dispersion containing Al-modified gold flat sugar-like fine particles with a solid content concentration of 30% by weight in a zirconia ball with a cap having a capacity of 30 ml, drying (200 ° C., 20 minutes), firing (700 ° C., 5 minutes), Add ₂ g Na ₂ O ₂ and ₁ g NaOH and melt for 15 minutes. Further, 50 ml of HCl and 200 ml of water were added and dissolved, and then diluted to 500 ml with pure water to prepare a sample. About the obtained sample, using ICP apparatus (Shimadzu Corporation make, ICPS-8100, analysis software ICPS-8000), titanium, tin, and silicon content are converted into oxide conversion standards (TiO ₂ , SnO ₂ , Measured with SiO ₂ ).

<Contents of aluminum, zirconium, sodium and potassium>
3 g of an aqueous dispersion containing Al-modified gold plain sugar-like fine particles with a solid content concentration of 30% by weight is collected in a platinum dish having a capacity of 100 ml, dried on a sand bath at 200 ° C. for 20 minutes, and then heated at 700 ° C. for 5 minutes with a burner. After removing organic matter, add 10 ml of HF and 5 ml of H ₂ SO ₄ and heat until white smoke is emitted. Furthermore, after diluting this with pure water so as to be 100 ml, aluminum and zirconium are converted into oxides (Al ₂ ) using an ICP device (manufactured by Shimadzu Corporation, ICPS-8100, analysis software ICPS-8000). O ₃ , ZrO ₂ ), sodium and potassium are oxide conversion standards (Na ₂ O, K ₂ O) using an atomic absorption device (manufactured by Hitachi, Ltd., Z-5300, software Z-2000) Measure with

(4) Method for measuring surface negative charge (PCD) 1.67 g of a dispersion containing Al-modified gold flat sugar-like fine particles with a solid content concentration of 30% by weight (the dispersion medium may be water or an organic solvent). The sample was collected, and 98.53 g of distilled water was added to prepare 100.00 g of a mixed solution having a solid content concentration of 0.5% by weight. An aqueous solution for measurement was prepared by adding an aqueous hydrochloric acid solution or an aqueous ammonia solution to the obtained mixed solution and adjusting the pH to 6.0 at 25 ° C. 20.00 g of the obtained aqueous solution for measurement was fractionated, and Poly-Dadmac (polydiallyldimethyl-ammonium chloride, molecular weight: weight by GPC measurement) as a cation standard titrant with a streaming potential measuring device (Mutetek, PCD-T3). The cation streaming potential titration value was measured using a molecular weight of about 4500 (in terms of polystyrene). The streaming potential titration value thus obtained was defined as the surface negative charge amount.

The value obtained by the above measurement is the surface negative charge amount (μeq / g) per 1 g of the solid content of the Al-modified confetti fine particles. A value obtained by dividing this value by the specific surface area (m ² / g) of the Al-modified gold flat sugar-like fine particles was defined as the negative charge amount existing per unit specific surface area of the Al-modified gold flat sugar-like fine particles, that is, the surface roughness. This is because the molecular occupation cross section of poly (diallyldimethyl-ammonium chloride) used for the measurement of the surface negative charge amount is larger than the molecular occupation cross section (16.2 の² ) of the N ₂ molecule used for the measurement of the specific surface area. Since it is not adsorbed by the micropores of the particles of the present application and is selectively adsorbed by the external surface (including irregularities) of the particles, the adsorption amount of poly (diallyldimethyl-ammonium chloride) per unit surface area Degree). The surface roughness is defined by the following formula.
Surface roughness = surface negative charge amount / specific surface area unit is (μeq / g) / (m ² / g) = μeq / m ² .
The value of surface roughness 0.07~0.2μeq / m ^2, preferably from 0.07~0.19 (μeq / m ^2).

(5) Method for measuring pH A pH meter in which a cell containing 50 ml of a sample has been corrected with standard solutions of pH 4, 7, and 9 in a thermostatic chamber maintained at a temperature of 25 ° C. (manufactured by Horiba, F22) A glass electrode was inserted to measure the pH value.

  At this time, when the dispersion medium of the dispersion liquid of Al-modified confetti fine particles is water, the aqueous dispersion liquid with a solid content concentration of 30% by weight is used as a sample, and when the dispersion medium is an organic solvent, the dispersion medium is solid. A sample was prepared by diluting an organic solvent dispersion of Al-modified gold flat sugar-like fine particles having a partial concentration of 30% by weight 10 times with distilled water to a solid content concentration of 3.0% by weight.

About the curable coating film (6) Measurement method of film hardness (Bayer value) Created in the preparation examples of the examples using an abrasion tester BTM (manufactured by Colts, USA) and a haze value measuring device (NDH2000 manufactured by NIPPON DENSHOKU). The Bayer value is measured based on the change in haze value between the tested lens and the reference lens. As the reference lens, a commercially available plastic lens base material CR-39 base material (diethylene glycol bisallyl carbonate, PPG monomer used, base material refractive index 1.60) is used, and each haze value is first measured. The initial haze value of the reference lens is D (std0), and the initial haze value of the lens under test is D (test0). Each lens is placed in an abrasion resistance tester pan, filled with 500 g of abrasive (exclusive sand), and vibrated 600 times to the left and right for testing. The haze value of the reference lens after the test is D (stdf), and the haze value of the lens under test is D (testf). The Bayer test value (R) is calculated from the following equation.
R = [D (stdf) -D (std0)] / [D (testf) -D (test0)]

(7) Evaluation method of coating film appearance (interference fringes) A fluorescent lamp "Product 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. , The light of the fluorescent lamp is reflected on the surface of the anti-reflection film formed on the hard coat layer film (including the metal oxide fine particles) of the sample substrate, and the generation of rainbow patterns (interference fringes) due to light interference is visually observed Confirm with 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 a glare interference fringe.

(8) Evaluation method of appearance (cloudiness) of coating film A fluorescent lamp “trade name: Mellow 5N” (manufactured by Toshiba Lighting & Technology Co., Ltd., three-wavelength type daylight white fluorescent lamp) is mounted in a box whose inner wall is black. A sample substrate having a hard coat layer film containing the metal oxide fine particles is placed vertically under a fluorescent lamp, and 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

(9) Evaluation method of scratch resistance of coating film The surface of the test piece prepared in the preparation example of the example was subjected to a load of 1 kg on Bonstar steel wool # 0000 (manufactured by Nippon Steel Wool Co., Ltd.) After rubbing the distance under the condition of 50 reciprocations / 100 seconds, the degree of flaws was visually determined and evaluated according to the following criteria.
A: Almost no flaws B: Some flaws enter C: Some flaws enter D: Most flawed areas are scratched.

(10) Method for evaluating adhesion of coating film On the lens surface of the sample substrate on which the hard coat layer film has been formed, cuts are made at intervals of 1 mm with a knife to form 100 squares of 1 mm square, and cellophane adhesive tape Is pressed strongly in the direction of 90 degrees with respect to the in-plane direction of the plastic lens substrate, this operation is performed a total of five 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.

(11) Evaluation method of weather-resistant adhesion of coating film After performing an exposure test on a sample substrate on which a hard coat layer film is formed with a xenon weather meter (X-75 type manufactured by Suga Test Instruments Co., Ltd.), the appearance is confirmed. And the same evaluation as the above-mentioned evaluation of adhesion is performed, and the following criteria are used for evaluation. The exposure time is 250 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.

(12) Method for evaluating light resistance of coating film Irradiation with ultraviolet ray for 50 hours with a mercury lamp for fading test (H400-E manufactured by Toshiba Corporation), visual confirmation of lens color before and after the test, and evaluation based on the following criteria To do. 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 composite oxide fine particles (core particles) mainly composed of titanium 93.7 kg of titanium tetrachloride aqueous solution containing 7.75% by weight of titanium tetrachloride (produced by Osaka Titanium Technologies Co., Ltd.) on a TiO ₂ basis, Then, 36.3 kg of ammonia water containing 15% by weight of ammonia (manufactured by Ube Industries, Ltd.) was mixed to prepare a white slurry liquid having a pH of 9.5. Next, this slurry was filtered and then washed with pure water 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 159.0 kg of pure water was further added to obtain 726.0 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. 9.1 kg of aqueous potassium solution was gradually added with stirring.

  Next, after separating a cation exchange resin (Mitsubishi Chemical Corporation) incorporating potassium ions and the like, a silica sol containing 15% by weight of silica fine particles having an average particle diameter of 7 nm (manufactured by JGC Catalysts & Chemicals Co., Ltd.) 0 .8 kg and 18.0 kg of pure water are mixed and heated in an autoclave (pressure-resistant glass industry, 120 L) at a temperature of 165 ° C. for 18 hours, whereby a composite oxide containing titanium as a main component is obtained. An aqueous dispersion of fine particles (core particles) was obtained.

After cooling the obtained aqueous dispersion to room temperature, it was concentrated with an ultrafiltration membrane device (Asahi Kasei Co., Ltd., ACV-3010) to obtain 10.0 kg of an aqueous dispersion having a solid content of 10% by weight. Obtained.
The core particles contained in the aqueous dispersion has a rutile-type crystal structure, TiO ₂ 75.2 wt% when the content was measured in the metal element contained in the core particles, SnO ₂ 9.3 wt % was SiO ₂ 12.2 wt% and K ₂ O3.3% by weight.

Preparation of core shell type fine particles Zirconium oxychloride (made by Taiyo Mining Co., Ltd.) 26.3% by weight in terms of ZrO _{2 is} added to 26.3 kg of zirconium oxychloride aqueous solution, and ammonia water containing 15% by weight of ammonia is gradually stirred. This was added 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 silicic acid solution 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 was added to 3.0 kg of the aqueous dispersion containing core particles containing titanium as a main component obtained in the above step to obtain a solid content of 2% by weight. Then, 1020 g of the above-mentioned zirconic acid aqueous solution and 795 g of the silicic acid aqueous solution were gradually added thereto, and after completion of the addition, the mixture was aged with stirring for 1 hour while maintaining the temperature at 90 ° C.

  Next, this mixed solution is put in an autoclave (manufactured by Pressure Glass Industrial Co., Ltd., 50 L), subjected to heat treatment at a temperature of 160 ° C. for 18 hours, cooled to room temperature, and then subjected to an ultrafiltration membrane device (Asahi Kasei). The surface of core particles mainly composed of titanium is coated with a shell made of a complex oxide containing zirconium and silicon by concentrating to a solid content of 10% by weight using SIP-1013 manufactured by Co., Ltd. An aqueous dispersion of core-shell type fine particles (hereinafter referred to as “CT-1”) was prepared.

The crystal structure of the core-shell type fine particles was a rutile type.
Further, when the metal components contained in the core-shell type fine particles were measured, TiO ₂ 61.5 wt%, SnO ₂ 7.6 wt%, SiO ₂ 22.2 wt%, ZrO ₂ 4.8 wt%, and K ₂ O3.9% by weight.
The average particle diameter of the core-shell fine particles was 13 nm and the specific surface area was 224 m ² / g as measured by transmission electron microscopy.

Preparation of silica-coated core-shell type fine particles Commercially available water glass (manufactured by AGC S-Tech Co., Ltd., JIS No. 3 water glass, SiO ₂ concentration 24 mass%) was diluted with pure water, and then cation exchange resin (Mitsubishi Chemical Corporation). )) To obtain a silicic acid aqueous solution having a pH of 2.3% containing a silicic acid solution on the basis of SiO _{2 in} terms of 2.3% by weight.

  The aqueous dispersion (CT-1) of core-shell fine particles obtained in the above step was dealkalized with 0.3 kg of a cation exchange resin (manufactured by Mitsubishi Chemical Corporation), and then the resin was separated and water was removed. A dispersed sol was obtained. Next, 1681.1 g of the aqueous silicic acid solution is gradually added to the water-dispersed sol with stirring. After the addition is completed, the core shell coated with silica is aged for 1 hour while stirring at 35 ° C. An aqueous dispersion of fine particles was obtained.

Next, a 10.0 wt% aqueous sodium hydroxide solution was added to the aqueous dispersion to adjust the pH to 10.0, and the mixture was aged with stirring for 1 hour while maintaining the temperature at 85 ° C.
In addition, the shape of the core-shell type fine particles coated with silica contained in the aqueous dispersion was rice-grained.

Preparation of fine inorganic oxide particles
Preparation of fine particles partially coated with a shell containing aluminum Next, 485.6 g of a sodium aluminate aqueous solution containing 0.9% by weight of sodium aluminate in terms of Al ₂ O ₃ was gradually added to the aqueous dispersion. Furthermore, after completion of the addition, a water dispersion of fine particles in which the surface of the silica-coated core-shell fine particles is partially covered with a shell containing aluminum by performing a heat treatment with stirring for 1.5 hours while maintaining the temperature at 90 ° C. Obtained.

  After cooling this aqueous dispersion to room temperature, a cation exchange resin (manufactured by Mitsubishi Chemical Corporation) was added to adjust the pH to 9.5, and then the resin was separated to give a solid content of 6. An aqueous dispersion (CTS-1) 5.0 kg of fine particles partially covered with a shell containing 9% by weight of aluminum was obtained.

Protrusion formation step 6.9 kg of ion-exchanged water was added to 5.0 kg of the fine particle aqueous dispersion (CTS-1) partially coated with the aluminum-containing shell obtained above, and water glass (AGC S-Tech ( Co., Ltd., JIS No. 3 water glass, SiO ₂ concentration 24% by mass) 69.4 g was added. Subsequently, the temperature of this mixed solution was raised to 87 ° C. and maintained at 87 ° C. for 30 minutes.

Next, after diluting water glass (manufactured by AGC S-Tech Co., Ltd., JIS No. 3 water glass, SiO ₂ concentration 24 mass%) with ion-exchanged water, a cation exchange resin (manufactured by Mitsubishi Chemical Corporation) was used. The dealkalization was carried out to obtain 2067.9 g of a 3.0 wt% aqueous silicic acid solution on the basis of SiO ₂ conversion. Then, after adding the total amount of the silicic acid aqueous solution at 87 ° C. over 3 hours to the total amount of the fine particle aqueous dispersion partially covered with the aluminum-containing shell maintained at a temperature of 87 ° C., 87 Grain growth was carried out by aging at 1 ° C. for 1 hour to obtain an aqueous dispersion of confetti-like inorganic oxide fine particles.

  Subsequently, after cooling this aqueous dispersion to room temperature, a cation exchange resin (manufactured by Mitsubishi Chemical Corporation) was added to adjust the pH to 9.5. Subsequently, it is concentrated with an ultrafiltration membrane device (ACV-3010, manufactured by Asahi Kasei Co., Ltd.), and an aqueous dispersion (CTC-1) of confetti-like inorganic oxide fine particles having a solid content of 30% by weight. 4 kg was obtained.

The inorganic oxide fine particles contained in the aqueous dispersion are composed of aluminum and a surface of a core particle mainly composed of titanium covered with a shell made of a composite oxide containing zirconium and silicon and a shell made of silica. It is a confetti-like fine particle formed with protrusions made of a composite oxide containing silicon, and the content of each component contained in the fine particle was measured. As a result, 54.5% by weight of TiO ₂ as an oxide, SnO ₂ 6.6 wt%, SiO ₂ 34.0 wt%, ZrO ₂ 2.1 wt%, Al ₂ O ₃ 1.2 wt%, was K ₂ O1.3% by weight and Na ₂ O0.3% by weight .
Further, the specific surface area of the confetti fine particles was 260 m ² / g.

Preparation of Al modified confetti fine particles (1)
Process (1)
1400 g of the aqueous dispersion (CTC-1) of the confetti-like inorganic oxide fine particles obtained in the above step was supplied to a 13-liter SUS reaction vessel equipped with a stirrer and a heating device, and stirred at a temperature of 25 ° C. While, 2712 g of 0.9 wt% sodium aluminate aqueous solution was added at a constant rate over 1 hour and 20 minutes based on Al ₂ O ₃ conversion standard to obtain a mixed solution.
At this time, Al ₂ O ₃ / SiO ₂ (mixing molar ratio) was 0.100, and the addition rate of the sodium aluminate aqueous solution was 1.5 × 10 ⁻² g / Hr.

Step (1.1)
The resulting mixed solution was heated to 95 ° C. with stirring, and then stirred for 6.0 hours while maintaining the temperature at 95 ° C. The pH of this mixed solution was 10.9, the solid content concentration based on SiO ₂ was 24.2% by weight, and the solid content concentration based on Al ₂ O ₃ was 0.36% by weight.

Step (1.2)
A cation exchange resin (Mitsubishi Chemical Corporation Diaion SK1BH) was added to the mixed solution obtained in the above step to adjust the pH to 9.

Step (2)
After separating and removing the resin from the mixed solution obtained in the above step, heat treatment was performed at 165 ° C. for 1 hour in an autoclave to obtain an aqueous dispersion of Al-modified confetti particles.

Step (3)
Next, after cooling the aqueous dispersion of Al-modified confetti fine particles obtained by the above process to room temperature, a cation exchange resin (Mitsubishi Chemical Corporation Diaion SK1BH) was added to adjust the pH to 3.5. The resin was not separated and aged for 7 hours while maintaining at 80 ° C. with stirring.
Thereafter, the cation exchange resin was separated and removed to obtain an aqueous dispersion of Al-modified confectionary fine particles having a solid content concentration of 24.2% by weight and a pH of 4.9 on the basis of SiO ₂ conversion.

The aqueous dispersion of Al-modified confetti particles is concentrated using an ultrafiltration membrane, and 1470 g of an aqueous dispersion of Al-modified confetti particles (hereinafter referred to as “CTA-1”) having a solid content of 30% by weight is obtained. Obtained. When the content of the metal component of the Al-modified gold flat sugar-like fine particles was measured, it was 54.5% by weight of TiO ₂ , 6.6% by weight of SnO ₂ , 33.9% by weight of SiO _{2 based on} oxide conversion standards of each metal component. ZrO ₂ 2.1 wt%, Al ₂ O ₃ 1.4 wt%, K ₂ O 1.3 wt% and Na ₂ O 0.3 wt%. Further, the specific surface area of the Al-modified gold flat sugar-like fine particles was 264 m ² / g, and the average particle size measured by a transmission electron microscope was 20 nm.

Moreover, the surface negative charge amount of the Al-modified gold flat sugar-like fine particles was 25 (μeq / g), the negative charge amount per unit specific surface area, and the surface roughness was 0.095 μeq / m ² .
In addition, the modification amount of aluminum modified on the surface of the Al-modified gold flat sugar-like fine particles was 0.5 × 10 ⁻⁶ mol / m ² in terms of Al ₂ O ₃ per unit surface area of the fine particles.

Preparation of Methanol Dispersion of Al-Modified Fried Saccharide Fine Particles A dispersion solvent of 1470 g of the aqueous dispersion (CTA-1) of Al-modified fried sugar-like fine particles obtained in the above step was used as an ultrafiltration membrane device (filter membrane manufactured by Asahi Kasei Co., Ltd.). SIP-1013) was used to replace water with methanol (Mayashi Junyaku Co., Ltd., methyl alcohol concentration: 99.9% by weight).

The water content of the obtained Al gold plain sugar-like methanol dispersion (hereinafter referred to as “CTM-1”) was about 0.5 wt%, and the solid content concentration was 30 wt%. In addition, the average particle diameter of the Al-modified gold flat sugar-like fine particles contained in the methanol dispersion is 20 nm, the specific surface area is 264 m ² / g, and the amount of aluminum modified per unit surface area is based on the Al ₂ O ₃ conversion standard. The amount of negative charge and the surface roughness per unit specific surface area of the Al-modified gold flat sugar-like fine particles of 1.5 × 10 ⁻⁶ mol / m ² was 0.095 μeq / m ² .

Preparation of coating composition (H1) for forming a hard coat layer film 182.7 g of γ-glycidoxypropyltrimethoxysilane (Z-6040 manufactured by Toray Dow Corning Co., Ltd.) and methanol (manufactured by Hayashi Junyaku Co., Ltd.) (Methyl alcohol concentration: 99.9% by weight) 62.3 g of a 0.01N hydrochloric acid aqueous solution was added dropwise to 32.4 g of the mixed liquid with stirring. Furthermore, this liquid mixture was stirred at room temperature all day and night to hydrolyze the silane compound.

  Next, 282.7 g of methanol (Mayashi Junyaku Co., Ltd., methyl alcohol concentration: 99.9 wt%) and a solid content concentration of 30 wt% prepared in this example were placed in a container containing these hydrolysis solutions. 390.9 g of a methanol-dispersed Al-modified gold flat sugar fine particle (CTM-1), 40.6 g of propylene glycol monomethyl ether (manufactured by Dow Chemical), tris (2,4-pentanedionato) aluminum III (Tokyo Chemical Industry ( Co., Ltd.) 7.3 g and 1.1 g of a silicone surfactant (manufactured by Toray Dow Corning Co., Ltd., L-7604) as a leveling agent were added, and the mixture was stirred overnight at room temperature to form a coating film for forming a hard coat layer Composition (H1) was prepared.

Preparation of Hard Coat Layer Film Forming Coating Composition (H2 ) 164.4 g of γ-glycidoxypropyltrimethoxysilane (Z-6040 manufactured by Toray Dow Corning Co., Ltd.) and methanol (manufactured by Hayashi Junyaku Co., Ltd.) (Methyl alcohol concentration: 99.9% by weight) 62.3 g of 0.01N hydrochloric acid aqueous solution was added dropwise to 29.1 g of the mixed liquid mixture while stirring. Furthermore, this liquid mixture was stirred at room temperature all day and night to hydrolyze the silane compound.

  Next, 250.1 g of methanol (Mayashi Junyaku Co., Ltd., methyl alcohol concentration: 99.9% by weight) and 30% by weight of the solid content prepared in this example were placed in a container containing these hydrolysates. 452.1 g of Al-modified gold plain sugar fine particles in methanol (CTM-1), 40.6 g of propylene glycol monomethyl ether (manufactured by Dow Chemical), tris (2,4-pentanedionato) aluminum III (Tokyo Chemical Industry ( 6.6 g) and 1.1 g of a silicone surfactant (manufactured by Toray Dow Corning Co., Ltd., L-7604) as a leveling agent were added, and the mixture was stirred overnight at room temperature to form a coating film for forming a hard coat layer film Composition (H2) was prepared.

Preparation of primer layer film-forming coating composition (P1 ) 162.8 g of polyurethane emulsion “Superflex 150” (Daiichi Kogyo Seiyaku, water-dispersed urethane elastomer solid content 30%), which is a commercially available thermoplastic resin A container was prepared, to which was added methanol dispersion CTM-1 (206.7 g of ion-modified water and 96.9 g of ion-exchanged water) prepared in this example and stirred for 1 hour.

  Next, 528.8 g of methanol (produced by Hayashi Junyaku Co., Ltd., methyl alcohol concentration: 99.9% by weight) was added to these mixed solutions, and a silicone surfactant (manufactured by Toray Dow Corning Co., Ltd.) as a leveling agent. , L-7604) was added and stirred at room temperature for a whole day and night to prepare a primer layer film-forming coating composition (P1).

Preparation of primer layer film-forming coating composition (P2 ) 127.4 g of polyurethane emulsion “Superflex 150” (Daiichi Kogyo Seiyaku Co., Ltd., water-dispersed urethane elastomer solid content 30%), which is a commercially available thermoplastic resin A container was prepared, and methanol-dispersed CTM-1206.7 g of Al-modified fried sugar-like fine particles prepared in this example and 96.9 g of ion-exchanged water were added thereto, followed by stirring for 1 hour.

  Next, 528.8 g of methanol (produced by Hayashi Junyaku Co., Ltd., methyl alcohol concentration: 99.9% by weight) was added to these mixed solutions, and a silicone surfactant (manufactured by Toray Dow Corning Co., Ltd.) as a leveling agent. , L-7604) 0.3 g was added and stirred for a whole day and night at room temperature to prepare a primer layer film-forming coating composition (P2).

[Example 2]
Preparation of Al modified confetti fine particles (2)
Preparation of Al-modified octopus sugar-like fine particles of Example 1 In step (1) of (1), an aqueous solution of sodium aluminate (concentration: 0.9% by weight) added to 1400 g of an aqueous dispersion of cinnamon-sugar fine particles (CTC-1) An aqueous dispersion (CTA-2) of Al-modified confetti sugar particles was obtained using the same method as in Example 1 except that the amount was changed from 2712 g to 1532 g and the addition time was changed from 80 minutes to 46 minutes.

The content of each metal component of the Al-modified gold flat sugar fine particles contained in this aqueous dispersion is 54.5% by weight of TiO ₂ , 6.6% by weight of SnO ₂ , 34.6% by weight of SiO ₂ , ZrO in terms of oxide. ₂ 2.1 wt%, Al ₂ O ₃ 0.6 wt%, was K ₂ O1.3% by weight and Na ₂ O0.3% by weight. Further, the specific surface area of the Al-modified gold flat sugar-like fine particles was 262 m ² / g, and the average particle size determined from a transmission electron micrograph was 20 nm.

Further, the surface-negative charge amount of the Al-modified gold flat sugar-like fine particles was 20 μeq / g, the negative charge amount existing per unit specific surface area, and the surface roughness was 0.076 μeq / m ² .
The modification amount of the aluminum modified on the surface of the Al-modified gold flat sugar-like fine particles was 0.2 × 10 ⁻⁶ mol / m ² in terms of Al ₂ O ₃ per unit surface area of the fine particles.

Preparation of methanol-dispersed Al-modified confetti fine particles (2)
In the step of preparing a methanol dispersion of Al-modified confetti particles in Example 1, instead of using 1470 g of an Al-modified confetti fine particle aqueous dispersion (CTA-1), the Al-modified confetti components obtained in this example were used. A methanol dispersion (CTM-2) of Al-modified gold flat sugar-like fine particles was obtained in the same manner as in Example 1 except that 1470 g of the fine particle aqueous dispersion (CTA-2) was used. The water content of the resulting Al-modified confetti fine particles in methanol dispersion (CTM-2) was about 0.5% by weight, and the solid content concentration was 30% by weight. Moreover, the average particle diameter of the Al-modified confetti particles contained in the methanol dispersion obtained by TEM was 20 nm, the specific surface area was 262 m ² / g, and the amount of aluminum modified into the Al-modified confetti particles was Al _2. The unit surface area in terms of O ₃ was 0.2 × 10 ⁻⁶ mol / m ² , the amount of negative charge existing per unit specific surface area of the Al-modified confetti fine particles, and the surface roughness was 0.076 μeq / m ² . .

Preparation of coating composition (H3) for forming a hard coat layer film 182.7 g of γ-glycidoxypropyltrimethoxysilane (Z-6040 manufactured by Toray Dow Corning Co., Ltd.) and methanol (manufactured by Hayashi Junyaku Co., Ltd.) (Methyl alcohol concentration: 99.9% by weight) 62.3 g of a 0.01N hydrochloric acid aqueous solution was added dropwise to 32.4 g of the mixed liquid with stirring. Furthermore, this liquid mixture was stirred at room temperature all day and night to hydrolyze the silane compound.

  Next, 282.7 g of methanol (Mayashi Junyaku Co., Ltd., methyl alcohol concentration: 99.9 wt%) and a solid content concentration of 30 wt% prepared in this example were placed in a container containing these hydrolysis solutions. 390.9 g of an Al-modified gold flat sugar-like fine particle dispersion (CPM-2), 40.6 g of propylene glycol monomethyl ether (manufactured by Dow Chemical), tris (2,4-pentanedionato) aluminum III (Tokyo Chemical Industry ( 7.3 g) and 1.1 g of a silicone surfactant (L-7604, Toray Dow Corning Co., Ltd.) were added as a leveling agent, and the mixture was stirred at room temperature all day and night. A coating composition for forming a hard coat layer film (H3) was prepared.

[Example 3]
Preparation of Al modified confetti fine particles (3)
In the step (1) for preparing the Al-modified confetti fine particles of Example 1, 2712 g of an aqueous sodium aluminate solution (concentration: 0.9 wt%) added to 1400 g of the aqueous dispersion of confetti fine particles (CTC-1). In the same manner as in Example 1, except that the addition time was changed from 80 minutes to 4.5 hours, an aqueous dispersion (CTA- 3) was obtained.

The content of each metal component of the Al-modified gold flat sugar fine particles contained in this dispersion is 54.1% by weight of TiO ₂ , 6.4% by weight of SnO ₂ , 34.1% by weight of SiO ₂ , ZrO _{2 in} terms of oxide. 2.0 wt%, Al ₂ O ₃ 1.8 wt%, was K ₂ O1.3% by weight and Na ₂ O0.3% by weight.

Further, the specific surface area of the Al-modified gold flat sugar-like fine particles was 268 m ² / g, and the average particle diameter determined from a transmission electron micrograph was 20 nm.
Further, the surface charge amount of the Al-modified gold flat sugar-like fine particles was 29 μeq / g, the negative charge amount existing per unit specific surface area, and the surface roughness was 0.110 μeq / m ² .
In addition, the modification amount of aluminum per unit surface area of the Al-modified gold flat sugar-like fine particles was 0.7 × 10 ⁻⁵ mol / m ² in terms of Al ₂ O ₃ .

Preparation of methanol-dispersed Al-modified confetti fine particles (3)
In the step (1) of preparing a methanol dispersion of Al-modified confetti particles in Example 1, instead of using 1470 g of the aqueous dispersion (CTA-1) of Al-modified confetti particles, the Al obtained in this example was used. A methanol dispersion (CTM-3) of Al-modified confectionary fine particles was obtained in the same manner as in Example 1 except that 1470 g of the aqueous dispersion (CTA-3) of modified confetti fine particles was used.

The resulting methanol dispersion (CTM-3) had a water content of about 0.5% by weight and a solid content concentration of 30% by weight. The average particle diameter of the Al-modified octopus sugar fine particles contained in the methanol dispersion obtained by TEM of the methanol dispersion is 20 nm, the specific surface area is 268 m ² / g. The amount is 0.6 × 10 ⁻⁶ mol / m ² in terms of unit surface area based on Al ₂ O _{3, the} amount of negative charge present per unit specific surface area of the Al-modified gold flat sugar-like fine particles, and the surface roughness is 0.110 μeq / m ² .

Preparation of coating composition (H4) for forming a hard coat layer film 182.7 g of γ-glycidoxypropyltrimethoxysilane (Z-6040 manufactured by Toray Dow Corning Co., Ltd.) and methanol (manufactured by Hayashi Junyaku Co., Ltd.) (Methyl alcohol concentration: 99.9% by weight) 62.3 g of a 0.01N hydrochloric acid aqueous solution was added dropwise to 32.4 g of a mixed solution while stirring. Furthermore, this liquid mixture was stirred at room temperature all day and night to hydrolyze the silane compound.

  Next, 282.7 g of methanol (Mayashi Junyaku Co., Ltd., methyl alcohol concentration: 99.9 wt%) and a solid content concentration of 30 wt% prepared in this example were placed in a container containing these hydrolysis solutions. 390.9 g of a methanol dispersion (CTM-3) of Al-modified gold flat sugar fine particles of 40.6 g of propylene glycol monomethyl ether (manufactured by Dow Chemical), tris (2,4-pentanedionato) aluminum III (Tokyo Chemical Industry ( Co., Ltd.) 7.3 g and 1.1 g of a silicone surfactant (manufactured by Toray Dow Corning Co., Ltd., L-7604) as a leveling agent were added, and the mixture was stirred overnight at room temperature to form a coating film for forming a hard coat layer A composition (H4) was prepared.

[Example 4]
Preparation of complex oxide fine particles (core particles) mainly composed of zirconium 0.50 kg of zirconium oxychloride octahydrate (manufactured by Taiyo Mining Co., Ltd., ZrOCl ₂ · 8H ₂ O) was dissolved in 18.57 kg of pure water. Then, 17.56 kg of a 10% strength by weight aqueous KOH solution was added thereto to prepare a zirconium hydroxide hydrogel (ZrO ₂ concentration 1% by weight). Next, the obtained zirconium hydroxide hydrogel was washed by an ultrafiltration membrane method until the conductivity reached 0.5 mS / cm or less.

After adding 10.24 kg of 10 wt% KOH aqueous solution to 102.75 kg of zirconium hydroxide hydrogel having a concentration of 1 wt% as ZrO ₂ obtained by the above operation and stirring sufficiently, hydrogen peroxide having a concentration of 35 wt% was added. 0.56 kg of aqueous solution was added. At this time, the solution foamed vigorously and the solution became transparent, and the pH was 11.4.

  Next, 5.63 kg of an aqueous ammonia solution having a concentration of 28.8 wt% was added to this solution and sufficiently stirred to obtain a precursor slurry of zirconia-based core particles. At this time, the slurry was light yellow and the pH was 13.4.

This precursor slurry is divided into three equal parts and filled in an autoclave (manufactured by Pressure Glass Industry Co., Ltd., 100 L), hydrothermally treated at 150 ° C. for 11 hours, and then zirconia composite oxide fine particles are separated by centrifugal sedimentation. This was thoroughly washed and then dispersed in ion exchange water to obtain 10.10 kg of an aqueous dispersion of composite oxide fine particles (core particles) mainly composed of zirconium. The solid content of the aqueous dispersion was 10% by weight on a ZrO ₂ conversion basis.

  Next, 10.10 kg of the aqueous dispersion of the core particles was spray-dried using a spray dryer (NIRO ATOMIZER manufactured by NIRO). As a result, 0.90 kg of a dry powder of composite oxide fine particles (core particles) mainly composed of zirconium was obtained. The average particle diameter of the core particles contained in the obtained dry powder was about 2 μm.

  Next, 0.90 kg of the dry powder obtained above was calcined in an air atmosphere at a temperature of 500 ° C. for 2 hours to obtain a calcined powder of composite oxide fine particles (core particles) mainly composed of zirconium. 0.84 kg was obtained.

  0.84 kg of the calcined powder obtained above was dispersed in 0.74 kg of pure water, and 0.55 kg of a 28.6% strength tartaric acid aqueous solution and 0.23 kg of a 50% strength by weight KOH aqueous solution were sufficiently added thereto. Stir. Next, alumina beads having a particle diameter of 0.1 mm (high-purity alumina beads manufactured by Daimei Chemical Industry Co., Ltd.) are added, and this is subjected to a wet pulverizer (batch type tabletop sand mill manufactured by Campehapio Co., Ltd.) for 180 minutes. The powder was pulverized and dispersed. Thereafter, the alumina beads are separated and removed using a stainless steel filter having an opening of 44 μm, and then 6.65 kg of pure water is added and stirred, and an aqueous dispersion 8 of complex oxide fine particles (core particles) containing zirconium is added. .84 kg was obtained. The solid content of this aqueous dispersion was 11% by weight.

Next, after washing with ion-exchanged water using an ultrafiltration membrane, 0.43 kg of anion exchange resin (manufactured by Mitsubishi Chemical Corporation: SANUPC) was added for deionization treatment, and then a centrifuge (Hitachi CR-21G manufactured by Kogyo Co., Ltd.) and processed for 1 hour at a speed of 12,000 rpm, and water of complex oxide fine particles (core particles) containing zirconium having a solid content concentration of 10% by weight in terms of ZrO ₂ conversion standard. 9.50 kg of dispersion (CZ-1) was obtained. The average particle diameter of the core particles contained in the aqueous dispersion (CZ-1) was 28 nm, and the specific surface area was 153 m ² / g.
Furthermore, the content of the metal component contained in the core particles was 98.5% by weight of ZrO ₂ and 1.5% by weight of K ₂ O on the basis of oxide conversion of each metal component.

Preparation of silica-coated core particles In the step of “Preparation of silica-coated core-shell type fine particles” described in Example 1, instead of using 3.0 kg of the core-shell type fine particle aqueous dispersion (CT-1) prepared in Example 1 The main component of zirconium was the same as in “Preparation of silica-coated core-shell fine particles” in Example 1, except that 3.0 kg of the aqueous dispersion of zirconia-based core particles (CZ-1) prepared in this example was used. An aqueous dispersion of silica-coated core particles obtained by coating the composite oxide fine particles (core particles) with silica with silica was obtained. The aqueous dispersion had a solid content of 6.9% by weight.

Preparation of gold-peeled inorganic oxide fine particles (4)
Preparation of fine particles partially coated with a shell containing aluminum (2)
Next, in place of the silica-coated core-shell type fine particles prepared in Example 1, the silica-coated core particles prepared in this example were used, except that “partially coated with a shell containing aluminum” described in Example 1. In the same manner as in “Preparation of fine particles”, 5.0 kg of a fine particle aqueous dispersion (CZS-1) partially covered with a shell containing aluminum was obtained.
The covered fine particles partially covered with the shell containing aluminum were fine particles in which the surface of the core particle mainly composed of zirconium was coated with silica, and the shell containing aluminum was present in the form of spots on the surface. .

Grain Growth Process Including the aluminum prepared in this example instead of using 5.0 kg of an aqueous dispersion sol containing an aqueous dispersion of fine particles (CTS-1) partially coated with an aluminum-containing shell prepared in Example 1 Same as “Grain growth step” in “Preparation of gold flat sugar-like inorganic oxide fine particles” described in Example 1, except that 5.0 kg of aqueous dispersion of fine particles partially coated with shell (CZS-1) was used. By this method, 0.7 kg of an aqueous dispersion (CZC-1) of confetti-like inorganic oxide fine particles having a solid content of 30% by weight was obtained.

The metal component content of the inorganic oxide fine particles contained in this aqueous dispersion (CZC-1) was 68.7% by weight of ZrO ₂ , 29.8% by weight of SiO ₂ , 1.2% by weight of Al ₂ O ₃ and Na _2. O was 0.3% by weight.
Further, the specific surface area of the inorganic oxide fine particles was 107 m ² / g, and the average particle size determined from a transmission electron micrograph was 25 nm.

Preparation of Al modified confetti fine particles (4)
Instead of using 1400 g of the aqueous dispersion (CTC-1) of gold flat sugar particles prepared in Example 1, 1400 g of an aqueous dispersion sol containing the aqueous dispersion of gold flat sugar particles (CZC-1) prepared in this example was used. Except for the above, an aqueous dispersion (CZA-1) of Al-modified confused sugar particles having a solid content of 30% by weight in the same manner as the process described in “Preparation of Al-modified confused sugar particles (1)” in Example 1 0.7 kg was obtained.

When the content of the metal component of the Al-modified gold plain sugar-like fine particles contained in this aqueous dispersion was measured, it was 68.4% by weight of ZrO ₂ , 29.9% by weight of SiO ₂ , Al _{2 They were} 1.4% by weight of ₂ O ₃ and 0.3% by weight of Na ₂ O.

Further, the specific surface area of the Al-modified gold flat sugar-like fine particles was 111 m ² / g, and the average particle size determined from a transmission electron micrograph was 25 nm.
Further, the surface charge amount of the Al-modified gold flat sugar-like fine particles was 29 μeq / g, the negative charge amount existing per unit specific surface area, and the surface roughness was 0.190 μeq / m ² .
Further, the modification amount of the aluminum modified on the surface of the Al-modified gold flat sugar-like fine particles was 1.2 × 10 ⁻⁶ mol / m ² on the basis of Al ₂ O ₃ conversion per unit area of the particles.

Preparation of methanol-dispersed Al-modified confetti fine particles (4)
Instead of using 1470 g of the aqueous dispersion of Al-modified octopus sugar-like fine particles (CTA-1) in the step of preparing the methanol dispersion of Al-modified octopus sugar-like fine particles in Example 1, the Al-modified octopus sugar-like fine particles prepared in this example were used. A methanol dispersion (CZM-1) of Al-modified gold flat sugar-like fine particles was obtained in the same manner as in Example 1 except that 1470 g of the aqueous dispersion (CZA-1) was used.

The water content of the Al-modified confetti fine particles in methanol (CZM-1) was about 0.5% by weight, and the solid content was 30% by weight. The average particle diameter measured by transmission electron micrographs of the Al-modified gold flat sugar particles contained in this methanol dispersion is 25 nm, the specific surface area is 111 m ² / g, and the aluminum modified per unit surface area is Al _2. The amount of negative charge existing per unit specific surface area was 0.190 μeq / m ² on the basis of O ₃ , 1.2 × 10 ⁻⁶ mol / m ² .

Preparation of Hard Coat Layer Film Forming Coating Composition (H5 ) 162.2 g of γ-glycidoxypropyltrimethoxysilane (Z-6040 manufactured by Toray Dow Corning Co., Ltd.) and methanol (manufactured by Hayashi Junyaku Co., Ltd.) (Methyl alcohol concentration: 99.9% by weight) 55.3 g of a 0.01N aqueous hydrochloric acid solution was added dropwise to 28.7 g of a mixed solution with stirring. Furthermore, this liquid mixture was stirred at room temperature all day and night to hydrolyze the silane compound.

  Next, 246.2 g of methanol (Mayashi Junyaku Co., Ltd., methyl alcohol concentration: 99.9 wt%) and a solid content concentration of 30 wt% prepared in this example were placed in a container containing these hydrolyzed solutions. 459.5 g of a methanol dispersion (CZM-1) of Al-modified gold flat sugar particles, 40.6 g of propylene glycol monomethyl ether (manufactured by Dow Chemical), tris (2,4-pentanedionato) aluminum III (Tokyo Chemical Industry ( Co., Ltd.) 7.3 g and 1.1 g of a silicone surfactant (manufactured by Toray Dow Corning Co., Ltd., L-7604) as a leveling agent were added, and the mixture was stirred overnight at room temperature to form a coating film for forming a hard coat layer A composition (H5) was prepared.

[Comparative Example 1]
Preparation of US granular core-shell type fine particles In step (1) of “Preparation of Al-modified confetti fine particles (1)” in Example 1, instead of using 1400 g of an aqueous dispersion of confetti-like inorganic oxide fine particles (CTC-1) Further, 1400 g of an aqueous dispersion (CT-1) of core-shell type fine particles prepared by coating the surface of core particles mainly composed of titanium prepared in Example 1 with a shell made of a composite oxide containing zirconium and silicon. In addition, the amount of sodium aluminate aqueous solution (concentration: 0.9% by weight) was further changed from 2712g to no addition by the same method as in Example 1, and the core-shell type having a solid content concentration of 30% by weight. An aqueous dispersion of fine particles (RCTA-1) was obtained.

In this aqueous dispersion was measured metal ingredient content of the core-shell particles contained in (RCTA-1), in terms of oxide based on the respective metal components, TiO ₂ 61.5% by weight, SnO ₂ 7.6% by weight , SiO ₂ 22.2 wt%, was ZrO ₂ 4.8 wt% and K ₂ O3.9% by weight. Further, the specific surface area of the core-shell fine particles was 224 m ² / g. Further, the core-shell type fine particles were in the form of rice grains, and the average particle size determined from a transmission electron micrograph was 13 nm.

In addition, the surface negative charge amount of the rice granular core-shell fine particles was 145 μeq / g, the negative charge amount per unit specific surface area, and the surface roughness was 0.650 μeq / m ² .
Further, the modification amount of aluminum modified on the surface of the rice granular core-shell type fine particles was 0 in terms of Al ₂ O ₃ conversion per unit area of the particles.

Preparation of Methanol Dispersion Containing Rice Granular Core-Shell Fine Particles In the process of preparing a methanol dispersion of Al-modified confectionary fine particles in Example 1, this comparative example was used instead of the aqueous dispersion (CTA-1) of A-modified confetti fine particles. A methanol dispersion (RCTM-1) containing rice granular core-shell type fine particles was prepared in the same manner as in Example 1 except that the aqueous dispersion (RCTA-1) of rice granular core-shell type fine particles prepared in (1) was used.

The resulting methanol dispersion (RCTM-1) had a water content of about 0.5% by weight and a solid content concentration of 30% by weight. The average particle diameter of the rice granular core-shell fine particles contained in the methanol dispersion obtained by TEM is 13 nm, the specific surface area is 224 m ² / g, and the amount of aluminum modified per unit surface area is Al ₂ O _3. unit surface area converted at 0 mol / m ² of the reference, negative charge amount present in the unit specific surface area per a rice grain core-shell type fine particles was 0.650Myueq / m ^2.

Preparation of Hard Coat Layer Film Forming Coating Composition (C1 ) 187.8 g of γ-glycidoxypropyltrimethoxysilane (Z-6040 manufactured by Toray Dow Corning Co., Ltd.) and methanol (manufactured by Hayashi Junyaku Co., Ltd.) (Methyl alcohol concentration: 99.9% by weight) 64.0 g of a 0.01N hydrochloric acid aqueous solution was added dropwise to 33.3 g of a mixed solution while stirring. Furthermore, this liquid mixture was stirred at room temperature all day and night to hydrolyze the silane compound.

  Next, 291.8 g of methanol (Mayashi Junyaku Co., Ltd., methyl alcohol concentration: 99.9 wt%) and a solid content concentration of 30 wt% prepared in this comparative example were placed in a container containing these hydrolyzed solutions. % Rice granular core shell type methanol dispersion (RCTM-1) 373.9g, propylene glycol monomethyl ether (Dow Chemical) 40.6g, Tris (2,4-pentanedionato) aluminum III (Tokyo Chemical Industry) 7.3 g (manufactured by Co., Ltd.) and 1.1 g of a silicone-based surfactant (manufactured by Toray Dow Corning Co., Ltd., L-7604) as a leveling agent were added, and the mixture was stirred overnight at room temperature to form a hard coat layer film A coating composition (C1) was prepared.

Preparation of Hard Coat Layer Film Forming Coating Composition (C2 ) 170.2 g of γ-glycidoxypropyltrimethoxysilane (Toray Dow Corning Co., Ltd. Z-6040) and methanol (manufactured by Hayashi Junyaku Co., Ltd.) (Methyl alcohol concentration: 99.9% by weight) 58.0 g of a 0.01 N hydrochloric acid aqueous solution was added dropwise to 30.1 g of a mixed solution with stirring. Furthermore, this liquid mixture was stirred at room temperature all day and night to hydrolyze the silane compound.

  Next, in a container containing these hydrolysates, 260.4 g of methanol (Mayashi Junyaku Co., Ltd., methyl alcohol concentration: 99.9 wt%) and the solid content concentration prepared in this comparative example were 30 wt. % Rice granular core-shell type fine particle dispersion (RCTM-1) 432.8 g, propylene glycol monomethyl ether (Dow Chemical) 40.6 g, Tris (2,4-pentanedionato) aluminum III (Tokyo Chemical Industry) 6.8 g (manufactured by Co., Ltd.) and 1.1 g of a silicone surfactant (manufactured by Toray Dow Corning Co., Ltd., L-7604) as a leveling agent are added and stirred at room temperature all day and night to form a hard coat layer film A coating composition (C2) was prepared.

Preparation of primer layer film-forming coating composition (Y1 ) 176.0 g of polyurethane emulsion “Superflex 150” (Daiichi Kogyo Seiyaku Co., Ltd., water-dispersed urethane elastomer solid content 30%) which is a commercially available thermoplastic resin A container was prepared, to which 193.6 g of a methanol dispersion (RCTM-1) of rice granular core-shell fine particles having a solid content concentration of 30% by weight and 96.9 g of ion-exchanged water were added and stirred for 1 hour.

  Next, 531.1 g of methanol (Mayashi Junyaku Co., Ltd., methyl alcohol concentration: 99.9% by weight) was added to these mixed solutions, and a silicone surfactant (manufactured by Toray Dow Corning Co., Ltd.) as a leveling agent. , L-7604) was added and stirred at room temperature for a whole day and night to prepare a primer layer film-forming coating composition (Y1).

Preparation of primer layer film forming coating composition (Y2 ) 142.1 g of polyurethane emulsion “Superflex 150” (Daiichi Kogyo Seiyaku Co., Ltd., water-dispersed urethane elastomer solid content: 30%), which is a commercially available thermoplastic resin. A container was prepared, and 227.4 g of a methanol dispersion (RCTM-1) of rice granular core-shell type fine particles having a solid content concentration of 30% by weight and 96.9 g of ion-exchanged water were added thereto, followed by stirring for 1 hour.

  Next, 531.1 g of methanol (Mayashi Junyaku Co., Ltd., methyl alcohol concentration: 99.9% by weight) was added to these mixed solutions, and a silicone surfactant (manufactured by Toray Dow Corning Co., Ltd.) as a leveling agent. , L-7604) 0.3 g was added and stirred for a whole day and night at room temperature to prepare a primer layer film-forming coating composition (Y2).

[Comparative Example 2]
Preparation of Al modified confetti fine particles (5)
In step (1) of preparation (1) of Al-modified gold flat sugar particles of Example 1, a sodium aluminate aqueous solution (concentration 0.9) added to 1400 g of an aqueous dispersion (CTC-1) of gold flat sugar oxide fine particles. An aqueous dispersion (RCTA-2) of Al-modified confetti sugar particles was obtained using the same method as in Example 1 except that the amount of (wt%) was changed from 2712 g to 45791 g.

The aqueous dispersion each metal component content of Al modified confetti-like particles contained in (RCTA-2) in terms of oxide basis, TiO ₂ 52.6 wt%, SnO ₂ 6.4 wt%, SiO ₂ 32. 4 wt%, ZrO ₂ 2.0 wt%, Al ₂ O ₃ 4.4 wt%, was K ₂ O1.3% by weight and Na ₂ O0.9% by weight. Further, the specific surface area of the Al-modified gold flat sugar-like fine particles was 271 m ² / g, and the average particle size determined from a transmission electron micrograph was 20 nm.

Further, the surface-negative charge amount of the Al-modified gold flat sugar-like fine particles was 65 μeq / g, the negative charge amount per unit specific surface area, and the surface roughness was 0.240 μeq / m ² .
Further, the modification amount of aluminum modified on the surface of the Al-modified gold flat sugar-like fine particles was 1.6 × 10 ⁻⁶ mol / m ² in terms of Al ₂ O ₃ per unit area of the particles.

Preparation of methanol-dispersed Al-modified confetti fine particles (5)
Instead of using 1470 g of the aqueous dispersion (CTA-1) of Al-modified confetti sugar particles in the process of “Preparation of methanol dispersion of Al-modified confetti particles (1)” in Example 1, Al prepared in this comparative example was used. A methanol dispersion (RCTM-2) of Al-modified confetti particles was obtained in the same manner as in Example 1 except that 1470 g of the aqueous dispersion (RCTA-2) of modified confetti particles was used.

Preparation of coating composition (C3) for forming a hard coat layer film 182.7 g of γ-glycidoxypropyltrimethoxysilane (Z-6040 manufactured by Toray Dow Corning Co., Ltd.) and methanol (produced by Hayashi Junyaku Co., Ltd.) (Methyl alcohol concentration: 99.9% by weight) 62.3 g of a 0.01N hydrochloric acid aqueous solution was added dropwise to 32.4 g of the mixed liquid with stirring. Furthermore, this liquid mixture was stirred at room temperature all day and night to hydrolyze the silane compound.

  Next, 282.7 g of methanol (Mayashi Junyaku Co., Ltd., methyl alcohol concentration: 99.9 wt%) and a solid content concentration of 30 wt% prepared in this comparative example were placed in a container containing these hydrolyzed solutions. % 39% Al-modified gold-peeled sugar dispersion (RCTM-2), 40.6g propylene glycol monomethyl ether (Dow Chemical), Tris (2,4-pentanedionato) aluminum III (Tokyo Chemical Industry) 7.3 g (manufactured by Co., Ltd.) and 1.1 g of a silicone-based surfactant (manufactured by Toray Dow Corning Co., Ltd., L-7604) as a leveling agent were added, and the mixture was stirred overnight at room temperature to form a hard coat layer film A coating composition (C3) was prepared.

[Comparative Example 3]
Preparation of Al modified confetti fine particles (6)
In step (1) of “Preparation of Al-modified confetti fine particles (1)” in Example 1, an aqueous sodium aluminate solution (concentration: 0.9% by weight) added to 1400 g of an aqueous dispersion (CTC-1) of confetti fine particles ) Was changed from 2712 g to 69 g using the same method as in Example 1 to obtain an aqueous dispersion of Al-modified gold flat sugar particles (RCTA-3).

The content of each metal component of the Al-modified gold flat sugar-like fine particles contained in this aqueous dispersion (RCTA-3) is TiO ₂ 54.51 wt%, SnO ₂ 6.6 wt%, SiO ₂ 35. 1 wt%, ZrO ₂ 2.1 wt%, Al ₂ O ₃ 0.1 wt%, was K ₂ O1.3% by weight and Na ₂ O0.3% by weight.

Further, the specific surface area of the Al-modified confetti fine particles was 260 m ² / g, and the average particle size determined by a transmission electron microscope was 20 nm.
Moreover, the surface negative charge amount of the Al-modified gold flat sugar-like fine particles was 11 μeq / g, the negative charge amount existing per unit specific surface area, and the surface roughness was 0.042 μeq / m ² .

Further, the modification amount of the aluminum modified on the surface of the Al-modified octopus fine particles was 4.5 × 10 ⁻⁸ mol / m ² in terms of Al ₂ O ₃ per unit area of the particles.
Furthermore, the specific surface area calculated | required from the average particle diameter calculated | required by TEM of the titanium type inorganic oxide fine particle contained in the said titanium type inorganic oxide fine particle aqueous dispersion sol was 92 m < ² > / g.

Preparation of Methanol Dispersion of Al-Modified Fried Saccharide Fine Particles In Example 1, “ Preparation of Methanol Dispersion of Al-Modified Fried Saccharide Fine Particles (1)”, instead of using 1470 g of an aqueous dispersion (CTA-1) of Al-modified frigate sugar-like fine particles In addition, a methanol dispersion of Al-modified gold flat sugar particles (RCTM-3) was used in the same manner as in Example 1 except that 1470 g of the Al-modified gold flat sugar particles aqueous dispersion (RCTA-3) obtained in this Comparative Example was used. Got. The water content of this methanol dispersion (RCTM-3) was about 0.5% by weight and the solid content concentration was 30% by weight.

Preparation of Hard Coat Layer Film Forming Coating Composition (C4 ) 182.7 g of γ-glycidoxypropyltrimethoxysilane (Z-6040 manufactured by Toray Dow Corning Co., Ltd.) and methanol (produced by Hayashi Junyaku Co., Ltd.) (Methyl alcohol concentration: 99.9% by weight) 62.3 g of a 0.01N hydrochloric acid aqueous solution was added dropwise to 32.4 g of the mixed liquid with stirring. Furthermore, this liquid mixture was stirred at room temperature all day and night to hydrolyze the silane compound.

Next, in a container containing these hydrolysis solutions, 282.7 g of methanol (Mayashi Junyaku Co., Ltd., methyl alcohol concentration: 99.9 wt%) and the solid content concentration prepared above were 30 wt%. 390.9g of methanol dispersion (RCTM-3) of Al-modified gold plain sugar fine particles, 40.6g of propylene glycol monomethyl ether (manufactured by Dow Chemical), Tris (2,4-pentanedionato) aluminum III (Tokyo Chemical Industry Co., Ltd.) )) 7.3 g and 1.1 g of a silicone surfactant (manufactured by Toray Dow Corning Co., Ltd., L-7604) as a leveling agent were added, and the mixture was stirred overnight at room temperature to form a coating composition for forming a hard coat layer film A product (C3) was prepared.
Table 1 shows the properties of the particles prepared in Examples 1 to 4 and Comparative Examples 1 to 3.

Preparation of test plastic lens substrate (test piece) (1) Pretreatment of plastic lens base material Commercially available plastic lens base material “monomer name: MR-8” (Mitsui Chemicals, Inc., refractive index of base material) 60) and “monomer name: MR-7” (manufactured by Mitsui Chemicals, Inc., base material refractive index 1.67) are immersed in a 10 wt% KOH aqueous solution kept at 40 ° C. for 2 minutes for etching treatment. Went. Further, these were taken out, washed with water, and then sufficiently dried.

(2) Formation of primer layer film A primer layer film-forming coating composition was applied to each pre-treated plastic lens substrate to form a coating film. In addition, application | coating of this coating composition was performed using the dipping method (pickup speed 120mm / min).
Next, the said coating film was heat-processed for 10 minutes at 100 degreeC, and the preliminary drying of the coating film (primer layer) was performed.
The film thickness of the primer layer thus formed after preliminary curing was approximately 0.5 to 0.7 μm.

(3) Formation of hard coat layer film A coating composition for forming a hard coat layer film is applied to the surface of the plastic lens substrate that has been subjected to the pretreatment or the plastic lens substrate on which the primer layer film has been formed. A film was formed. 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). At this time, the main curing of the primer layer was also performed simultaneously.
In addition, the film thickness after hardening of the said hard-coat layer film | membrane formed in this way was 3.0-3.5 micrometers in general.

(4) Formation of antireflection film layer An inorganic oxide component having the following constitution was deposited on the surface of the hard coat layer film 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. Each of the layers of the antireflection layer film laminated in (1) was formed. The design wavelength λ was 520 nm.

Appearance, scratch resistance, adhesion, and weather resistance evaluation Examples 1 to 4 and coating compositions H1, H2, H3, H4, H5, C1 for forming a hard coat layer film obtained in Comparative Examples 1 to 3, Using C2, C3, C4 and primer layer film-forming coating compositions P1 and Y1, a primer layer film and a hard coat layer film were formed on a plastic lens substrate that had been pretreated in the combinations shown in Table 2. Test pieces 1 to 12 were prepared.

  In addition, the base material of the test piece 7 which apply | coated the coating composition P1 for primer layer film formation, and the coating composition H1 for hard coat layer film formation, and formed the antireflection layer film, and the coating composition Y1 for primer layer film formation A test piece 8 was prepared by applying the coating composition C1 for forming a hard coat layer film and forming an antireflection layer film.

  Furthermore, the base material of the test piece 9 which applied the primer layer film-forming coating composition P2 and the hard coat layer film-forming coating composition H20 to form an antireflection layer film, and the primer layer film-forming coating composition Y2 As a base material of test pieces 9 to 10 coated with a coating composition C2 for forming a hard coat layer film and forming an antireflection layer film, “monomer name: MR-7” (manufactured by Mitsui Chemicals, Inc. Refractive index 1.67) was used, and “monomer name: MR-7” (manufactured by Mitsui Chemicals, Inc., base material refractive index 1.67) was used as the base material of the other test pieces.

  About the test pieces 1-10 obtained in this way, using the above-described evaluation test method, the appearance (interference fringes), appearance (cloudiness), scratch resistance, film hardness, adhesion, weather resistance, and light resistance were measured. Tested and evaluated. The results are shown in Table 3.

  As is clear from this result, it was found that the test piece obtained by applying the coating composition prepared in the example had a relatively high scratch resistance and no transparency and high transparency. Moreover, it turned out that adhesiveness, a weather resistance, and light resistance are high.

Claims (6)

It has a core-shell structure consisting of a core particle containing one or more metal elements selected from zirconium, tin, titanium, niobium, tungsten, antimony, and indium, and a shell containing silicon, and many on the surface of the base particle On the surface of the inorganic oxide particles having the shape of
Aluminum is modified in a range of 0.1 × 10 ^{−6 to} 1.5 × 10 ⁻⁶ mol / m ^{2 in} terms of Al ₂ O ₃ per unit surface area ,
The surface negative charge amount (μeq / g) obtained as a cation potential measurement value when the pH of the aqueous solution for measurement was adjusted to 6 with a streaming potential measuring device was measured, and the specific surface area (m ² / m ² ) surface roughness obtained by dividing g) (μeq / m ²⁾ is, Al modified inorganic oxide fine particles, characterized in <br/> in the range of 0.07~0.2μeq / m ^2. The negative surface charge amount (μeq / g) obtained as a cation potential measurement value when measured by adjusting the pH of the aqueous solution for measurement to 6 with a streaming potential measuring device is in the range of 15 to 35 μeq / g. The Al-modified inorganic oxide fine particles according to claim 1. Al-modified inorganic oxide fine particles according to claim 1 or 2 average particle diameter measured using the Al-modified inorganic oxide fine particles of a transmission electron microscope (TEM) is being in the range of 8~60nm . A dispersion containing the Al-modified inorganic oxide fine particles according to any one of claims 1 to 3 . And Al-modified inorganic oxide fine particles according to any one of claims 1 to 3 coating composition comprising a binder component. A process according to claim 1 to 3 of any one Al-modified inorganic oxide according to paragraph microparticles, see containing silicon as following steps (1) at least the surface, and a number of projections on the surface of base particles A step of producing an aqueous dispersion containing inorganic oxide fine particles having a shape having a pH of 9.0 to 11.5;
(2) When silicon contained in the aqueous dispersion is represented by SiO ₂ and aluminum contained in the aluminum source is represented by Al ₂ O ₃ , the molar ratio (Al ₂ O ₃ / SiO ₂ ) is 0.0005. Mixing the aluminum source at a rate such that 0.050;
(3) heating the obtained mixed liquid to a temperature of 60 to 200 ° C. and stirring for 0.5 to 20 hours;
A method for producing Al-modified inorganic oxide fine particles, comprising: