JP6080583B2 - Surface-modified inorganic composite oxide fine particles, production method thereof, dispersion containing the fine particles, coating solution for optical substrate, coating film for optical substrate, and coated substrate - Google Patents

Description

  The present invention relates to surface-modified inorganic composite oxide fine particles, a method for producing the same, a dispersion containing the fine particles, a coating solution for an optical substrate, a coating film for an optical substrate, and a substrate with a coating film.

Conventionally known is a method of facilitating dispersion in an organic solvent or resin by modifying the surface of inorganic oxide fine particles with a silane coupling agent or the like. As a wet method, it is represented by Unexamined-Japanese-Patent No. 2001-240769 (patent document 1) by M (OR) _q (M is a metal element, q is a valence of M, R is a hydrogen atom, an alkyl group, etc.). Organosilicon represented by metal alkoxides and / or (partial) hydrolyzed (condensed) products thereof and Y _m SiX _n (Y is an organic functional group such as an alkyl group, X is a hydrolyzable group such as an alkoxy group) It is disclosed that inorganic fine particles are surface-treated with a compound and / or a (partial) hydrolyzed (condensed) product thereof. Specific examples of M include Al, Ti, and Zr, and inorganic fine particles include ITO fine particles, ATO fine particles, and In-supported ZnO fine particles.

  On the other hand, as a dry method, Japanese Unexamined Patent Application Publication No. 2008-304686 (Patent Document 2) discloses a tetrafunctional inorganic oxidation as a first step treatment in a gas phase for inorganic oxide fine particles having a primary particle diameter of 1 to 30 nm. There is disclosed a method for producing optically modified surface particles for optical use, in which a heat treatment is performed by adding a precursor, and a monofunctional surface treating agent is added and heat-treated as a second stage treatment.

JP 2001-240769 A JP 2008-304686 A

  These surface-modified inorganic oxide fine particles are used as a filler dispersed in a resin for forming an optical coating film, and have excellent characteristics such as strength, hardness and durability against abrasion. However, in a hydrophobic dispersion medium such as a resin or an organic solvent, these surface-modified inorganic oxide fine particles tend to aggregate with each other. In some cases, unevenness in function expression or spot-like defects may occur, leaving room for improvement.

  In addition, when blending inorganic oxide fine particles in a coating film, etc., it is required to improve the transparency and strength of the resulting coating film, particularly hard coat films and primer films of optical lenses such as glasses. In such applications, improvement of the refractive index of the film is required. Furthermore, a material that is highly economical in storage and transportation is required as the inorganic oxide fine particles.

  In view of the above circumstances, the present invention can reduce storage space and transport space, can be easily dispersed in a hydrophobic medium such as a resin or an organic solvent, has high transparency, high hardness, scratch resistance, and a substrate. Inorganic oxide fine particles for forming a coating film excellent in adhesion, weather resistance and light resistance, dispersions such as coating solutions for optical substrates, and coating films and coating-coated bases excellent in these properties The purpose is to obtain materials.

The gist of the present invention is the following [1] to [23].
[1]
The inorganic composite oxide fine particles are represented by the following formula (1), an organosilicon compound A or a partially hydrolyzed product thereof, and the following formula (2). The boiling point at 1 atm is 120 ° C. or less. Surface-modified inorganic composite oxide fine particles obtained by surface modification with a certain organosilicon compound B or a partial hydrolyzate thereof and having a carbon atom content of 2 to 10% by weight.
Si (OR ¹ ) _4-n (OH) _n (1)
R ² ₃ Si (OR ³ ) (2)
(In the formula, R ¹ is an unsubstituted or substituted hydrocarbon group having 1 to 4 carbon atoms, which may be the same or different, and n is an integer of 0 to 3.

R ² is an unsubstituted or substituted hydrocarbon group having 1 to ² carbon atoms, which may be the same or different, and R ³ is a hydrogen atom or an unsubstituted or substituted carbon group having 1 to 3 carbon atoms. It is a substituted hydrocarbon group. )

[2]
The surface-modified inorganic composite oxide fine particles as described in [1] above, wherein the inorganic composite oxide fine particles have a core-shell structure.

[3]
The inorganic composite oxide fine particles are
(1) A core particle characterized by being an inorganic composite oxide containing at least one metal element selected from the group consisting of titanium, zirconium, niobium, cerium and zinc, and silicon, and (2) the core particle The surface according to the above [2], comprising a shell layer made of an oxide containing at least one metal element selected from the group consisting of zirconium, aluminum and antimony and / or silicon. Modified inorganic composite oxide fine particles.

[4]
The surface modification according to the above [2] or [3], further comprising at least one metal element selected from the group consisting of tin, tungsten, antimony and indium as the metal element constituting the core particle. Inorganic composite oxide fine particles.

[5]
The inorganic composite oxide fine particles include composite oxide fine particles containing at least one metal element selected from the group consisting of titanium, zirconium, niobium, cerium, aluminum, antimony, tin, tungsten, indium and zinc, and silicon, or The surface-modified inorganic composite oxide fine particles as described in [1] above, which are composite oxide fine particles containing at least two kinds of the metal elements.

[6]
The surface-modified inorganic composite oxide fine particles according to any one of the above [1] to [5], wherein the inorganic composite oxide fine particles have an average particle diameter of 5 to 200 nm.

[7]
Wherein represents the weight of the organic silicon compound A or a partial hydrolyzate thereof and M _A, the weight of the organic silicon compound B or a partial hydrolyzate thereof expressed as M _B, the weight of the inorganic composite oxide particles as M ₁ When expressed, the surface-modified inorganic composite according to any one of the above [1] to [6], wherein the weight ratio (M _A + M _B ) / M ₁ is in the range of 0.4 to 2.0. Oxide fine particles.

[8]
The addition amount of the organosilicon compound A or a partial hydrolyzate thereof per surface area of the inorganic composite oxide fine particles is in the range of 0.5 to 6.0 mg / m ² , and the organosilicon compound B or the partial hydrolyzate thereof. The addition amount of the decomposition product per surface area of the inorganic composite oxide fine particles is in the range of 1.5 to 4.5 mg / m ² , according to any one of the above [1] to [7] Surface modified inorganic composite oxide fine particles.

[9]
A surface-modified inorganic composite oxide fine particle dispersion comprising the surface-modified inorganic composite oxide fine particles according to any one of [1] to [8] and a dispersion medium.

[10]
The organic solvent dispersion containing the surface-modified inorganic composite oxide particles according to [9] above, wherein the dispersion medium is an organic solvent or an organic solvent and water.

[11]
A method for producing the surface-modified inorganic composite oxide fine particles according to [1] above,
(1) preparing an aqueous dispersion of the inorganic composite oxide fine particles;
(2) adding the organosilicon compound A or a partial hydrolyzate thereof to the aqueous dispersion to modify the surface of the inorganic composite oxide fine particles;
(3) replacing the water contained in the dispersion obtained in the step (2) with an organic solvent,
(4) A step of further modifying the surface of the inorganic composite oxide fine particles by adding the organosilicon compound B or a partial hydrolyzate thereof to the organic solvent dispersion obtained in the step (3).
(5) A method for producing surface-modified inorganic composite oxide fine particles, comprising a step of removing the organic solvent from the organic solvent dispersion obtained in the step (4).

[12]
[11] In the step (4), the operation of adding the organosilicon compound B or a partial hydrolyzate thereof to modify the surface of the inorganic composite oxide fine particles is repeated 1 to 10 times. A method for producing the surface-modified inorganic composite oxide fine particles described in 1 above.

[13]
It includes the step (6) of further modifying the surface of the fine particles by adding the organosilicon compound B or a partial hydrolyzate thereof to the surface-modified inorganic composite oxide fine particles obtained in the step (5). The method for producing surface-modified inorganic composite oxide fine particles according to [11] or [12] above.

[14]
It represents the weight of the inorganic composite oxide fine particles with M _1, the weight of the organic silicon compound A or a partial hydrolyzate thereof represented as M _A, the weight of the organic silicon compound B or a partial hydrolyzate thereof and M _B When expressed, the surface-modified inorganic composite according to any one of [11] to [13] above, wherein the value of (M _A + M _B ) / M ₁ is in the range of 0.4 to 2.0. A method for producing fine oxide particles.

[15]
The addition amount of the organosilicon compound A or a partial hydrolyzate thereof per specific surface area of the inorganic composite oxide fine particles is in the range of 0.5 to 6.0 mg / m ² , and the organosilicon compound B or a portion thereof Any of the above [11] to [14], wherein the amount of the hydrolyzate added per specific surface area of the inorganic composite oxide fine particles is in the range of 1.5 to 4.5 mg / m ^2. A method for producing the surface-modified inorganic composite oxide fine particles as described.

[16]
A coating solution for an optical substrate comprising an organic solvent dispersion containing the surface-modified inorganic oxide fine particles according to any one of [1] to [8].

[17]
The coating solution for an optical substrate as described in [16] above, which is a coating solution for forming a hard coat layer film.

[18]
The coating solution for an optical substrate as described in [16] above, which is a coating solution for forming a primer layer film.

[19]
The optical substrate coating liquid according to any one of [16] to [18], wherein the optical substrate is a plastic lens.

[20]
The coating film formed from the coating liquid for optical base materials in any one of said [16]-[19].
[21]
A plastic substrate and a primer layer and / or a hard coat layer coating film formed from the coating solution for optical substrates according to any one of the above [16] to [19] formed on the substrate. A substrate with a coating film, characterized in that.

[22]
Each of the hard coat layer and the primer layer contains 100 parts by volume of the surface-modified inorganic oxide fine particles and 200 to 1000 parts by volume of a matrix component. Base material.

[23]
The hard coat layer is provided, and an antireflection film is provided on a surface of the hard coat layer opposite to the plastic substrate side. Base material.

  The surface-modified inorganic composite oxide fine particles according to the present invention can be easily dispersed in a nanosize in a hydrophobic medium such as a resin or an organic solvent, and the surface-modified inorganic composite oxide fine particles are dispersed in a dispersion (for example, an optical group). By using it in the form of a coating solution for materials, etc., a coating film excellent in transparency, hardness, scratch resistance, adhesion, weather resistance, and light resistance can be formed. Furthermore, the surface-modified inorganic composite oxide fine particles according to the present invention can be reduced in transportation costs as compared with the dispersion, and are excellent in economic efficiency.

  In addition, the coating film and the substrate with a coating film according to the present invention are excellent in transparency, hardness, scratch resistance, adhesion, weather resistance, and light resistance.

Hereinafter, the surface-modified inorganic composite oxide fine particles according to the present invention and the production method thereof, the dispersion containing the fine particles, the coating solution for the optical substrate, the coating film for the optical substrate, and the coated substrate are specifically described. To do.
<Surface modified inorganic composite oxide fine particles>
The surface-modified inorganic composite oxide fine particles according to the present invention are obtained by surface-modifying the surface of the inorganic composite oxide fine particles with an organosilicon compound A or a partially hydrolyzed product thereof and an organosilicon compound B or a partially hydrolyzed product thereof. And containing 2 to 10% by weight of carbon atoms (the weight of the surface-modified inorganic composite oxide fine particles is 100% by weight).

<Inorganic composite oxide fine particles>
The inorganic composite oxide fine particles preferably contain at least one metal element selected from the group consisting of titanium, zirconium, niobium, cerium and zinc and silicon from the viewpoint of a high refractive index.

  The inorganic composite oxide fine particles may further contain at least one selected from the group consisting of tin, tungsten, antimony and indium as a metal element. The fine particles may contain a small amount of alkali metal elements (sodium, potassium, etc.) in the production process, depending on the production method.

  The fine particles include composite oxide fine particles containing the metal element and silicon, oxide fine particles of the metal element or the surface of the composite oxide fine particles coated with a silicon-containing oxide, and the metal element and silicon. Examples thereof include those in which the surface of the composite oxide fine particles is coated with a silicon-containing oxide. Examples of these include fine particles of composite oxide of titanium, tin and silicon, and composite oxide fine particles containing zirconium oxide and silicon coated with a silicon-containing oxide.

  The fine particles are preferably crystalline fine particles. That the fine particles are crystalline means that the crystallite diameter of the fine particles obtained from the X-ray diffraction pattern exceeds 3 nm. The crystal structure includes an anatase type, a rutile type, and a brookite type depending on the type of metal element. Since the fine particles are crystalline, the surface-modified inorganic composite oxide fine particles have a high refractive index.

  The average particle diameter of the fine particles is preferably 5 to 200 nm, more preferably 5 to 50 nm. The value of the average particle diameter is an average value of the average values of the lengths in the major axis and minor axis directions of the fine particles measured based on an image observed with a scanning electron microscope (SEM). The observation conditions are the conditions employed in the examples described later or conditions equivalent thereto. If the average particle size is excessively smaller than the above range, the primary particles tend to aggregate together, so that the dispersion of the fine particles tends to thicken, and the average particle size is excessively larger than the above range, There is a tendency that the transparency of the dispersion liquid of the fine particles is lowered.

Examples of the shape of the inorganic oxide fine particles include a spherical shape, a fiber shape, a needle shape, a tube shape, and a sheet shape.
As the inorganic oxide fine particles as described above, inorganic oxide fine particles obtained by a conventionally known wet preparation method or dry preparation method can be used. Inorganic oxide fine particles described in 2009-15596, and inorganic oxide fine particles described in JP 2010-168266 A, JP 2011-132484 A, and JP 2011-136850 A, and the like. As fine particles containing zirconium, core-shell type inorganic oxide fine particles described in JP 2012-056816 A, inorganic oxide fine particles described in JP 2011-037659 A, and the like can be used.

<Organic silicon compound A>
The organosilicon compound A is a tetrafunctional alkoxysilane compound represented by the following general formula (1).
Si (OR ¹ ) _4-n (OH) _n (1)
(In the formula, R ¹ is an unsubstituted or substituted hydrocarbon group having 1 to 4 carbon atoms, which may be the same or different, and n is an integer of 0 to 3. )

Examples of R ¹ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, and tert-butyl group.
Specific examples of the organosilicon compound A include tetramethoxysilane, tetraethoxysilane, tetra (n-propoxy) silane, tetra (isopropoxy) silane, tetra (n-butoxy) silane, tetra (isobutoxy) silane, tetra (sec -Butoxy) silane, tetra (tert-butoxy) silane, diethoxydimethoxysilane and the like. Among these, tetramethoxysilane and tetraethoxysilane are particularly preferable.

<Organic silicon compound B>
The organosilicon compound B is a monofunctional alkoxysilane represented by the following general formula (2).
R ² ₃ Si (OR ³ ) (2)
(In the formula, R ² is an unsubstituted or substituted hydrocarbon group having 1 to ² carbon atoms, which may be the same as or different from each other, and R ³ is a hydrogen atom or having 1 to 3 carbon atoms. An unsubstituted or substituted hydrocarbon group.)

Examples of R ² include a methyl group and an ethyl group, and among these, a methyl group is preferable.
Examples of R ³ include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.

  When the surface-modified inorganic composite oxide fine particles of the present invention are used for a coating film on an optical substrate, considering the operation temperature when forming the coating film on the substrate, the organosilicon compound B is 1 Those having a boiling point at atmospheric pressure of 120 ° C. or lower are preferred, and those having a boiling point not exceeding 110 ° C. are more preferred.

  Examples of the organosilicon compound B include trimethylmethoxysilane, trimethylethoxysilane, trimethyl (n-propyloxy) silane, trimethyl (isopropyloxy) silane, trimethyl (isopropenyloxy) silane, dimethylethylmethoxysilane, dimethylethylethoxysilane. Etc. Of these, trimethylmethoxysilane and trimethylethoxysilane are particularly preferable.

  The surface-modified inorganic composite oxide fine particles according to the present invention contain carbon components derived from the organosilicon compounds A and B. The amount of the carbon component (carbon atom) is in the range of 2 to 10% by weight, preferably in the range of 2 to 6% by weight when the total weight of the surface-modified inorganic composite oxide fine particles is 100% by weight. . If the amount of carbon atoms is less than 2% by weight, the hydrophobicity of the surface is lowered and the dispersibility in the nonpolar dispersion solvent is lowered. If it is more than 10% by weight, the dispersibility in the polar dispersion solvent is lowered.

  The refractive index of the surface-modified inorganic composite oxide fine particles according to the present invention is preferably 1.6 to 2.6, and more preferably 1.7 to 2.4. When the refractive index is excessively smaller than 1.6, an interference fringe defect is caused when the coating liquid for optical substrate is coated on a substrate having a refractive index of 1.56 or more, and the refractive index is excessively larger than 2.6. If it is too large, the ratio of the surface-modified inorganic composite oxide fine particles to the binder component must be reduced, so that it is difficult to obtain desired mechanical strength (abrasion resistance, abrasion resistance) in the coating film.

<Method for producing surface-modified inorganic composite oxide fine particles>
The production method of the surface-modified inorganic composite oxide fine particles according to the present invention preferably includes a production method including the following steps (1) to (5).
(1) preparing an aqueous dispersion of the inorganic composite oxide fine particles;
(2) The inorganic composite oxide fine particles are surface-modified by adding the organosilicon compound A or a partial hydrolyzate thereof (hereinafter collectively referred to as “organosilicon compound A etc.”) to the aqueous dispersion. Quality process,
(3) A step of replacing the water contained in the aqueous dispersion obtained in the step (2) with an organic solvent,
(4) The organosilicon compound B or a partial hydrolyzate thereof (hereinafter collectively referred to as “organosilicon compound B etc.”) is added to the organic solvent dispersion obtained in the step (3). Further modifying the surface of the inorganic composite oxide fine particles,
(5) A step of removing the organic solvent from the organic solvent dispersion obtained in the step (4).

Step (1):
In step (1), an aqueous dispersion in which the inorganic composite oxide fine particles are dispersed is prepared.
The details of the inorganic composite oxide fine particles are as described above.
To prepare the aqueous dispersion, the inorganic composite oxide fine particles may be dispersed in water to prepare the aqueous dispersion, or the inorganic composite oxide fine particles may be produced in the form of an aqueous dispersion. May be.

Step (2):
In the step (2), the organic silicon compound A or the like is added to the aqueous dispersion to modify the surface of the inorganic composite oxide fine particles.

The details of the organosilicon compound A are as described above.
In the step (2), for example, the organic silicon compound A or a partial hydrolyzate thereof is added to the aqueous dispersion prepared in the step (1) at 30 to 70 ° C. while stirring the aqueous dispersion. After completion of the addition, stirring is continued for about 1 to 20 hours to hydrolyze the organosilicon compound A or a partial hydrolyzate thereof and to react with OH groups present on the surface of the inorganic composite oxide fine particles. be able to. Moreover, you may add water, a hydrolysis catalyst, etc. as needed.

  When performing the next step (3), all of the hydrolyzable groups of the organosilicon compound A and the like are in a state of reacting with OH groups present on the surface of the inorganic composite oxide fine particles. However, it may be in a state in which a part thereof remains unreacted.

The addition amount of the organosilicon compound A and the like takes into account the types and proportions of the organosilicon compounds A and B so that the carbon content of the surface-modified inorganic composite oxide fine particles as the target product is 2 to 10% by weight. Is set. This addition amount varies depending on the surface area of the inorganic composite oxide fine particles, but may be an amount such that the addition amount per surface area of the inorganic composite oxide fine particles is in the range of 0.5 to 6.0 mg / m ^2. The amount is preferably in the range of 1.0 to 5.5 mg / m ² .

When the amount of the organosilicon compound A or the like is in the above range, the trialkylsilyl group of the organosilicon compound B can be efficiently bonded to the surface of the inorganic composite oxide fine particles. That is, Si (OH) ₄ which is a hydrolyzate of the organic silicon compound A or the like is bonded to the surface of the inorganic composite oxide fine particles, and the trialkylsilyl group of the organic silicon compound B can be efficiently bonded to this OH group. it can.

  If the addition amount of the organosilicon compound A or the like is too small, the trialkylsilyl group of the organosilicon compound B may not be efficiently bonded to the surface of the inorganic composite oxide fine particles.

  If the added amount of the organosilicon compound A or the like is too large, the bonding of trialkylsilyl groups such as the organosilicon compound B will not be further increased or become efficient, but rather the OH on the surface of the inorganic composite oxide fine particles. Many groups may remain, and the dispersibility of the surface-modified inorganic composite oxide fine particles in the hydrophobic matrix-forming component may decrease.

Step (3):
Next, the water contained in the aqueous dispersion containing the surface-modified inorganic composite oxide fine particles obtained in the step (2) is replaced with 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. , Aliphatic hydrocarbon compounds having 5 to 12 carbon atoms such as pentane, hexane and heptane, ester compounds such as ethyl acetate and butyl acetate, aromatic compounds such as toluene and xylene, and alicyclic compounds such as cyclopentane and cyclohexane Etc.

  In this replacement operation, a conventionally known solvent replacement device such as an ultrafiltration device or a rotary evaporator can be used as the solvent replacement device. The operating conditions of the solvent displacement device vary depending on the solvent displacement device to be used, the type of the organic solvent, and the like. For example, when performing using an ultrafiltration device (Asahi Kasei Co., Ltd., SIP-1013), The water dispersion obtained in step (2) and the organic solvent to be replaced with water (for example, methanol) are fed into the apparatus equipped with an ultrafiltration membrane, and are subjected to general conditions (for example, pump discharge). It is preferable that the solvent is replaced with a pressure of 10 to 20 MPa, a water content after the solvent replacement of 0.1 to 5% by weight, or the like.

  When the concentration of the surface-modified inorganic composite oxide fine particles contained in the aqueous dispersion is much lower than the desired solid concentration of the organic solvent dispersion, the aqueous dispersion is used as an ultrafiltration device or the like. It is preferable to carry out the above-mentioned replacement operation after concentrating the solution to increase the solid content concentration of the aqueous dispersion.

Step (4):
In the step (4), the organic silicon compound B is added to the organic solvent dispersion of the inorganic composite oxide fine particles (inorganic composite oxide fine particles surface-modified with the organic silicon compound A or the like) obtained in the step (3). Etc. are added to further modify the surface of the inorganic composite oxide fine particles.

  In the step (4), for example, the organosilicon compound B or a partial hydrolyzate thereof is added to the organic solvent dispersion obtained in the step (3) at 30 to 70 ° C. while stirring the organic solvent dispersion. After the addition is completed, stirring is continued for about 1 to 20 hours to hydrolyze the organosilicon compound B or a partial hydrolyzate thereof, and the surface is modified by the inorganic composite oxide fine particles (organosilicon compound A or the like). The reaction can be performed by reacting with OH groups present on the surface of the inorganic composite oxide fine particles. Moreover, you may add water, a hydrolysis catalyst, etc. as needed.

  When performing the next step (5), all of the hydrolyzable groups possessed by the organosilicon compound B and the like are converted into the inorganic composite oxide fine particles (inorganic composite oxide whose surface is modified by the organosilicon compound A and the like). Although it is preferably in a state of reacting with OH groups present on the surface of the fine particles), it may be in a state in which a part thereof remains unreacted.

Further, in the step (4), an operation of surface-modifying the inorganic composite oxide fine particles (inorganic composite oxide fine particles surface-modified with the organosilicon compound A) by adding the organosilicon compound B or the like. It is preferable to repeat the process a plurality of times (for example, 1 to 10 times). By doing so, it is possible to introduce a large amount of R ² on the surface of the surface-modified inorganic composite oxide fine particles obtained by the production method according to the present invention and to facilitate the dispersion of the fine particles in an organic solvent.

The addition amount of the organosilicon compound B and the like is determined in consideration of the types and ratios of the organosilicon compounds A and B so that the carbon content of the surface-modified inorganic composite oxide fine particles as the target product is 2 to 10% by weight. Is set. This addition amount varies depending on the surface area of the inorganic composite oxide fine particles, but may be an amount such that the addition amount per surface area of the inorganic composite oxide fine particles is in the range of 1.5 to 4.5 mg / m ^2. The amount is preferably in the range of 2.0 to 4.2 mg / m ² .

  When the addition amount of the organosilicon compound B or the like is in the above range, the inorganic composite oxide fine particles (inorganic composite oxide fine particles whose surface is modified by the organosilicon compound A or the like) can be efficiently converted to the trialkylsilyl group of the organosilicon compound B. ).

  If the amount of the organosilicon compound B added is too small, the trialkylsilyl group of the organosilicon compound B may not be efficiently bonded to the surface of the inorganic composite oxide fine particles.

  If the amount of the organosilicon compound B added is too large, the bonding of the trialkylsilyl group of the organosilicon compound B will not increase or become efficient, but rather the OH group on the surface of the inorganic composite oxide fine particles. In some cases, the dispersibility of the surface-modified inorganic composite oxide fine particles in the hydrophilic matrix-forming component may decrease.

Step (5):
In the step (5), the dispersion is removed from the organic solvent dispersion of the surface-modified inorganic composite oxide fine particles obtained in the step (4).
In this operation, a conventionally known solvent replacement device such as a rotary evaporator or an ultrafiltration device can be used.

Step (6):
The production method according to the present invention includes the step (6) of further modifying the surface of the fine particles by adding an organosilicon compound B or the like to the surface-modified inorganic composite oxide fine particles obtained in the step (5). You may do it.

  This step (6) may be a wet method in which the surface-modified inorganic composite oxide fine particles are redispersed with an organic solvent to surface-modify the fine particles (that is, the steps (4) and (5) are repeated). Well, the surface-modified inorganic composite oxide fine particles are put in an airtight reaction vessel, a predetermined amount of an organosilicon compound B or the like is added, and after sealing, the fine particles are surface-modified by heating (vapor phase) It may be a law.

  In the step (6), the number of operations for further surface modification of the fine particles by adding the organosilicon compound B or the like is preferably 1 to 10 times. Even if it is repeated over 10 times, the effect is very small, which is not preferable in terms of productivity.

<Optical coating liquid containing surface-modified inorganic composite oxide fine particles>
The optical coating liquid according to the present invention contains surface-modified inorganic composite oxide fine particles, and an organic solvent and / or an organic solvent and water as a dispersion medium.

  Examples of the organic solvent include alcohol compounds such as methanol, ethanol, butanol, propanol and isopropyl alcohol, ether compounds such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether and propylene glycol monoethyl ether, methyl ethyl ketone, and γ-butyrolactone. C 5-12 aliphatic hydrocarbon compounds such as ketone compounds, pentane, hexane, heptane, ester compounds such as ethyl acetate and butyl acetate, aromatic compounds such as toluene and xylene, and alicyclic compounds such as cyclopentane and cyclohexane Compound etc. are mentioned.

  Among these, alcohol compounds such as methanol and ether compounds such as propylene glycol monomethyl ether are preferable. The reason for this is that the drying speed of the coating film is relatively fast and it is easy to form a film.

When the coating liquid according to the present invention is an organic solvent dispersion, a small amount (for example, about 10% by weight of water may be contained with respect to 100% by weight of the total dispersion medium).
The content of the surface-modified inorganic composite oxide fine particles in the coating liquid according to the present invention varies depending on the application of the coating liquid, the type of the dispersion medium, and the like. It is. If the organic solvent dispersion according to the present invention is used as a coating liquid for an optical substrate (a coating liquid for forming a hard coat layer film, a coating liquid for forming a primer layer film, etc.) described later, the surface-modified inorganic composite oxidation The content of the fine particles is preferably 10 to 50% by weight (the total amount of the dispersion is 100% by weight).

<Optical substrate coating liquid, coating film formed using the coating liquid, and substrate with coating film>
<Coating liquid for optical substrate>
The organic solvent dispersion of the surface-modified inorganic composite oxide fine particles according to the present invention can be used, for example, as an optical substrate coating solution, specifically, as the following two types of coating solutions.
a. Hard coat layer film forming coating solution b. Coating liquid for primer layer film formation

a. Hard coat layer coating solution:
This coating liquid for forming a hard coat layer film is composed of an organic solvent dispersion of the surface-modified inorganic composite oxide fine particles according to the present invention, and further, an organosilicon compound (C) as a binder component (matrix component) (that is, Vehicle component).
Examples of the organosilicon compound (C) include an organosilicon compound represented by the following general formula (3) and / or a hydrolyzate thereof.
R ⁴ _a R ⁵ _b Si (OR ⁶ ) _{4- (a + b)} (3)
(In the formula, R ⁴ is an alkyl group having 1 to 6 carbon atoms, an organic group having 8 or less carbon atoms containing a vinyl group, an organic group having 8 or less carbon atoms containing an epoxy group, or 8 carbon atoms containing a methacryloxy group. The following organic group, an organic group having 1 to 5 carbon atoms containing a mercapto group, or an organic group having 1 to 5 carbon atoms containing an amino group, and R ⁵ is an alkyl group, alkylene group, cyclohexane having 3 or less carbon atoms. An alkyl group, a halogenated alkyl group or an allyl group, and R ⁶ is an alkyl group having 3 or less carbon atoms, an alkylene group or a cycloalkyl group, a is an integer of 0 or 1, b is 0, 1 or 2 Is an integer.)

  As the organosilicon compound represented by the general formula (3), an alkoxysilane compound is exemplified as a typical example, and specific examples thereof include tetraethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane, and γ-methacryloxy. Propyltrimethoxysilane, trimethylchlorosilane, α-glycidoxymethyltrimethoxysilane, α-glycidoxyethyltrimethoxysilane, β-glycidoxyethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ- Glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) -ethyltrimethoxysilane, β- (3 4-epoxycyclohexyl) Ethyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β (aminoethyl) -γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) -γ-aminopropylmethyl Examples include diethoxysilane. Among these, tetraethoxysilane, methyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) -ethyltrimethoxysilane, etc. Is preferably used. These organosilicon compounds may be used alone or in combination of two or more.

  In preparing the coating liquid for forming the hard coat layer film, the organosilicon compound (C) is preferably partially hydrolyzed in the absence of a solvent or in a polar organic solvent such as alcohol in the presence of an acid and water. Or after hydrolyzing, it mixes with the organic solvent dispersion liquid (the said organic solvent dispersion liquid which does not contain the said organosilicon compound (C)) of the surface modification inorganic complex oxide fine particle mentioned above. The organosilicon compound (C) may be partially hydrolyzed or hydrolyzed after mixing with the organic solvent dispersion.

In addition to the above components, the coating liquid for forming the hard coat layer film improves the dyeability of the hard coat layer film and the adhesion to the plastic lens substrate, and further prevents the occurrence of cracks. In addition, an uncrosslinked epoxy compound may be contained. Examples of the uncrosslinked epoxy compound include 1,6-hexanediol diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, and the like. Among these, it is preferable to use 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, or the like. These uncrosslinked epoxy compounds may be used alone or in combination of two or more. Further, the hard coat layer film-forming coating solution is a hard coat layer film-forming coating solution. Components other than the above which may be usually contained, for example, a surfactant, a leveling agent or an ultraviolet absorber may be contained.

  The amount of the organosilicon compound (C) in the hard coat layer film-forming coating solution is preferably 200 to 1000 parts by volume with respect to 100 parts by volume of the surface-modified inorganic composite oxide fine particles.

b. Coating liquid for primer layer film formation:
This primer layer film-forming coating solution is composed of an organic solvent dispersion of the surface-modified inorganic composite oxide fine particles according to the present invention, and is further a thermosetting resin or thermoplastic resin (D) as a binder component (matrix component). ) (That is, a resin component).

  Examples of the thermosetting resin or the thermoplastic resin (D) include urethane resins, epoxy resins, and melamine resins as long as they are thermosetting resins. Among these, urethane resins and epoxy resins are used. Is preferred.

  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 examples of the epoxy resin include polyalkylene ether. Examples include modified epoxy resins and epoxy group-containing compounds in which a flexible skeleton (soft segment) is introduced into the molecular chain. Examples of the melamine resins include cured products of etherified methylol melamine, polyester polyol, and polyether polyol. It is done. Among these, a urethane resin that is a cured product of a block type isocyanate and a polyol is preferable. Moreover, these thermosetting resins may be used individually by 1 type, and may use 2 or more types together.

  Moreover, as said thermosetting resin or thermoplastic resin (D), if it is a thermoplastic resin, as this, for example, acrylic resin, urethane resin, and ester resin will be mentioned, among these, urethane resin And ester resins are preferred.

  Examples of the acrylic resin include a water-based emulsion obtained from a (meth) acrylic acid alkyl ester monomer, and a polymer emulsion obtained by copolymerizing the monomer with styrene, acrylonitrile, and the urethane resin. For example, an aqueous emulsion formed by reacting a polyol compound such as polyester polyol, polyether polyol, polycarbonate polyol and polyisocyanate can be mentioned. Examples of the ester resin include polyester for a hard segment and polyether or polyester for a soft segment. A water-dispersed elastomer of a multi-block copolymer using Among these, it is preferable to use a water-dispersed urethane resin obtained from polyester polyol or polyether polyol and polyisocyanate. Moreover, these thermoplastic resins may be used individually by 1 type, and may use 2 or more types together.

  Further, the primer layer film-forming coating solution may contain components other than those usually mentioned above, such as neutralizing agents, surfactants or ultraviolet absorbers, which are usually contained in the primer layer film-forming coating solution. .

  The amount of the thermosetting resin or thermoplastic resin (D) in the primer layer film forming coating solution is preferably 200 to 1000 parts by volume with respect to 100 parts by volume of the surface-modified inorganic composite oxide fine particles. is there.

<Coating film for optical substrate (cured film) and substrate with coating film>
Examples of the optical base material for applying the coating liquid for the optical base material include various plastic base materials. When this is used as an optical lens, for example, a polystyrene resin, an allyl resin (especially an aromatic resin). Allyl resin), polycarbonate resin, polythiourethane resin, polythioepoxy resin, and the like. Moreover, as a plastic base material used other than an optical lens, the plastic base material comprised by PMMA resin, ABS resin, an epoxy resin, polysulfone resin etc. is mentioned, for example.

  Recently, optical substrates (such as plastic lens substrates) having a relatively high refractive index of 1.7 or higher, more specifically 1.71 to 1.81, have been developed. The coating solution for a substrate can be applied to these high refractive optical substrates. On the other hand, the coating liquid for an optical substrate according to the present invention can be applied to an optical substrate having a relatively low refractive index of 1.50 to 1.70, more specifically 1.52 to 1.67. .

  The primer layer film forming coating solution is directly applied onto the optical substrate by a conventionally known method. On the other hand, the coating liquid for forming the hard coat layer film is applied directly on the optical substrate by a conventionally known method, or a coating film (primer layer film) formed from the coating liquid for forming the primer layer film. ) Is applied on top.

  The coating film thus formed on the optical substrate is cured by a conventionally known method to form a desired coating film for an optical substrate (cured film), that is, a hard coat layer film or a primer layer film. Is done.

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.
[Measurement method and evaluation test method]
Measurement methods and evaluation test methods used in Examples and others of the present invention are as follows.

(1) Measuring method of average particle diameter The average particle diameter of inorganic composite oxide fine particles and surface-modified inorganic composite oxide fine particles (hereinafter also referred to as “inorganic composite oxide fine particles” without distinction) is as follows: Measurement was performed as follows. First, a dispersion (or mixed solution) containing inorganic composite oxide fine particles or the like is diluted with distilled water in the case of an aqueous dispersion sol, or about 1,000 times diluted with methanol in the case of a methanol dispersion sol, and a metal grid with a collodion film. The sample was applied to (Oken Shoji Co., Ltd.) and irradiated with a 250 W lamp for 30 minutes to scatter the solvent to prepare a measurement sample. Using this measurement sample, a high-resolution scanning electron microscope (SEM) (manufactured by Hitachi High-Technologies Corporation, S-5500) was used to take a SEM photograph at a magnification of 250,000 times under the condition of an acceleration voltage of 30 kV. Then, the particle diameters of any 100 or more inorganic composite oxide fine particles or the like photographed in this photograph were observed visually, and the average was obtained.

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

(3) Composition analysis method for inorganic composite oxide fine particles <content of titanium, silicon, tin>
3 g of an aqueous dispersion (or mixed solution) containing inorganic composite oxide fine particles having a solid content concentration of 10% by weight was collected in a zirconia ball with a lid having a capacity of 30 ml, dried (200 ° C., 20 minutes), and fired (700 ° C. 5 minutes), ₂ g Na ₂ O ₂ and 1 g NaOH were added and melted 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 an ICP apparatus (Shimadzu Corporation make, ICPS-8100, analysis software ICPS-8000), the content of titanium, tin, and silicon was converted into oxide conversion standards (TiO ₂ , SnO ₂ , Measured with SiO ₂ ).

<Contents of aluminum, zirconium, sodium and potassium>
After 9 g of an aqueous dispersion (or mixed solution) containing inorganic composite oxide fine particles having a solid content concentration of 10% by weight is collected in a 100 ml platinum dish and heated at 200 ° C. for 20 minutes on a sand bath and dried. After removing organic substances by heating at 700 ° C. for 5 minutes with a burner, 10 ml of HF and 5 ml of H ₂ SO ₄ were added and heated until white smoke was emitted. Furthermore, after which was diluted with pure water so that the 100 ml, aluminum and zirconium ICP apparatus (manufactured by Shimadzu Corporation, ICPS-8100, the analysis software ICPS-8000) in terms of oxide based with (Al ₂ 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). Measured with

<Carbon content>
0.1 g of inorganic composite oxide fine particles, etc. are collected in a measuring crucible and used in an oxygen stream combustion (high-frequency heating furnace method) -infrared absorption carbon analyzer (EMIA-520FA, manufactured by Horiba, Ltd.). Carbon was quantitatively measured.

(4) Moisture content measurement method About 0.1 ml of a dispersion (or mixed solution) of inorganic composite oxide fine particles or the like is collected, and a Karl Fischer method moisture measurement device (manufactured by Mitsubishi Chemical Analytech, CA-200). The amount of water was measured using

(5) Measuring method of crystallinity About 30 ml of dispersion liquid (or mixed liquid) such as inorganic composite oxide fine particles was collected in a magnetic crucible (B-2 type), heated at 110 ° C. for 12 hours and dried, It put into the desiccator and cooled to room temperature. Next, after cooling the cooled product in a mortar for 15 minutes, the crystal form was measured using an X-ray diffractometer (RINT1400, manufactured by Rigaku Corporation). In addition, the crystal | crystallization form said by this invention shows the form (for example, rutile type etc.) determined from this measurement result.

(6) Measurement of liquid haze 20.0 g of an organic solvent dispersion sol prepared by redispersing inorganic composite oxide fine particles and the like in methanol to a solid content concentration of 20% by weight is put in a quartz cell having an optical path length of 33 mm, and color difference / turbidity The liquid haze of the organic solvent-dispersed sol was measured using a degree meter (Nippon Denshoku Industries Co., Ltd., COH-300A).

(Measurement of cured coating)
(7) Method for measuring film hardness (Bayer value) Using a wear tester BTM (manufactured by Colts, USA) and a haze value measuring device (manufactured by NIPPON DENSHOKU, NDH2000), using the dispersion liquid of the examples or comparative examples. The Bayer value was calculated based on the change in haze value between the plastic lens substrate (hereinafter also referred to as “the lens under test”) and the reference lens. As a reference lens, a commercially available plastic lens base material CR-39 base material (diethylene glycol bisallyl carbonate, using monomer manufactured by PPG, base material refractive index 1.60) was used.

Specifically, first, the haze value of each lens was measured, the initial haze value of the reference lens was D (std0), and the initial haze value of the lens under test was D (test0). Each lens was placed in the pan of the wear tester, and 500 g of abrasive material (exclusive sand) was filled thereon, and the pan was vibrated left and right 600 times. The haze value of the lens after vibration was measured, the haze value of the reference lens was D (stdf), and the haze value of the lens under test was D (testf). The Bayer test value (R) was calculated from the following formula.
R = [D (stdf) -D (std0)] / [D (testf) -D (test0)]

(8) Evaluation method of appearance of coating film (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. Fluorescent lamp light is reflected on the hard coat layer film or antireflection layer film surface of the plastic lens substrate manufactured using the dispersion liquid of the example or comparative example, and the rainbow pattern (interference fringes) is generated by the interference of light. Was visually confirmed and evaluated according to the following criteria.
S: There is almost no interference fringe. A: The interference fringe is not conspicuous. B: Although the interference fringe is recognized, it is within an allowable range. C: The interference fringe is conspicuous. D: There is a glare interference fringe.

(9) 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 attached in a box whose inner wall is black. Place the plastic lens substrate directly under the fluorescent lamp, with the hard coat layer film side or antireflection layer film side facing the fluorescent lamp, and check their transparency (cloudiness) with a haze meter (made by NIPPON DENSHOKU, NDH2000) And evaluated according to the following criteria.
A: Haze value is less than 0.3% B: Haze value is from 0.3% to less than 1.0% C: Haze value is from 1.0% to less than 5.0% D: Haze value is 5.0 %that's all.

(10) Evaluation Method of Abrasion Resistance of Coating Film The surface of the plastic lens substrate produced in the examples or comparative examples on the hard coat layer film side or antireflection layer film side was treated with Bonstar Steel Wool # 0000 (Nippon Steel Wool Co., Ltd.). ))), A 1 cm width and a 3 cm distance were rubbed under the condition of 50 reciprocations / 100 seconds, and then the area of the scratch itself relative to the steel wool sliding area was visually determined. evaluated.
A: Less than 2% B: 2% or more and less than 30% C: 30% or more and less than 60% D: 60% or more.

(11) Evaluation method of coating film adhesion The surface of the plastic lens substrate having the hard coat layer film on the hard coat layer film side or the antireflection layer film side is cut with a knife at intervals of 1 mm, and a square of 1 mm is provided. 100 eyes were formed, and cellophane adhesive tape was pressed strongly into these squares, and then pulled abruptly in the direction of 90 degrees with respect to the in-plane direction of the plastic lens substrate. The number of squares that were not used was counted and evaluated according to the following criteria.
○: The number of cells not peeled is 95 or more. ×: The number of cells not peeled is less than 95.

(12) Evaluation method of weather resistance of coating film (weather resistance) Exposure test of plastic lens substrate having hard coat layer film with xenon weather meter (X-75 type, manufactured by Suga Test Instruments Co., Ltd.) After the evaluation, the same evaluation as the confirmation of the appearance and the evaluation of the adhesion was performed, and the evaluation was performed according to the following criteria. The exposure time was 250 hours for a substrate having an antireflection film, and 50 hours for a substrate having no antireflection film.
○: The number of cells not peeled is 95 or more. ×: The number of cells not peeled is less than 95.

(13) Method for evaluating light resistance of coating film Irradiation with ultraviolet ray for 50 hours by a mercury lamp for fading test (Toshiba Corp., H400-E), and measuring transmittance of plastic lens substrate before and after the test (JEOL Ltd. ), V-550), and evaluated according to the following criteria. The distance between the lamp and the plastic lens substrate was 70 mm, and the output of the lamp was adjusted so that the surface temperature of the plastic lens substrate was 45 ± 5 ° C. This test was conducted on a plastic lens substrate having an antireflection layer film provided on the surface of the hard coat layer film.
○: Change in transmittance is less than 5% Δ: Change in transmittance is 5% or more and less than 10% ×: Change in transmittance is 10% or more.

(14) Method for Measuring Refractive Index of Particles The refractive index of the inorganic composite oxide fine particles and the like was determined by employing a calculation method based on the coating film refractive index. Specifically, a coating film was prepared according to the procedure described in [0105] to [0110] of JP 2010-168266 A, and the refractive index was measured using a spectroscopic ellipsometer (manufactured by Sopra, SOPRA ESVG). Calculated.

A. Preparation of fine particle dispersion, coating composition, etc. [Example 1]
<Step (1)>
(Operation 1.1) Preparation of inorganic composite oxide fine particles 1b
a. Preparation of core particles 1a 100 kg of titanium tetrachloride aqueous solution containing 2.0% by weight of titanium tetrachloride (produced by Osaka Titanium Technologies Co., Ltd.) in terms of TiO _2, and aqueous ammonia containing 15% by weight of ammonia (Ube Industries ( 39 kg) was mixed to prepare a white slurry liquid having a pH of 8.5. Next, this slurry was filtered and then washed with pure water to obtain 20 kg of a hydrous titanate cake having a solid content of 10% by weight.

Next, to this cake 20 kg, hydrogen peroxide containing 35% by weight of hydrogen peroxide (manufactured by Mitsubishi Gas Chemical Co., Inc.) 22.84 kg and pure water 57.16 kg were added, and then at a temperature of 80 ° C. The mixture was heated with stirring for a period of time to obtain 100 kg of an aqueous solution of titanic acid peroxide containing 2% by weight of titanic acid peroxide in terms of TiO ₂ . This aqueous solution of titanic acid peroxide was transparent yellowish brown and had a pH of 8.1.

  Next, 496.5 g of silica sol (manufactured by JGC Catalysts & Chemicals Co., Ltd., silica sol SN-350) containing 22.5 kg of the aqueous solution of titanic acid peroxide and 15% by weight of silica fine particles having an average particle diameter of 7 nm and 29.45 kg of pure water. Were mixed and hydrothermally treated in an autoclave (pressure-resistant glass industry, 120 L) at a temperature of 165 ° C. for 18 hours.

  Next, after cooling the obtained aqueous solution to room temperature, it is concentrated using an ultrafiltration membrane device (Asahi Kasei Co., Ltd., ACV-3010), and an aqueous dispersion 5 having a solid content of 10% by weight. Obtained 245 kg.

The inorganic oxide fine particles contained in the aqueous dispersion thus obtained were measured by the above method. As a result, composite oxide fine particles containing titanium and silicon having an anatase type crystal structure (hereinafter referred to as “inorganic composite oxidation”). It was referred to as “fine particles 1a”). Furthermore, when the content of the metal component contained in the inorganic composite oxide fine particles 1a was measured, it was 88.0% by weight of TiO ₂ and 12.0% by weight of SiO _{2 on} the oxide conversion standard of each metal component. It was.

b. Formation of shell layer Zirconium oxychloride containing 2 wt% of zirconium oxychloride (Taiyo Mining Co., Ltd.) in terms of ZrO _{2 is} added to 26.3 kg of aqueous solution, and ammonia water containing 15 wt% of ammonia is gradually added with stirring. Thus, a slurry solution having a pH of 8.5 containing zirconium hydrate was obtained. The slurry was then filtered and washed with pure water to obtain 5.26 kg of a cake containing 10% by weight of the zirconium component on a ZrO ₂ conversion basis.

Next, 1.80 kg of pure water was added to 200 g of this cake, and 120 g of an aqueous potassium hydroxide solution containing 10% by weight of potassium hydroxide (manufactured by Kanto Chemical Co., Ltd.) was added to make it alkaline. 400 g of hydrogen peroxide containing wt% was added and heated to a temperature of 50 ° C. to dissolve this cake. Further, 1.48 kg of pure water was added to obtain 4.0 kg of an aqueous solution of zirconate peroxide containing 0.5 wt% of zirconate peroxide in terms of ZrO ₂ on a conversion basis. The pH of this aqueous zirconate peroxide solution was 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 silicic acid is converted into SiO ₂ standard. An aqueous silicic acid solution containing 2% by weight was obtained. The silicic acid aqueous solution had a pH of 2.3.

  Next, by adding 12.0 kg of pure water to 3.0 kg of the aqueous dispersion containing the inorganic composite oxide fine particles 1a obtained by the above operation (a. Preparation of core particles 1a), the solid content is increased. Yielded a 2% by weight aqueous dispersion. Next, the aqueous dispersion was heated to a temperature of 90 ° C., and then 14.2 kg of the aqueous zirconate peroxide solution and 10.7 kg of the silicic acid aqueous solution were gradually added thereto. Stirring was continued for 1 hour while maintaining the temperature of.

Next, this mixed solution was put into an autoclave (manufactured by Pressure Glass Industrial Co., Ltd., 50 L), and hydrothermally treated at a temperature of 165 ° C. for 18 hours.
Next, after cooling the obtained liquid mixture to room temperature, it concentrates with an ultrafiltration membrane apparatus (Asahi Kasei Co., Ltd. make, SIP-1013), and the aqueous dispersion whose solid content is 10 weight%. 85 kg was obtained.

  The inorganic composite oxide fine particles contained in the aqueous dispersion thus obtained were measured by the above method. As a result, the composite oxide fine particles (core particles) containing titanium and silicon having an anatase type crystal structure were obtained. The surface was inorganic composite oxide fine particles (hereinafter referred to as “inorganic composite oxide fine particles 1b”) formed by coating the surface with a composite oxide (coating) containing zirconium and silicon. The appearance of the aqueous dispersion containing the inorganic composite oxide fine particles 1b was transparent and light milky white.

When the amount of the metal component contained in the inorganic composite oxide fine particle 1b was measured, TiO ₂ was 50.1 wt%, SiO ₂ was 30.2 wt%, and ZrO ₂ was an oxide conversion standard of each metal component. 14.4 wt% and K ₂ O was 5.3 wt%.
Furthermore, the average particle diameter of the inorganic composite oxide fine particles 1b was 8 nm, the specific surface area of the dry powder was 230 m ² / g, and the carbon content was 0% by weight.

<Step (2)>
(Operation 1.2) Preparation of Mixed Dispersion of Surface-Modified Inorganic Composite Oxide Fine Particles 1A Cations were added to 5.85 kg (solid content: 10% by weight) of the aqueous dispersion of inorganic composite oxide fine particles 1b obtained in Operation 1.1. The dispersion obtained by mixing the exchange resin and performing deionization treatment to separate the ion exchange resin was added to the organosilicon compound A, tetraethoxysilane (manufactured by Tama Chemical Industry Co., Ltd., boiling point 168). C.) After adding 448 g of methanol solution in which 448 g was dissolved, the mixture was heated and stirred at a temperature of 50 ° C. for 1 hour to prepare a water / methanol mixed dispersion of the surface-modified inorganic composite oxide fine particles 1A. The weight ratio (M _A / M ₁ ) was 0.77, where the weight of the organosilicon compound A or its partial hydrolyzate was M _A and the weight of the inorganic composite oxide fine particles 1b was M ₁ .

<Step (3)>
(Operation 1.3) Preparation of Methanol Dispersion of Surface-Modified Inorganic Composite Oxide Fine Particles 1A Next, after cooling the mixed dispersion of surface-modified inorganic composite oxide fine particles 1A obtained in the above operation 1.2 to room temperature, The dispersion medium was replaced from water to methanol (manufactured by China Essential Oil Co., Ltd.) using an ultrafiltration membrane.

  Further, the obtained methanol dispersion was concentrated with an ultrafiltration membrane (SIP-1013, manufactured by Asahi Kasei Co., Ltd.) to disperse methanol in the surface-modified inorganic composite oxide fine particles 1A having a solid content of 30% by weight. 1.95 kg of liquid was prepared.

The appearance of the methanol dispersion of the surface-modified inorganic composite oxide fine particles 1A was a transparent light blue white.
When the amount of the metal component contained in the surface-modified inorganic composite oxide fine particles 1A was measured, TiO ₂ was 47.6% by weight, SiO ₂ was 36.3% by weight on the oxide conversion standard of each metal component, ZrO ₂ was 13.4% by weight and K ₂ O was 2.6% by weight.
Further, the water content of the dispersion of the surface modified inorganic composite oxide fine particles 1A was 0.2% by weight, the specific surface area of the dried powder was 236 m ² / g, and the carbon content was 0.8% by weight. It was.

<Process (4)>
(Operation 1.4) Preparation of Methanol Dispersion of Surface-Modified Inorganic Composite Oxide Fine Particles 1 1.95 kg of methanol dispersion of surface-modified inorganic composite oxide fine particles 1A obtained in operation 1.3 is the organosilicon compound B. Then, 175.5 g of methoxytrimethylsilane (manufactured by Shin-Etsu Chemical Co., Ltd., boiling point: 58 ° C.) as a surface treatment agent was added with stirring, followed by heating and stirring at a temperature of 50 ° C. for 18 hours. And the weight M _B of the methoxytrimethylsilane, the weight ratio when the weight of the inorganic composite oxide particles 1b was _{M 1 (M B / M 1} ) was 0.30.

  Furthermore, after adding 175.5 g of methoxytrimethylsilane (manufactured by Shin-Etsu Chemical Co., Ltd.) as a surface treatment agent to the dispersion thus obtained with stirring, the mixture was heated at a temperature of 50 ° C. for 18 hours. The mixture was stirred to obtain a methanol dispersion containing the surface-modified inorganic composite oxide fine particles 1.

And the weight M _B of the methoxytrimethylsilane, the weight ratio when the weight of the inorganic composite oxide particles 1b was _{M 1 (M B / M 1} ) was 0.30.
The appearance of the methanol dispersion of the surface-modified inorganic composite oxide fine particles 4 was a transparent light blue white. Furthermore, the water content of the dispersion was 0.2% by weight.

<Step (5)>
(Operation 1.5) Removal of the solvent from the methanol dispersion of the surface-modified inorganic composite oxide fine particles 1 The dispersion containing the surface-modified inorganic composite oxide fine particles 1 obtained above was adjusted to a pressure of 200 hPa with a rotary evaporator. While gradually lowering until it was, dried at a bath temperature of 50 ° C. for 1 hour to prepare 616 g of surface-modified inorganic composite oxide fine particles 1.

When the amount of the metal component contained in the surface-modified inorganic composite oxide fine particles 1 was measured, TiO ₂ was 46.4% by weight, SiO ₂ was 38.2% by weight based on the oxide conversion standard of each metal component, ZrO ₂ was 12.9% by weight and K ₂ O was 2.5% by weight.

Furthermore, the carbon content in the surface-modified inorganic composite oxide fine particles 1 was 3.1% by weight, and the specific surface area was 238 m ² / g.
And the weight M _A of the organic silicon compound A or a partial hydrolyzate thereof, when the weight M _B of the organosilicon compound B or a partial hydrolyzate thereof, the weight of the inorganic composite oxide particles was M _1, the weight ratio (( M _A + M _B ) / M ₁ ) was 1.37. Furthermore, in the surface-modified inorganic composite oxide fine particles 1, the addition amount of the organosilicon compound A or its partial hydrolyzate per surface area of the inorganic composite oxide fine particles 1b is 3.33 mg / m ^2. The amount of organic silicon compound B or its partial hydrolyzate added per unit was 2.61 mg / m ² .

(Operation 1.6) Preparation of Surface Modified Inorganic Composite Oxide Fine Particle Dispersion Liquid (MP-1) 200.0 g of the surface modified inorganic composite oxide fine particles 1 obtained in the above operation 1.5 was mixed with methanol (Chinese essential oil). (Made by Co., Ltd.) was added and stirred to prepare a methanol dispersion (MP-1) in which the surface-modified inorganic composite oxide fine particles 1 were redispersed at a solid content concentration of 20% by weight.

  The average particle diameter of the surface modified inorganic composite oxide fine particles 1 was 8 nm, and did not change from the average particle diameter of the inorganic composite oxide fine particles 1b before the surface modification. Furthermore, the dispersion liquid (MP-1) was transparent light milky white, and the liquid haze was 54%.

(Operation 1.7) Preparation of Hard Coat Layer Film Forming Coating Composition (H1 ) 205.0 g of γ-glycidoxypropyltrimethoxysilane (Z-6040 manufactured by Toray Dow Corning Co., Ltd.) and methanol (Hayashi Junyaku ( 69.9 g of 0.01N hydrochloric acid aqueous solution was added dropwise with stirring to a mixture of 36.3 g (Methyl alcohol concentration: 99.9% by weight). Furthermore, the obtained mixed liquid was stirred at room temperature for a whole day and night to hydrolyze the silane compound to obtain a hydrolyzed liquid.

  Next, 163.8 g of methanol (Mayashi Junyaku Co., Ltd., methyl alcohol concentration: 99.9 wt%) and a solid content concentration of 20 wt% prepared in the above operation 1.6 were placed in a container containing the hydrolyzate. 475.1 g of methanol dispersion (MP-1) of surface-modified inorganic composite oxide fine particles 1, 40.6 g of propylene glycol monomethyl ether (manufactured by Dow Chemical), tris (2,4-pentanedionato) aluminum III (Tokyo) 8.2 g of Kasei Kogyo Co., Ltd. and 1.1 g of a silicone surfactant (manufactured by Toray Dow Corning Co., Ltd., L-7604) as a leveling agent were added and stirred at room temperature all day and night to form a hard coat layer film A forming coating composition (H1) was prepared.

(Operation 1.8) Preparation of Hard Coat Layer Film Forming Coating Composition (H2 ) 168.3 g of γ-glycidoxypropyltrimethoxysilane (Z-6040 manufactured by Toray Dow Corning Co., Ltd.) and methanol (Hayashi Junyaku ( 57.4 g of a 0.01N hydrochloric acid aqueous solution was added dropwise with stirring to a mixture of 29.8 g of Methyl Alcohol (99.9% by weight). Furthermore, this mixed liquid was stirred at room temperature for a whole day and night to hydrolyze the silane compound, thereby obtaining a hydrolyzed liquid.

  Next, 37.7 g of methanol (Mayashi Junyaku Co., Ltd., methyl alcohol concentration: 99.9 wt%) and a solid content concentration of 20 wt% prepared in the above operation 1.6 were placed in a container containing the hydrolyzate. 658.4 g of methanol dispersion (MP-1) of surface-modified inorganic composite oxide fine particles 1, 40.6 g of propylene glycol monomethyl ether (manufactured by Dow Chemical), Tris (2,4-pentanedionato) aluminum III (Tokyo) 6.7 g of Kasei Kogyo Co., Ltd.) and 1.1 g of a silicone surfactant (manufactured by Toray Dow Corning Co., Ltd., L-7604) as a leveling agent were added and stirred at room temperature all day and night to form a hard coat layer film A forming coating composition (H2) was prepared.

(Operation 1.9) Preparation of primer layer film-forming coating composition (Y1) Polyurethane emulsion “Superflex 150”, a commercially available thermoplastic resin (Daiichi Kogyo Seiyaku Co., Ltd., water-dispersed urethane elastomer solid content: 30%) A container containing 243.6 g was prepared. To this, 450.2 g of methanol (Mayashi Junyaku Co., Ltd., methyl alcohol concentration: 99.9% by weight) and the surface-modified inorganic composite oxidation prepared in the above operation 1.6 were prepared. 190.0 g of methanol dispersion liquid MP1 and 97.1 g of ion-exchanged water were added and stirred for 1 hour.

  Next, 0.3 g of a silicone surfactant (manufactured by Toray Dow Corning Co., Ltd., L-7604) as a leveling agent is added to the obtained mixed solution, and the mixture is stirred at room temperature all day and night to form a primer layer film. A coating composition (Y1) was prepared.

(Operation 1.10) Preparation of primer layer film-forming coating composition (Y2) Polyurethane emulsion “Superflex 150” which is a commercially available thermoplastic resin (Daiichi Kogyo Seiyaku Co., Ltd., water-dispersed urethane elastomer solid content: 30%) A container containing 207.6 g was prepared, and 450.2 g of methanol (produced by Hayashi Junyaku Co., Ltd., methyl alcohol concentration: 99.9% by weight) and the surface-modified inorganic composite oxidation prepared in the above operation 1.6 were prepared. 242.9 g of methanol dispersion liquid MP1 and 96.9 g of ion-exchanged water were added and stirred for 1 hour.

  Next, 0.3 g of a silicone surfactant (manufactured by Toray Dow Corning Co., Ltd., L-7604) as a leveling agent is added to the obtained mixed solution, and the mixture is stirred at room temperature all day and night to form a primer layer film. A coating composition (Y2) was prepared.

[Example 2]
<Step 1>
(Operation 2.1) Preparation of inorganic composite oxide fine particles 2
a. Preparation of Core Particle 2a Titanium tetrachloride aqueous solution containing 7.75% by weight of titanium tetrachloride (manufactured by Osaka Titanium Technologies Co., Ltd.) on a TiO ₂ basis, and ammonia water containing 15% by weight of ammonia (Ube) 36.3 kg of Kosan Co., 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, a cation exchange resin (manufactured by Mitsubishi Chemical Corporation) incorporating potassium ions and the like is separated, and then a silica sol (manufactured by JGC Catalysts & Chemicals, SN) containing 15% by weight of silica fine particles having an average particle diameter of 7 nm. -350) 0.8 kg of pure water 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, so that titanium is a main component. An aqueous dispersion of composite oxide fine particles (core particles) was obtained.

After cooling the obtained aqueous dispersion to room temperature, it was concentrated with an ultrafiltration membrane device (ACV-3010, manufactured by Asahi Kasei Co., Ltd.) to obtain 9.7 kg of an aqueous dispersion having a solid content of 10% by weight. Obtained.
The core particles contained in the aqueous dispersion have a rutile-type crystal structure, and the content of the metal element contained in the core particles was measured. As a result, 75.2% by weight of TiO _{2 and} 9.3% of SnO ₂ were obtained. 3% by weight, SiO ₂ was 12.2% by weight and K ₂ O was 3.3% by weight.

b. Formation of shell layer Zirconium oxychloride containing 2 wt% of zirconium oxychloride (Taiyo Mining Co., Ltd.) in terms of ZrO _{2 is} added to 26.3 kg of aqueous solution, and ammonia water containing 15 wt% of ammonia is gradually added with stirring. Thus, a slurry liquid having a pH of 8.5 was obtained. 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 silicic acid is converted into SiO ₂ standard. An aqueous silicic acid solution containing 2% by weight was obtained. The pH of the aqueous silicic acid solution was 2.3.

  Next, 18.70 kg of pure water is added to 4.68 kg of the aqueous dispersion containing core particles containing titanium as a main component obtained in the above operation (a. Preparation of core particles 2a), so that the solid content is 2 After heating to a temperature of 90 ° C., 5.85 kg of the zirconic acid aqueous solution and 4.38 kg of the silicic acid aqueous solution were gradually added thereto, and after the addition was completed, the temperature was raised to 90 ° C. The mixture was aged with stirring for 1 hour.

  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. Thus, 5.85 kg of an aqueous dispersion of core-shell type fine particles 2b (inorganic composite oxide fine particles 2b) was prepared.

The crystal structure of the core-shell type fine particles was a rutile type.
When the amount of the metal component contained in the core-shell type fine particles 2b was measured, TiO ₂ was 61.5% by weight, SnO ₂ was 7.6% by weight, and SiO ₂ was 22.2% based on the oxide conversion standard of each metal component. % By weight, 4.8% by weight of ZrO ₂ and 3.9% by weight of K ₂ O.
The average particle diameter of the core-shell type fine particles 2b was 12 nm, the specific surface area of the dry powder was 218 m ² / g, and the carbon content was 0% by weight.

<Step (2)>
(Operation 2.2) Preparation of mixed dispersion of surface-modified inorganic composite oxide fine particles 2A Inorganic prepared in Operation 2.1 above instead of 5.85 kg of aqueous dispersion of inorganic oxide fine particles 1b prepared in Operation 1.1 of Example 1 A water / methanol mixed dispersion of surface-modified inorganic composite oxide fine particles 2A was prepared in the same manner as in Operation 1.2 of Example 1 except that 5.85 kg of the aqueous dispersion of composite oxide fine particles 2b was used.

<Step (3)>
(Operation 2.3) Preparation of Methanol Dispersion of Surface-Modified Inorganic Composite Oxide Fine Particles 2A Prepared in Operation 2.2 instead of the mixed dispersion of surface-modified inorganic composite oxide fine particles 1A prepared in Operation 1.2 of Example 1. A methanol dispersion of the surface-modified inorganic composite oxide fine particles 2A was prepared in the same manner as in Operation 1.3 of Example 1 except that the mixed dispersion of the surface-modified inorganic composite oxide fine particles 2A was used.

The appearance of the methanol dispersion of the surface-modified inorganic composite oxide fine particles 2A was transparent light blue white.
When the amount of the metal component contained in the surface-modified inorganic composite oxide fine particles 2A was measured, TiO ₂ was 57.3% by weight, SnO ₂ was 7.0% by weight based on the oxide conversion standard of each metal component, SiO ₂ was 29.4 wt%, ZrO ₂ was 4.2 wt%, and K ₂ O was 2.2 wt%.
Furthermore, the water content of the dispersion of the surface-modified inorganic composite oxide fine particles 2A was 0.2% by weight, the specific surface area of the dry powder was 222 m ² / g, and the carbon content was 0.7% by weight. It was.

<Process (4)>
(Operation 2.4) Preparation of Methanol Dispersion Containing Surface-Modified Inorganic Composite Oxide Fine Particles 2 Prepared in Procedure 2.3 instead of the methanol dispersion of surface-modified inorganic composite oxide fine particles 1A prepared in Operation 1.3 of Example 1. A methanol dispersion of the surface-modified inorganic composite oxide fine particles 2 was prepared in the same manner as in Operation 1.4 of Example 1 except that the methanol dispersion of the surface-modified inorganic composite oxide fine particles 2A was used.
The appearance of the methanol dispersion of the surface-modified inorganic composite oxide fine particles 2 was a transparent light blue white. Furthermore, the water content of the dispersion was 0.2% by weight.

<Step (5)>
(Operation 2.5) Removal of the solvent from the methanol dispersion of the surface-modified inorganic composite oxide fine particles 2 In place of the methanol dispersion of the surface-modified inorganic composite oxide fine particles 1 prepared in the operation 1.4 of Example 1, the operation 2.4 described above was performed. Surface-modified inorganic composite oxide fine particles 2 were prepared in the same manner as in Operation 1.5 of Example 1 except that the methanol dispersion of the surface-modified inorganic composite oxide fine particles 2 prepared in Step 1 was used.

When the amount of metal component contained in the surface-modified inorganic composite oxide fine particles 2 was measured, TiO ₂ was 55.5% by weight, SnO ₂ was 7.0% by weight based on the oxide conversion standard of each metal component, SiO ₂ was 31.4 wt%, ZrO ₂ was 4.0 wt%, and K ₂ O was 2.1 wt%.

Further, the carbon content of the surface-modified inorganic composite oxide fine particles 2 was 3.2% by weight, and the specific surface area was 225 m ² / g.
And the weight M _A of the organic silicon compound A or a partial hydrolyzate thereof, and the weight M _B of the organosilicon compound B or a partial hydrolyzate thereof, the weight of the inorganic composite oxide particles 2b is taken as M _1, the weight ratio ( (M _A + M _B ) / M ₁ ) was 1.37. Further, in the surface-modified inorganic composite oxide fine particles 2, the addition amount of the organosilicon compound A or its partial hydrolyzate per surface area of the inorganic composite oxide fine particles 2b is 3.51 mg / m ² , and the surface area of the fine particles 2b The amount of the organic silicon compound B or its partial hydrolyzate added was 2.75 mg / m ² .

(Operation 2.6) Preparation of Surface Modified Inorganic Composite Oxide Fine Particle Dispersion (MP-2) Surface Prepared in Procedure 2.5 Instead of Surface Modified Inorganic Composite Oxide Fine Particle 1 Prepared in Operation 1.5 of Example 1 A methanol dispersion (MP-2) of surface-modified inorganic composite oxide fine particles 2 was prepared in the same manner as in Operation 1.6 of Example 1 except that the modified inorganic composite oxide fine particles 2 were used.

  Here, the average particle diameter of the surface-modified inorganic composite oxide fine particles 2 obtained above was 12 nm, and did not change from the average particle diameter of the inorganic composite oxide fine particles 2b before the surface modification. Furthermore, the dispersion liquid (MP-2) was transparent and light milky white, and its liquid haze was 58%.

(Operation 2.7) Preparation of Hard Coat Layer Film Forming Coating Composition (H3 ) 223.3 g of γ-glycidoxypropyltrimethoxysilane (Z-6040 manufactured by Toray Dow Corning Co., Ltd.) and methanol (Hayashi Junyaku ( 76.1 g of 0.01N hydrochloric acid aqueous solution was added dropwise to 39.6 g of a mixed solution (manufactured by Co., Ltd., methyl alcohol concentration: 99.9% by weight). Furthermore, this mixed liquid was stirred at room temperature for a whole day and night to hydrolyze the silane compound, thereby obtaining a hydrolyzed liquid.

  Next, 227.0 g of methanol (Mayashi Junyaku Co., Ltd., methyl alcohol concentration: 99.9 wt%) and a solid content concentration of 20 wt% prepared in the above operation 2.6 were placed in a container containing the hydrolyzate. 383.4 g of methanol dispersion (MP-2) of surface-modified inorganic composite oxide fine particles 2, 40.6 g of propylene glycol monomethyl ether (manufactured by Dow Chemical), Tris (2,4-pentanedionato) aluminum III (Tokyo) 8.9 g of Kasei Kogyo Co., Ltd.) and 1.1 g of a silicone surfactant (manufactured by Toray Dow Corning Co., Ltd., L-7604) as a leveling agent were added and stirred at room temperature all day and night to form a hard coat layer film A forming coating composition (H3) was prepared.

[Example 3]
<Step 1>
(Operation 3.1) Preparation of inorganic composite oxide fine particles 3
a. Preparation of core particles 3a Zirconium oxychloride octahydrate (ZrOCl ₂ · 8H ₂ O, 0.50 kg, manufactured by Taiyo Mining Co., Ltd.) was dissolved in 18.58 kg of pure water, and 10% by weight KOH aqueous solution 17 was dissolved therein. .55 kg was added to prepare zirconium hydroxide hydrogel (ZrO ₂ 1 wt%). Next, the obtained zirconium hydroxide hydrogel was washed with water by an ultrafiltration membrane method until the conductivity reached 0.5 mS / cm or less.

After adding 7.18 kg of 10 wt% KOH aqueous solution to 36.6 kg of 1 wt% zirconium hydroxide hydrogel as ZrO ₂ obtained by the above operation, 200 g of 35 wt% aqueous hydrogen peroxide solution was added. added. At this time, the solution foamed vigorously and the solution became transparent, and the pH was 11.4.

  Next, 2.00 kg of 28.8 wt% aqueous ammonia solution was added to this solution and stirred sufficiently to obtain a precursor slurry of zirconia composite oxide fine particles. At this time, the slurry was light yellow and the pH was 13.4.

164.5 g of silica sol (manufactured by JGC Catalysts & Chemicals Co., Ltd., silica sol SI-550) containing 20% by weight of silica fine particles having an average particle diameter of 5 nm is added to this precursor slurry by autoclave (manufactured by Pressure Glass Industrial Co., Ltd., 100 L). And after performing hydrothermal treatment at 150 ° C. for 11 hours, the zirconia composite oxide fine particles are separated by centrifugal sedimentation, washed thoroughly, and then dispersed in ion-exchanged water to obtain a zirconia composite oxide. 4.02 kg of an aqueous dispersion of fine particles was obtained. The solid content of the aqueous dispersion was 10% by weight on a ZrO ₂ conversion basis.

  Next, 4.02 kg of an aqueous dispersion of the zirconia composite oxide fine particles was applied to a spray dryer (NIRO ATOMIZER manufactured by NIRO) and spray-dried. As a result, 0.36 kg of a dry powder of zirconia composite oxide fine particles was obtained. The average particle diameter of the zirconia composite oxide fine particles contained in the obtained dry powder was about 2 μm.

Next, 0.36 kg of the dry powder obtained above was calcined in an air atmosphere at a temperature of 500 ° C. for 2 hours to obtain 0.34 kg of calcined powder of zirconia composite oxide fine particles.
0.21 kg of the calcined powder obtained above was dispersed in 0.19 kg of pure water, and 0.14 kg of a 28.6% tartaric acid aqueous solution and 0.06 kg of a 50 wt% KOH aqueous solution were added thereto and stirred sufficiently. . Next, alumina beads having a particle diameter of 0.1 mm (manufactured by Daimei Chemical Co., Ltd., high-purity alumina beads) are added, and this is subjected to a wet pulverizer (Kampe Co., Ltd., batch type tabletop sand mill) for 180 minutes, The fired powder was pulverized and dispersed. Thereafter, the alumina beads were separated and removed using a stainless steel filter having an opening of 44 μm, and 1.70 kg of pure water was further added and stirred to obtain 2.26 kg of an aqueous dispersion of zirconia composite oxide fine particles. . The solid content of this aqueous dispersion was 11% by weight.

Next, after washing with ion-exchanged water using an ultrafiltration membrane, 0.11 kg of anion exchange resin (Mitsubishi Chemical Corporation: SANUPC) was added for deionization treatment, and then a centrifuge (Hitachi CR-21G manufactured by Kogyo Co., Ltd.) and treated for 1 hour at a speed of 12,000 rpm, and an aqueous dispersion 2 of zirconia-based inorganic composite oxide fine particles 3a having a solid content concentration of 10% by weight based on ZrO ₂ conversion standard. .43 kg was obtained. The zirconia-based inorganic composite oxide core particles 3a had an average particle size of 20 nm and a specific surface area of 153 m ² / g.

Further, the content of the metal component contained in the core particle is 96.5% by weight of ZrO ₂ , 1.8% by weight of SiO ₂ and 1.7% of K ₂ O in terms of oxides of each metal component. % By weight.

b. Formation of shell layer Zirconium oxychloride containing 2 wt% of zirconium oxychloride (Taiyo Mining Co., Ltd.) in terms of ZrO _{2 is} added to 26.3 kg of aqueous solution, and ammonia water containing 15 wt% of ammonia is gradually added with stirring. Thus, a slurry liquid having a pH of 8.5 was obtained. 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 on a conversion basis.

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 silicic acid is converted into SiO ₂ standard. An aqueous silicic acid solution containing 2% by weight was obtained. The pH of the aqueous silicic acid solution was 2.3.

  Next, 90% of the water dispersion obtained by the above step was added to 5.5 kg of the aqueous dispersion containing the zirconia-based inorganic composite oxide core fine particles 3a to obtain 2% by weight of solid content by adding 21.9 kg of pure water. 1.9 kg of the above-mentioned zirconic acid aqueous solution and 1.8 kg of silicic acid aqueous solution were gradually added thereto, and after completion of the addition, the mixture was aged for 1 hour with stirring 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 the zirconia-based inorganic composite oxide core fine particles is covered with a shell made of a composite oxide containing zirconium and silicon by concentrating to a solid content of 10% by weight using SIP-1013 manufactured by Co., Ltd. Thus, 5.85 kg of an aqueous dispersion of core-shell type fine particles 3b (inorganic composite oxide fine particles 3b) was prepared.

The crystal structure of the core-shell type fine particles was a crystal type composed of a monoclinic system and a cubic system.
Further, when the amount of the metal component contained in the core-shell type fine particles was measured, ZrO ₂ was 89.5% by weight, SiO ₂ was 8.8% by weight, and K ₂ O was 1 in terms of oxide conversion standard of each metal component. 0.7% by weight.
The average particle diameter of the core-shell fine particles was 20 nm, the specific surface area of the dry powder was 167 m ² / g, and the carbon content was 0% by weight.

<Step (2)>
(Operation 3.2) Preparation of Mixed Dispersion of Surface-Modified Inorganic Composite Oxide Fine Particles 3A Prepared in the above-mentioned Operation 3.1 instead of 5.85 kg of the aqueous dispersion of inorganic composite oxide fine particles 1b prepared in Operation 1.1 of Example 1. A water / methanol mixed dispersion of surface-modified inorganic composite oxide fine particles 3A was prepared in the same manner as in Operation 1.2 of Example 1 except that 5.85 kg of the aqueous dispersion of inorganic composite oxide fine particles 3b was used.

<Step (3)>
(Operation 3.3) Preparation of Methanol Dispersion of Surface-Modified Inorganic Composite Oxide Fine Particles 3A In place of the mixed dispersion of surface-modified inorganic composite oxide fine particles 1A prepared in Operation 1.2 of Example 1, it was prepared in Operation 3.2. A methanol dispersion of the surface-modified inorganic composite oxide fine particles 3A was prepared in the same manner as in Operation 1.3 of Example 1 except that the mixed dispersion of the surface-modified inorganic composite oxide fine particles 3A was used.

The appearance of the methanol dispersion containing the surface-modified inorganic composite oxide fine particles 3A was transparent light blue white.
When the amount of the metal component contained in the surface-modified inorganic composite oxide fine particles 3A was measured, ZrO ₂ was 88.6% by weight, SiO ₂ was 10.5% by weight on the oxide conversion standard of each metal component, and K ₂ O was 0.9% by weight.
Furthermore, the water content of the dispersion was 0.2% by weight, the specific surface area of the dry powder was 171 m ² / g, and the carbon content was 0.6% by weight.

<Process (4)>
(Operation 3.4) Preparation of Methanol Dispersion of Surface-Modified Inorganic Composite Oxide Fine Particles 3 In place of the methanol dispersion of surface-modified inorganic composite oxide fine particles 1A prepared in Operation 1.3 of Example 1, it was prepared in Operation 3.3. A methanol dispersion of the surface-modified inorganic composite oxide fine particles 3 was prepared in the same manner as in Operation 1.4 of Example 1 except that the methanol dispersion of the surface-modified inorganic composite oxide fine particles 3A was used.
The appearance of the methanol dispersion of the surface-modified inorganic composite oxide fine particles 3 was a transparent light blue white. Furthermore, the water content of the dispersion was 0.2% by weight.

<Step (5)>
(Operation 3.5) Removal of the solvent from the methanol dispersion of the surface-modified inorganic composite oxide fine particles 3 In place of the methanol dispersion of the surface-modified inorganic composite oxide fine particles 1 prepared in the operation 1.4 of Example 1, the operation 3.4 described above was performed. Surface-modified inorganic composite oxide fine particles 3 were prepared in the same manner as in Operation 1.5 of Example 1 except that the methanol dispersion of the surface-modified inorganic composite oxide fine particles 3 prepared in Step 1 was used.

When the amount of metal component contained in the surface-modified inorganic composite oxide fine particles 3 was measured, ZrO ₂ was 86.8% by weight, SiO ₂ was 12.4% by weight based on the oxide conversion standard of each metal component, and K ₂ O was 0.8% by weight.

Furthermore, the carbon content of the surface-modified inorganic composite oxide fine particles 3 was 3.0% by weight, and the specific surface area was 225 m ² / g.
And the weight M _A of the organic silicon compound A or a partial hydrolyzate thereof, and the weight M _B of the organosilicon compound B or a partial hydrolyzate thereof, the weight of the inorganic composite oxide fine particles 3b is taken as M _1, the weight ratio ( (M _A + M _B ) / M ₁ ) was 1.37. Furthermore, in the surface-modified inorganic composite oxide fine particles 3, the addition amount of the organosilicon compound A or its partial hydrolyzate per surface area of the inorganic composite oxide fine particles 3b is 4.59 mg / m ² , and the surface area of the fine particles 3b The amount of the organic silicon compound B or its partial hydrolyzate added was 3.59 mg / m ² .

(Operation 3.6) Preparation of Dispersion Liquid (MP-3) of Surface Modified Inorganic Composite Oxide Fine Particle 3 In place of the surface modified inorganic composite oxide fine particle 1 prepared in operation 1.5 of Example 1, it was prepared in the above operation 3.5. A methanol dispersion (MP-3) of the surface-modified inorganic composite oxide fine particles 3 was prepared by the same method as in Operation 1.6 of Example 1 except that the surface-modified inorganic composite oxide fine particles 3 were used.

  The average particle diameter of the surface-modified inorganic composite oxide fine particles 3 was 20 nm, and the average particle diameter of the inorganic composite oxide fine particles 3b before the surface modification was not changed. Furthermore, the dispersion liquid (MP-3) was transparent light milky white, and the liquid haze was 60%.

(Operation 3.7) Preparation of coating composition (H4) for forming a hard coat layer film 223.3 g of γ-glycidoxypropyltrimethoxysilane (Z-6040 manufactured by Toray Dow Corning Co., Ltd.) and methanol (Hayashi Junyaku ( 76.1 g of 0.01N hydrochloric acid aqueous solution was added dropwise to 39.6 g of a mixed solution (manufactured by Co., Ltd., methyl alcohol concentration: 99.9% by weight). Furthermore, this mixed liquid was stirred at room temperature for a whole day and night to hydrolyze the silane compound, thereby obtaining a hydrolyzed liquid.

  Next, 227.0 g of methanol (Mayashi Junyaku Co., Ltd., methyl alcohol concentration: 99.9 wt%) and a solid content concentration of 20 wt% prepared in the above operation 3.6 were placed in a container containing the hydrolyzate. 383.4 g of methanol dispersion (MP-3) of surface-modified inorganic composite oxide fine particles 3, 40.6 g of propylene glycol monomethyl ether (manufactured by Dow Chemical), Tris (2,4-pentanedionato) aluminum III (Tokyo) 8.9 g of Kasei Kogyo Co., Ltd.) and 1.1 g of a silicone surfactant (manufactured by Toray Dow Corning Co., Ltd., L-7604) as a leveling agent were added and stirred at room temperature all day and night to form a hard coat layer film A forming coating composition (H3) was prepared.

[Example 4]
<Steps 1-3>
(Operations 4.1 to 4.3)
A methanol dispersion of the surface-modified inorganic composite oxide fine particles 1A was prepared in the same manner as in the operations 1.1 to 1.3 in Example 1.

<Process (4)>
(Operation 4.4) Preparation of Methanol Dispersion of Surface-Modified Inorganic Composite Oxide Fine Particles 4 In place of 175.5 g of methoxytrimethylsilane, ethoxytrimethylsilane (Wako Pure Chemical ( A methanol dispersion of the surface-modified inorganic composite oxide fine particles 4 was prepared in the same manner as in Operation 1.4 in Example 1 except that 175.5 g (boiling point, 75 ° C.) was used.
The appearance of the methanol dispersion of the surface-modified inorganic composite oxide fine particles 4 was a transparent light blue white. Furthermore, the water content of the dispersion was 0.2% by weight.

<Step (5)>
(Operation 4.5) Removal of the solvent from the methanol dispersion of the surface-modified inorganic composite oxide fine particles 4 In place of the methanol dispersion of the surface-modified inorganic composite oxide fine particles 1 prepared in the operation 1.4 of Example 1, the operation 4.4 described above was performed. Surface-modified inorganic composite oxide fine particles 4 were prepared in the same manner as in Operation 1.5 of Example 1 except that the methanol dispersion of the surface-modified inorganic composite oxide fine particles 4 prepared in Step 1 was used.

When the amount of the metal component contained in the surface-modified inorganic composite oxide fine particles 4 was measured, TiO ₂ was 46.5% by weight, SiO ₂ was 38.1% by weight on the oxide conversion standard of each metal component, ZrO ₂ was 12.9% by weight and K ₂ O was 2.5% by weight.

Further, the carbon content of the surface-modified inorganic composite oxide fine particles 4 was 2.9% by weight, and the specific surface area was 236 m ² / g.
And the weight M _A of the organic silicon compound A or a partial hydrolyzate thereof, and the weight M _B of the organosilicon compound B or a partial hydrolyzate thereof, the weight of the inorganic composite oxide particles 1b when the M _1, the weight ratio ( (M _A + M _B ) / M ₁ ) was 1.37. Furthermore, the addition amount of the organosilicon compound A or its partial hydrolyzate per surface area of the inorganic composite oxide fine particles 1b in the inorganic composite oxide fine particles 4 is 3.33 mg / m ² , and the organic content per surface area of the fine particles 1b is The amount of silicon compound B or its partial hydrolyzate added was 2.61 mg / m ² .

(Operation 4.6) Preparation of Dispersion Liquid (MP-4) of Surface-Modified Inorganic Composite Oxide Fine Particles Surface prepared in Operation 4.5 instead of surface-modified inorganic composite oxide fine particles 1 prepared in Operation 1.5 of Example 1 A methanol dispersion (MP-4) of the surface-modified inorganic composite oxide fine particles 4 was prepared in the same manner as in the operation 1.6) of Example 1 except that the modified inorganic composite oxide fine particles 4 were used.

  The average particle diameter of the surface modified inorganic composite oxide fine particles 4 was 8 nm, and did not change from the average particle diameter of the inorganic composite oxide fine particles 1b before the surface modification. Furthermore, the dispersion liquid (MP-4) was transparent light milky white, and its liquid haze was 51%.

(Operation 4.7) Preparation of Hard Coat Layer Film Forming Coating Composition (H5 ) 205.0 g of γ-glycidoxypropyltrimethoxysilane (Z-6040 manufactured by Toray Dow Corning Co., Ltd.) and methanol (Hayashi Junyaku ( 69.9 g of 0.01N hydrochloric acid aqueous solution was added dropwise with stirring to a mixture of 36.3 g (Methyl alcohol concentration: 99.9% by weight). Furthermore, this mixed liquid was stirred at room temperature for a whole day and night to hydrolyze the silane compound, thereby obtaining a hydrolyzed liquid.

  Next, 163.8 g of methanol (Mayashi Junyaku Co., Ltd., methyl alcohol concentration: 99.9 wt%) and a solid content concentration of 20 wt% prepared in the above operation 4.6 were placed in a container containing the hydrolyzate. 475.1 g of methanol dispersion (MP-4) of surface-modified inorganic composite oxide fine particles 4, 40.6 g of propylene glycol monomethyl ether (manufactured by Dow Chemical), Tris (2,4-pentanedionato) aluminum III (Tokyo) 8.2 g of Kasei Kogyo Co., Ltd. and 1.1 g of a silicone surfactant (manufactured by Toray Dow Corning Co., Ltd., L-7604) as a leveling agent were added and stirred at room temperature all day and night to form a hard coat layer film A forming coating composition (H5) was prepared.

[Example 5]
<Steps 1-3>
(Operations 5.1 to 5.3)
A methanol dispersion of the surface-modified inorganic composite oxide fine particles 1A was prepared in the same manner as in the operations 1.1 to 1.3 in Example 1.

<Process (4)>
(Operation 5.4) Preparation of Methanol Dispersion of Surface-Modified Inorganic Composite Oxide Fine Particles 5 In place of methoxytrimethylsilane, (n-propoxy) trimethylsilane (Shin-Etsu Silicone) as the surface treatment agent, which is the organosilicon compound B, is used. A methanol dispersion of surface-modified inorganic composite oxide fine particles 5 was prepared in the same manner as in Operation 1.4 of Example 1 except that 175.5 g (boiling point, 100 ° C.) was used.
The appearance of the methanol dispersion of the surface-modified inorganic composite oxide fine particles 5 was a transparent light blue white. Furthermore, the water content of the dispersion was 0.2% by weight.

<Step (5)>
(Operation 5.5) Removal of the solvent from the methanol dispersion of the surface-modified inorganic composite oxide fine particles 5 In place of the methanol dispersion of the surface-modified inorganic composite oxide fine particles 1 prepared in the operation 1.4 of Example 1, the above operation 5.4 Surface-modified inorganic composite oxide fine particles 5 were prepared in the same manner as in Operation 1.5 of Example 1 except that the methanol dispersion of the surface-modified inorganic composite oxide fine particles 5 prepared in Step 1 was used.

When the amount of metal component contained in the surface-modified inorganic composite oxide fine particles 5 was measured, TiO ₂ was 46.5% by weight, SiO ₂ was 38.1% by weight based on oxide conversion standards of each metal component, ZrO ₂ was 12.9% by weight and K ₂ O was 2.5% by weight.

Further, the carbon content of the surface-modified inorganic composite oxide fine particles 5 was 2.8% by weight, and the specific surface area was 236 m ² / g.
And the weight M _A of the organic silicon compound A or a partial hydrolyzate thereof, and the weight M _B of the organosilicon compound B or a partial hydrolyzate thereof, the weight of the inorganic composite oxide particles 1b when the M _1, the weight ratio ( (M _A + M _B ) / M ₁ ) was 1.37. Furthermore, in the surface-modified inorganic composite oxide fine particles 5, the addition amount of the weight M _A of the organosilicon compound A or its partial hydrolyzate per surface area of the inorganic composite oxide fine particles 1b is 3.33 mg / m ² , amount of weight M _B of the organosilicon compound B or a partial hydrolyzate thereof per surface area of the fine particles 1b was 2.61mg / m ^2.

(Operation 5.6) Preparation of Surface Modified Inorganic Composite Oxide Fine Particle Dispersion (MP-5) Surface Prepared in Operation 5.5 Instead of Surface Modified Inorganic Composite Oxide Fine Particle 1 Prepared in Operation 1.5 of Example 1 A methanol dispersion (MP-5) of the surface-modified inorganic composite oxide fine particles 5 was prepared in the same manner as in Operation 1.6 of Example 1 except that the modified inorganic composite oxide fine particles 5 were used.

  The average particle diameter of the surface modified inorganic composite oxide fine particles 5 was 8 nm, and did not change from the average particle diameter of the inorganic composite oxide fine particles 1b before the surface modification. Furthermore, the dispersion liquid (MP-5) was transparent light milky white, and the liquid haze was 53%.

(Operation 5.7) Preparation of Hard Coat Layer Film Forming Coating Composition (H6 ) 205.0 g of γ-glycidoxypropyltrimethoxysilane (Z-6040 manufactured by Toray Dow Corning Co., Ltd.) and methanol (Hayashi Junyaku ( 69.9 g of 0.01N hydrochloric acid aqueous solution was added dropwise with stirring to a mixture of 36.3 g (Methyl alcohol concentration: 99.9% by weight). Furthermore, this mixed liquid was stirred at room temperature for a whole day and night to hydrolyze the silane compound, thereby obtaining a hydrolyzed liquid.

  Next, 163.8 g of methanol (Mayashi Junyaku Co., Ltd., methyl alcohol concentration: 99.9 wt%) and a solid content concentration of 20 wt% prepared in the operation 5.6 were placed in a container containing the hydrolyzate. 475.1 g of methanol dispersion (MP-5) of surface-modified inorganic composite oxide fine particles 5, 40.6 g of propylene glycol monomethyl ether (manufactured by Dow Chemical), Tris (2,4-pentanedionato) aluminum III (Tokyo) 8.2 g of Kasei Kogyo Co., Ltd. and 1.1 g of a silicone surfactant (manufactured by Toray Dow Corning Co., Ltd., L-7604) as a leveling agent were added and stirred at room temperature all day and night to form a hard coat layer film A forming coating composition (H6) was prepared.

[Example 6]
<Step 1>
An aqueous dispersion of inorganic composite oxide fine particles 1b was prepared in the same manner as in Operation 1.1 of Example 1.

<Step (2)>
(Operation 6.2)
In the operation 1.2 of Example 1, instead of tetraethoxysilane, tetra (n-propyl) silane (manufactured by Wako Pure Chemical Industries, Ltd., boiling point 94 ° C.) 175, which is the organosilicon compound A, as a surface treatment agent. A water / methanol mixed dispersion of surface-modified inorganic composite oxide fine particles 6A was prepared in the same manner as in Operation 1.2 of Example 1 except that 0.5 g was used.

<Step (3)>
(Operation 6.3)
Instead of the mixed dispersion of the surface modified inorganic composite oxide fine particles 1A prepared in the operation 1.2 of Example 1, the mixed dispersion of the surface modified inorganic composite oxide fine particles 6A obtained in the operation 6.2 was used. Except for the above, a methanol dispersion of the surface-modified inorganic composite oxide fine particles 6A was prepared in the same manner as in Operation 1.3 of Example 1.

<Process (4)>
(Operation 6.4) Preparation of Methanol Dispersion of Surface-Modified Inorganic Composite Oxide Fine Particles 6 In place of the methanol dispersion of surface-modified inorganic composite oxide fine particles 1A prepared in Operation 1.3 of Example 1, it was prepared in Operation 6.3. A methanol dispersion of the surface-modified inorganic composite oxide fine particles 6 was prepared in the same manner as in Operation 1.4 of Example 1 except that the methanol dispersion of the surface-modified inorganic composite oxide fine particles 6A was used.
The appearance of the methanol dispersion of the surface-modified inorganic composite oxide fine particles 6 was transparent light blue white. Furthermore, the water content of the dispersion was 0.2% by weight.

<Step (5)>
(Operation 6.5) Removal of the solvent from the methanol dispersion of the surface-modified inorganic composite oxide fine particles 6 In place of the methanol dispersion of the surface-modified inorganic composite oxide fine particles 1 prepared in the operation 1.4 of Example 1, the above operation 6.4 Surface-modified inorganic composite oxide fine particles 6 were prepared in the same manner as in Operation 1.5 of Example 1 except that the methanol dispersion of the surface-modified inorganic composite oxide fine particles 6 prepared in Step 1 was used.

When the amount of the metal component contained in the surface-modified inorganic composite oxide fine particles 6 was measured, TiO ₂ was 46.4% by weight, SiO ₂ was 38.3% by weight based on the oxide conversion standard of each metal component, ZrO ₂ was 12.8% by weight and K ₂ O was 2.5% by weight.

Further, the carbon content of the surface-modified inorganic composite oxide fine particles 6 was 3.0% by weight, and the specific surface area was 236 m ² / g.
And the weight M _A of the organic silicon compound A or a partial hydrolyzate thereof, and the weight M _B of the organosilicon compound B or a partial hydrolyzate thereof, the weight of the inorganic composite oxide particles 1b when the M _1, the weight ratio ( (M _A + M _B ) / M ₁ ) was 0.820. Furthermore, in the surface-modified inorganic composite oxide fine particles 6, the addition amount of the weight M _A of the organosilicon compound A or its partial hydrolyzate per surface area of the inorganic composite oxide fine particles 1b is 3.33 mg / m ² , amount of weight M _B of the organosilicon compound B or a partial hydrolyzate thereof per surface area of the fine particles 1b was 2.61mg / m ^2.

(Operation 6.6) Preparation of Surface Modified Inorganic Composite Oxide Fine Particle Dispersion (MP-6) Surface Prepared in Procedure 6.5 Instead of Surface Modified Inorganic Composite Oxide Fine Particle 1 Prepared in Operation 1.5 of Example 1 A methanol dispersion (MP-6) of the surface-modified inorganic composite oxide fine particles 6 was prepared by the same method as in Operation 1.6 of Example 1 except that the modified inorganic composite oxide fine particles 6 were used.

  The average particle diameter of the surface-modified inorganic composite oxide fine particles 6 was 8 nm, and did not change from the average particle diameter of the inorganic composite oxide fine particles 6b before the surface modification. Further, the dispersion (MP-6) was transparent and light milky white, and its liquid haze was 54%.

(Operation 6.7) Preparation of Hard Coat Layer Film Forming Coating Composition (H7 ) 205.0 g of γ-glycidoxypropyltrimethoxysilane (Z-6040 manufactured by Toray Dow Corning Co., Ltd.) and methanol (Hayashi Junyaku ( 69.9 g of 0.01N hydrochloric acid aqueous solution was added dropwise with stirring to a mixture of 36.3 g (Methyl alcohol concentration: 99.9% by weight). Furthermore, this mixed liquid was stirred at room temperature for a whole day and night to hydrolyze the silane compound, thereby obtaining a hydrolyzed liquid.

  Next, 163.8 g of methanol (Mayashi Junyaku Co., Ltd., methyl alcohol concentration: 99.9 wt%) and a solid content concentration of 20 wt% prepared in the above operation 6.6 were placed in a container containing the hydrolyzate. 475.1g of methanol dispersion (MP-6) of surface-modified inorganic composite oxide fine particles 6, 40.6g of propylene glycol monomethyl ether (manufactured by Dow Chemical), Tris (2,4-pentanedionato) aluminum III (Tokyo) 8.2 g of Kasei Kogyo Co., Ltd. and 1.1 g of a silicone surfactant (manufactured by Toray Dow Corning Co., Ltd., L-7604) as a leveling agent were added and stirred at room temperature all day and night to form a hard coat layer film A forming coating composition (H7) was prepared.

[Comparative Example 1]
<Steps 1-3>
(Operations C1.1 to C1.3)
A methanol dispersion of the surface-modified inorganic composite oxide fine particles 1A was prepared in the same manner as in the operations 1.1 to 1.3 in Example 1.

<Process (4)>
(Operation C1.4) Preparation of Methanol Dispersion of Surface-Modified Inorganic Composite Oxide Fine Particles C1A Operation 1.4 of Example 1 was not performed in this comparative example.

  The appearance of the methanol dispersion containing the surface-modified inorganic composite oxide fine particles 1A thus obtained (hereinafter also referred to as “surface-modified inorganic composite oxide fine particles C1A”) was transparent light blue white. Furthermore, the water content of the dispersion was 0.2% by weight.

<Step (5)>
(Operation C1.5) Removal of solvent from methanol dispersion of surface-modified inorganic composite oxide fine particles C1A Instead of the methanol dispersion of surface-modified inorganic composite oxide fine particles 1 prepared in operation 1.4 of Example 1, Surface-modified inorganic composite oxide fine particles C1 were prepared in the same manner as in Operation 1.5 of Example 1 except that the methanol dispersion of the surface-modified inorganic composite oxide fine particles C1A prepared in Operation C1.4 was used. .

When the amount of the metal component contained in the surface-modified inorganic composite oxide fine particles C1 was measured, TiO ₂ was 47.6% by weight, SiO ₂ was 36.3% by weight on the oxide conversion standard of each metal component, ZrO ₂ was 13.4% by weight and K ₂ O was 2.6% by weight.

Furthermore, the carbon content of the surface-modified inorganic composite oxide fine particles C1 was 0.8% by weight, and the specific surface area was 236 m ² / g.
And the weight M _A of the organic silicon compound A or a partial hydrolyzate thereof, and the weight M _B of the organosilicon compound B or a partial hydrolyzate thereof, the weight of the inorganic composite oxide particles 1b when the M _1, the weight ratio ( (M _A + M _B ) / M ₁ ) was 0.77. Further, in the surface-modified inorganic composite oxide fine particles C1, the addition amount of the organosilicon compound A or its partial hydrolyzate per surface area of the inorganic composite oxide fine particles 1b is 3.33 mg / m ² , and the surface area of the fine particles 1b The amount of the organosilicon compound B or its partial hydrolyzate added was 0 mg / m ² .

(Operation C1.6) Preparation of Liquid (MC-1) of Surface-Modified Inorganic Composite Oxide Fine Particles C1 Instead of the surface-modified inorganic composite oxide fine particles 1 prepared in Operation 1.5 of Example 1, the operation C1.5 The surface-modified inorganic composite oxide fine particles C1 in methanol solution (MC-1) (solid content) were prepared in the same manner as in Operation 1.6 of Example 1 except that the surface-modified inorganic composite oxide fine particles C1 prepared in Step 1 were used. Concentration: 20% by weight) was prepared.

  The average particle size of the surface-modified inorganic composite oxide fine particles C1 was 100 nm or more, which was significantly increased from the average particle size of the inorganic composite oxide fine particles 1b before being surface-modified. Furthermore, in the liquid (MC-1), the particles did not disperse and remained settled, so the liquid haze was not measured and a coating composition for forming a hard coat layer film was not prepared.

[Comparative Example 2]
<Step 1>
(Operation C2.1)
An aqueous dispersion of inorganic composite oxide fine particles 1b was prepared in the same manner as in Operation 1.1 of Example 1.

<Step (2)>
(Operation C2.2)
A water / methanol mixed dispersion of surface-modified inorganic composite oxide fine particles C2A was prepared in the same manner as in Operation 1.2 of Example 1 except that tetraethoxysilane was not used in Operation 1.2 of Example 1.

<Step (3)>
(Operation C2.3)
The mixed dispersion of the surface-modified inorganic composite oxide fine particles C2A prepared in the operation C2.2 was used instead of the mixed dispersion of the surface-modified inorganic composite oxide fine particles 1A prepared in the operation 1.2 of Example 1. A methanol dispersion of the surface-modified inorganic composite oxide fine particles C2A was prepared in the same manner as in Operation 1.3 of Example 1 except that.

<Process (4)>
(Operation C2.4) Preparation of Methanol Dispersion of Surface-Modified Inorganic Composite Oxide Fine Particles C2 In place of the methanol dispersion of surface-modified inorganic composite oxide fine particles 1A prepared in Operation 1.3 of Example 1, the operation C2. A methanol dispersion of the surface-modified inorganic composite oxide fine particles C2 was prepared in the same manner as in Operation 1.4 of Example 1 except that the methanol dispersion of the surface-modified inorganic composite oxide fine particles C2A prepared in 3 was used. did.
The appearance of the methanol dispersion of the surface-modified inorganic composite oxide fine particles C2 was transparent light blue white. Furthermore, the water content of the dispersion was 0.2% by weight.

<Step (5)>
(Operation C2.5) Removal of solvent from methanol dispersion of surface-modified inorganic composite oxide fine particles C2 Instead of the methanol dispersion of surface-modified inorganic composite oxide fine particles 1 prepared in operation 1.4 of Example 1, Surface-modified inorganic composite oxide fine particles C2 were prepared in the same manner as in Operation 1.5 of Example 1 except that the methanol dispersion of the surface-modified inorganic composite oxide fine particles C2 prepared in Operation C2.4 was used. .

When the amount of the metal component contained in the surface-modified inorganic composite oxide fine particles C2 was measured, TiO ₂ was 47.6% by weight, SiO ₂ was 36.3% by weight on the oxide conversion standard of each metal component, ZrO ₂ was 13.4% by weight and K ₂ O was 2.6% by weight.

Furthermore, the carbon content of the surface-modified inorganic composite oxide fine particles C2 was 1.0% by weight, and the specific surface area was 236 m ² / g.
And the weight M _A of the organic silicon compound A or a partial hydrolyzate thereof, and the weight M _B of the organosilicon compound B or a partial hydrolyzate thereof, the weight of the inorganic composite oxide particles 1b when the M _1, the weight ratio ( (M _A + M _B ) / M ₁ ) was 0.60. Further, in the surface-modified inorganic composite oxide fine particles C2, the addition amount of the organosilicon compound A or a partial hydrolyzate thereof per surface area of the inorganic composite oxide fine particles 1b is 0 mg / m ² , The amount of the organosilicon compound B or its partial hydrolyzate added was 2.61 mg / m ² .

(Operation C2.6) Preparation of Surface Modified Inorganic Composite Oxide Fine Particle C2 Liquid (MC-2) In place of the surface modified inorganic composite oxide fine particle 1 prepared in Operation 1.5 of Example 1, the above operation C2.5 In the same manner as in Operation 1.6 of Example 1 except that the surface-modified inorganic composite oxide fine particles C2 prepared in Step 1 were used, methanol solution (MC-2) (solid content of the surface-modified inorganic composite oxide fine particles C2 was obtained. Concentration: 20% by weight) was prepared.

  The average particle diameter of the surface-modified inorganic composite oxide fine particles C2 was 100 nm or more, which was significantly increased from the average particle diameter of the inorganic composite oxide fine particles 1b before the surface modification. Furthermore, in the liquid (MC-2), the particles did not disperse and remained settled, so the liquid haze was not measured and a coating composition for forming a hard coat layer film was not prepared.

[Comparative Example 3]
<Steps 1-3>
(Operations C3.1 to C3.3)
A methanol dispersion of the surface-modified inorganic composite oxide fine particles 1A was prepared in the same manner as in the operations 1.1 to 1.3 in Example 1.

<Process (4)>
(Operation C3.4) Preparation of Methanol Dispersion Containing Surface-Modified Inorganic Composite Oxide Fine Particles C3 Triethyl (ethoxy) silane (Tokyo Chemical Industry) as the surface treatment agent, which is the organosilicon compound B, instead of methoxytrimethylsilane A methanol dispersion of the surface-modified inorganic composite oxide fine particles C3 was prepared in the same manner as in the operation 1.4 of Example 1 except that 175.5 g (manufactured by Kogyo Co., Ltd., boiling point 154 ° C.) was used.
The appearance of the methanol dispersion of the surface-modified inorganic composite oxide fine particles C3 was transparent light blue white. Furthermore, the water content of the dispersion was 0.2% by weight.

<Step (5)>
(Operation C3.5) Step of removing solvent from methanol dispersion of surface-modified inorganic composite oxide fine particles C3 Instead of the methanol dispersion of surface-modified inorganic composite oxide fine particles 1 prepared in operation 1.4 of Example 1. The surface-modified inorganic composite oxide fine particles C3 were prepared in the same manner as in the operation 1.5 of Example 1 except that the methanol dispersion of the surface-modified inorganic composite oxide fine particles C3 prepared in the operation C3.4 was used. did.

When the amount of the metal component contained in the surface-modified inorganic composite oxide fine particles C3 was measured, TiO ₂ was 46.3% by weight, SiO ₂ was 38.3% by weight on the oxide conversion standard of each metal component, ZrO ₂ was 12.9% by weight and K ₂ O was 2.5% by weight.

Furthermore, the carbon content of the surface-modified inorganic composite oxide fine particles C3 was 4.3% by weight, and the specific surface area was 237 m ² / g.
And the weight M _A of the organic silicon compound A or a partial hydrolyzate thereof, and the weight M _B of the organosilicon compound B or a partial hydrolyzate thereof, the weight of the inorganic composite oxide particles 1b when the M _1, the weight ratio ( (M _A + M _B ) / M ₁ ) was 1.37. Further, in the surface-modified inorganic composite oxide fine particles 3C, the addition amount of the organosilicon compound A or a partial hydrolyzate thereof per surface area of the inorganic composite oxide fine particles 1b is 3.33 mg / m ^2. The amount of organic silicon compound B or its partial hydrolyzate added per unit was 2.61 mg / m ² .

(Operation C3.6) Preparation of Surface Modified Inorganic Composite Oxide Fine Particle Dispersion (MC-3) In place of the surface modified inorganic composite oxide fine particle 1 prepared in Operation 1.5 of Example 1, the above operation C3.5 In the same manner as in Operation 1.6 of Example 1 except that the surface-modified inorganic composite oxide fine particles C3 prepared in Step 1 were used, a methanol dispersion (MC-3) of the surface-modified inorganic composite oxide fine particles C3 (solid (Partial concentration: 20% by weight).

  The average particle diameter of the surface modified inorganic composite oxide fine particles C3 was 8 nm, and the average particle diameter of the inorganic composite oxide fine particles 1b before the surface modification was not changed. Furthermore, the dispersion liquid (MC-3) was transparent and light milky white, and the liquid haze was 56%.

(Operation C3.7) Preparation of Hard Coat Layer Film Forming Coating Composition (R1) 205.0 g of γ-glycidoxypropyltrimethoxysilane (Z-6040 manufactured by Toray Dow Corning Co., Ltd.) and methanol (Jun Hayashi) To a mixed solution of 36.3 g (manufactured by Yakuhin Co., Ltd., methyl alcohol concentration: 99.9% by weight), 69.9 g of 0.01N hydrochloric acid aqueous solution was added dropwise with stirring. Furthermore, this mixed liquid was stirred at room temperature for a whole day and night to hydrolyze the silane compound, thereby obtaining a hydrolyzed liquid.

  Next, 163.8 g of methanol (Mayashi Junyaku Co., Ltd., methyl alcohol concentration: 99.9% by weight) and a solid content concentration of 20 wt. % Of surface-modified inorganic composite oxide fine particles C3 in methanol (MC-3) 475.1 g, propylene glycol monomethyl ether (manufactured by Dow Chemical) 40.6 g, tris (2,4-pentanedionato) aluminum III Add 8.2 g (manufactured by Tokyo Chemical Industry Co., Ltd.) and 1.1 g of a silicone surfactant (manufactured by Toray Dow Corning Co., Ltd., L-7604) as a leveling agent, stir at room temperature all day and night, and hard coat A coating composition (R1) for forming a layer film was prepared.

(Operation C3.8) Preparation of Hard Coat Layer Film Forming Coating Composition (R2) 168.3 g of γ-glycidoxypropyltrimethoxysilane (Z-6040 manufactured by Toray Dow Corning Co., Ltd.) and methanol (Jun Hayashi) 57.4 g of 0.01N hydrochloric acid aqueous solution was added dropwise with stirring to 29.8 g of a mixed solution (manufactured by Yakuhin Co., Ltd., methyl alcohol concentration: 99.9 wt%). Furthermore, this mixed liquid was stirred at room temperature for a whole day and night to hydrolyze the silane compound, thereby obtaining a hydrolyzed liquid.

  Next, 37.7 g of methanol (produced by Hayashi Junyaku Co., Ltd., methyl alcohol concentration: 99.9 wt%) and a solid content concentration of 30 wt. % Surface-modified inorganic composite oxide fine particles C3 in methanol (MC-3) 658.4 g, propylene glycol monomethyl ether (manufactured by Dow Chemical) 40.6 g, tris (2,4-pentanedionato) aluminum III 6.7 g (manufactured by Tokyo Chemical Industry Co., Ltd.) and 1.1 g of a silicone surfactant (manufactured by Toray Dow Corning Co., Ltd., L-7604) as a leveling agent were added and stirred at room temperature all day and night to hard coat A coating composition (R2) for forming a layer film was prepared.

(Operation C3.9) Preparation of primer layer film-forming coating composition (Z1) Polyurethane emulsion “ Superflex 150” (Daiichi Kogyo Seiyaku Co., Ltd., water-dispersed urethane elastomer solid content 30 ) which is a commercially available thermoplastic resin %) 243.6 g was prepared. To this was added 469.0 g of methanol (Mayashi Junyaku Co., Ltd., methyl alcohol concentration: 99.9 wt%) and the surface modification prepared in the above-mentioned operation C3.6. 190.0 g of a methanol dispersion (MC-3) of fine inorganic composite oxide fine particles C3 and 97.1 g of ion-exchanged water were added and stirred for 1 hour.

  Next, 0.3 g of a silicone surfactant (manufactured by Toray Dow Corning Co., Ltd., L-7604) as a leveling agent is added to this mixed solution, and the mixture is stirred at room temperature all day and night to form a primer layer film-forming coating composition. (Z1) was prepared.

(Operation C3.10) Preparation of primer layer film-forming coating composition (Z2) Polyurethane emulsion “ Superflex 150”, a commercially available thermoplastic resin (Daiichi Kogyo Seiyaku, water-dispersed urethane elastomer solid content 30 %) 207.6 g was prepared. To this was added 450.2 g of methanol (Mayashi Junyaku Co., Ltd., methyl alcohol concentration: 99.9% by weight) and the surface modification prepared in the above operation C3.6. 242.9 g of a methanol dispersion (MC-3) of fine inorganic composite oxide fine particles C3 and 96.9 g of ion-exchanged water were added and stirred for 1 hour.

  Next, 0.3 g of a silicone surfactant (manufactured by Toray Dow Corning Co., Ltd., L-7604) as a leveling agent is added to this mixed solution, and the mixture is stirred at room temperature all day and night to form a primer layer film-forming coating composition. (Z2) was prepared.

[Comparative Example 4]
<Step 1>
(Operation C4.1)
An aqueous dispersion of inorganic composite oxide fine particles 1b was prepared in the same manner as in Operation 1.1 of Example 1.

<Step (2)>
(Operation C4.2)
A water / methanol mixed dispersion of surface-modified inorganic composite oxide fine particles C4A was prepared in the same manner as in Operation 1.2 of Example 1 except that the amount of tetraethoxysilane added as organosilicon compound A was changed from 448 g to 102 g. Prepared.

<Step (3)>
(Operation C4.3)
Instead of the mixed dispersion of the surface modified inorganic composite oxide fine particles 1A prepared in the operation 1.2 of Example 1, the mixed dispersion of the surface modified inorganic composite oxide fine particles C4A prepared in the operation C4.2 is used. A methanol dispersion of the surface-modified inorganic composite oxide fine particles C4A was prepared in the same manner as in the operation 1.3 of Example 1 except that the above was observed.

<Process (4)>
(Operation C4.4) Preparation of Methanol Dispersion of Surface-Modified Inorganic Composite Oxide Fine Particle C4A Example 1 except that the addition amount of methoxytrimethylsilane was changed from 175.5 g to 9.2 g per addition. A methanol dispersion of the surface-modified inorganic composite oxide fine particles C4 was prepared in the same manner as in Operation 1.4.
The appearance of the methanol dispersion of the surface-modified inorganic composite oxide fine particles C4 was transparent light blue white. Furthermore, the water content of the dispersion was 0.2% by weight.

<Step (5)>
(Operation C4.5) Removal of solvent from methanol dispersion containing surface-modified inorganic composite oxide fine particles C4 Instead of the methanol dispersion of surface-modified inorganic composite oxide fine particles 1 prepared in operation 1.4 of Example 1. Surface modified inorganic composite oxide fine particles C4 were prepared in the same manner as in Operation 1.5 of Example 1 except that the methanol dispersion of the surface modified inorganic composite oxide fine particles C4 prepared in the above operation C4.4 was used. did.

When the amount of the metal component contained in the surface-modified inorganic composite oxide fine particles C4 was measured, TiO ₂ was 46.5% by weight, SiO ₂ was 38.3% by weight on the oxide conversion standard of each metal component, ZrO ₂ was 12.8% by weight and K ₂ O was 2.4% by weight.

Furthermore, the carbon content of the surface-modified inorganic composite oxide fine particles C4 was 0.6% by weight, and the specific surface area was 238 m ² / g.
And the weight M _A of the organic silicon compound A or a partial hydrolyzate thereof, when the weight M _B of the organosilicon compound B or a partial hydrolyzate thereof, the weight of the inorganic composite oxide particles was M _1, the weight ratio (( M _A + M _B ) / M ₁ ) was 0.15. Further, in the surface-modified inorganic composite oxide fine particles C4, the addition amount of the organosilicon compound A or its partial hydrolyzate per surface area of the inorganic composite oxide fine particles 1b is 0.22 mg / m ² , and the surface area of the fine particles 1b The amount of the organic silicon compound B or its partial hydrolyzate added was 0.43 mg / m ² .

(Operation C4.6) Preparation of Surface Modified Inorganic Composite Oxide Fine Particle Dispersion (MC-4) In place of the surface modified inorganic composite oxide fine particle 1 prepared in Operation 1.5 of Example 1, the above operation C4.5 In the same manner as in Operation 1.6 of Example 1 except that the surface-modified inorganic composite oxide fine particles C4 prepared in Step 1 were used, a methanol dispersion (MC-4) of the surface-modified inorganic composite oxide fine particles C4 (solid (Partial concentration: 20% by weight).

  The average particle diameter of the surface-modified inorganic composite oxide fine particles C4 was 50 nm, which was increased from the average particle diameter of the inorganic composite oxide fine particles 1b before being surface-modified. Furthermore, the dispersion (MC-4) was milky white and the liquid haze was 91%.

(Operation C4.7) Preparation of coating composition (R3) for forming a hard coat layer film 205.0 g of γ-glycidoxypropyltrimethoxysilane (Z-6040 manufactured by Toray Dow Corning Co., Ltd.) and methanol (Jun Hayashi) To a mixed solution of 36.3 g (manufactured by Yakuhin Co., Ltd., methyl alcohol concentration: 99.9% by weight), 69.9 g of 0.01N hydrochloric acid aqueous solution was added dropwise with stirring. Furthermore, this mixed liquid was stirred at room temperature for a whole day and night to hydrolyze the silane compound, thereby obtaining a hydrolyzed liquid.

  Next, 163.8 g of methanol (Mayashi Junyaku Co., Ltd., methyl alcohol concentration: 99.9% by weight) and 20% by weight of the solid content prepared in the above operation C4.6 were placed in a container containing the hydrolyzate. % Surface-modified inorganic composite oxide fine particles C4 in methanol (MC-4) 475.1 g, propylene glycol monomethyl ether (manufactured by Dow Chemical) 40.6 g, tris (2,4-pentanedionato) aluminum III Add 8.2 g (manufactured by Tokyo Chemical Industry Co., Ltd.) and 1.1 g of a silicone surfactant (manufactured by Toray Dow Corning Co., Ltd., L-7604) as a leveling agent, stir at room temperature all day and night, and hard coat A coating composition for forming a layer film (R3) was prepared.

[Comparative Example 5]
<Step 1>
(Operation C5.1)
An aqueous dispersion of inorganic composite oxide fine particles 1b was prepared in the same manner as in Operation 1.1 of Example 1.

<Step (2)>
(Operation C5.2)
A water / methanol mixed dispersion of surface-modified inorganic composite oxide fine particles C5A was prepared in the same manner as in Operation 1.2 of Example 1 except that the amount of tetraethoxysilane added was changed from 448 g to 877 g.

<Step (3)>
(Operation C5.3)
Instead of the mixed dispersion of the surface modified inorganic composite oxide fine particles 1A prepared in the operation 1.2 of Example 1, the mixed dispersion of the surface modified inorganic composite oxide fine particles C5A prepared in the operation C5.2 is used. A methanol dispersion of the surface-modified inorganic composite oxide fine particles C5A was prepared in the same manner as in the operation 1.3 of Example 1 except for the above.

<Process (4)>
(Operation C5.4) Preparation of Methanol Dispersion of Surface-Modified Inorganic Composite Oxide Fine Particles C5 Example 1 except that the addition amount of methoxytrimethylsilane was changed from 175.5 g to 351.0 g per addition. A methanol dispersion of the surface-modified inorganic composite oxide fine particles C5 was prepared in the same manner as in Operation 1.4.
The appearance of the methanol dispersion of the surface-modified inorganic composite oxide fine particles C5 was a transparent light blue white. Furthermore, the water content of the dispersion was 0.2% by weight.

<Step (5)>
(Operation C5.5) Removal of solvent from methanol dispersion of surface-modified inorganic composite oxide fine particles C5 Instead of the methanol dispersion of surface-modified inorganic composite oxide fine particles 1 prepared in operation 1.4 of Example 1, Surface-modified inorganic composite oxide fine particles C5 were prepared in the same manner as in Operation 1.5 of Example 1 except that the methanol dispersion of the surface-modified inorganic composite oxide fine particles C5 prepared in Operation C5.4 was used. .

When the amount of the metal component contained in the surface-modified inorganic composite oxide fine particles C5 was measured, TiO ₂ was 46.4% by weight, SiO ₂ was 38.1% by weight based on the oxide conversion standard of each metal component, ZrO ₂ was 13.0% by weight and K ₂ O was 2.5% by weight.

Furthermore, the carbon content of the surface-modified inorganic composite oxide fine particles C5 was 11.3 wt%, and the specific surface area was 238 m ² / g.
And the weight M _A of the organic silicon compound A or a partial hydrolyzate thereof, and the weight M _B of the organosilicon compound B or a partial hydrolyzate thereof, the weight of the inorganic composite oxide particles 1b when the M _1, the weight ratio ( (M _A + M _B ) / M ₁ ) was 2.70. Further, in the surface-modified inorganic composite oxide fine particles C5, the addition amount of the organosilicon compound A or a partial hydrolyzate thereof per surface area of the inorganic composite oxide fine particles 1b is 6.52 mg / m ^2. The amount of the organic silicon compound B or its partial hydrolyzate added was 5.22 mg / m ² .

(Operation C5.6) Preparation of Surface Modified Inorganic Composite Oxide Fine Particle Dispersion (MC-5) In place of the surface modified inorganic composite oxide fine particle 1 prepared in Operation 1.5 of Example 1, the above operation C5.5 In the same manner as in Operation 1.6 of Example 1 except that the surface-modified inorganic composite oxide fine particles C5 prepared in Step 1 were used, a methanol dispersion (MC-5) of the surface-modified inorganic composite oxide fine particles C5 (solid) (Partial concentration: 20% by weight).

  The average particle diameter of the surface-modified inorganic composite oxide fine particles C5 was 30 nm, which was increased from the average particle diameter of the inorganic composite oxide fine particles 1b before being surface-modified. Further, the dispersion (MC-5) was transparent milky white and its liquid haze was 78%.

(Operation C5.7) Preparation of Hard Coat Layer Film Forming Coating Composition (R4) 205.0 g of γ-glycidoxypropyltrimethoxysilane (Z-6040 manufactured by Toray Dow Corning Co., Ltd.) and methanol (Jun Hayashi) To a mixed solution of 36.3 g (manufactured by Yakuhin Co., Ltd., methyl alcohol concentration: 99.9% by weight), 69.9 g of 0.01N hydrochloric acid aqueous solution was added dropwise with stirring. Furthermore, this mixed liquid was stirred at room temperature for a whole day and night to hydrolyze the silane compound, thereby obtaining a hydrolyzed liquid.

  Next, 163.8 g of methanol (Mayashi Junyaku Co., Ltd., methyl alcohol concentration: 99.9% by weight) and 20% by weight of the solid content prepared in the above operation C5.6 were placed in a container containing the hydrolyzate. % Surface-modified inorganic composite oxide fine particles C5 in methanol dispersion (MC-5) 475.1 g, propylene glycol monomethyl ether (Dow Chemical) 40.6 g, tris (2,4-pentanedionato) aluminum III Add 8.2 g (manufactured by Tokyo Chemical Industry Co., Ltd.) and 1.1 g of a silicone surfactant (manufactured by Toray Dow Corning Co., Ltd., L-7604) as a leveling agent, stir at room temperature all day and night, and hard coat A coating composition (R4) for forming a layer film was prepared.

[Comparative Example 6]
<Steps 1-3>
(Operations C6.1 to C6.3)
A methanol dispersion of the surface-modified inorganic composite oxide fine particles 1A was prepared in the same manner as in the operations 1.1 to 1.3 in Example 1.

<Process (4)>
(Operation C6.4) Preparation of Methanol Dispersion Containing Surface Modified Inorganic Composite Oxide Fine Particles C3 Instead of methoxytrimethylsilane , dimethoxydimethylsilane (Shin-Etsu Chemical Co., Ltd.) as the surface treatment agent, which is the organosilicon compound B, is used. A methanol dispersion of surface-modified inorganic composite oxide fine particles C6 was prepared in the same manner as in Operation 1.4 of Example 1 except that 175.5 g (boiling point, 81 ° C.) was used.
The appearance of the methanol dispersion of the surface-modified inorganic composite oxide fine particles C6 was transparent light blue white. Furthermore, the water content of the dispersion was 0.2% by weight.

<Step (5)>
(Operation C6.5) Step of removing the solvent from the methanol dispersion of the surface-modified inorganic composite oxide fine particles C6 Instead of the methanol dispersion of the surface-modified inorganic composite oxide fine particles 1 prepared in operation 1.4 of Example 1. Surface-modified inorganic composite oxide fine particles C6 were prepared in the same manner as in Operation 1.5 of Example 1 except that the methanol dispersion of surface-modified inorganic composite oxide fine particles C6 prepared in Step C6.4 was used. did.

When the amount of the metal component contained in the surface-modified inorganic composite oxide fine particles C6 was measured, TiO ₂ was 46.2% by weight, SiO ₂ was 38.4% by weight on the oxide conversion standard of each metal component, ZrO ₂ was 12.9% by weight and K ₂ O was 2.5% by weight.

Furthermore, the carbon content of the surface-modified inorganic composite oxide fine particles C6 was 3.8% by weight, and the specific surface area was 238 m ² / g.
And the weight M _A of the organic silicon compound A or a partial hydrolyzate thereof, and the weight M _B of the organosilicon compound B or a partial hydrolyzate thereof, the weight of the inorganic composite oxide particles 6b when the M _1, the weight ratio ( (M _A + M _B ) / M ₁ ) was 1.37. Furthermore, in the surface-modified inorganic composite oxide fine particles 6C, the addition amount of the organosilicon compound A or its partial hydrolyzate per surface area of the inorganic composite oxide fine particles 6b is 3.33 mg / m ² , and the surface area of the fine particles 6b The amount of organic silicon compound B or its partial hydrolyzate added per unit was 2.61 mg / m ² .

(Operation C6.6) Preparation of Surface Modified Inorganic Composite Oxide Fine Particle C6 Liquid (MC-6) In place of the surface modified inorganic composite oxide fine particle 1 prepared in Operation 1.5 of Example 1, the above operation C6.5 In the same manner as in Operation 1.6 of Example 1 except that the surface-modified inorganic composite oxide fine particles C6 prepared in Step 1 were used, methanol solution (MC-6) (solid content of the surface-modified inorganic composite oxide fine particles C6 was obtained. Concentration: 20% by weight) was prepared.

The average particle diameter of the surface-modified inorganic composite oxide fine particles C6 was 100 nm or more, and was significantly increased from the average particle diameter of the inorganic composite oxide fine particles 6b before the surface modification. Furthermore, in the liquid (MC-6), the particles did not disperse and remained settled, so the liquid haze was not measured, and a coating composition for forming a hard coat layer film was not prepared.
Table 1 shows the properties of the particles prepared in Examples 1 to 6 and Comparative Examples 1 to 6.

B. Production and evaluation of plastic lens substrate (test piece) for test < Production of plastic lens substrate (test piece)>
(1) Pretreatment of plastic lens substrate Commercially available plastic lens substrate “monomer name: MR-8” (manufactured by Mitsui Chemicals, Inc., refractive index of substrate 1.60) and “monomer name: MR-7” Etching was carried out by immersing (with Mitsui Chemicals, Inc., base material refractive index 1.67) in a 10 wt% KOH aqueous solution kept at 40 ° C. for 2 minutes. 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.

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 1.0 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.

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.
The thickness of the hard coat layer film thus formed after curing was approximately 3.0 to 3.5 μm.

(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.

<Evaluation of plastic lens substrate (test piece)>
Coating compositions H1, H2, H3, H4, H5, H6, H7, R1, R2, R3, R4 and primer layers for forming hard coat layer films obtained in Examples 1 to 6 and Comparative Examples 3 to 5 Using a coating composition for film formation Y1, Y2, Z1, and Z2, 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 4, and test pieces 1 to 13 was produced.

  In addition, the base material of the test piece 10 which applied the coating composition Y1 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 Z1 for primer layer film formation A test piece 11 was prepared by coating the coating composition R1 for forming a hard coat layer film and forming an antireflection layer film.

  Furthermore, the base material of the test piece 12 which applied the coating composition Y2 for forming the primer layer film and the coating composition H2 for forming the hard coat layer film to form the antireflection layer film, and the coating composition Z2 for forming the primer layer film Then, a test piece 13 in which an antireflection layer film was formed by applying the coating composition R2 for forming a hard coat layer film was prepared. Here, “monomer name: MR-7” (manufactured by Mitsui Chemicals, Inc., refractive index 1.67 of the base material) is used as the base material of the test pieces 12 to 13, and the other test piece base materials are used. Used was “monomer name: MR-8” (manufactured by Mitsui Chemicals, Inc., refractive index of substrate 1.60).

  About the test pieces 1-13 obtained in this way, using the above-described evaluation test method, appearance (interference fringes), appearance (cloudiness), scratch resistance, film hardness, adhesion, weather resistance, light resistance, The refractive index was tested and evaluated. The results are shown in Table 5.

  As is clear from this result, it was found that the test piece obtained by applying the coating composition prepared in the example had very high scratch resistance and film hardness, and had no cloudiness and high transparency. Further, it was found that the appearance interference fringes were good, and the adhesion, weather resistance and light resistance were high.

  The surface-modified inorganic oxide fine particles and dispersions thereof according to the present invention can be used for optical material applications, and can be used in various applications such as hard cord materials, adhesive materials, sealing materials, highly reflective materials, and ultraviolet light absorbing materials. Can be used.

Claims (24)

The inorganic composite oxide fine particles are represented by the following formula (1), an organosilicon compound A or a partially hydrolyzed product thereof, and the following formula (2). The boiling point at 1 atm is 120 ° C. or less. Surface-modified inorganic composite oxide fine particles obtained by surface modification with a certain organosilicon compound B or a partial hydrolyzate thereof and having a carbon atom content of 2 to 10% by weight.
Si (OR ¹ ) _4-n (OH) _n (1)
R ² ₃ Si (OR ³ ) (2)
(In the formula, R ¹ is an unsubstituted or substituted hydrocarbon group having 1 to 4 carbon atoms, which may be the same or different, and n is an integer of 0 to 3.
R ² is an unsubstituted or substituted hydrocarbon group having 1 to ² carbon atoms, which may be the same or different, and R ³ is a hydrogen atom or an unsubstituted or substituted carbon group having 1 to 3 carbon atoms. It is a substituted hydrocarbon group. )   The surface of the inorganic composite oxide fine particle is represented by the following general formula (1), an organosilicon compound A or a partially hydrolyzed product thereof, and the following general formula (2). Surface-modified inorganic composite oxide fine particles coated with the following organosilicon compound B or a partial hydrolyzate thereof, and having a carbon atom content of 2 to 10% by weight.
      Si (OR ¹ ) _4-n (OH) _n       ... (1)
      R ² _Three Si (OR ^Three (2)
(Wherein R ¹ Is an unsubstituted or substituted hydrocarbon group having 1 to 4 carbon atoms, which may be the same or different from each other, and n is an integer of 0 to 3.
  R ² Is an unsubstituted or substituted hydrocarbon group having 1 to 2 carbon atoms, which may be the same or different from each other, and R ^Three Is a hydrogen atom or an unsubstituted or substituted hydrocarbon group having 1 to 3 carbon atoms. ) The surface-modified inorganic composite oxide fine particles according to claim 1 or 2 , wherein the inorganic composite oxide fine particles have a core-shell structure. The inorganic composite oxide fine particles are
(1) A core particle characterized by being an inorganic composite oxide containing at least one metal element selected from the group consisting of titanium, zirconium, niobium, cerium and zinc, and silicon, and (2) the core particle 4. The surface modification according to claim 3 , comprising a shell layer made of an oxide containing at least one metal element selected from the group consisting of zirconium, aluminum and antimony and / or silicon. Inorganic composite oxide fine particles. The surface-modified inorganic composite according to claim 3 or 4 , further comprising at least one metal element selected from the group consisting of tin, tungsten, antimony and indium as the metal element constituting the core particle. Oxide fine particles. The inorganic composite oxide fine particles include composite oxide fine particles containing at least one metal element selected from the group consisting of titanium, zirconium, niobium, cerium, aluminum, antimony, tin, tungsten, indium and zinc, and silicon, or surface modified inorganic composite oxide fine particles according to claim 1 or 2, characterized in that a composite oxide particles comprising at least two of the metal element. The surface-modified inorganic composite oxide fine particles according to any one of claims 1 to 6 , wherein the inorganic composite oxide fine particles have an average particle diameter of 5 to 200 nm. Wherein represents the weight of the organic silicon compound A or a partial hydrolyzate thereof and M _A, the weight of the organic silicon compound B or a partial hydrolyzate thereof expressed as M _B, the weight of the inorganic composite oxide particles as M ₁ represents the weight ratio _{(M a + M B) /} M 1 is the surface modified inorganic composite oxide fine particles according to any one of claims 1 to 7, characterized in that in the range of 0.4 to 2.0 . The addition amount of the organosilicon compound A or a partial hydrolyzate thereof per surface area of the inorganic composite oxide fine particles is in the range of 0.5 to 6.0 mg / m ² , and the organosilicon compound B or the partial hydrolyzate thereof. decomposition products, surface modification according to any one of claims 1 to 8, the addition amount per surface area of the inorganic composite oxide fine particles being in the range of 1.5~4.5mg / m ² Inorganic composite oxide fine particles. A surface-modified inorganic composite oxide fine particle dispersion comprising the surface-modified inorganic composite oxide fine particles according to any one of claims 1 to 9 and a dispersion medium. 11. The organic solvent dispersion containing surface-modified inorganic composite oxide fine particles according to claim 10 , wherein the dispersion medium is an organic solvent or an organic solvent and water. A method for producing the surface-modified inorganic composite oxide fine particles according to claim 1 or 2 ,
(1) preparing an aqueous dispersion of the inorganic composite oxide fine particles;
(2) adding the organosilicon compound A or a partial hydrolyzate thereof to the aqueous dispersion to modify the surface of the inorganic composite oxide fine particles;
(3) replacing the water contained in the dispersion obtained in the step (2) with an organic solvent,
(4) A step of further modifying the surface of the inorganic composite oxide fine particles by adding the organosilicon compound B or a partial hydrolyzate thereof to the organic solvent dispersion obtained in the step (3).
(5) A method for producing surface-modified inorganic composite oxide fine particles, comprising a step of removing the organic solvent from the organic solvent dispersion obtained in the step (4). In the step (4), in claim 12, characterized in that repeated the organic silicon compound B or 10 times the operation of the addition of the partial hydrolyzate surface modification of the inorganic composite oxide fine particles A method for producing the surface-modified inorganic composite oxide fine particles as described. It includes the step (6) of further modifying the surface of the fine particles by adding the organosilicon compound B or a partial hydrolyzate thereof to the surface-modified inorganic composite oxide fine particles obtained in the step (5). The method for producing surface-modified inorganic composite oxide particles according to claim 12 or 13 . It represents the weight of the inorganic composite oxide fine particles with M _1, the weight of the organic silicon compound A or a partial hydrolyzate thereof represented as M _A, the weight of the organic silicon compound B or a partial hydrolyzate thereof and M _B When expressed, the surface-modified inorganic composite oxide fine particles according to any one of claims 12 to 14 , wherein a value of (M _A + M _B ) / M ₁ is in a range of 0.4 to 2.0. Manufacturing method. The addition amount of the organosilicon compound A or a partial hydrolyzate thereof per surface area of the inorganic composite oxide fine particles is in the range of 0.5 to 6.0 mg / m ² , and the organosilicon compound B or the partial hydrolyzate thereof. decomposition products, surface modification according to any one of claims 12 to 15, the addition amount per surface area of the inorganic composite oxide fine particles being in the range of 1.5~4.5mg / m ² A method for producing fine inorganic composite oxide particles. Surface modified inorganic oxide optical substrate coating solution comprising an organic solvent dispersion containing fine particles of any of claims 1-9. The coating liquid for optical substrate according to claim 17 , which is a coating liquid for forming a hard coat layer film. The coating liquid for an optical substrate according to claim 17 , which is a coating liquid for forming a primer layer film. The optical substrate coating liquid according to any one of claims 17 to 19 , wherein the optical substrate is a plastic lens. A coating film comprising the surface-modified inorganic composite oxide fine particles according to claim 1 . It has a plastic substrate and a coating film which is a primer layer and / or a hard coat layer containing the surface-modified inorganic composite oxide fine particles according to any one of claims 1 to 9 formed on the substrate. The base material with a coating film characterized. The base with a coating film according to claim 22 , wherein each of the hard coat layer and the primer layer contains 100 parts by volume of the surface-modified inorganic oxide fine particles and 200 to 1000 parts by volume of a matrix component. Wood. The base material with a coating film according to claim 22 or 23 , further comprising an antireflection film on the surface of the hard coat layer opposite to the plastic base material side.