JP2000204301A - Coating solution for forming covered film and lens made of synthetic resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coating solution for forming a covered film capable of forming a highly refractive index film having colorless transparency and high refractive index, and further excellent in resistance to hot water, resistance to sweat, weatherability, light resistance, abrasion resistance, wear resistance, impact resistance, flexibility and dyeability, and adhesiveness with a base material. SOLUTION: This coating solution contains complex oxide fine particles and a matrix. The complex oxide fine particles are composed of (i) nucleus particles and (ii) a covering layer covering the nucleus particles and each of the nucleus particles (i) is composed of an oxide of titanium and tin, or a complex solid solution oxide having a rutile-type structure, then the covering layer (ii) is composed of a complex oxide of a silicon oxide and an oxide of zirconium and/or aluminum.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coating solution for forming a film, a substrate with a film, and a lens made of a synthetic resin. More specifically, the present invention relates to a colorless and transparent resin having a high refractive index, hot water resistance, sweat resistance, weather resistance, and the like. Light resistance, scratch resistance, abrasion resistance, impact resistance,
A coating solution for forming a high-refractive-index coating on the surface of a substrate, which has excellent flexibility and dyeing properties, and also has excellent adhesion to substrates such as glass and plastic, and a high-refractive-index hard coat film. The present invention relates to a synthetic resin lens having no formed interference fringes.

[0002]

BACKGROUND OF THE INVENTION Conventionally, the purpose of forming a hard coat film having a refractive index equal to the refractive index of a substrate on the surface of a substrate such as transparent plastic or glass has been developed.
Various methods for forming a high refractive index hard coat film have been proposed.

In this connection, diethylene glycol bis (allyl carbonate) resin lenses are particularly superior in safety, workability, fashionability, etc. as compared with glass lenses. With the development of, it is spreading rapidly. However, since the refractive index of diethylene glycol bis (allyl carbonate) resin is 1.50, which is lower than that of a glass lens, when diethylene glycol bis (allyl carbonate) resin is used for a myopic lens, the outer peripheral portion becomes thicker than a glass lens. Have. For this reason, in the field of spectacle lenses made of synthetic resin, technical development for reducing the thickness of the lens with a high refractive index resin material has been actively performed. For this reason, for example, Japanese Unexamined Patent Application Publication No.
JP, JP-A-63-46213, JP-A-2-2
Japanese Patent Publication No. 70859 and the like propose a high refractive index resin material having a refractive index of 1.60 or more.

[0004] Incidentally, plastic spectacle lenses have the disadvantage that they are easily scratched. Therefore, a silicon-based hard coat film is usually provided on the surface of the plastic lens.

However, if a similar hard coat film is formed on a lens using a high refractive index resin having a refractive index of 1.54 or more, interference fringes due to a difference in the refractive index between the resin lens and the coating film occur, which causes poor appearance. There was something.

To solve this problem, Japanese Patent Publication No.
JP-A-54331 and JP-B-63-37142 disclose the colloidal dispersion of fine particles of silicon dioxide used in a coating solution for forming a silicon-based film (hereinafter, the coating solution for forming a film may be referred to as a coating composition). A proposal has been made in which a high refractive index Al, Ti, Zr, Sn, and Sb inorganic oxide fine particles are replaced by a colloidal dispersion. Further, as such a colloidal dispersion, Japanese Patent Application Laid-Open No. Hei 1-301517 discloses a method for producing a composite sol of titanium dioxide and cerium dioxide. Furthermore, JP-A-2-264902 discloses Ti and Ce composite inorganic oxide fine particles, and JP-A-3-68901 treats a composite oxide of Ti, Ce and Si with an organosilicon compound. It is disclosed that the obtained fine particles are used in a coating composition.

Further, Japanese Patent Application Laid-Open No. H5-2102 discloses fine composite oxide particles of Ti and Fe or Ti and Fe.
There is disclosed a hard coat film containing composite oxide fine particles of Si and Si.

However, the coating compositions described in JP-B-61-54331 and JP-B-63-37142 have not always produced satisfactory hard coat films. For example, Al, Zr, Sn, S
When the colloidal dispersion of oxide fine particles b) is used as a coating composition for a high-refractive-index resin lens having a refractive index of 1.54 or more, compared with a silicon-based coating composition,
The degree of interference fringes after curing can be improved. However, A
When 1 or Sb oxide fine particles were used, the refractive index as a coating film was limited, so that it was impossible to completely suppress interference fringes for a lens substrate of 1.60 or more. . This is because Al or Sb oxide fine particles have a high refractive index of 1.60 or more as a simple substance, but when they are generally used as a coating material, an organosilicon compound, an epoxy resin, or the like is used as a film forming component. This is because, due to the mixing, the filling rate decreases, and the refractive index of the coating film becomes lower than that of the base lens. Also,
Since the dispersibility of the oxide particles of Zr or Sn is unstable, a transparent coating could not be obtained when used in large amounts.

On the other hand, when a colloidal dispersion of fine particles of Ti oxide is used as a coating composition, TiO ₂ itself has a higher refractive index than the oxides of Al, Zr, Sn and Sb. There is an advantage that a film having a refractive index of about 1.60 or more can be formed, and at the same time, the range of selection of the refractive index of the film can be widened. However, since TiO ₂ has extremely low weather resistance, in a film formed from a coating composition containing TiO ₂ , the organosilicon compound and the epoxy resin component of the film forming component are decomposed, and furthermore, the TiO ₂ on the resin substrate surface There has been a problem that the durability of the film is insufficient due to deterioration of the film or the like. There is also a problem that the formed coating film has poor adhesion to the substrate.

A coating composition containing fine particles of a composite oxide of titanium dioxide and cerium dioxide described in JP-A-2-264909 and JP-A-3-68901, or JP-A-5-2102. In the coating composition containing the composite oxide fine particles of titanium dioxide and iron oxide described above, compared to the case of using titanium dioxide alone, although the weather resistance is improved, it does not necessarily have a satisfactory weather resistance. Was. Further, the coating film obtained from the coating composition containing such composite oxide fine particles has a problem of coloring.

Under these circumstances, the inventors of the present application have
JP-A-8-48940 discloses that titanium, silicon, zirconium and / or titanium which can be suitably used for a lens substrate having a refractive index of 1.54 or more (specifically, 1.59 to 1.66) is used.
Alternatively, a coating liquid for forming a coating film containing composite oxide fine particles composed of an aluminum oxide and a matrix has been proposed.

Incidentally, in recent years, JP-A-9-71580, JP-A-9-110797, and JP-A-9-25
No. 5781 proposes a lens substrate (optical material) obtained from an esbisulphide compound having a high refractive index of 1.67 to 1.70 and an Abbe number exceeding 30.

For this reason, there is also a demand for the development of a coating liquid for forming a film which can be suitably used for such a lens substrate having a high refractive index and a high Abbe number.

[0014]

SUMMARY OF THE INVENTION The object of the present invention is to solve the above-mentioned problems in the prior art and to provide a coating liquid for forming a coating film which can be suitably used for a substrate having a high refractive index and a high Abbe number. It has been made, it is colorless and transparent, has a high refractive index, and further has hot water resistance, sweat resistance, weather resistance, light resistance,
Provided is a coating liquid for forming a coating capable of forming a high refractive index film having excellent scratch resistance, abrasion resistance, impact resistance, flexibility and dyeability, and also excellent adhesion to a substrate. It is intended to be. In addition, the present invention can form a colorless, transparent, and durable hard coat film on the surface of a resin lens having a refractive index of 1.54 or more, and can prevent interference fringes from being generated by the hard coat film. Another object of the present invention is to provide a thin synthetic resin lens having a thin coating liquid and a high refractive index hard coat film formed thereon.

[0015]

SUMMARY OF THE INVENTION A coating solution for forming a film according to the present invention comprises:
(A) a composite oxide fine particle, comprising (B) a matrix, wherein the composite oxide fine particle comprises (i) a core particle and (ii) a coating layer covering the core particle, and (i) the core particle Is composed of an oxide of titanium and tin, and is a composite solid solution oxide having a rutile structure; and (ii) the coating layer is composed of a composite oxide of silicon oxide and an oxide of zirconium and / or aluminum. It is characterized by.

In the composite oxide fine particles (A), (i)
The amount of titanium and tin contained in the core particles is determined by converting titanium to TiO ₂ and converting tin to SnO _2.
O ₂ / SnO ₂ (weight ratio) is in the range of 1 / 9.9~14 / 1, (ii ) silicon contained in the coating layer, the amount of zirconium and aluminum, in terms of silicon SiO ₂ When zirconium is converted to ZrO ₂ and aluminum is converted to Al ₂ O ₃ , SiO ₂ / ZrO ₂ (weight ratio) is in the range of 50/50 to 99/1, or A
l ₂ O ₃ / SiO ₂ (weight ratio) is 0.01 / 25 to 0.2
It is preferably in the range of 0/25.

In the coating solution for forming a film according to the present invention, the core particles are composed of a composite solid solution oxide containing an oxide of titanium and tin and an oxide of silicon and / or zirconium, and have a rutile structure. It may be something.

(I) The core particles are composed of a composite solid solution oxide containing an oxide of titanium and tin and an oxide of silicon and / or zirconium, and are composed of a composite solid solution oxide having a rutile structure. Is preferred.

Further, the synthetic resin lens according to the present invention comprises:
A hard coat layer formed from a coating solution containing the composite solid solution oxide is provided on the surface of a lens substrate having a refractive index of 1.54 or more. An antireflection film made of an inorganic substance may be laminated on the surface of the hard coat layer.

As such a lens substrate, a sulfur-containing material obtained by reacting one or more mercapto compounds represented by the following formulas (1) and / or (2) with one or more polyisocyanates: Urethane resin:

[0021]

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A copolymer obtained from the monomer represented by the formula (3) and another polymerizable monomer:

[0023]

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(Where R ⁵ is a hydrogen atom or a methyl group, R ⁶ is a CH ₂ CH ₂ group or CH ₂ CH (OH) CH
₂ group, X is a halogen atom exclusive of a hydrogen atom or a fluorine atom, m and n are both m + n is from 0 8
Is an integer selected from the integers ), A copolymer obtained from a (meth) acrylic monomer and / or a vinyl monomer having a sulfur atom and an aromatic ring as a constituent element and another polymerizable monomer. And a polymer of an episulfide compound having a cyclic skeleton:

[0025]

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(Wherein, X represents S or O, and the number of S is, on average, 5 with respect to the sum of S and O constituting the three-membered ring)
0% or more. ) Are preferably used.

[0027]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the present invention will be described specifically.

First, the coating liquid for forming a high refractive index film according to the present invention will be described.

The coating solution for forming a high refractive index film according to the present invention comprises a matrix and composite oxide fine particles. [(A) Composite oxide fine particles] The composite oxide particles used in the present invention comprise (i) a core particle and (ii) a coating layer covering the core particle.

(I) Core Particles Core particles are composite solid solution oxides composed of oxides of titanium and tin and having a rutile structure. Such a core particle has a crystal particle size of about 10
It is composed of a rutile type single crystal particle of 150 ° (Debye-Scherrer method) or a polycrystalline substance of rutile type single crystal particle (such a structure is called a rutile type structure).

The average particle diameter of the core particles is about 1 to 100 nm.
Is desirably within the range.

X-ray diffraction diagrams of the composite solid solution oxide having such a rutile structure are shown in FIGS.

The weight ratio of Ti and Sn constituting the core particles is as follows:
In terms of oxide, TiO ₂ / SnO ₂ as 1 / 9.9
To 14/1, preferably 1/5 to 10/1. When the content is within the range of TiO ₂ / SnO ₂ , the core particles become a composite solid solution oxide having a high refractive index and a rutile structure having high crystallinity. A suitable coating solution for forming a film is obtained. Also,
When the weight ratio of TiO ₂ / SnO ₂ is less than 1 / 9.9, a coating liquid having a sufficient refractive index cannot be obtained, and when the weight ratio of TiO ₂ / SnO ₂ exceeds 14/1, the crystallinity is high. A composite solid solution oxide having a rutile structure may not be easily obtained, and may be a mixed crystal composite solid solution oxide of a rutile type and an anatase type.

The core particles may contain an oxide of silicon and / or zirconium together with an oxide of titanium and tin. The amount of silicon oxide in the core particles was 95 / (weight ratio of (TiO ₂ + SnO ₂ ) / SiO ₂ )
It is preferably in the range of 5 to 75/25, preferably 90/10 to 80/20. Also, the amount of zirconium oxide in the core particles is (TiO ₂ + SnO ₂ + SiO ₂ ) /
(ZrO ₂ ) 90/10 to 99.5 / 0.5 by weight ratio,
Preferably, it is in the range of 95/5 to 99.3 / 0.7. When zirconium oxide is contained in this range, composite oxide fine particles having excellent weather resistance can be obtained. Although the refractive index of the composite solid solution oxide having such a rutile structure varies depending on the crystallinity and composition, and further depending on the measurement method, it usually shows a value in the range of 2.2 to 2.7, and Al, Zr, It is higher than the refractive index of Sn and Sb oxides.

The core particles containing titanium as a main component are 230 to 3
It absorbs and activates 20 nm ultraviolet rays, which may cause a decrease in weather resistance. However, by combining zirconium oxide with the core particles, activation of the core particles containing titanium as a main component is prevented. The weather resistance can be improved. By compounding zirconium oxide and / or silica, the stability and weather resistance of titanium oxide can be improved more than in the conventional case of compounding cerium oxide. In addition, by using zirconium oxide, the composite fine particles can be made more colorless.

(Ii) Coating Layer The coating layer is composed of a composite oxide composed of a silicon oxide and an oxide of zirconium and / or aluminum.

Specifically, the coating layer comprises (1) an oxide (composite) of silicon and zirconium, (2) an oxide (composite) of silicon and aluminum, and (3) an oxide of silicon, zirconium and aluminum. (Composite) oxide means composite oxide fine particles corresponding to any of the following.

The SiO ₂ / ZrO ₂ weight ratio in such a coating layer is preferably in the range of 99/1 to 50/50, and the Al ₂ O ₃ / SiO ₂ weight ratio is preferably 0.01 / 25 to 50/50.
It is preferably in the range of 0.20 / 25.

Composite Oxide Fine Particles The composite oxide fine particles used in the present invention include core particles (X).
And the weight ratio (X / Y) of the coating layer (Y) is 100 / 0.5.
~ 100/200, preferably 100/1 ~ 100/1
Desirably, it is in the range of 00.

In the composite oxide fine particles used in the present invention,
At least a part of the composite oxide may be in a hydrated state or a state having a hydroxyl group.

The average particle size of the composite oxide fine particles used in the present invention is 1 to 800 nm, preferably 1 to 300 n.
m is desirable. In particular, when the base material used is a synthetic resin lens, the thickness is preferably in the range of 1 to 60 nm.

When the average particle size exceeds 800 nm,
When the average particle diameter is less than 1 nm, the obtained coating has insufficient hardness, poor scratch resistance and abrasion resistance, and has a refractive index of less than 1 nm. Tend not to be sufficiently high.

Such composite oxide fine particles are represented by (A)
It is preferable that the composite oxide fine particles are prepared by the following steps (a) to (c).

(A) Hydrogen peroxide is added to a hydrous titanic acid gel or sol to dissolve the hydrous titanic acid, and a tin compound and optionally a silicon compound and / or zirconium are added to the obtained aqueous solution of peroxotitanic acid. Adding a compound and then heating to prepare a dispersion of core particles composed of a composite solid solution oxide having a rutile structure, (b) a silicon compound, a zirconium compound and / or an aluminum compound in the dispersion of core particles Is added, followed by heating to form a coating layer on the surface of the core particles to prepare a sol in which the composite oxide particles are dispersed, and (c) a step of further heating the sol in which the composite oxide is dispersed.

The details of the steps (a) to (c) will be described later.

The surface of the above-mentioned composite oxide fine particles is preferably treated with an organosilicon compound or an amine. When the surface of the composite oxide fine particles is modified by treating it with an organosilicon compound or an amine, the dispersion state of the composite oxide fine particles in the coating solution containing the composite oxide fine particles and the matrix is stabilized over a long period of time. In addition, even when an ultraviolet curable resin is used as the matrix, the dispersed state of the composite oxide fine particles in the coating liquid becomes stable. Further, the composite oxide fine particles whose surface is modified with an organosilicon compound or an amine have improved reactivity and affinity with the matrix, and as a result, a coating solution containing the composite oxide fine particles surface-treated with these. Is higher in hardness, transparency, abrasion resistance, adhesion to a substrate, abrasion resistance, and flexibility than a coating obtained from a coating solution containing complex oxide fine particles not subjected to surface treatment. Also excellent in dyeability. Further, the affinity between the composite oxide fine particles in the coating solution and the solvent is further improved as compared with the case where the composite oxide particles are not surface-treated.

When the surface of the composite oxide fine particles is modified with an organosilicon compound, a known organosilicon compound known as a silane coupling agent can be used.
The type is appropriately selected according to the type of the matrix and the solvent used in the coating solution according to the present invention.

[0048] At this time, as the organic silicon compound used, the _{formula: R 3 SiX R 2 SiX 2} RSiX 3 SiX 4 organosilicon compound represented by and the like. (In the formula, R is an organic group having an alkyl group, a phenyl group, a vinyl group, a methacryloxy group, a mercapto group, an amino group, and an epoxy group, and X is a hydrolyzable group.) Specifically, trimethylsilane, Examples include dimethylphenylsilane, dimethylvinylsilane, dimethylsilane, diphenylsilane, methylsilane, phenylsilane, tetraethoxysilane, and the like. When performing the treatment with the organosilicon compound, the treatment may be performed without decomposing the hydrolyzable group, or may be performed by hydrolysis. Further, after the treatment, the state in which the hydrolyzed organosilicon compound has reacted with the —OH group of the fine particles is preferable, but there is no problem even if a part remains.

Examples of the amine compound include ammonium or an alkylamine such as ethylamine, triethylamine, isopropylamine and n-propylamine;
Examples include aralkylamines such as benzylamine, alicyclic amines such as piperidine, and alkanolamines such as monoethanolamine and triethanolamine.

In order to modify the surface of the composite oxide fine particles with an organosilicon compound or an amine compound, for example, the composite oxide fine particles are mixed in an alcohol solution of these compounds, and a predetermined amount of water and, if necessary, a catalyst are mixed. After the addition, the mixture may be left at room temperature for a predetermined time or may be subjected to a heat treatment.

The surface of the composite oxide fine particles can also be modified by adding a hydrolyzate of these compounds and composite oxide fine particles to a mixed solution of water and alcohol and subjecting the mixture to heat treatment.

The amount of the organosilicon compound or amine compound used at this time is appropriately selected according to the amount of hydroxyl groups present on the surfaces of the composite oxide fine particles. [(B) Matrix] The matrix contained in the coating solution according to the present invention is represented by the following formula: R ¹ R ² _a Si (OR ³ ) _3-a (where R ¹ is a hydrocarbon having 1 to 6 carbon atoms) An organic group having a group, vinyl group, methacryloxy group, mercapto group, amino group or epoxy group, R ² is a hydrocarbon group having 1 to 4 carbon atoms, R ^{3 is} a hydrocarbon group having 1 to 4 carbon atoms, an alkoxyalkyl group Or an acyl group, a represents 0 or 1.), an organic silicon compound represented by the formula:
At least one selected from a partial condensate of the hydrolyzate and a mixture thereof (hereinafter, referred to as component (B)) is used.

As the organosilicon compound represented by the above formula, specifically, methyltrimethoxysilane, ethyltriethoxysilane, methyltriethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, phenylmethyldimethoxysilane, vinyl Trimethoxysilane, vinyltriethoxysilane, vinyltris (β-
Methoxyethoxy) silane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3 , 4-epoxycyclohexyl) ethyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ
-Aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane and the like. These may be used alone or as a mixture of two or more. Further, it is preferable to use them after hydrolysis in the presence of an acid in the absence of a solvent or in a polar organic solvent such as an alcohol.
Further, it may be mixed with the composite oxide fine particles after hydrolysis, or may be hydrolyzed after mixing with the composite oxide fine particles. The proportion of the coating component derived from the organosilicon compound of the component (B) in the cured coating is 1%.
A range of 0 to 90% by weight is suitable. If the content is less than 10%, the adhesion between the substrate and the coating is reduced, which is not preferable. If the content is more than 90% by weight, a coating having a high refractive index may not be obtained.

In the present invention, as the matrix,
General paint resins such as acrylic resins, melamine resins, ultraviolet curable resins, urethane resins, and phosphagen resins can also be used. A high refractive index coating formed on a substrate using a coating liquid containing such a coating resin,
Colorless, transparent, excellent in weather resistance, dyeability, flexibility,
In addition, the refractive index of the coating can be made equal to the refractive index of the substrate. Further, the coating liquid for forming a coating film using the above-mentioned coating resin as a matrix can be suitably used as a coating liquid for forming a primer film which absorbs an impact between a plastic lens and a hard coat film. When used as such a primer film, a urethane-based resin is particularly preferably used as a coating resin. [Other Coating Solution Components] The coating solution according to the present invention contains at least one of the following components (C) to (G) together with the (A) composite oxide particles and the (B) matrix. May be. Component (C) The component (C) is at least one hydrolyzate and / or partial condensate of a tetrafunctional organosilicon compound represented by the formula: Si (OR ⁴ ) ₄ (where R ⁴ is Represents a hydrocarbon group having 1 to 8 carbon atoms, an alkoxyalkyl group or an acyl group).

The organosilicon compound represented by the above formula is used for the purpose of easily adjusting the refractive index of the formed film while maintaining the transparency of the film, and further increasing the curing speed of the film after application of the coating solution. Used. By using the component (C), the refractive index of the cured film can be appropriately adjusted according to the refractive index of the base lens, and even if the content of the composite oxide is reduced to some extent, the adhesion of the antireflection film is reduced. Sex can be obtained.
Further, when a tetrafunctional organosilicon compound is blended in the coating composition as the component (C), the curing speed at the time of forming the film is increased, and particularly, a base material such as a sulfur-containing urethane-based resin from which the dye is easily removed from the fabric lens. When a film is formed on the surface, the amount of stain loss can be suppressed, and the change in color tone of the dyed lens before and after the film is formed can be reduced.

Specific examples of such a tetrafunctional organosilicon compound include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetrabutoxysilane, tetraphenoxysilane, tetraacetoxysilane, and tetraallyloxy. Silane, tetrakis (2-methoxyethoxy) silane, tetrakis (2-ethylbutoxysilane), tetrakis (2
-Ethylhexyloxy) silane and the like. These may be used alone or as a mixture of two or more.
Further, these are preferably used after hydrolysis in the absence of a solvent or in an organic solvent such as an alcohol in the presence of an acid.

The proportion of the component (C) in the cured film is preferably less than 50% by weight. When the proportion of the component (C) is 50% by weight or more, cracks may be easily formed in the cured film. Component (D): The component (D) is composed of Si, Al, Sn, Sb,
Oxide fine particles of one or more elements selected from Ta, Ce, La, Fe, Zn, W, Zr and In, or Si,
Al, Sn, Sb, Ta, Ce, La, Fe, Zn,
Composite oxide microparticles composed of oxides of two or more elements selected from W, Zr, In and Ti (however, T
Composite oxide fine particles composed of any one of i, Sn, and Si and an oxide of Zr and / or Al are excluded. ).

The component (D) is used to improve the refractive index of the obtained coating film, adhesion to a substrate, dyeability, heat resistance and the like.

Specifically, the component (D) is SiO 2_Two,
Al_TwoO_Three, SnO_Two, Sb_TwoO_Five, Ta _TwoO_Three, CeO_Two,
La_TwoO_Three, Fe_TwoO_Three, ZnO, WO_Three, ZrO_Two, I
n_TwoO_ThreeOf inorganic oxide particles in water or organic solvent
Those dispersed in an id shape are used. Also, these acids
Composed of oxides containing two or more kinds of constituent elements
Composite oxide particles are colloidal in water or organic solvents
A dispersed one can also be used. In any case
In this case, the particle diameter is preferably about 1 to 30 μm. Naoko
The amount of component (D) used depends on the desired film performance.
More appropriately selected.

Further, in order to enhance the dispersion stability of these fine particles in a coating solution, those obtained by treating the surfaces of fine particles with an organosilicon compound or an amine compound in the same manner as described above can be used. Component (E): Component (E) is a polyfunctional epoxy compound,
One or more compounds selected from polyhydric alcohols, polycarboxylic acids and polycarboxylic anhydrides. The component (E) is used for improving the dyeability of the formed film or improving the durability.

Examples of the polyfunctional epoxy compound include diglycidyl ethers of difunctional alcohols such as (poly) ethylene glycol, propylene glycol, polypropylene glycol, neopentyl glycol, catechol, resorcinol, and alkylene glycol, glycerin, trimethylolpropane and the like. And di- or triglycidyl ethers of trifunctional alcohols.

Examples of the polyhydric alcohols include difunctional alcohols such as (poly) ethylene glycol, propylene glycol, polypropylene glycol, neopentyl glycol, catechol, resorcinol, and alkylene glycol; trifunctional alcohols such as glycerin and trimethylolpropane; Polyvinyl alcohol and the like.

Examples of the polycarboxylic acid include malonic acid, succinic acid, adipic acid, azelaic acid, maleic acid, orthophthalic acid, terephthalic acid, fumaric acid, itaconic acid, oxaloacetic acid and the like.

Examples of the polycarboxylic anhydride include succinic anhydride, maleic anhydride, itaconic anhydride, 1.2-dimethylmaleic anhydride, and phthalic anhydride.

The proportion of the coating component derived from the component (E) in the cured coating is preferably less than 40% by weight. When the amount of the component (E) is 40% by weight or more, the adhesion between the cured film and the antireflection film formed thereon may be reduced. (F) component: The hindered amine compound of the F component is used for the purpose of improving the dyeability of the formed film.
As the F component, specifically, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, 1- [2- [3- (3,5-di-t-
Butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3,5-di-t-butyl-4-hydroxyphenyl)
Propionyloxy] -2,2,6,6-tetramethylpiperidine, 8-benzyl-7,7,9,9-tetramethyl-3-octyl-1,
3,8-triazaspiro [4,5] undecane-2,4-dione, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 8-
Acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro [4,5] undecane-2,4-dione, dimethyl succinate 1- (2-hydroxyethyl)- 4-hydroxy-2,2,6,
6-tetramethylpiperidine polycondensate, poly [[(6- (1,1,3,
(3-tetramethylbutyl) amino-1,3,5-triazine-2,4-
Diyl] [2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]｝, N, N′-bis ( 3-aminopropyl) ethylenediamine / 2,4-bis [N-butyl- (1,2,2,6,6-pentamethyl-4-piperidyl) amino] -6-chloro-1,3,5-triazine condensate , 2- (3,5-di-t-butyl-4-hydroxybenzyl) -2
bis- (1,2,2,6,6-pentamethyl-4-piperidyl) -n-butylmalonate;

The upper limit of the amount of the component (F) used is preferably 3% by weight or less based on the total solids in the coating solution. , Warm water resistance and the like may be reduced. Component (G): The component (G) is at least one selected from amines, amino acids, metal acetylacetonates, metal salts of organic acids, perchloric acids, salts of perchloric acids, acids and metal chlorides. Compound. This component (G) is a curing catalyst used for accelerating the curing of silanol or epoxy groups. By using such a component (G), the curing speed of the coating film can be increased.

Specific examples of such a component (G) include:
Amines such as n-butylamine, triethylamine, guanidine, biguanide, amino acids such as glycine, metal acetylacetonates such as aluminum acetylacetonate, chromium acetylacetonate, titanyl acetylacetonate, cobalt acetylacetonate, sodium acetate, naphthene Metal salts of organic acids such as zinc acid, cobalt naphthenate, zinc octylate and tin octylate; perchloric acids such as perchloric acid, ammonium perchlorate and magnesium perchlorate or salts thereof, hydrochloric acid, phosphoric acid, and nitric acid , Acids such as paratoluenesulfonic acid,
Or SnCl ₂ , AlCl ₃ , FeCl ₃ , TiCl ₄ ,
Examples thereof include metal chlorides which are Lewis acids such as ZnCl ₂ and SbCl ₃ .

The type and amount of the component (G) are appropriately selected and used depending on the composition of the coating solution and the like. The upper limit of the amount used is 5 to the solid content in the coating solution.
It is desirable to use it in an amount of less than 10% by weight.

Further, in order to improve the coating properties and the performance of the coating film formed on the substrate from the coating liquid, a small amount of a surfactant, an antistatic agent, UV absorbers, antioxidants, disperse dyes, oil-soluble dyes,
Fluorescent dyes, pigments, photochromic compounds, thixotropic agents and the like may be added. Solvent: In the coating solution for forming a film according to the present invention, each of the above components is dispersed or dissolved in water. As a solvent, to adjust the solid content concentration contained in the coating solution, or to adjust the surface tension, viscosity, evaporation rate, etc. of the coating solution,
An organic solvent may be used.

Specific examples of the organic solvent used include alcohols such as methanol, ethanol, and isopropyl alcohol; cellosolves such as methyl cellosolve and ethyl cellosolve; glycols such as ethylene glycol; and methyl acetate and ethyl acetate. Esters, diethyl ether, ethers such as tetrahydrofuran, acetone, ketones such as methyl ethyl ketone, halogenated hydrocarbons such as dichloroethane, toluene,
Aromatic hydrocarbons such as xylene, carboxylic acids and
N, N-dimethylformamide and the like. These solvents may be used as a mixture of two or more kinds.

It is desirable that the coating liquid for forming a film according to the present invention contains the composite oxide fine particles (A) in an amount of 0.25 to 63% by weight, preferably 1 to 40% by weight. . (B) The matrix is 0.5 to 66.5.
%, Preferably 2 to 40% by weight.

Method for Producing Coating Solution for Forming Film The coating solution for forming a film according to the present invention is prepared by using fine powdery or sol-like composite oxide fine particles prepared by various methods. It is preferable to prepare a sol in which sol-shaped composite oxide fine particles are dispersed in water and / or an organic solvent, and to prepare a coating solution using this sol.

The method for preparing such a composite oxide sol is not particularly limited, but (a) a step of preparing a core particle dispersion liquid, (b) a step of preparing a composite oxide particle dispersion sol, and (c) a sol heating step It is desirable to prepare by. (a) Step of preparing core particle dispersion First, a gel or sol of hydrated titanium oxide is prepared by a conventionally known method. The gel of hydrated titanium oxide can be obtained, for example, by neutralizing an aqueous solution of a titanium salt such as titanium chloride or titanium sulfate by adding an alkali, and washing the resultant. The hydrated titanium oxide sol can be obtained by passing an aqueous solution of a titanium salt through an ion exchange resin to remove anions, or hydrolyzing a titanium alkoxide. The specific surface area of the hydrated titanium oxide particles in the gel or sol obtained at this time is preferably 150 m ² / g or more, more preferably 155 m ² / g or more.

The term "hydrated titanium oxide" as used herein is a generic term including a hydrate of titanium oxide, a titanium hydroxide (titanium hydroxide) or hydrous titanic acid obtained by the above method.

The specific surface area of the hydrated titanium oxide particles in the gel or sol can be determined by drying the gel or sol,
Is a value measured by the BET method for the powder baked for 16 hours.

Next, to the hydrated titanium oxide sol or gel obtained as described above, hydrogen peroxide is added to dissolve the hydrated titanium oxide to form a uniform aqueous solution (hereinafter sometimes referred to as a titanic acid aqueous solution). Prepare. At this time, a hydrated titanium oxide sol and a hydrated titanium oxide gel may be mixed and used. In preparing the aqueous solution of titanic acid, it is preferable to heat or stir to about 50 ° C. or higher as necessary.

If the concentration of the hydrated titanium oxide is too high, it takes a long time to dissolve the hydrated titanium oxide, and further, an undissolved gel may precipitate or the resulting aqueous solution may become viscous. Therefore, the TiO ₂ concentration is about 10
Desirably, it is less than about 5% by weight, preferably about 5% by weight or less.

The amount of hydrogen peroxide added is H ₂ O ₂ / T
The iO ₂ weight ratio is 1 or more, preferably 2 to 6. With such a weight ratio of H ₂ O ₂ / TiO ₂ , the hydrated titanium oxide can be completely dissolved. Note that H
_{If the 2} O ₂ / TiO ₂ weight ratio is less than 1, the hydrated titanium oxide may not be completely dissolved, and an unreacted gel or sol may remain. When the weight ratio of H ₂ O ₂ / TiO ₂ is increased, the dissolution of the hydrated titanium oxide is accelerated, and the reaction is completed in a short time. However, even if excessive hydrogen peroxide is used, unreacted hydrogen peroxide is used. Only remains in a large amount in the system, resulting in poor economic efficiency.

When hydrogen peroxide is used in such an amount,
The hydrated titanium oxide dissolves completely in 0.5 to 20 hours.

Next, a tin compound is added to the obtained aqueous solution of titanic acid.

Examples of the tin compound include tin salts such as tin chloride and tin nitrate, stannates such as potassium stannate, and oxides;
A hydroxide is used.

These tin compounds are usually added in the form of an aqueous solution, but may be added in the form of a powder. Moreover,
A gel or sol of tin oxide hydrate may be added.

The addition amount of the tin compound is selected from the range of TiO ₂ / SnO ₂ of 1 / 9.9 to 14/1, preferably 2 / 9.9 to 10/1 in terms of weight ratio in terms of oxide.

When the weight ratio is less than 1 / 9.9, a sufficient refractive index cannot be obtained, and when the weight ratio is higher than 14/1, a composite solid solution oxide having a rutile structure having high crystallinity can be easily obtained. May not be obtained and may become anatase type titanium oxide, which is not preferable.

The mixed solution to which the tin compound is added is then heated to a temperature of about 50 ° C. or higher, preferably 80 ° C. or higher, and hydrolyzed to obtain a sol of a composite solid solution oxide (nuclear particle dispersion sol) having a desired rutile structure. ) Is obtained.

The composite solid solution oxide refers to a crystalline oxide composed of a plurality of components in which the metal atoms of the crystal lattice are in a state of being substituted with each other (ie, in a solid solution state).
A bonding model in which such metal atoms are in a mutually substituted state is illustrated below.

OM1-OM2-O-M1-OM2-OM-OM3-OM-OM1-OM2-OM-M3-OM4-O (M1, M2, M3 and M4 Are a plurality of metal atoms different from each other, and the bonding order is not limited to the above. The method for mixing the aqueous solution of titanic acid and the tin compound is not particularly limited, and a predetermined amount of the aqueous solution of titanic acid and the tin compound are mixed at once. Alternatively, a method in which a titanic acid aqueous solution and a part of a tin compound are first mixed and heated, and then the remaining titanic acid aqueous solution may be added.

The mixing time of the tin compound does not necessarily have to be after the hydrated titanium oxide is dissolved in the hydrogen peroxide, but may be mixed in a gel or sol stage before being dissolved in the hydrogen peroxide. Further, they may be mixed at the time of preparing a gel or sol of hydrated titanium oxide. In short, when the titanic acid aqueous solution is heated and hydrolyzed, the tin compound described above may be present in the reaction system.

In the present invention, a silicon compound or a zirconium compound may coexist in a mixed aqueous solution of a titanic acid aqueous solution and a tin compound, followed by heating and hydrolysis.
When a silicon compound or a zirconium compound coexists, the stability of the composite solid solution oxide sol having a rutile structure can be increased, and the hardness of the finally obtained coating film may be increased in some cases.

When a silicon compound or a zirconium compound is added, the addition amount of the silicon compound or the zirconium compound is (TiO ₂ + Sn
In O ₂₎ / SiO ₂ weight ratio, 95 / 5-75 / 25, preferably in the range of 90 / 10-80 / 20 or (Ti,
O ₂ + SnO ₂ + SiO ₂ ) / (ZrO ₂ ) weight ratio of 90
/ 10 to 99.5 / 0.5, preferably 95/5 to 99.
The silicon compound is preferably an alkali metal silicate such as water glass, or a silicic acid solution obtained by dealkalizing an aqueous alkali metal silicate solution, or silica gel or silica sol. Examples of the zirconium compound include inorganic salts, organic salts, oxides, hydroxides, and alkoxides.

The mixed solution to which the silicon compound or zirconium compound has been added is then heated to a temperature of about 50 ° C. or higher, preferably 80 ° C. or higher, and hydrolyzed to form a composite having a rutile structure containing silicon or zirconium. A sol of solid solution oxide (nuclear particle dispersion sol) is obtained.

There are no particular restrictions on the timing of addition and mixing method of the silicon compound and / or zirconium compound, and a predetermined amount of the silicon compound and / or zirconium compound can be added before the addition of the tin compound.
The addition may be carried out simultaneously or later, or after the addition of the tin compound and heating at a high temperature. At that time, they may be mixed at once, or may be divided and partially mixed one by one.

The particles dispersed in the sol of the composite solid solution oxide having the rutile structure thus obtained have a crystal particle size of about 10 to 150 ° (Debye.
The sol is composed of rutile-type single crystal particles according to the Scherrer method) or polycrystals thereof and in which extremely uniform particles having an average particle diameter in the range of about 1 to 100 nm are dispersed. (b) Composite oxide particle dispersion sol preparation step A zirconium compound and / or an aluminum compound and a silicon compound are added in predetermined amounts to the core particle dispersion sol of the composite solid solution oxide having a rutile structure obtained as described above. Mix. Examples of the silicon compound used in this case include silica gel, silica sol, silicic acid solution, alkali metal silicate, silicon alkoxide, and the like.
Zirconium compounds and aluminum compounds are inorganic salts,
It is preferably selected from organic salts, oxides, hydroxides and alkoxides. These are preferably used in the form of an aqueous solution or slurry. For example, when describing a zirconium compound, an aqueous solution in which a hydrated oxide of zirconium obtained by adding hydrogen peroxide to a hydrated oxide of zirconium obtained by hydrolyzing a zirconium salt is preferably used.

While maintaining the resulting mixture of the composite solid solution oxide dispersion sol having a rutile structure and the zirconium compound and / or the aluminum compound and the silicon compound alkaline, the mixture is kept at 80 ° C. or higher, preferably 85 to 85 ° C. When heated to 98 ° C., a sol in which the surface of the composite solid solution oxide core fine particles having a rutile structure is dispersed with at least one oxide selected from zirconium and aluminum and the silicon oxide coated with silicon oxide is obtained. Can be

Further, for example, a mixture of the composite solid solution oxide dispersion sol having a rutile structure and a silicon compound is kept alkaline and heated to 80 ° C. or higher to disperse the composite oxide fine particles coated with silicon oxide. After preparing the prepared sol, at least one compound selected from a zirconium compound and an aluminum compound is added to the sol and heated to 80 ° C. or more, the surface of the composite solid solution oxide core fine particles having a rutile structure is oxidized. A sol is obtained in which fine particles of a complex oxide, which are coated with silicon and whose surface is coated with at least one oxide selected from zirconium oxide and aluminum oxide, are dispersed. (c) heat treatment step the sol in which the composite oxide fine particles thus obtained are dispersed,
Usually, it is heated to 80 to 300 ° C, preferably to 85 to 200 ° C.

By heating, a more stable sol can be obtained.

The coating liquid according to the present invention can be obtained by mixing the composite oxide fine particles obtained as described above with a matrix and, if necessary, other components.

In the case of using the heat-treated composite oxide fine particle dispersion sol obtained as described above as it is in producing the coating solution according to the present invention, the composite oxide fine particle dispersion sol may be used as necessary. Concentration may be performed, the solvent of the composite oxide fine particle dispersion sol may be replaced with an organic solvent to form an organoform, and the mixed solution after the solvent replacement may be further concentrated.

At this time, the composite oxide fine particle dispersion sol may be directly dispersed in a predetermined organic solvent or the like, or may be dispersed after the solvent is replaced with an organic solvent in advance.

The amount of the composite oxide fine particles contained in the coating liquid according to the present invention is determined by converting titanium contained in the composite oxide fine particles into TiO ₂ , converting silicon into SiO _2, and converting zirconium. Is converted to ZrO ₂ , and when aluminum is converted to Al ₂ O ₃ , the total converted weight thereof is preferably 5 to 900 parts by weight, more preferably 10 to 500 parts by weight, based on 100 parts by weight of the matrix. .

In producing the coating solution for forming a coating film according to the present invention, it is possible to use the composite oxide fine particles which have been washed and dried and taken out as a powder after the above-mentioned steps (a) to (c). Good.

Coated Substrate Next, the coated substrate according to the present invention will be described.

The coated substrate according to the present invention has a substrate and a high-refractive-index coating or a high-refractive-index hard coating formed on the surface of the substrate from the coating solution according to the present invention.

As the substrate, various substrates made of glass, plastic, and the like are used. Specifically, various optical lenses such as spectacle lenses and cameras, various display element filters, looking glasses, window glasses, automobiles, etc. And light covers used in automobiles and the like.

The thickness of the film formed on the surface of the substrate varies depending on the use of the substrate with the film.
0 μm is preferred.

The substrate with a coating according to the present invention is obtained by applying and drying the coating solution according to the present invention on the surface of the substrate as described above by a dip pink method, a spinner method, a spray method or a flow method. And then heating the coating thus formed on the surface of the substrate to a temperature equal to or lower than the heat-resistant temperature of the substrate. In particular, for a lens substrate having a heat deformation temperature of less than 100 ° C., a spinner method that does not require fixing the lens substrate with a jig is preferable. When the substrate for forming a film is a resin lens, it is preferable to form a film by applying a coating solution on the substrate and then heating and drying at 40 to 200 ° C. for several hours.

When an ultraviolet curable resin is used as a matrix component of the coating liquid, the coating liquid is applied to the surface of the substrate, and then the ultraviolet light having a predetermined wavelength is applied to the surface of the substrate to which the coating liquid is applied. The coated substrate according to the present invention can be manufactured by a method of irradiating and curing.

Further, in producing the coated substrate according to the present invention, the surface of the substrate is previously treated with an alkali, an acid or a surfactant for the purpose of improving the adhesion between the substrate, for example, the lens substrate and the coating. Treatment, polishing treatment with inorganic or organic fine particles, primer treatment or plasma treatment may be performed.

The substrate with a coating according to the present invention includes:
A primer film may be provided between the substrate and the hard coat layer.

In the case of a plastic lens using an optical material having a high refractive index, the thickness of the lens is also reduced, and a hard coat layer (film) as described above is formed on the surface. A multi-coat layer is formed. In this multi-coat layer forming process, the plastic lens substrate is distorted, and the lens may be easily broken due to impact such as dropping. Therefore, a flexible primer film that absorbs the impact between the plastic lens and the hard coat film is formed. Is provided.

If the refractive index of the primer film is not equal to the refractive index of the substrate, interference fringes may occur. However, in the coating solution for forming a film according to the present invention, (B) the matrix component is used as described above. When a coating liquid for forming a coating containing a coating resin is used, a primer film having a refractive index similar to that of the substrate can be formed.

When such a primer film is formed, the coating liquid is applied by the method described above, and then the coating is cured.

Synthetic Resin Lens Next, the synthetic resin lens according to the present invention will be described.

The synthetic resin lens according to the present invention contains the above-mentioned component (B) as a composite oxide fine particle and a matrix on the surface of a resin lens substrate having a refractive index of 1.54 or more. It is characterized by having a high refractive index film (hard coat film) formed from a coating solution containing at least one of components (C) to (G) (hereinafter, referred to as a coating composition of the present invention).

In order to obtain a thin synthetic resin lens having excellent appearance and durability, the refractive index of the lens substrate is preferably 1.54 or more, and furthermore, transparency, dyeing property, heat resistance, water absorption and bending strength are preferred. As a base lens which can satisfy desired characteristics in terms of impact resistance, weather resistance, workability, and the like, a sulfur-containing urethane-based, (meth) acrylic, or episulfide-based lens base material is preferable. -71580,
JP-A-9-110979, JP-A-9-25578
A lens substrate obtained from an esbisulphide compound having a high refractive index of 1.67 to 1.70 and having an Abbe number of more than 30 disclosed in JP-A-1 is preferred.

Further, on such a hard coat layer,
A single-layer or multi-layer antireflection film made of inorganic material may be provided.
In addition, by forming an anti-reflection film,
The function as a spectacle lens can be improved
Can be further improved. As inorganic substances, S
iO, SiO_Two, Si_ThreeN_Four, TiO_Two, ZrO_Two, Al_TwoO
_Three, MgF_Two, Ta_TwoO_ThreeThin film type such as vacuum evaporation method
An antireflection film can be formed by a forming method.

Further, when a transparent film and an antireflection film are provided on the hard coat layer, a primer film is provided between the substrate and the hard coat layer to improve the impact resistance and the adhesion. be able to. At this time, the primer film can be formed by a coating liquid for forming a film containing a resin for a coating material, preferably a resin for a urethane-based coating material, as a matrix.

Hereinafter, the lens substrate used in the synthetic resin lens according to the present invention will be described in detail.

In the present invention, a sulfur-containing urethane resin lens can be used as the lens substrate.

The sulfur-containing urethane-based resin lens comprises a polyisocyanate compound and the following formula (1):

[0121]

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4-mercaptomethyl-3,6-dithio-1,8-octadithiol and / or the following formula (2):

[0123]

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A mixed solution of a thiol compound of pentaerythritol tetra (3-mercaptopropionate) represented by the following formula is injected into a mold composed of a glass mold and a gasket, and is heated and polymerized. The refractive index of such a sulfur-containing urethane resin is usually from 1.58 to 1.58.
It is in the range of 1.66.

Examples of the polyisocyanate compound include tolylene diisocyanate, diphenylmethane diisocyanate, polymeric diphenylmethane diisocyanate, tolidine diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate, isophorodiisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, Methyl xylylene diisocyanate, 2,5-bis (isocyanatomethyl) bicyclo
[2,2,1] heptane, 2,6-bis (isocyanatomethyl)
Bicyclo [2,2,1] heptane, 3,8-bis (isocyanatomethyl) tricyclo [5,2,1,0] ^2,6 ] -decane, 3,9-bis (isocyanatomethyl) tricyclo [5,2 , 1,0] ^2,6 ] -decane, 4,8-bis (isocyanatomethyl) tricyclo
[5,2,1,0] ^2,6] - decane, 4,9-bis (isocyanatomethyl) tricyclo [5,2,1,0] ^2,6] - decane, polyisocyanate compounds such as dimer acid diisocyanate And allophanate-modified, buret-modified, and isocyanurate-modified compounds of these compounds. These compounds may be used alone or as a mixture of two or more. Further, the use ratio of the polyisocyanate compound and the thiol compound is such that the NCO / SH (functional group) molar ratio is usually 0.5 to
3.0, preferably in the range of 0.5 to 1.5. In addition, an internal release agent, a chain extender, a crosslinking agent, a light stabilizer, an ultraviolet absorber, an antioxidant, for example, a coloring agent such as a disperse dye and an oil-soluble dye, and a reaction catalyst may be appropriately added to the raw material. it can. By providing a cured film made of the coating composition of the present invention on the sulfur-containing urethane-based resin lens substrate thus obtained, the appearance is good, the various film durability is excellent, the refractive index and the number of Abbe are high, and the impact strength is high. A spectacle lens having a strong characteristic can be provided.

In the present invention, a (meth) acrylic resin lens represented by the following formula (3) can be used as the lens substrate.

[0127]

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(Where R ⁵ is a hydrogen atom or a methyl group, R ⁶ is a CH ₂ CH ₂ group or CH ₂ CH (OH) CH
₂ group, X is a halogen atom exclusive of a hydrogen atom or a fluorine atom, m and n are both m + n is from 0 8
Is an integer selected from the integers The refractive index of such (meth) acrylic resin is usually
It is in the range of 1.58 to 1.66.

The (meth) acrylic monomer represented by the formula (3) includes 2,2-bis (3,5-dibromo-4- (meth) acryloyloxyethoxyphenyl) propane,
2,2-bis (4- (meth) acryloyloxyethoxyphenyl) propane, 2,2-bis [4- (β-hydroxy-γ-
(Meth) acryloyloxyethoxyphenyl) propoxyphenyl] propane.

Other polymerizable monomers used simultaneously include aromatic monofunctional vinyl monomers such as styrene, chlorostyrene, bromostyrene and α-methylstyrene, divinylbenzene and its chlorine / bromine-substituted derivatives. Aromatic polyfunctional vinyl monomer, methyl (meth) acrylate, ethyl (meth) acrylate,
Monofunctional (meth) acrylate monomers such as 2-hydroxyethyl (meth) acrylate, glycidyl methacrylate, benzyl methacrylate, phenoxy methacrylate, and cyclohexyl methacrylate; ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, Multifunctional (meta) such as triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, and di (meth) acrylate of butanediol ) Acrylic monomers, and further thiolation of thiol compounds represented by the above formula (1) or (2), pentaerythritol, tetra (mercaptoacetate), etc. Thing, and the like. Two or more of these monomers can be used simultaneously.

At the time of molding, a composition comprising 20 to 80% by weight of the (meth) acrylic monomer represented by the above formula (3) and 80 to 20% by weight of another polymerizable monomer is mixed with a glass mold and a gasket. Into a mold consisting of
Perform thermal polymerization and / or photopolymerization. At this time, general thermal polymerization initiators such as organic peroxides and azo compounds and / or
Or a general photopolymerization initiator such as acetephenone-based, benzoin-based, benzophenone-based, a crosslinking agent, a light stabilizer, an ultraviolet absorber, an antioxidant, and a coloring agent such as a disperse dye, an oil-soluble dye, and a pigment are appropriately added. can do. By providing a cured film made of the coating composition of the present invention on the (meth) acrylic resin lens substrate thus obtained, it has good appearance, excellent durability of various films, and high refractive index and excellent bending strength. A spectacle lens having features can be provided.

In the present invention, a copolymer obtained from a (meth) acrylic monomer and / or a vinyl monomer having a sulfur atom and an aromatic ring as constituents and another polymerizable monomer is used as a lens substrate. Can also be used. Examples of the (meth) acrylic monomer and / or vinyl monomer having a sulfur atom and an aromatic ring as constituents include compounds represented by the following formulas (7) and (8).

[0133]

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(Here, R ⁷ represents a hydrogen atom or a methyl group, and R ⁸ and R ⁹ each represent an alkylene group having 1 to 9 carbon atoms.) Other polymerizable monomers include the above (meth) acrylic monomers. Aromatic monofunctional vinyl monomer, aromatic polyfunctional vinyl monomer, monofunctional (meth) acrylate monomer, polyfunctional (meth) acrylic monomer used in obtaining a copolymer containing a derived polymer unit Or a thiol compound or the like.

At the time of molding, 20 to 80% by weight of a (meth) acrylic monomer and / or vinyl monomer having a sulfur atom and an aromatic ring as constituents, and 80 to 20% by weight of another polymerizable monomer. Is injected into a mold composed of a glass mold and a gasket, and subjected to thermal polymerization and / or photopolymerization. At this time, organic peroxide,
General thermal polymerization initiators such as azo compounds and / or general photopolymerization initiators such as acetephenone-based, benzoin-based, benzophenone-based, cross-linking agents, light stabilizers, ultraviolet absorbers, antioxidants, disperse dyes, Colorants such as oil-soluble dyes and pigments can be appropriately added. By providing a cured film made of the coating composition of the present invention on the resin lens substrate thus obtained, spectacles having characteristics that the appearance is good, the durability of various films is excellent, and the refractive index is high and the heat resistance is excellent. Lens can be provided.

In the present invention, a polymer of an episulfide compound having two or more structures represented by the following formula (4) can be used as the lens substrate.

[0137]

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(In the formula, X represents S or O, and the number of S is 50% or more on average with respect to the total of S and O constituting the three-membered ring.) ), The refractive index of a polymer of an episulfide compound having two or more structures is usually 1.6.
The range is 7 to 1.71, and the Abbe number is in the range of 35 to 40.

As such an episulfide compound, JP-A-9-110797 and JP-A-9-7
One represented by the following formula (5) or the following formula (6) described in Japanese Patent No. 1580 can be used.

[0140]

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(In the formula, m represents an integer of 1 to 6, and n represents 0
Represents an integer of from 4 to 4. X represents S or O, and the number of S is an average of 50 with respect to the sum of S and O constituting the three-membered ring.
% Or more) As such an episulfide compound represented by the formula (5),

[0142]

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And the like.

[0144]

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Examples of the episulfide compound represented by the formula (6) include C (CH ₂ SE _PS ) ₄ ,

[0146]

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[0147] _{CH 3 C (CH 2 SE PS} ) 3, CH 3 CH 2 C
(CH ₂ SE _PS ) _{3 and the} like.

Examples of the episulfide compound having two or more structures represented by the formula (4) include 1,3-bis (β-epithiopropylthio) cyclohexane and 1,4-bis (β-epithiopropylthio) Cyclohexane, 1,3-bis (β-epithiopropylthiomethyl) cyclohexane, 1,4-bis (β-epithiopropylthiomethyl) cyclohexane,
Bis [4- (β-epithiopropylthio) cyclohexyl] methane, 2,2, -bis [4- (β-epithiopropylthio) cyclohexyl] propane, bis [4- (β-epithiopropylthio) cyclohexyl An aliphatic skeleton such as sulfide, 2,5-bis (β-epithiopropylthio) -1,4-dithiane is used as an episulfide compound, 1,3-bis (β-epithiopropylthio) benzene, 1,4- Bis (β-epithiopropylthiomethyl) benzene, 1,3-bis (β-epithiopropylthiomethyl) benzene, 1,4-bis (β-epithiopropylthiomethyl) benzene, bis [4- (β- Epithiopropylthio) phenyl] methane, 2,2, -bis [4- (β-
Epithiopropylthio) phenyl] propane, bis [4-
(Β-epithiopropylthio) phenyl] sulfide,
An aromatic skeleton such as 2,5-bis (β-epithiopropylthio) binifer is used as an episulfide compound,

[0149]

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(Where E _PS is β as in the above equation (4).
-An epithiopropyl group or a glycidyl group,
It is _{- (CH 2 CH 2 S)} - represents, Z is a hydrogen atom, a carbon number 1
5 alkyl group or, - (CH ₂₎ represents an _m SY _n E _PS, U represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms,
m represents an integer of 1 to 5 and n represents an integer of 0 to 4) The episulfide compound having two or more structures represented by the formula (4) is polymerized by heating to produce a resin for an optical material. You. At this time, the heat polymerization is preferably carried out in the presence of a curing catalyst. As the curing catalyst, amines, phosphines, mineral acids, Lewis acids, organic acids, silicic acids, tetrafluoroboric acid and the like are used. . Such a catalyst is generally used in an amount of 0.0001 to 1.0 mol based on 1 mol of the episulfide compound having two or more structures represented by the formula (4).

Furthermore, in the present invention, a copolymer of an episulfide compound having two or more structures represented by the formula (4) and a compound capable of reacting with the episulfide compound can be used as the lens substrate. . Examples of the compound capable of reacting with the episulfide compound having two or more structures represented by the formula (4) include an epoxy compound and a compound represented by the formula (4)
An episulfide compound having one structure represented by: , Polyphenols, amines, amides and the like.

When an episulfide compound having two or more structures represented by the formula (4) is polymerized and cured to obtain a resin for an optical material, a known antioxidant, ultraviolet absorber, material, A release agent may be added.

The structure represented by the above formula (4) is
When molding an optical material such as a lens from an episulfide compound having at least two compounds, usually, an episulfide compound having at least two structures represented by the formula (4) is mixed with a catalyst, a comonomer, and various additives. After pouring into a glass or metal mold and heating to promote the polymerization and curing reaction,
This is done by removing it from the mold. The heating temperature is usually -10 to 160C, preferably -10 to 140C, and the curing time is usually 0.1 to 100 hours, preferably 1 to 48 hours. After curing, the obtained optical material is further heated at a temperature of 50 to 150 ° C. for 10 minutes.
Annealing may be performed for about a minute to about 5 hours to remove distortion of the optical material.

[0154]

According to the present invention, the refractive index of the film formed on the substrate is changed by changing the ratio of the matrix-forming component to the composite oxide fine particles in the coating solution and the composition of the composite oxide. Can be controlled freely. When the refractive index of the coating is made equal to the refractive index of the substrate in this way, interference fringes caused by the difference between the two refractive indexes can be eliminated. On the other hand, when the refractive index of the coating is very high compared to the refractive index of the substrate, the gloss of the surface of the substrate becomes very high. Such a film having a very high refractive index formed on the substrate using the coating solution for forming a film according to the present invention contains titanium oxide as a main component in the composite oxide fine particles in the film. Since it has an excellent ultraviolet shielding effect and also has a high gloss, it is suitable as a paint film and / or a top coat film for automobiles and the like. Further, the film formed on the substrate using the coating solution for forming a film according to the present invention is colorless and transparent, and has good adhesion to the substrate, weather resistance, light resistance, flexibility and dyeability. It is suitable for providing various optical lenses such as spectacle lenses and cameras, various display element filters, and looking glasses, etc. because of its excellent surface hardness and excellent scratch resistance and abrasion resistance. It is. Then, a high-refractive-index hard coat layer for forming a multilayer antireflection film having a colorless, transparent, and high surface hardness on the surface of a base material such as a looking glass, a window glass, and various display element filters is used for forming a film according to the present invention. When formed with a coating liquid, the contents can be clearly seen through the substrate with the hard coat film. If such an antireflection film is formed on various display element surfaces, a fluorescent lamp or the like is not reflected on these display element surfaces, so that the image is clear and eyestrain is eliminated.

Further, the high-refractive-index film formed on the substrate by using a coating solution containing a coating resin as a matrix-forming component is colorless and transparent, and is excellent in weather resistance, dyeability and flexibility. In addition, since the refractive index of the coating can be made equal to the refractive index of the base material as described above, a coating such as a plastic film having a hard coating film (cured coating) and a transparent coating or an anti-reflection coating formed on a high refractive index coating. It can be suitably used as a primer film of a coated substrate, and the obtained coated substrate has excellent impact resistance.

Further, by providing a cured film formed from the coating composition of the present invention on a synthetic resin lens substrate having a refractive index of 1.54 or more, interference fringes appear or the cured film is colored. Thus, a lightweight and thin synthetic resin lens excellent in weather resistance and various durability can be provided.

By laminating an antireflection film made of an inorganic material on the cured film, surface reflection can be suppressed and the function as a spectacle lens can be further improved.

[0158]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

[0159]

Example 1 (1) Preparation of core particle dispersion sol (preparation liquid A) 93.665 kg of a titanium tetrachloride solution having a concentration of 7.75% by weight in terms of TiO ₂ and ammonia water having a concentration of 15% by weight After mixing and neutralizing with 36.295 kg, the mixture was washed with pure water to obtain 54.579 kg of hydrous titanic acid. The obtained hydrous titanic acid was dried at 110 ° C., and then calcined at 280 ° C. for 18 hours.
It was 0 m2 / g.

To 7.519 kg of this hydrous titanic acid, 11.429 kg of a hydrogen peroxide solution having a concentration of 35% by weight and 11.5 kg of water
After adding 9.148 kg and heating and melting at 80 ° C. for 2 hours, 21.9 kg of water was added to prepare an aqueous solution of polyperoxytitanic acid.

To the obtained aqueous solution of polyperoxytitanic acid, 8.906 kg of an aqueous solution of potassium stannate having a concentration of 1.02% by weight was further added so as to become 90.9 g in terms of SnO ₂ , and then sufficiently stirred. After that, a deionization treatment was performed with a cation exchange resin.

After the deionization treatment, 27 in terms of SiO ₂ was calculated.
1671 g of silica sol was added to 2.7 g, and 25.6 kg of water was added so that the solid concentration became 1% by weight. Then, the mixture was placed in a 200 L autoclave, and stirred at 175 ° C. for 18 hours. Heat and hydrolyze,
The obtained colloid solution is concentrated, and a solid particle dispersion sol (preparation liquid A) of a composite solid solution oxide composed of titanium, tin, and silicon and having a rutile-type structure and having a solid content of 10% by weight is prepared.
3.15 kg were obtained. The average particle size of the core particles was 7 nm. FIG. 1 shows an X-ray diffraction pattern of the core particles. (2) Preparation of zirconium compound solution 26.3 kg of zirconium oxychloride was added to 474 kg of pure water, and 15% by weight of aqueous ammonia was added to an aqueous solution of zirconium oxychloride having a concentration of 2% by weight when converted to ZrO _2. Was added to obtain a slurry of zirconia gel having a pH of 8.5. This slurry was filtered and washed to obtain a cake having a concentration of 10% by weight when converted to ZrO ₂ .

[0163] Pure water 1.55kg was added to the cake 170 g, further it was made alkaline by addition of aqueous KOH, which was dissolved by heating the addition of concentration 35% by weight of aqueous hydrogen peroxide 340 g, ZrO ₂ 3.4 kg of a zirconium hydrogen peroxide solution (preparation liquid B) having a concentration of 0.5% by weight when converted to was prepared. (3) Preparation of Silicic Acid Solution Commercially available water glass was diluted with pure water and then dealkalized with a cation exchange resin to prepare a silicic acid solution having a SiO ₂ concentration of 2% by weight. (4) Preparation of Composite Oxide Particle Dispersion Sol To 1 kg of the prepared solution A, 4 kg of pure water was added to make the solid content concentration 2% by weight, and then heated to 90 ° C.
g and 2.65 kg of a silicic acid solution were gradually added, followed by heat treatment in an autoclave at 175 ° C. for 18 hours, and further concentrated to obtain a light milky white transparent composite oxide fine particle having a solid content concentration of 20% by weight. An aqueous dispersion sol was prepared.

Then, the water of this dispersion medium was placed in methanol.
And concentrated until the solid content concentration becomes 20% by weight.
The average particle diameter is 7 nm and the core particles are TiO._Two/ SnO_Two(weight
Ratio) is 11, (TiO_Two+ SnO_Two) / SiO_Two(Weight ratio)
Is 8/2, and SiO of the coating layer is _Two/ ZrO_Two3.118, nuclear
Particles / core particles having a coating layer (weight ratio) of 100 / 7.012
Of organometallic composite oxide particles having rutile structure
(A1) was obtained. (5) Preparation of a coating solution for forming a hard coat film Ethyl cell solvent was placed in a flask equipped with a stirrer.
15 g, γ-glycidoxypropyltrimethoxysilane
47.26 g and 4.56 g of tetramethoxysilane were stirred.
While adding 12.9 g of 0.05N hydrochloric acid.
And stirred for 30 minutes. Next, silicon-based surfactant
0.07
g and aged at 5 ° C for 24 hours to form a matrix-forming component
Was prepared.

To the liquid containing the matrix-forming component, 231 g of the above-mentioned organosol (A1) was added, and 1 g of aluminum acetylacetonate was further added. After sufficiently stirring, the mixture was aged at 0 ° C. for 48 hours to form a hard coat film. A coating solution (A1) was prepared.

[0166]

Example 2 In Example 1, 13.6 k of the prepared solution B was used.
g, 10.6 kg of silicic acid solution (core particles / coating layer (weight ratio) =
An organosol (A2) of composite oxide fine particles having an average particle diameter of 8 nm and having core particles having a rutile structure was obtained in the same manner as in Example 1 except that 100/23) was used.

Using this sol A2, a coating solution (A2) for forming a hard coat film was prepared in the same manner as in Example 1.

[0168]

Example 3 A rutile-type structure was prepared in the same manner as in Example 1, except that the amount of the aqueous solution of potassium stannate having a concentration of 1% by weight was changed to 100 kg when preparing a dispersion sol of core particles. A sol (dispersion liquid A ') of a composite solid solution oxide having core particles was obtained. The average particle diameter of the core particles was 2 nm, and the TiO ₂ / SnO ₂ (weight ratio) of the core particles was 1.0. FIG. 2 shows an X-ray diffraction pattern of the obtained core particles.

Using the thus obtained core particle dispersion sol (preparation solution A ′), an organosol (A3) of composite oxide fine particles was obtained in the same manner as in Example 1. The obtained sol A3
And a coating solution (A3) for forming a hard coat film was prepared in the same manner as in Example 1.

[0170]

Example 4 A rutile-type structure was prepared in the same manner as in Example 1 except that the amount of the aqueous solution of potassium stannate having a concentration of 1% by weight was changed to 900 kg when preparing a nuclear particle dispersion sol. A sol (dispersion liquid A ″) of a composite solid solution oxide having the following composition was obtained. The average particle diameter of the core particles was 2 nm, and the TiO ₂ / SnO ₂ (weight ratio) of the core particles was 1/9. The X-ray diffraction diagram of the obtained core particles is shown in FIG.

Using the nucleus particle-dispersed sol (preparation solution A ″) thus obtained, an organosol (A4) of composite oxide fine particles was obtained in the same manner as in Example 1. The obtained sol A3
And a coating solution (A4) for forming a hard coat film was prepared in the same manner as in Example 1.

[0172]

[Example 5] In Example 1, 36.6 k
g, except that the silicic acid solution was 28.35 kg (core particles / coating layer (weight ratio) = 100/75).
An organosol (A5) of composite oxide fine particles having an average particle diameter of 9 nm and core particles having a rutile structure was obtained. Using this sol A5, a coating solution (A5) for forming a hard coat film was prepared in the same manner as in Example 1.

[0173]

Example 6 In Example 1, the mixing ratio (T
iO ₂ + SnO ₂ ) / SiO ₂ (weight ratio) is 86.5 / 1
Except that the mixing ratio of the silica sol was changed so as to be 3.5, a core particle dispersion sol of a composite solid solution oxide having a rutile structure (preparation liquid A ″ ′) was obtained in the same manner as in Example 1. The average particle diameter of the obtained core particles was 7 nm.

Using the thus obtained core particle dispersion sol (preparation solution A ″ ′), an organosol (A6) of composite oxide fine particles was obtained in the same manner as in Example 1. The resulting organosol (A6) ) Was prepared in the same manner as in Example 1 to prepare a coating solution (A6) for forming a hard coat film.

[0175]

Example 7 In Example 1, as a preparation liquid A, an aqueous solution of potassium stannate was added to an aqueous solution of polyperoxytitanic acid, deionized with an ion exchange resin, and silica sol was added thereto. In the same manner as in Example 1 except that 1040 g of Preparation Liquid B was added, a core particle dispersion sol of a composite solid solution oxide composed of titanium, tin, silicon and zirconium and having a rutile structure (Preparation Liquid A ″ ″) was obtained. The average particle size of the core particles was 7 nm.

Next, this core particle dispersion sol (prepared solution)
A ")) in the same manner as in Example 1,
An organosol (A′1) of particles was obtained. The resulting organo
The composite oxide fine particles contained in the sol (A′1) have core particles
Has a rutile structure, and has an average particle diameter of 7 nm;
Core particle TiO_Two/ SnO_Two(Weight ratio) is 11, (TiO_Two
+ SnO_Two) / SiO_Two(Weight ratio) is 8/2, (TiO_Two+
SnO_Two+ SiO_Two) / ZrO _Two(Weight ratio) is 136.36 /
In 5.2, the SiO of the coating layer_Two/ ZrO_Two(Weight ratio) is 3.1
18. The core particle / coating layer (weight ratio) is 100 / 7.0
Was.

Using the organosol (A'1) thus obtained, a coating solution (A'1) for forming a hard coat film was prepared in the same manner as in Example 1.

[0178]

Example 8 Preparation solution A of Example 1 was mixed with preparation solution B, a silicic acid solution, and 40 g of a sodium aluminate aqueous solution having a concentration of 0.3% by weight in terms of Al ₂ O _3. As in Example 1, the core particles have a rutile structure,
TiO ₂ / SnO ₂ (weight ratio) 11 of core particles, (TiO ₂
+ SnO ₂ ) / SiO ₂ (weight ratio) is 8/2, and the coating layer has a SiO ₂ / ZrO ₂ (weight ratio) of 3.118 and SiO ₂
/ Al ₂ O ₃ (weight ratio) is 53 / 0.12, the core particle / coating layer (weight ratio) is 100 / 7.0, and the average particle diameter is 7 nm. I got

Using this organosol (B1), a coating liquid (B1) for forming a hard coat film was prepared in the same manner as in Example 1.

[0180]

Embodiment 9 The coating layer had an SiO ₂ / Al ₂ O ₃ (weight ratio) of 5
In the same manner as in Example 8 except that the amount of the sodium aluminate aqueous solution was changed so as to be 3 / 0.4, the core particles had a rutile structure, and the core particles were TiO ₂ / SnO ₂ (weight ratio). )
Is 11 and (TiO ₂ + SnO ₂ ) / SiO ₂ (weight ratio) is 8
/ 2, the coating layer SiO ₂ / ZrO ₂ (weight ratio) is 3.11
8, SiO ₂ / Al2 O3 (weight ratio) of 53 / 0.4, core particle / coating layer is (weight ratio) 100 / 7.04, and an average particle diameter of 7nm composite oxide fine particles of the organosol (B2 ) Got.

Using this organosol (B2), a coating liquid (B2) for forming a hard coat film was prepared in the same manner as in Example 1.

[0182]

Example 10 The organosol prepared in Example 1 (A
1) 1000 g was placed in a reaction vessel, and after adding 56 g of methyltrimethoxysilane and 20 g of pure water, the mixture was heated to 50 ° C. and stirred for 18 hours. Then, after removing unreacted methyltrimethoxysilane, the mixture was concentrated to a solid content of 20%.
An organosol (A7) of fine particles of the surface-treated composite oxide was obtained with the use of methyltrimethoxysilane in an amount of 5% by weight.

Using this organosol (A7), a coating solution (A7) for forming a hard coat film was prepared in the same manner as in Example 1.

[0184]

Example 11 An organosol of composite oxide fine particles in which core particles surface-treated with vinyltrimethoxysilane had a rutile structure in the same manner as in Example 10 except that methyltrimethoxysilane was replaced with vinyltrimethoxysilane. A8) was obtained.

Using this organosol (A8), a coating solution (A8) for forming a hard coat film was prepared in the same manner as in Example 1.

[0186]

Example 12 In Example 10, the organosol (A
Instead of 1), the organosol prepared in Example 2 (A
In the same manner as in Example 10, except that 2) was used and tetraethoxysilane was used instead of methyltrimethoxysilane, the core particles surface-treated with tetraethoxysilane had an organosol of composite oxide fine particles having a rutile structure ( A
9) got.

Using this organosol (A9), a coating solution (A9) for forming a hard coat film was prepared in the same manner as in Example 1.

[0188]

Example 13 A surface treatment was performed with γ-glycidoxypropyltrimethoxysilane in the same manner as in Example 12, except that γ-glycidoxypropyltrimethoxysilane was used instead of tetraethoxysilane. An organosol (A10) of composite oxide fine particles was obtained.

Using this organosol (A10), a coating solution (A10) for forming a hard coat film was prepared in the same manner as in Example 1.

[0190]

Example 14 The organosol prepared in Example 8 (B
An organosol (B3) of composite oxide fine particles surface-treated with methyltrimethoxysilane was obtained in the same manner as in Example 10 except that 1) was used in place of the organosol (A1).

Using this organosol (B3), a coating solution (B3) for forming a hard coat film was prepared in the same manner as in Example 1.

[0192]

Example 15 The organosol prepared in Example 11 (A
8) Collect 1000g in a rotary evaporator,
Then, 4000 g of methylcellosolve was added, followed by distillation under reduced pressure to obtain a methylcellosolve dispersion sol (A11) having a solid content of 20% by weight.

The resulting methyl cellosolve dispersion sol (A1
Using 1), a coating solution (A11) for forming a hard coat film was prepared in the same manner as in Example 1.

[0194]

Example 16 In Example 7, the amount of the preparation liquid B was changed to 14
Except that it was 0 g, titanium, tin,
Nuclear particle dispersion sol of composite solid solution oxide composed of silicon and zirconium and having a rutile structure (Preparation solution A ""')
I got The average particle size of the core particles was 7 nm.

Then, an organosol (A'2) of composite oxide fine particles was obtained in the same manner as in Example 1 by using this nucleus particle dispersion sol (preparation solution A ""). The composite oxide fine particles contained in the obtained organosol (A'2) have core particles having a rutile structure, an average particle diameter of 7 nm, and TiO ₂ / SnO ₂ (weight ratio) of the core particles. 11, (T
iO ₂ + SnO ₂ ) / SiO ₂ (weight ratio) is 8/2, (Ti
O ₂ + SnO ₂ + SiO ₂ ) / ZrO ₂ (weight ratio) is 136.
36 / 0.7, SiO ₂ / ZrO ₂ (weight ratio) of the coating layer
Is 3.118, and the core particle / coating layer (weight ratio) is 100/7.
It was 0.

Using the organosol (A'2) thus obtained, a coating solution (A'2) for forming a hard coat film was prepared in the same manner as in Example 1.

[0197]

Example 17 In Example 1, (TiO 2)
₂ + SnO ₂ ) / SiO ₂ (weight ratio), the average particle diameter was 9 nm and the TiO ₂ / core particles were the same as in Example 1 except that the mixing ratio of the silica sol was changed so as to be 96/4. Sn
O ₂ (weight ratio) is 11, (TiO ₂ + SnO ₂ ) / SiO ₂
(Weight ratio) of 96/4, a coating layer of SiO ₂ / ZrO ₂ is 3.118, core particle / coating layer (weight ratio) 100 / 7.0
As a result, an organosol (A12) of composite oxide fine particles having 12 core particles having a rutile structure was obtained.

Using this organosol (A12), a coating solution (A12) for forming a hard coat film was prepared in the same manner as in Example 1.

[0199]

Example 18 In a flask equipped with a stirrer, 41.5 g of ethyl cellosolve, 15.26 g of γ-glycidoxypropyltrimethoxysilane, 32.00 g of γ-glycidoxypropylmethyldimethoxysilane, and tetramethoxysilane 8 .45 g were added in order with stirring.
After adding 12.90 g of 0.05N hydrochloric acid and stirring for 30 minutes, the mixture was aged at 5 ° C. for 24 hours to form (prepare) a matrix. Subsequently, 0.04 g of a silicon-based surfactant (trade name “L-7001” manufactured by Nippon Unicar Co., Ltd.) and the organosol (A12) prepared in Example 17 were 231.0.
g, glycerin diglycidyl ether (Nagase & Co., Ltd.)
5.1 g of trade name and 0.411 g of magnesium perchlorate as a curing catalyst were added and dissolved in this order, followed by aging at 0 ° C. for 48 hours to form a hard coat film. A coating solution (A13) was prepared.

[0200]

Example 19 A hard coat film was prepared in the same manner as in Example 1, except that the amount of tetramethoxysilane was changed to 7.6 g and the amount of the organosol (A1) was changed to 225 g. Coating solution for coating film formation (A
14) was prepared.

[0201]

Example 20 Preparation of Plastic Lens Substrate (1) Preparation of Lens (R1) 94.2 g of 1,2-dimethylcaptoethane and 185.0 g of epichlorohydrin were cooled to 10 ° C. An aqueous solution of 4 g dissolved in 4 ml of water was added, and the mixture was stirred at this temperature for 1 hour. Thereafter, the liquid temperature is raised to 40 to 45 ° C.
The mixture was stirred for 2 hours while keeping it back and forth. After returning to room temperature, an aqueous solution in which 80.0 g of sodium hydroxide was dissolved in 80 ml of water was added dropwise while maintaining the liquid temperature at about 40 to 45 ° C, and the mixture was stirred at this temperature for 3 hours. 200 ml of water was added to the reaction mixture, and the mixture was extracted with 300 ml of toluene.
Washed three times with 0 ml. The toluene layer was dried over anhydrous sodium sulfate, and the solvent was distilled off to obtain 202.0 g of 1,2-bis (glycidylthio) ethane as a colorless and transparent liquid. Then, into a flask equipped with a stirrer, thermometer and nitrogen inlet tube
79.9 g of 1,2-bis (glycidylthio) ethane, 40 ml of ethanol and 87.5 g of potassium thiocyanate in water 6
The solution was added to an aqueous solution dissolved in 0 ml, the liquid temperature was raised to 45 ° C. over 1 hour, and the reaction was carried out at this temperature for 5 hours. 500 ml of water was added to the reaction mixture, extracted with 500 ml of toluene, and the toluene layer was washed three times with 500 ml of water. The toluene layer was dried over anhydrous sodium sulfate, the solvent was distilled off, and 1,2-bis (β-epithiopropylthio) ethane was added to 7
8.1 g were obtained.

[0202] 0.78 g of tributylamine was added thereto, and the mixture was sufficiently stirred and then poured into a mold composed of a glass mold and a gasket. Next, after polymerizing and curing at 80 ° C. for 5 hours, the mixture was cooled, and the glass mold and the gasket were removed.
An episulfide resin lens (R1) was obtained. The obtained lens (R1) had a refractive index of 1.71 and an Abbe number of 38. (2) Preparation of lens (R2) 20.4 g of 2- (2-methylcaptoethylthio) -1,3-dimercaptopropane and 277.5 g of epichlorohydrin were cooled to 10 ° C. 6g water 6
An aqueous solution dissolved in ml was added, and the mixture was stirred at this temperature for 1 hour. Thereafter, the mixture was stirred for 2 hours while maintaining the liquid temperature at about 40 to 45 ° C. Return to room temperature and add sodium hydroxide 120.0
g was dissolved in 120 ml of water.
The solution was added dropwise while maintaining the temperature at about 5 ° C., and the mixture was stirred at this temperature for 3 hours. 200 ml of water was added to the reaction mixture, and toluene 300
and the toluene layer was washed three times with 200 ml of water. The toluene layer was dried over anhydrous sodium sulfate and the solvent was distilled off to obtain 368.1 g of 2- (2-glycidylthioethylthio) -1,3-bis (glycidylthio) propane. Then, into a flask equipped with a stirrer, thermometer and nitrogen inlet tube
110.6 g of 2- (2-glycidylthioethylthio) -1,3-bis (glycidylthio) propane and 40 ml of ethanol were added to an aqueous solution in which 87.5 g of potassium thiocyanate was dissolved in 60 ml of water, and the solution was added for 1 hour. The temperature was raised to 45 ° C and the reaction was carried out at this temperature for 5 hours. Water 5 in the reaction mixture
After adding 00 ml, the mixture was extracted with 500 ml of toluene, and the toluene layer was washed three times with 500 ml of water. The toluene layer was dried over anhydrous sodium sulfate, the solvent was distilled off, and 2- (2-β-
106.6 g of (epithiopropylthioethylthio) -1,3-bis (β-epithiopropylthio) propane was obtained.

[0203] To this, 1.07 g of tributylamine was added, and after sufficiently stirring, the mixture was poured into a mold composed of a glass mold and a gasket. Next, after polymerizing and curing at 80 ° C. for 5 hours, the mixture was cooled, and the glass mold and the gasket were removed.
An episulfide resin lens (R2) was obtained. The obtained lens (R2) had a refractive index of 1.69 and an Abbe number of 36. (3) Preparation of lens (R3) 4-mercaptomethyl-3,6-dithio-1,8-octanedithiol 87 g, m-xylylene diisocyanate 94 g, dibutyltin dilaurate 0.02 g, internal mold release agent 0.1
5 g and 2- (5-methyl-2-hydroxyphenyl) benzotriazole (0.09 g) were mixed and thoroughly stirred.
Degassing was performed under a vacuum of mmHg for 60 minutes. Then, it is poured into a mold composed of a glass mold and a gasket,
C. for 7 hours, then from 40 ° C. to 120 ° C. for 10 hours
Polymerization was carried out in a heating furnace in which the temperature was raised over time, and after cooling, the glass mold and the gasket were removed to obtain a sulfur-containing urethane-based resin lens (R3). The obtained lens (R3) had a refractive index of 1.67 and an Abbe number of 33. (4) Preparation of lens (R4) 50 g of styrene, 48.5 g of 2,2-bis (3,5-dibromo-4-methacryloyloxyethoxyphenyl) propane,
Diethylene glycol bisallyl carbonate 2.8
g, diisopropyl peroxydicarbonate 1.5
g, and 0.2 g of 2- (5-methyl-2-hydroxyphenyl) benzotriazole were mixed, sufficiently stirred, and then poured into a mold composed of a glass mold and a gasket. Then, 4 hours at 30 ℃, 10 hours from 30 ℃ to 50 ℃,
2 hours from 50 ° C to 70 ° C, 1 hour at 70 ° C, 80 ° C
After heating for 2 hours, the glass mold and the gasket were removed to obtain a methacrylic resin lens (R4).
The obtained lens (R4) had a refractive index of 1.60 and an Abbe number of 3.
It was 2.

Formation of Hard Coat Film (1) The produced episulfide resin lens (R1) was immersed in a 13% by weight aqueous solution of NaOH for 5 minutes, washed sufficiently with water, and dried. Examples 7 to 11,
Using the coating liquid for forming a hard coat film prepared in Examples 14 to 16 and Example 18, coating was performed by a spin coating method. The spin-coating conditions were as follows: after applying the hard coat liquid during low rotation, spin-off was performed at a rotation speed of 2500 rpm and a rotation time of 1 second. After the application, the coating was temporarily dried at 90 ° C. for 18 minutes, heat-cured at 106 ° C. for 30 minutes, cooled, and then applied and temporarily dried on the remaining surface under the same conditions.
Heating and curing were performed at 106 ° C. for 120 minutes to form a hard coat film. The thickness of the obtained hard coat film is 2.3.
μm.

The lens having a hard coat film formed using the coating solution (A13) for forming a hard coat film of Example 18 was heated at 90 ° C. using a commercially available dye (described below) (Amber D for Seiko Plux). Spectrophotometer (Otsuka Electronics Co., Ltd.)
(MCPD-1000), the total light transmittance was 54%, indicating good dyeability.

Formation of Hard Coat Film (2) Using the prepared episulfide resin lens (R2),
Using the coating liquid for forming a hard coat film prepared in Example 19, a hard coat film was formed in the same manner as in the formation of the hard coat film (1). The thickness of the obtained hard coat film was 2.3 μm.

Formation of Hard Coat Film (3) Using the prepared sulfur-containing urethane resin lens (R3) and the coating liquid for forming a hard coat film prepared in Examples 2, 12, and 13, A hard coat film was formed in the same manner as in the formation of the hard coat film (1). The thickness of each of the obtained hard coat films was 2.3 μm.

Formation of Hard Coat Film (4) Using the obtained methacrylic resin lens (R4) and the coating liquid for forming a hard coat film prepared in Examples 4 and 5, a hard coat film was formed. A hard coat film was formed in the same manner as in the formation (1). The thickness of each of the obtained hard coat films was 2.3 μm.

[0209] Each of the lenses was dyed with a commercially available dye (Amber D for Seiko Plux) in a dyeing bath at 92 ° C for 5 minutes, and the coating solution for forming a hard coat film was similarly used. A hard coat film was formed. The transmittance before and after the formation of the hard coat film was measured using a spectrophotometer (MCPD-1000, manufactured by Otsuka Electronics Co., Ltd.), and the color difference (ΔE) was determined. Except when used, ΔE was 0.4 or less, and no significant change in color tone was observed.

Properties of Hard Coat Film The following properties were evaluated for the hard coat film obtained as described above. Table 1 shows the results.

Appearance: The presence or absence of coloring of a lens (white lens) with a hard coat film, which was not subjected to fabric dyeing, was visually observed.

Transmittance: The average transmittance of visible light of an unstained lens (white lens) was measured with a spectrophotometer.

Interference fringes: Regarding the occurrence of interference fringes,
The light of the fluorescent lamp was reflected on the lens surface while the background was blackened, and the occurrence of a rainbow pattern due to light interference was visually observed. The judgment was made as follows.

：: No rainbow pattern was observed.

Δ: A slight rainbow pattern is observed.

X: A rainbow pattern is clearly observed.

Scratch resistance: The state of the film after 10 reciprocations with a load of 1 kg / cm ² using # 0000 steel wool was observed.

A: No damage at all.

B: Almost no damage.

C: Slightly scratched.

D: Many scratches are made.

Adhesion: After immersion in hot water at 70 ° C. for 2 hours, 11 parallel line-shaped scratches were made at 1 mm intervals on the lens surface at intervals of 1 mm each to form 100 squares and adhere cellophane tape. -The number of squares remaining without peeling off the film after peeling was observed. (Cross-cut tape test) Weather resistance: The following evaluation was performed after exposing for 200 hours using a sunshine weather meter (manufactured by Suga Test Instruments Co., Ltd.) having a carbon arc electrode.

I) Appearance: The presence or absence of coloring of an unstained lens (white lens) was visually evaluated.

Ii) Transmittance: After the test, the average transmittance of visible light of the unstained lens (white lens) was measured with a spectrophotometer.

Iii) Adhesion: For the lens after the test,
The same cross cut tape test as described above was performed on the exposed surface.

Long-term stability: After storing the coating solution for forming a hard coat film at 10 ° C. for 25 days and 45 days, a hard coat film was formed as described above, and the above evaluations were carried out. The difference from the hard coat film formed immediately after preparing the coating solution was evaluated on a three-point scale of ○, Δ, and ×.

…: No difference was observed Δ: Slight decrease in performance was observed X: Clearly decrease in performance was observed

[0228]

Comparative Example 1 In Example 1, the organosol (A1) was used.
Was changed to titanium oxide, iron oxide, and silicon oxide composite oxide sol (Optreak 1120F, manufactured by Catalyst Chemical Industry Co., Ltd.) in the same manner as in Example 1, except that the coating solution for forming a hard coat film (C1) was used. Was prepared. Using this coating solution, a hard coat film was formed on the lens (R1) in the same manner as in Example 20, and the characteristics of the obtained hard coat film were evaluated. Table 1 shows the results.

[0229]

Comparative Example 2 In Example 1, the organosol (A1)
Is composed of titanium oxide and silicon oxide, TiO ₂ / Si
It consists of anatase-type core particles having an O ₂ (weight ratio) of 86.5 / 13.5, silicon oxide and zirconium oxide, and has a SiO ₂ / ZrO ₂ (weight ratio) of 5.3 / 1.7. Oxide sol (C2) [TiO ₂ / S
iO ₂ / ZrO ₂ (weight ratio) is 86.5 / 18.8 / 1.7,
A coating solution (C2) for forming a hard coat film was prepared in the same manner as in Example 1 except that the core particle / coating layer (weight ratio) was changed to 100/5]. Using this coating solution, a hard coat film was formed on the lens (R1) in the same manner as in Example 20, and the characteristics of the obtained hard coat film were evaluated.
Table 1 shows the results.

[0230]

Comparative Example 3 Example 1 was repeated except that the organosol (A1) of Example 10 was replaced with the composite oxide sol (C2) of Comparative Example 2.
In the same manner as in Example 0, a methanol-dispersed organosol (C3) was obtained. A coating liquid (C3) for forming a hard coat film was prepared in the same manner as in Example 1 using this organosol (C3). Using this coating solution, a hard coat film was formed on the lens (R1) in the same manner as in Example 20, and the properties of the obtained hard coat film were evaluated. Table 1 shows the results.

[0231]

[Table 1]

[0232]

Example 21 A coating solution for forming a hard coat film (A3),
Using (A6) and (A12), the lens (R
A hard coat film was formed in the same manner as in Example 20 except that a silicon wafer whose surface was polished was used as a substrate instead of 1). A spectrophotometer (Murakami Color Research Laboratory: GC)
M-4). Table 2 shows the results.

[0233]

[Table 2]

[0234]

Embodiment 22 36.295 kg of 15% by weight ammonia water of Example 1 was replaced by 108.degree.
A hydrated titanic acid having a specific surface area of 170 m2 / g was obtained in the same manner as in Example 1 except that the amount was changed to 885 kg. Using this hydrous titanic acid, the average particle diameter was 6 in the same manner as in Example 1.
nm, the TiO ₂ / SnO ₂ (weight ratio) of the core particles is 11,
(TiO ₂ + SnO ₂ ) / SiO ₂ (weight ratio) is 8/2,
Organosol of composite oxide fine particles (A15) in which the coating layer has SiO ₂ / ZrO ₂ of 3.118 and the core particles / coating layer (weight ratio) is 100 / 7.012 and the core particles have a rutile structure.
I got

Using this organosol (A15), a coating solution for forming a hard coat film (A1
5) was prepared. Then, using this coating solution, Example 2 was used.
A hard coat film was formed on the lens (R1) in the same manner as in Example 1. The thickness of the obtained hard coat film was 2.2 μm. The properties of the hard coat film thus obtained were evaluated. Table 1 shows the results.

[0236]

Example 23 Preparation of a coating solution for forming a primer film A surface treatment was carried out with γ-glycidoxypropyltrimethoxysilane in the same manner as in Example 13 except that the organosol (A1) was used instead of the organosol (A2). A methanol-dispersed organosol (A14) of composite oxide fine particles having core particles having a rutile structure was obtained.

To 2000 g of this organosol (A14),
A 30 wt% urethane elastomer aqueous dispersion (Daiichi Kogyo Seiyaku Co., Ltd .: Superflex 150) 5
The resulting mixture was mixed with 00 g to prepare a high refractive coating liquid for primer.

Formation of Primer Film Next, the plastic lens (R1) obtained in Example 20
Was immersed in a 5% by weight aqueous solution of NaOH for 5 minutes, washed sufficiently with water, and dried.

Next, the plastic lens (R1)
Was immersed in the primer coating solution, pulled up at a pulling rate of 95 mm / min, and heated and cured at 85 ° C. for 120 minutes and at 104 ° C. for 60 minutes to form a primer film on the lens surface.

Formation of Hard Coat Film Next, a hard coat film was formed on this lens in the same manner as in Example 20, except that the coating solution (A7) for forming a hard coat film of Example 10 was used.

Formation of antireflection film Next, the plastic lens provided with the high-refractive-index primer film and the high-refractive-index hard coat film was exposed to argon gas plasma having a power of 200 W in vacuum for 30 seconds. SiO from side to atmosphere side
_2, ZrO _2, SiO _2, to form a thin film of ZrO _2, SiO ₂ of 5 layers.

[0242] The optical film thickness of the formed anti-reflection film, in turn SiO ₂ is about lambda / 4, the total thickness of the next ZrO ₂ and SiO ₂ is about lambda / 4, the next ZrO _2, About λ / 4, and the uppermost SiO ₂ was about λ / 4. (Design wavelength λ is 510 nm) After forming the antireflection film, the characteristics of the hard coat film were evaluated in the same manner as in Example 20. Table 1 shows the results.

[0243] Impact resistance test The primer layer obtained as described above, the impact resistance test with a hard coat film and the antireflection film coated plastic lens was carried out. The test method for impact resistance was as follows: from a height of 126 cm, weight of 16.2 g, 100
g, 200 g, and 400 g of steel balls were vertically dropped on a plastic lens, and the presence or absence of cracks was judged.
Table 3 shows the results.

[0244]

Example 24 The coating liquid (A7) for forming a hard coat film prepared in Example 10 was used to form a hard coat film on the lens (R1) in the same manner as in Example 20, and then in the same manner as in Example 23. An antireflection film was formed by a vacuum deposition method, and an impact resistance test was performed. Table 3 shows the results.

[0245]

[Table 3]

[0246]

[Brief description of the drawings]

FIG. 1 is an X-ray diffraction diagram of the core particles prepared in Example 1.

FIG. 2 is an X-ray diffraction diagram of the core particles prepared in Example 3.

FIG. 3 is an X-ray diffraction diagram of the core particles prepared in Example 4.

Claims (20)

[Claims] 1. A composite oxide fine particle comprising: (A) a composite oxide fine particle; and (B) a matrix, wherein the composite oxide fine particle comprises (i) a core particle and (ii) a coating layer for coating the core particle. i) the core particles are composed of titanium and tin oxides,
And (ii) the coating layer is made of a composite oxide of silicon oxide and zirconium and / or aluminum oxide, wherein the coating layer is made of a composite solid solution oxide having a rutile structure. 2. The amount of titanium and tin contained in (i) the core particles of the (A) composite oxide fine particles is as follows: when converting titanium to TiO ₂ and converting tin to SnO ₂ , TiO ₂ / SnO ₂ (weight ratio) is in the range of 1 / 9.9 to 14/1, and (ii) the amount of silicon, zirconium and aluminum contained in the coating layer is such that zirconium is calculated by converting silicon to SiO _2. Is converted to ZrO ₂ , and when aluminum is converted to Al ₂ O ₃ , SiO ₂ / ZrO ₂ (weight ratio) is in the range of 50/50 to 99/1, or Al ₂ O ₃ / SiO ₂ ( The coating liquid according to claim 1, wherein the weight ratio is in the range of 0.01 / 25 to 0.20 / 25. 3. The method according to claim 1, wherein the composite oxide fine particles (A) are of the following (a):
3. The coating liquid for forming a coating film according to claim 1 or 2, wherein the coating liquid is a sol-like composite oxide fine particle prepared by the steps (a) to (c). Step of adding hydrogen to dissolve hydrous titanic acid, adding a tin compound to the obtained aqueous solution of peroxotitanic acid, and then heating to prepare a dispersion of core particles composed of a composite solid solution oxide having a rutile structure. (B) After adding a silicon compound, a zirconium compound and / or an aluminum compound to the dispersion liquid of the core particles, the mixture is heated to form a coating layer on the surface of the core particles, and the sol in which the composite oxide particles are dispersed is formed. (C) further heating the sol in which the composite oxide is dispersed. (I) The core particles are composed of a composite solid solution oxide containing an oxide of titanium and tin and an oxide of silicon and / or zirconium, and are composed of a composite solid solution oxide having a rutile structure. 2. The method according to claim 1, wherein
4. The coating liquid for forming a coating film according to any one of items 1 to 3. 5. The amount of titanium, tin, silicon and zirconium contained in (i) the core particles of the composite oxide fine particles (A) is such that titanium is converted to TiO ₂ , and tin is converted to SnO ₂ , When silicon is converted to SiO ₂ and zirconium is converted to ZrO ₂ , (TiO ₂ + SnO ₂ ) / SiO ₂ (weight ratio)
Is in the range of 75/25 to 95/5, or (TiO ₂
+ SnO ₂ + SiO ₂ ) / ZrO ₂ (weight ratio) is 90/1
The coating liquid according to claim 4, wherein the coating liquid is in a range of 0 to 99.5 / 0.5. 6. The composite oxide fine particles (A) described below,
6. The coating solution for forming a coating film according to claim 4 or 5, wherein the coating solution is a sol-like composite oxide fine particle prepared by the steps (c) to (c): (a) peroxidation to a hydrous titanic acid gel or sol; Hydrogen is added to dissolve hydrous titanic acid, and a tin compound, a silicon compound and / or a zirconium compound are added to the obtained aqueous peroxotitanic acid solution, and then heated to form a rutile-type composite solid solution oxide. A step of preparing a dispersion of core particles, (b) adding a silicon compound, a zirconium compound and / or an aluminum compound to the dispersion of core particles, and then heating to form a coating layer on the surface of the core particles; A step of preparing a sol in which oxide particles are dispersed; and (c) a step of heating the sol in which the composite oxide is dispersed. 7. The coating solution according to claim 1, wherein the surface of the composite oxide fine particles (A) is treated with an organosilicon compound or an amine. 8. The coating liquid for forming a coating film according to claim 1, further comprising at least one of the following components (C) to (G): A hydrolyzate and / or partial condensate of the organosilicon compound represented by 2), Si (OR ⁴ ) ₄ (2) (wherein R ⁴ is a hydrocarbon group having 1 to 8 carbon atoms, an alkoxyalkyl group or (D) Si, Al, Sn, Sb, Ta, Ce, La, F
oxide fine particles composed of oxides of one or more elements selected from e, Zn, W, Zr and In and / or Si, Al, Sn, Sb, Ta, Ce, La, Fe, Z
From oxides of two or more elements selected from n, W, Zr, In and Ti (excluding composite oxide fine particles composed of Ti, Sn, Si and oxides of Zr and / or Al) Composite oxide fine particles, (E) a compound selected from a polyfunctional epoxy compound, a polyhydric alcohol, a polycarboxylic acid and a polycarboxylic anhydride, (F) a hindered amine compound, (G) an amine, Compounds selected from amino acids, metal acetylacetonates, metal salts of organic acids, perchloric acids, salts of perchloric acids, acids and metal chlorides. 9. The method according to claim 1, wherein the matrix (B) comprises a component comprising at least one hydrolyzate and / or partial condensate of an organosilicon compound represented by the following formula (1). 9. The coating liquid for forming a coating film according to any one of items 1 to 8. R ¹ R ² _a Si (OR ³ ) _3-a (1) (wherein, R ¹ is a hydrocarbon group having 1 to 6 carbon atoms, a vinyl group,
A methacryloxy group, a mercapto group, an organic group having an amino group or an epoxy group, R ² is a hydrocarbon group having 1 to 4 carbon atoms, R ³ is a hydrocarbon group having 1 to 8 carbon atoms, an alkoxyalkyl group or an acyl group, a Represents 0 or 1. ) 10. The coating liquid for forming a coating film according to any one of claims 1 to 8, wherein a coating resin is contained as the matrix (B). 11. The coating solution according to claim 10, wherein the coating resin is a urethane resin. 12. A coated substrate comprising a substrate and a high-refractive-index hard coat film formed on the surface of the substrate from the coating solution for forming a film according to any one of claims 1 to 9. Wood. 13. A substrate with a film, comprising a primer film formed from the coating solution for forming a film according to claim 10 between the substrate and a hard coat layer. 14. A synthetic resin comprising a lens substrate having a refractive index of 1.54 or more and a hard coat layer formed from the coating solution according to claim 1 provided on a surface of the lens substrate. lens. 15. A hard coat layer formed from the coating liquid according to claim 1 on a surface of a lens substrate having a refractive index of 1.54 or more, and an inorganic coating is formed on the hard coat layer. A synthetic resin lens characterized in that an antireflection film made of a substance is laminated. 16. A sulfur-containing urethane-based lens material obtained by reacting at least one mercapto compound represented by the following formula (1) and / or (2) with at least one polyisocyanate: The synthetic resin lens according to claim 14, wherein the lens is a resin. Embedded image 17. The synthetic resin according to claim 14, wherein the lens substrate is a copolymer obtained from a monomer represented by the following formula (3) and another polymerizable monomer. Made lens. Embedded image (Where R ⁵ is a hydrogen atom or a methyl group, R ⁶ is CH ₂
CH ₂ group or CH ₂ CH (OH) CH ₂ group, X represents a hydrogen atom or a halogen atom excluding a fluorine atom, and m and n are each an integer in which m + n is selected from an integer of 0 to 8 It is. ) 18. A lens base material comprising a copolymer obtained from a (meth) acrylic monomer and / or a vinyl monomer having a sulfur atom and an aromatic ring as constituents and another polymerizable monomer. 14. A method according to claim 14, wherein:
6. The synthetic resin lens according to 5. 19. The synthetic resin lens according to claim 14, wherein the lens substrate is a polymer of an episulfide compound having two or more structures represented by the following formula (4). Embedded image (In the formula, X represents S or O, and the number of S is 50% or more on average with respect to the total of S and O constituting the three-membered ring.) 20. The synthetic resin lens according to claim 19, wherein the episulfide compound is represented by the following formula (5) or (6). Embedded image