JPH10245522A - Coating composition and optical member - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prevent the occurrence of interference fringes and improve the marring resistance, surface hardness, wear resistance, flexibility, transparency, antistatic properties, dyeability, heat resistance, chemical resistance, tight adhesion, etc., by using a specified silylated substance and specified titanium dioxide/ tin oxide composite colloid particles as the constituents. SOLUTION: At least one silylated substance selected from (partially hydrolyzed) organosilicon compounds of formula I [wherein R<1> and R<3> are each (halogenated) alkyl, (halogenated) aryl, alkenyl, or an organic group having an epoxy, (meth)acryloyl, mercapto, amino, or cyano group and bound to an Si atom through an Si-C bond; R<2> is a 1-8C alkyl, alkoxyalkyl, or acyl; and a and b are each 0 to 2, provided that a+b=(0 to 2)] and formula II (wherein R<4> is a 1-5C alkyl; X is a 1-4C alkyl, or acyl; Y is methylene, or a 2-20C alkylene; and c is 0 or 1), in an amount of 100 pts.wt. is compounded with titanium dioxide/tin oxide composite colloid particles having a primary particle diameter of 2-20nm, in an amount of 1-500 pts.wt., preferably 100-300 pts.wt.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an optical member such as an eyeglass lens, a camera lens, a window glass for an automobile, an optical filter attached to a liquid crystal display, a plasma display, or the like. The present invention relates to a coating composition for obtaining a coating film having excellent transparency, heat resistance, light resistance, weather resistance, and water resistance, and an optical member using the coating composition.

[0002] The invention of the present application is based on the fact that the formed coating has excellent warm water resistance, and even if a coating of an inorganic oxide (such as an anti-reflection coating) is formed on the coating, the coating has weather resistance and light resistance. The present invention relates to a coating composition and an optical member that do not reduce the amount of the resin.

[0003]

2. Description of the Related Art Plastic moldings are used in large quantities, taking advantage of their advantages such as light weight, easy processability, and impact resistance. However, on the other hand, plastic moldings have insufficient hardness, are easily scratched, and are easily attacked by solvents. It has drawbacks such as being charged and adsorbing dust, and having insufficient heat resistance, and has been practically insufficient to be used as a spectacle lens, window material or the like as compared with an inorganic glass molded article.

Therefore, it has been proposed to apply a protective coat to a plastic molded body. Numerous types of coating compositions used for coating have been proposed. For example, a coating composition containing an organosilicon compound or a hydrolyzate thereof as a main component (a resin component or a film-forming component) is used for a spectacle lens. Used for hard coat. But,
This coating agent has insufficient scratch resistance. Further, JP-A-53-111336 discloses that a silica sol is added and a coating agent containing colloidal silica particles is used for a hard coat for an eyeglass lens.

Conventionally, most plastic spectacle lenses have been produced by cast polymerization of diethylene glycol bisallyl carbonate in a monomer state. The lens manufactured in this way has a refractive index of about 1.50, which is lower than the refractive index of a glass lens of 1.52. Therefore, in the case of a myopic lens, there is a problem that the edge thickness increases. Therefore, in recent years, development of a monomer having a higher refractive index than diethylene glycol bisallyl carbonate has been promoted. Those high refractive index resin materials are, for example,
JP-A-55-13747, JP-A-56-1662
No. 14, JP-A-57-23611, JP-A-57-23611
JP-A-7-54901, JP-A-59-133211, JP-A-60-199016, JP-A-64-5
No. 4021 is disclosed.

Japanese Patent Application Laid-Open Nos. 62-151801 and 63-275682 disclose a high refractive index lens using the above high refractive index resin material, in which a colloid of metal oxide fine particles of Sb or Ti is used. Coatings containing the dispersion are disclosed.

[0007]

A coating agent containing colloidal silica by adding a silica sol has a problem that a film obtained by applying and curing the coating agent produces interference fringes, and the appearance of the lens is unfavorable. There's a problem. In addition, in many lenses, an antireflection film (consisting of a multilayer structure film of an inorganic oxide thin film based on the theory of optical interference) is formed on a coating film. In this case, for example, the antireflection film exhibits an extremely light green reflection color, but this reflection color changes according to the position of the lens surface, and there is also a problem that there is unevenness.

[0008] The coating agent containing colloidal tin oxide by adding the tin oxide sol is stable because the tin oxide sol has low compatibility with organosilicon compounds such as silane coupling agents and silicon-containing substances such as hydrolyzates thereof. The film obtained by applying and curing the coating agent has insufficient water resistance due to a decrease in the water resistance. The coating agent containing colloidal titanium oxide by adding titanium oxide sol has low stability because titanium oxide sol has low compatibility with organosilicon compounds such as silane coupling agents and silicon-containing substances such as hydrolysates thereof. , The film obtained by applying and curing the coating agent has insufficient water resistance. In addition, there was a problem that the color was changed to blue by ultraviolet irradiation.

The coating agent containing colloidal antimony oxide by adding the antimony oxide sol has a compatibility between the antimony oxide sol and an organic silicon compound such as a silane coupling agent or a silicon-containing substance such as a hydrolyzate thereof. Although the stability is improved, the film obtained by applying and curing the coating agent has a problem that the refractive index is not sufficiently high.

The present invention is directed to a film obtained by applying and curing a coating agent on a high refractive index optical member using a high refractive index resin material having a high refractive index of nd = 1.54 to 1.70. It is an object of the present invention to provide a coating composition which gives a film in which interference fringes are not visible and which has no reflection color, and an optical member using the coating composition. Also,
The present invention provides a coating composition for plastics having excellent scratch resistance, surface hardness, abrasion resistance, flexibility, transparency, antistatic properties, dyeing properties, heat resistance, water resistance, chemical resistance, and the like, and its coating. An object of the present invention is to provide an optical member using a composition. In particular, the present invention is abrasion resistance, adhesion,
An object of the present invention is to provide a coating agent which is excellent in water resistance, transparency and light resistance and which gives a film free of interference fringes.

[0011]

The present invention provides the following (A)
Component and component (B); component (A): general formula (I) (R ¹ ) _a (R ³ ) _b Si (OR ² ) _{4- (a + b)} (I) (where R ¹ and R ³ Is an organic group having an alkyl group, an aryl group, a halogenated alkyl group, a halogenated aryl group, an alkenyl group, or an epoxy group, an acryloyl group, a methacryloyl group, a mercapto group, an amino group, or a cyano group, respectively, and Si-C R ² is an alkyl group having 1 to 8 carbon atoms, an alkoxyalkyl group, or an acyl group,
a and b are each an integer of 0, 1, or 2, and a +
b is an integer of 0, 1, or 2. ) And the general formula (I
I) [(R ⁴ ) _c Si (OX) _{3 -c} ] ₂ Y (II) (where R ⁴ represents an alkyl group having 1 to 5 carbon atoms, and X represents an alkyl group having 1 to 4 carbon atoms or acyl) Y is a methylene group or an alkylene group having 2 to 20 carbon atoms, and c is an integer of 0 or 1.), and an organic silicon compound represented by the formula: A coating composition comprising: at least one silicon-containing substance; and component (B): titanium oxide-tin oxide composite colloid particles having a primary particle diameter of 2 to 20 nm.

[0012]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The general formula (I), (R ¹ ) _a (R ³ ) _b Si (OR ² ) _{4- (a + b} ) in the component (A) used in the coating composition of the present invention. ₎ (I) includes organosilicon compounds in which R ¹ and R ³ are the same or different organic groups, or where a and b are the same or different integers. The organosilicon compound represented by the general formula (I) in the component (A) is, for example,
Tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane,
Tetra-n-butoxysilane, tetraacetoxysilane,
Methyltrimethoxysilane, methyltripropoxysilane, methyltriacetoxysilane, methyltributoxysilane, methyltripropoxysilane, methyltriamyloxysilane, methyltriphenoxysilane, methyltribenzyloxysilane, methyltriphenethyloxysilane, Sidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, α-glycidoxyethyltrimethoxysilane, α-glycidoxyethyltriethoxysilane, β-glycidoxyethyltrimethoxysilane, β-glycidoxy Ethyltriethoxysilane, α-glycidoxypropyltrimethoxysilane, α
-Glycidoxypropyltriethoxysilane, β-glycidoxypropyltrimethoxysilane, β-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ -Glycidoxypropyltripropoxysilane, γ-glycidoxypropyltributoxysilane, γ-glycidoxypropyltriphenoxysilane, α-glycidoxybutyltrimethoxysilane, α-
Glycidoxybutyltriethoxysilane, β-glycidoxybutyltriethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycidoxybutyltriethoxysilane, δ-glycidoxybutyltrimethoxysilane, δ- Glycidoxybutyltriethoxysilane,
(3,4-epoxycyclohexyl) methyltrimethoxysilane, (3,4-epoxycyclohexyl) methyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ) Ethyltriethoxysilane, β
-(3,4-epoxycyclohexyl) ethyltripropoxysilane, β- (3,4-epoxycyclohexyl) ethyltributoxysilane, β- (3,4-epoxycyclohexyl) ethyltriphenoxysilane, γ-
(3,4-epoxycyclohexyl) propyltrimethoxysilane, γ- (3,4-epoxycyclohexyl)
Propyltriethoxysilane, δ- (3,4-epoxycyclohexyl) butyltrimethoxysilane, δ-
(3,4-epoxycyclohexyl) butyltriethoxysilane, glycidoxymethylmethyldimethoxysilane, glycidoxymethylmethyldiethoxysilane, α-
Glycidoxyethylmethyldimethoxysilane, α-glycidoxyethylmethyldiethoxysilane, β-glycidoxyethylmethyldimethoxysilane, β-glycidoxyethylethyldimethoxysilane, α-glycidoxypropylmethyldimethoxysilane, α -Glycidoxypropylmethyldiethoxysilane, β-glycidoxypropylmethyldimethoxysilane, β-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane , Γ-glycidoxypropylmethyldipropoxysilane, γ-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethyldiphenoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycid Xypropylethyldiethoxysilane, γ-glycidoxypropylvinyldimethoxysilane, γ-glycidoxypropylvinyldiethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriethoxysilane Acetoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropyltriacetoxysilane, 3,
3,3-trifluoropropyltrimethoxysilane, γ-
Methacryloxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, β-cyanoethyltriethoxysilane, chloromethyltrimethoxysilane, chloromethyltriethoxysilane, N- (β-aminoethyl) γ-aminopropyltrimethoxysilane, N- (β
-Aminoethyl) γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldimethoxysilane,
N- (β-aminoethyl) γ-aminopropyltriethoxysilane, N- (β-aminoethyl) γ-aminopropylmethyldiethoxysilane, dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldiethoxysilane, phenylmethyldiphenyl Ethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropylmethyldiethoxysilane, dimethyldiacetoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-mercaptopropylmethyldimethoxy Silane, γ-mercaptomethyldiethoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, and the like. These can be used alone or in combination of two or more. .

The hydrolyzate of the organosilicon compound of the general formula (I) in the component (A) used in the coating composition of the present invention is obtained by hydrolyzing the organosilicon compound of the above general formula (I). As a result, a compound in which part or all of R ² is substituted with a hydrogen atom is obtained. These hydrolysates of the organosilicon compound of the general formula (I) can be used alone or in combination of two or more. The hydrolysis is performed by adding an acidic aqueous solution such as an aqueous solution of hydrochloric acid, an aqueous solution of sulfuric acid, or an aqueous solution of acetic acid to the above organosilicon compound and stirring the mixture.

The organosilicon compound represented by the general formula (II) and [(R ⁴ ) _c Si (OX) _{3 -c} ] ₂ Y (II) in the component (A) used in the coating composition of the present invention. Examples thereof include methylenebismethyldimethoxysilane, ethylenebisethyldimethoxysilane, propylenebisethyldiethoxysilane, butylenebismethyldiethoxysilane and the like, and these can be used alone or in combination of two or more.

The hydrolyzate of the organosilicon compound of the formula (II) in the component (A) used in the coating composition of the present invention is obtained by hydrolyzing the organosilicon compound of the formula (II). As a result, a compound in which part or all of X is substituted with a hydrogen atom is obtained. These hydrolysates of the organosilicon compound of the general formula (II) can be used alone or in combination of two or more. The hydrolysis is performed by adding an acidic aqueous solution such as an aqueous solution of hydrochloric acid, an aqueous solution of sulfuric acid, or an aqueous solution of acetic acid to the above organosilicon compound and stirring the mixture.

The component (A) used in the coating composition of the present invention is selected from the group consisting of organosilicon compounds represented by the general formulas (I) and (II), and a hydrolyzate thereof. At least one silicon-containing material. (A) used in the coating composition of the present invention
The component is preferably at least one silicon-containing substance selected from the group consisting of an organosilicon compound represented by the general formula (I) and a hydrolyzate thereof. In particular, ^one of R ¹ and R ³ is an organic group having an epoxy group, R ² is an alkyl group, and a and b are each 0 or 1, and a + b satisfies the condition of 1 or 2. Organosilicon compounds of the general formula (I) and hydrolysates thereof are preferred. Examples of preferred organosilicon compounds are glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, α-glycidoxyethyltriethyl. Methoxysilane, α-glycidoxyethyltriethoxysilane, β-glycidoxyethyltrimethoxysilane,
β-glycidoxyethyltriethoxysilane, α-glycidoxypropyltrimethoxysilane, α-glycidoxypropyltriethoxysilane, β-glycidoxypropyltrimethoxysilane, β-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltripropoxysilane, γ-glycidoxypropyltributoxysilane, γ
-Glycidoxypropyltriphenoxysilane, α-glycidoxybutyltrimethoxysilane, α-glycidoxybutyltriethoxysilane, β-glycidoxybutyltriethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ -Glycidoxybutyltriethoxysilane, δ-glycidoxybutyltrimethoxysilane, δ-
Glycidoxybutyltriethoxysilane, glycidoxymethylmethyldimethoxysilane, glycidoxymethylmethyldiethoxysilane, α-glycidoxyethylmethyldimethoxysilane, α-glycidoxyethylmethyldiethoxysilane, β-glycid Xylethylmethyldimethoxysilane, β-glycidoxyethylethyldimethoxysilane, α-glycidoxypropylmethyldimethoxysilane, α-glycidoxypropylmethyldiethoxysilane, β-glycidoxypropylmethyldimethoxysilane, β-gly Sidoxypropylethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, γ-glycidoxypropylmethyl Butoxysilane, γ-glycidoxypropylmethyldiphenoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane, γ-glycidoxypropylvinyldimethoxysilane, γ-glycidoxy Propylvinyldiethoxysilane.

Further preferred are γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane and their hydrolysates, which are used alone. Alternatively, they can be used as a mixture. Also, γ-glycidoxypropyltrimethoxysilane, γ
-Glycidoxypropylmethyldiethoxysilane, γ-
Glycidoxypropylmethyldimethoxysilane or a hydrolyzate thereof is furthermore represented by a + b in the general formula (I).
A tetrafunctional compound corresponding to = 0 can be used in combination.
Examples of compounds corresponding to tetrafunctionality include tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetra-n-propoxysilane, tetra-n-butoxysilane, tetra-tert-butoxysilane, tetrasec-
Butoxysilane and the like.

The component (B) used in the coating composition of the present invention is a titanium oxide-tin oxide composite colloid particle having a primary particle diameter of 2 to 20 nm. The titanium oxide-tin oxide composite colloid particles are titanium oxide-
It is preferable to use tin oxide composite colloid particles as a sol dispersed in a liquid medium. As the liquid medium in which the titanium oxide-tin oxide composite colloid particles are dispersed, an aqueous medium or a hydrophilic organic solvent such as methanol, ethanol, or isopropanol is preferable. The titanium oxide-tin oxide composite colloid particles have a primary particle diameter of 2 to 20 nm.
(Nanometers). Here, the primary particle diameter is not the diameter of the titanium oxide-tin oxide composite colloid particles in the aggregated form, but the diameter of one titanium oxide-tin oxide composite colloid particle when separated individually. Can be measured.

As the sol containing the titanium oxide-tin oxide composite colloid particles used in the present invention, those produced by any method can be used. This titanium oxide
The sol containing the tin oxide composite colloid particles is particularly preferably produced by the following method. That is, the titanium oxide-tin oxide composite sol can be produced by a method in which a titanium salt and metal tin are reacted in an aqueous medium in the presence of hydrogen peroxide.

More specifically, the following steps (a) and (b)
Process and (c) process; (a): hydrogen peroxide solution and metallic tin are treated with 2 to 3 H_TwoO_Two
/ Titanium salt water simultaneously or alternately while maintaining the molar ratio
When added to the solution, the titanium and tin components _TwoAnd S
nO_Two0.25-10 TiO_Two/ SnO_TwoMo
Ratio and TiO_TwoAnd SnO_TwoTotal concentration converted to 5-50
Produces an aqueous solution of a basic salt of titanium-tin in a weight%.
Step, (b): basic salt of titanium-tin obtained in step (a)
The aqueous solution is heated to 50-100 ° C. over 0.1-100 hours.
Aggregation of Titanium Oxide-Tin Oxide Composite Colloids
(C): titanium oxide-tin oxide complex produced in step (b)
Removal of electrolytes from aggregate slurries of colloids
Of a titanium oxide-tin oxide composite aqueous sol comprising:
Method.

The titanium salt used in the above step (a) includes titanium tetrachloride, titanium sulfate, titanium nitrate and the like. These titanium salts are preferably used in an aqueous solution. Metallic tin can be used in powder or granular form.
For example, metal tin powder obtained by melting and spray-solidifying an ingot by an atomization method, or flake-shaped metal tin powder produced by cutting an ingot with a lathe or a file can be used.

As the hydrogen peroxide, a commercially available aqueous solution having a concentration of 35% by weight can be used at a desired concentration. In the step (a), a hydrogen peroxide solution and metal tin are simultaneously or alternately added to the titanium salt aqueous solution to obtain a titanium-tin basic salt aqueous solution. An aqueous titanium salt solution is placed in a reaction vessel equipped with a stirrer, and aqueous hydrogen peroxide and metal tin are added simultaneously or alternately from separate addition ports with stirring. Since the slurry containing the aqueous solution of the basic salt in the step (a) and the aggregate of the titanium oxide-tin oxide composite colloid in the step (b) that follows is acidic, the reaction apparatus used in those steps is a glass reaction. It is preferable to use an apparatus or a reaction apparatus made of glass lining (enamel).

The H ₂ O ₂ / Sn molar ratio between the hydrogen peroxide solution and the metal tin is added to the titanium salt aqueous solution while maintaining the H ₂ O ₂ / Sn molar ratio at 2-3. More specifically, 1/3 to 1/30 parts by weight of the total weight of the hydrogen peroxide solution and metal tin to be added is collected, and the addition of the hydrogen peroxide solution to the titanium salt aqueous solution and the A successive addition of metal tin and a series of steps in which the reaction is performed for 2 to 20 minutes may be repeated 3 to 30 times. Also, 1/3 to 1/30 parts by weight of the total weight of the hydrogen peroxide solution and the metal tin to be added are collected, and the addition of the metal tin to the titanium salt aqueous solution and the subsequent hydrogen peroxide A series of steps of adding water and performing a reaction for 2 to 20 minutes may be repeated 3 to 30 times. At this time, first add the entire amount of hydrogen peroxide to the acidic titanium salt aqueous solution, and then add metal tin, most of the hydrogen peroxide is decomposed at the beginning of the reaction, and the amount of hydrogen peroxide becomes insufficient, In addition, the decomposition reaction of hydrogen peroxide is dangerous because it is an exothermic reaction and is not preferable. The reaction is possible even if the molar ratio of H ₂ O ₂ / Sn slightly exceeds 3, but it is not preferable that the molar ratio greatly exceeds 3 for the above-mentioned reason. If the H ₂ O ₂ / Sn molar ratio is less than 2, the oxidation becomes insufficient, which is not preferable. The addition time of the aqueous hydrogen peroxide and the metal tin is, for example, 0.4 to 10 when an aqueous solution of titanium salt in which 1 mol of titanium salt is dissolved is used.
It can be added over a period of time, preferably 0.4 to 5 hours. If the addition time is less than 0.4 hours, the exothermic reaction is so severe that control cannot be performed, and unreacted metal tin tends to remain, which is not preferable. Also, 10
Although it may be longer than time, it is not preferable because it is not economical.

The basic salt of titanium-tin formed in the step (a) is obtained by converting a titanium component and a tin component to titanium oxide (T
TiO ₂ / S converted to iO ₂ ) and tin oxide (SnO ₂ )
nO ₂ molar ratio of 0.25 to 10, preferably 0.4 to
It can be set to 4.0. Even if the molar ratio is less than 0.25, an aqueous solution of a basic salt of titanium-tin can be prepared. However, the molar ratio of the counter anion is decreased, so that a colloid is easily formed, and the refractive index is also decreased. Even when the molar ratio exceeds 10, an aqueous solution of a basic salt of titanium-tin can be prepared.
It is not preferable because the effect of suppressing discoloration of the tin oxide composite sol due to ultraviolet rays is reduced. In the step (a), the total concentration of the titanium-tin basic salt aqueous solution in terms of (TiO ₂ + SnO ₂ ) is preferably 5 to 50% by weight. Although less than 5% by weight is possible, it is inefficient and not economical. Although it is possible to exceed 50% by weight, it is not preferred because the viscosity is high, stirring becomes difficult and the reaction becomes non-uniform.

In the step (a), the reaction of the titanium salt, metallic tin and aqueous hydrogen peroxide in the aqueous medium is 30 to 95.
C., preferably at 40-85.degree. Since the reaction between hydrogen peroxide and metal tin is an oxidation reaction, it is an exothermic reaction, and the decomposition reaction of hydrogen peroxide also occurs at the same time, and this reaction is also an exothermic reaction, so care must be taken in controlling the temperature during the reaction, It can be cooled as needed. Although the reaction temperature may be lower than 30 ° C., the reaction is exothermic and requires excessive cooling, so that the reaction takes too much time and is not economical. If the reaction temperature is in a boiling state of 95 ° C. or higher, coarse colloid particles are generated in the step (a), which is not preferable.

The step (b) is a step of obtaining an aggregate of a titanium oxide-tin oxide composite colloid by hydrolyzing the basic salt of titanium-tin obtained in the step (a). In the step (b), the titanium-tin basic salt aqueous solution has a total concentration (TiO ₂ + SnO ₂ ) of 2 to 15% by weight in terms of titanium oxide (TiO ₂ ) and tin oxide (SnO ₂ ).
It is preferable to prepare. Less than 2% by weight is possible, but inefficient and not economical. Although it is possible to exceed 15% by weight, it is not preferred because the viscosity is high, stirring becomes difficult, and the hydrolysis reaction becomes uneven. Further, in order to control the particle diameter, hydrolysis can be carried out after adding a basic substance in advance and adjusting the pH. Examples of the basic substance include sodium hydroxide, potassium hydroxide, ammonia, and alkylamines such as ethylamine, n-propylamine and isopropylamine, alkanolamines such as triethanolamine, and quaternary ammonium hydroxide. And the pH is preferably adjusted to 1-2.

In step (b), the hydrolysis temperature is 50
Temperatures of １００100 ° C. are preferred. Although it may be lower than 50 ° C., it is not preferable because the hydrolysis takes too much time. 10
Although the temperature may be higher than 0 ° C., a special hydrothermal treatment device such as an autoclave is required, and the secondary aggregate of the colloid formed by the hydrothermal treatment becomes strong, and the obtained titanium oxide-tin oxide composite sol This is not preferable because transparency is reduced.

The time required for hydrolysis in step (b) is preferably 0.1 to 100 hours. If the time is less than 0.1 hour, the hydrolysis becomes insufficient, which is not preferable. If the time exceeds 100 hours, the primary particle diameter becomes large and a strong secondary aggregate is formed, which is not preferable. This (b)
The primary particle diameter of the titanium oxide-tin oxide composite colloid particles obtained by the process is 2 to 20 nm (nanometers). The primary particle size can be observed with an electron microscope.

The step (c) comprises removing excess electrolyte (mainly anions) from the slurry of the titanium oxide-tin oxide composite colloid obtained in the step (b) to obtain a titanium oxide-tin oxide composite colloid. This is a step of pulverizing particles to obtain a sol. By removing excess electrolyte, a sol in which titanium oxide-tin oxide composite colloid particles are dispersed in a state close to primary particles can be obtained. This washing can be carried out by coagulation and sedimentation, decanting the supernatant, ultrafiltration, ion exchange, etc., but when a large amount of electrolyte is contained, washing by repeating ultrafiltration → water injection → ultrafiltration The method is particularly preferred.

Through the step (c), a titanium oxide-tin oxide composite aqueous sol is obtained. The primary particle diameter of the titanium oxide-tin oxide composite colloid particles in the sol obtained in the step (c) is 2 to 20 nm. If the primary particle size is less than 2 nm, the viscosity of the titanium oxide-tin oxide composite sol produced using the same increases, and the water resistance also decreases, such being undesirable. Further, when the primary particle size is 20 nm or more, the transparency of the titanium oxide-tin oxide composite sol produced using the same is not preferred, which is not preferable.

As the step (d), a step of anion-exchanging the titanium oxide-tin oxide composite aqueous sol obtained in the step (c) can be added. By this anion exchange treatment, a stable sol can be obtained even at a high concentration. For the anion exchange in the step (d), a commercially available anion exchange resin can be used, and the anion exchange resin is used after being adjusted to a hydroxyl group type. Anion exchange can be easily performed by passing a titanium oxide-tin oxide composite aqueous sol through a column filled with an anion exchange resin. The liquid passing temperature is preferably 0 to 60 ° C., and the liquid passing speed is preferably a space velocity SV1 to 10 hours. In the step (d), before and / or after the anion exchange treatment, a basic substance can be added to the titanium oxide-tin oxide composite aqueous sol to increase the stability. The basic substance used in the step (d) is preferably an organic base, for example, alkylamines such as ethylamine, n-propylamine and isopropylamine, alkanolamines such as triethanolamine, and quaternary ammonium hydroxide. Used.

Although the alkaline titanium oxide-tin oxide composite sol obtained in the step (d) is stable as it is, it is concentrated by an ultrafiltration method or an evaporation method as needed to obtain a high-concentration stable sol. I can do it. (E) As a process,
A step of replacing the aqueous medium of the titanium oxide-tin oxide composite aqueous sol obtained in the step (c) or the step (d) with an organic solvent can be added.

At the time of the solvent replacement in the step (e), the solvent replacement can be performed stably by adding a small amount of an organic base and / or an organic acid as a stabilizer. Examples of the organic base include ethylamine, n-propylamine,
Alkylamines such as isopropylamine, alkanolamines such as triethanolamine, and quaternary ammonium hydroxides. Examples of organic acids include glycolic acid, tartaric acid, malic acid, oxycarboxylic acids such as citric acid, And phenylphosphonic acid. This solvent replacement can be performed by a commonly used method such as a distillation method and an ultrafiltration method. Examples of the organic solvent include lower alcohols such as methanol, ethanol and isopropanol; linear amides such as dimethylformamide and N, N-dimethylacetamide; cyclic amides such as N-methyl-2-pyrrolidone; glycol ethers such as ethyl cellosolve. And the like; ethylene glycol and the like.

The primary particle diameter of the titanium oxide-tin oxide composite colloid particles in the sol obtained through the steps (d) and (e) is also 2 to 20 nm. Titanium oxide (T
Since iO ₂ ) has an ultraviolet absorbing ability, a powder having a particle diameter of about 0.1 to 10 μm is added to various plastics and fibers as an ultraviolet-resistant pigment or a filler,
in use. In addition, titanium oxide used as a microfiller in optical-related applications, for example, a coating composition applied to an optical member or a transparent film, is used as a sol having a primary particle diameter of 100 nm or less, preferably 20 nm or less. ing. Titanium oxide having a small primary particle diameter is very sensitive to ultraviolet light, so that the ultraviolet absorption effect is improved. On the other hand, the reduction reaction of titanium oxide to TiO ₂ → TiO partially occurs due to the ultraviolet light, and it appears dark blue. Has disadvantages. Stannous oxide (Sn
O ₂₎ also has a primary particle diameter of 100nm or less, partly SnO ₂ → Sn by ultraviolet especially equal to or less than the sol 30nm
It has the disadvantage of exhibiting a brown or blue-green color due to the reduction reaction to O.

The titanium oxide-tin oxide composite sol used in the present invention is prepared by adding hydrogen peroxide and metallic tin to a titanium salt aqueous solution while maintaining the H ₂ O ₂ / Sn molar ratio in the range of 2-3. Thus, an aqueous solution of a basic salt of titanium-tin is prepared and hydrolyzed to form an aqueous solution of a titanium oxide-tin oxide composite colloid. Therefore,

[0036]

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It is considered that the bond is formed. Therefore, when each of the oxides is a single oxide by irradiation with ultraviolet rays,
Alternatively, the reduction to TiO or SnO is remarkably suppressed as compared with the case where the respective oxides are mixed, and almost no discoloration occurs. Further, the sol used in the present invention can be formed into TiO ₂ particles or SnO ₂ particles even after performing operations such as electrolyte removal, ion exchange, and solvent replacement in the steps (c), (d) and (e). At the atomic level because there is nothing to separate

[0038]

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It is considered that the bond shown in FIG.
Further, since the titanium oxide-tin oxide composite sol used in the present invention is uniformly compounded (solid solution) at an atomic level,
When used as a material for various ceramics, it is possible to reduce the sintering temperature and to provide more uniform material characteristics of titanium oxide-tin oxide.

The coating composition of the present invention comprises (C)
As a component, at least one metal compound selected from the group consisting of metal salts, metal alkoxides and metal chelates can be contained as a curing catalyst. By adding the above-mentioned component (C), when the coating composition of the present invention is applied to the surface of an optical base material and cured, a curing reaction can be accelerated, and a sufficiently cured film can be obtained in a short time. I can do it.

The above component (C) is composed of organic carboxylic acid, chromic acid, hypochlorous acid, boric acid, perchloric acid, bromic acid, selenous acid, thiosulfuric acid, orthosilicic acid, thiocyanic acid, nitrous acid, aluminate And alkali metal salts such as carbonic acid, alkaline earth metal salts, and polyvalent metal salts, and metal alkoxides containing aluminum, zirconium, and titanium, and metal chelate compounds thereof. Particularly, the component (C) is preferably a metal chelate compound. Examples of the metal chelate compound include an acetylacetonate complex, for example, aluminum acetylacetonate. Acetylacetone CH ₃ COCH ₂ COCH
_The anion in which one proton is dissociated from the CH ₂ group of No. 3 is an acetylacetonate ligand (abbreviation acac), and aluminum acetylacetonate has a structure of Al (acac) ₃ .

The component (C) includes allylamine,
Amines such as ethylamine, and various acids and bases including Lewis acids and Lewis bases can also be used. The coating composition of the present invention can contain a particulate metal oxide to match the refractive index of various optical members, for example, a lens. Examples of these particulate metal oxides include aluminum oxide, titanium oxide, antimony oxide, zirconium oxide, silicon oxide, and cerium oxide.

Further, the coating composition of the present invention comprises:
Various surfactants can be contained to improve the wettability when applied to the surface of the optical member and to improve the smoothness of the cured film. Further, ultraviolet absorbers, antioxidants and the like can be added as long as they do not affect the physical properties of the obtained film. The coating composition of the present invention,
The colloidal particles of titanium oxide-tin oxide can be contained in an amount of 1 to 500 parts by weight, preferably 100 to 300 parts by weight, based on 100 parts by weight of the silicon-containing substance (A). If the titanium oxide-tin oxide composite colloidal particles are less than 1 part by weight, the resulting film will have a low refractive index,
The range of application to the substrate is significantly limited. On the other hand, when the amount exceeds 500 parts by weight, cracks and the like are easily generated between the cured film and the substrate, and the possibility of lowering the transparency is undesirably increased.

According to the present invention, an optical member having on its surface a cured film composed of the above-mentioned coating composition is obtained. As a method of forming a cured film made of the coating composition of the present invention on an optical member, there is a method of applying the above-described coating composition to an optical member and then curing the optical member. As a coating means, a commonly used method such as a dipping method, a spin method and a spray method can be applied, but the dipping method and the spin method are particularly preferable from the viewpoint of the surface smoothness of the obtained film.

Prior to applying the above-mentioned coating composition to the optical member, a chemical treatment with an acid, an alkali, various organic solvents, a physical treatment with plasma, ultraviolet light, etc., a detergent treatment with various detergents, and a resin treatment are carried out. The adhesion between the optical member and the cured film can be improved by using a primer treatment using a. The coating composition of the present invention can be applied to an optical member and then cured to form a cured film. Curing of the coating composition of the present invention can be performed by hot air drying or active energy ray irradiation. When using hot air drying, the drying is preferably performed in hot air at 70 to 200 ° C, particularly preferably 90 to 150 ° C. Also,
Far infrared rays can be used as the active energy rays, and damage due to heat can be suppressed to a low level.

According to the present invention, it is possible to obtain an optical member having on its surface a film obtained by laminating a cured film comprising the above-mentioned coating composition and an antireflection film. This anti-reflective coating,
It can be provided on a cured film made of the coating composition of the present invention. This antireflection film is preferably a multilayer film, and is obtained by alternately stacking low-refractive-index films and high-refractive-index films. Examples of the high-refractive-index film used for the antireflection film include a zirconium oxide vapor-deposited film and a mixed vapor-deposited film of zirconium oxide and a metal oxide containing tantalum oxide and yttrium oxide. Examples of the film include a deposited film of silica. The above-mentioned zirconium oxide vapor-deposited film, or a mixed vapor-deposited film of metal oxides containing tantalum oxide and yttrium oxide in zirconium oxide, zirconium oxide powder alone, or tantalum oxide powder and zirconium oxide powder mixed with yttrium oxide powder, An antireflection film can be provided by evaporating a pellet formed by pressing, sintering, or the like onto a film made of the coating composition of the present invention by an electron beam heating method.

Further, the cured film made of the coating composition of the present invention has a high refractive index and can be used as an antireflection film by itself, and further has a functional component such as antifogging, photochromic, and antifouling. Can be used as a multifunctional film. The optical member used in the present invention is preferably a transparent plastic molded body,
Examples of the transparent plastic include, in addition to spectacle lenses, camera lenses, automobile window glasses, optical filters attached to liquid crystal displays, plasma displays, and the like.

The coating composition of the present invention comprises (A)
(B) at least one silicon-containing substance selected from the group consisting of organosilicon compounds represented by the general formulas (I) and (II) and a hydrolyzate thereof;
It contains titanium oxide-tin oxide composite colloid particles as a component. The coating composition of the present invention is obtained by hydrolyzing the organosilicon compound of the component (A) with an acidic aqueous solution, and (B)
It can be produced by mixing with an organosol containing titanium oxide-tin oxide composite colloid particles containing the components. As the organosol containing the titanium oxide-tin oxide composite colloid particles, a sol in which the titanium oxide-tin oxide composite colloid particles are dispersed in a methanol solvent can be preferably used.

The above coating composition is applied to an optical member and cured to obtain excellent scratch resistance, surface hardness, abrasion resistance, transparency, heat resistance, light resistance, weather resistance, water resistance, and refraction. Even when applied to a member having a high refractive index of 1.54 or more, an optical member having high transparency and good appearance without interference fringes can be obtained. Specific examples will be described in detail in the following examples. However, the present invention is not limited to the following embodiments.

[0050]

【Example】

Reference Example 1 (Preparation of Titanium Oxide-Tin Oxide Composite Sol) (a) Step: Titanium tetrachloride (in terms of TiO ₂ ) 27.
2 wt%, Cl 32.0 wt%, Sumitomo Sitix Co., Ltd.
587.5 g (159.8 g in terms of TiO ₂ )
And 477.8 g of water were placed in a 3 liter jacketed glass separable flask and a titanium chloride aqueous solution 106 was added.
5.3 g (concentration of 15.0% by weight in terms of TiO ₂ ) was prepared.

The aqueous solution was heated to 60 ° C. while being stirred with a glass stirring rod, and then cooled and cooled with 486.0 g of 35% by weight aqueous hydrogen peroxide (industrial) and metal tin powder (Yamaishi Metal Co., Ltd.). ), Trade name AT-Sn, No. 20
0) 237.4 g was added. First, 24.3 g of hydrogen peroxide solution (0.25 g) was added.
Mol) and then 11.87 g (0.1 mol) of tin metal. After the reaction was completed (5 to 10 minutes), 24.3 g (0.25 mol) of aqueous hydrogen peroxide and then 11.87 g (0.1 mol) of metal tin were gradually added. By repeating the addition of metal tin subsequent to the addition of the hydrogen peroxide solution at intervals of 5 to 10 minutes for a total of 20 times, 24.3 g of hydrogen peroxide solution and 20 times of metal tin were added. 87 g x 20 additions were made.

The reaction is exothermic and the temperature becomes 80 to 85 ° C. by the addition of metallic tin.
The temperature dropped to 0 to 70 ° C. The reaction temperature was therefore between 60 and 85 ° C. during the above addition. The ratio of hydrogen peroxide to metal tin at the time of addition was 2.5 in terms of H ₂ O ₂ / Sn molar ratio. The time required for adding the aqueous hydrogen peroxide and the metal tin was 2.5 hours. Since water evaporates due to the reaction, an appropriate amount was replenished. After completion of the reaction, 2258 g of a pale yellow transparent basic titanium chloride-tin complex salt aqueous solution was obtained. In the obtained basic titanium chloride-tin complex salt aqueous solution, the titanium component had a concentration of 7.08 in terms of titanium oxide (TiO ₂ ).
The weight percentage of the tin component was 13.35% by weight in terms of a concentration in terms of tin oxide (SnO ₂ ), and the molar ratio in terms of TiO ₂ / SnO ₂ was 1.0. The (Ti + Sn) / Cl molar ratio was 0.73.

Step (b): Water (301) was added to 980.4 g of the basic titanium chloride-tin complex salt aqueous solution obtained in step (a).
9.6 g was added, and the mixture was diluted to 5% by weight in terms of TiO ₂ + SnO ₂ . This aqueous solution is heated at 95-98 ° C for 1 hour.
Hydrolysis was performed for 2 hours to obtain an aggregate slurry of a titanium oxide-tin oxide composite colloid having a primary particle diameter of 4 to 8 nm.

Step (c): The procedure of concentration → water injection → concentration of the aggregate of the titanium oxide-tin oxide composite colloid aggregate obtained in the step (b) is repeated using about 8 liters of water in an ultrafiltration apparatus. After washing and removing excess electrolyte, the mixture is deflocculated and acidic titanium oxide-tin oxide composite aqueous sol 3624 g
I got The primary particle diameter of the titanium oxide-tin oxide composite colloid particles measured by an electron microscope was 4 to 8 nm.

Step (d): After adding 6.0 g of isopropylamine to 3624 g of the acidic titanium oxide-tin oxide composite aqueous sol obtained in step (c), an anion exchange resin (Amberlite IRA-410, organo ( 20)
The solution was passed through a column packed with 0 ml to obtain 4696 g of an alkaline titanium oxide-tin oxide composite aqueous sol.
This sol was concentrated under reduced pressure using a rotary evaporator to obtain a titanium oxide-tin oxide composite aqueous concentrated sol 18.
20.8 g were obtained. The obtained sol had a specific gravity of 1.100, a viscosity of 16.3 mPa · s, a pH of 8.91, and a conductivity of 1005.
μs / cm, the concentration in terms of TiO ₂ was 3.8% by weight,
The concentration in terms of SnO ₂ was 7.2% by weight.

Step (e): The alkaline titanium oxide-tin oxide composite aqueous concentrated sol obtained in step (d) 1877.
While stirring to 1 g, tartaric acid 12 g, diisopropylamine 1
After adding 8 g, the aqueous medium was replaced with methanol by a method of distilling off water while gradually adding 40 liters of methanol under reduced pressure using a rotary evaporator to prepare 915 g of a titanium oxide-tin oxide composite methanol sol. . The obtained methanol sol had a specific gravity of 1.096 and a primary particle diameter of titanium oxide-tin oxide composite colloidal particles of 4 to
8 nm, viscosity 4.3 mPa · s, pH (1 + 1) 7.4
0, conductivity (1 + 1) 1405 μs / cm, the concentration in terms of TiO ₂ was 10.6% by weight, the concentration in terms of SnO ₂ was 19.9% by weight and the water content 0.44% by weight.

Reference Example 2 (Preparation of Titanium Oxide-Tin Oxide Composite Sol) (a) Step: Titanium tetrachloride (in terms of TiO ₂ )
2 wt%, Cl 32.0 wt%, Sumitomo Sitix Co., Ltd.
587.5 g (159.8 g in terms of TiO ₂ )
And 744.2 g of water were placed in a 3-liter glass separable flask with a jacket, and an aqueous titanium chloride solution 133 was added.
1.7 g (concentration of 12.0% by weight in terms of TiO ₂ ) was prepared. This aqueous solution was heated to 50 ° C. while being stirred with a glass stirring rod, and then cooled, and 797.0 g of 35% by weight hydrogen peroxide solution (for industrial use) and metallic tin powder (manufactured by Yamaishi Metal Co., Ltd.) Product name AT-Sn, No. 20
0) 474.8 g were added.

For the addition of the hydrogen peroxide solution and the metal tin, first, 26.4 g (0.22 mol) of the metal tin and 44.3 g (0.46 mol) of the hydrogen peroxide solution were gradually added.
After the reaction was completed (5 to 10 minutes), 26.4 g (0.22 mol) of metal tin and then 44.3 g (0.46 mol) of aqueous hydrogen peroxide were gradually added. In this manner, the addition of the aqueous solution of hydrogen peroxide following the addition of the tin metal is 5 to 10
By repeating 17 times at intervals of one minute, (26.4 g of metal tin and 44.3 g of hydrogen peroxide) × 17 divided additions were performed, and finally 26.0 g of metal tin was then peroxided. 43.9 g of hydrogen water was added, and a total of 18 divided additions were performed.

The reaction is exothermic and reaches 70-75 ° C. by the addition of metallic tin.
The temperature dropped to 0 to 60 ° C. Therefore, the reaction temperature is 50-75 ° C
Met. At the time of addition, the ratio of aqueous hydrogen peroxide to metallic tin is H
_The molar ratio of ₂ O ₂ / Sn was 2.09. The time required for adding the aqueous hydrogen peroxide and the metal tin was 3.0 hours. Since water evaporates due to the reaction, an appropriate amount was replenished.
After the completion of the reaction, 2730.9 g of a pale yellow transparent basic titanium chloride-tin complex salt aqueous solution was obtained. In the obtained aqueous solution of basic titanium chloride-tin complex salt, the titanium component had a concentration of 5.85% by weight in terms of titanium oxide (TiO ₂ ),
The tin component had a concentration of 22.07% by weight in terms of tin oxide (SnO ₂ ) and a molar ratio of 0.5 in terms of TiO ₂ / SnO ₂ . The (Ti + Sn) / Cl molar ratio was 1.10.

Step (b): Water (119.7 g) was added to 2569.7 g of the aqueous solution of the basic titanium chloride-tin complex salt obtained in step (a).
407 g and 211 g of 28% by weight aqueous ammonia were added, and diluted to 5% by weight in terms of TiO ₂ + SnO ₂ . This aqueous solution was hydrolyzed at 95 ° C. for 10 hours to obtain an aggregate slurry of a titanium oxide-tin oxide composite colloid having a primary particle diameter of 4 to 8 nm.

Step (c): The procedure of concentration → injection → concentration of the aggregated slurry of the titanium oxide-tin oxide composite colloid obtained in step (b) using an ultrafiltration device using about 15 liters of water is repeated. After washing away excess electrolyte, it is deflocculated to obtain an acidic titanium oxide-tin oxide composite aqueous sol 1583.
0 g was obtained. The primary particle diameter of the titanium oxide-tin oxide composite colloid particles measured by an electron microscope was 4 to 8 nm.

Step (d): 137 g of isopropylamine was added to 15830 g of the acidic titanium oxide-tin oxide composite sol obtained in step (c) to make it alkaline, and then about 24 liters of water was used in an ultrafiltration apparatus. The operation of concentration, water injection, and concentration is repeated to wash and remove excess electrolyte, and an alkaline titanium oxide-tin oxide composite aqueous sol 14602 g
I got Furthermore, an anion exchange resin (Amberlite IRA)
The solution was passed through a column packed with 200 ml of -410 (manufactured by Organo Corporation) to obtain 15273 g of an alkaline titanium oxide-tin oxide composite aqueous sol having a small anion content. This sol was concentrated under reduced pressure using a rotary evaporator to obtain 4848.9 g of an aqueous concentrated titanium oxide-tin oxide composite sol. The obtained sol had a specific gravity of 1.120, a viscosity of 5.5 mPa · s, and a pH of 9.9.
2. Conductivity 1230 μs / cm, the concentration converted to TiO ₂ is 3.04% by weight, and the concentration converted to SnO ₂ is 11.
46% by weight.

Step (e): The alkaline concentrated titanium oxide-tin oxide composite aqueous sol 192 obtained in step (d)
After adding 12 g of tartaric acid and 18 g of diisopropylamine to 4.7 g with stirring, the aqueous medium was replaced with methanol by a method of distilling off water while gradually adding 40 liters of methanol under reduced pressure using a rotary evaporator. 915 g of titanium oxide-tin oxide composite methanol sol
It was created. The resulting methanol sol had a specific gravity of 1.09.
6. Primary particle diameter of titanium oxide-tin oxide composite colloid particles 4 to 8 nm, viscosity 3.5 mPa · s, pH (1 + 1)
7.38, conductivity (1 + 1) 1305 μs / cm, Ti
The concentration calculated as O ₂ was 6.4% by weight, the concentration calculated as SnO ₂ was 24.1% by weight, and the water content was 0.41% by weight.

Reference Example 3 (Preparation of methanol sol of titanium oxide) Titanium tetrachloride (27.2% by weight in terms of TiO ₂ , C
132.0% by weight, manufactured by Sumitomo Citix Co., Ltd.)
5 g (159.8 g in terms of TiO ₂ ) and water 260
8.5 g was placed in a 3 liter jacketed glass separable flask with a titanium chloride aqueous solution (3196 g (T
(a concentration of 5.0% by weight in terms of iO ₂ ).

After adding 50 g of 28% by weight ammonia water to this aqueous solution while stirring with a glass stirring rod,
This aqueous solution was hydrolyzed at 95 ° C. for 10 hours to obtain an aggregate slurry of titanium oxide colloid having a primary particle diameter of 4 to 8 nm. This aggregate slurry of titanium oxide colloid is 5
Suction filtration was performed using B filter paper, and then water washing was performed using about 40 liters of water to remove excess electrolyte to obtain 620 g of a titanium oxide wet cake. After dispersing the obtained wet cake in 2576 g of water, 8.0 g of isopropylamine was added to make it alkaline, and then 200 ml of an anion exchange resin (Amberlite IRA-410, manufactured by Organo Corporation) was filled. The solution was passed through a column to obtain 3890 g of an aqueous sol of alkaline titanium oxide. This sol is reduced under reduced pressure with a rotary evaporator.
After concentration, alkaline titanium oxide aqueous concentrated sol 10
70 g were obtained. Tartaric acid 12.1 is added to the obtained sol with stirring.
g and 26.1 g of diisopropylamine, and methanol 2 was added under reduced pressure using a rotary evaporator.
The aqueous medium was replaced with methanol by a method of distilling off water while gradually adding 5 liters to prepare 775.2 g of a titanium oxide methanol sol. The obtained methanol sol has a specific gravity of 0.970 and a primary particle diameter of titanium oxide particles of 4 to 8
nm, viscosity 4.5 mPa · s, pH (1 + 1) 8.9
8, conductivity 1600 μs / cm, TiO ₂ 20.2% by weight, moisture 3.4% by weight.

(Preparation of Coating Solution) Example 1 To a glass container equipped with a magnetic stirrer, 105.3 parts by weight of γ-glycidoxypropyltrimethoxysilane corresponding to the above-mentioned component A was added, and the liquid temperature was lowered. 5-1
Keep at 0 ° C. and stir with stirring.
Parts by weight were added dropwise over 3 hours. After completion of the dropwise addition, the mixture was stirred for 0.5 hour to obtain a partial hydrolyzate of γ-glycidoxypropyltrimethoxysilane. Next, the titanium oxide-tin oxide composite methanol sol (TiO ₂
The concentration in terms of + SnO ₂ is 30.5% by weight.
8 parts by weight, 65 parts by weight of butyl cellosolve, and 4.2 parts by weight of aluminum acetylacetonate as a curing agent were added to 142.1 parts by weight of the above-mentioned partial hydrolyzate of γ-glycidoxypropyltrimethoxysilane. After stirring, filtration was performed to prepare a coating liquid.

Example 2 To a glass container equipped with a magnetic stirrer, 105.3 parts by weight of γ-glycidoxypropyltrimethoxysilane corresponding to the above-mentioned component A was added, and the liquid temperature was adjusted to 5-1.
Keep at 0 ° C. and stir with stirring.
Parts by weight were added dropwise over 3 hours. After completion of the dropwise addition, the mixture was stirred for 0.5 hour to obtain a partial hydrolyzate of γ-glycidoxypropyltrimethoxysilane. Next, the titanium oxide-tin oxide composite methanol sol (TiO ₂
The concentration in terms of + SnO ₂ is 30.5% by weight.
8 parts by weight, 65 parts by weight of butyl cellosolve, and 4.2 parts by weight of aluminum acetylacetonate as a curing agent were added to 142.1 parts by weight of the above-mentioned partial hydrolyzate of γ-glycidoxypropyltrimethoxysilane. After stirring, filtration was performed to prepare a coating liquid.

Example 3 In a glass container provided with a magnetic stirrer, 22.3 tetraethoxysilane corresponding to the above-mentioned component A was added.
Parts by weight and 77.9 parts by weight of γ-glycidoxypropylmethyldiethoxysilane were added, and 36.8 parts by weight of 0.01 N hydrochloric acid was added dropwise with stirring while maintaining the liquid temperature at 5 to 10 ° C. did. After completion of the dropwise addition, the mixture was stirred for 0.5 hour to obtain a partial hydrolyzate of tetraethoxysilane and γ-glycidoxypropylmethyldiethoxysilane. Next, the titanium oxide-tin oxide composite methanol sol (TiO ₂ + SnO ₂ concentration obtained in Reference Example 1 described above was 30.
397.8 parts by weight), 65 parts by weight of butyl cellosolve, 2.6 parts by weight of aluminum acetylacetonate as a curing agent and 0.5 part by weight of ammonium perchlorate were added to the above-mentioned tetraethoxysilane and γ-glycidic acid. Partially hydrolyzed product of xypropylmethyldiethoxysilane 13
In addition to 7 parts by weight, the mixture was sufficiently stirred and filtered to prepare a coating liquid.

Example 4 In a glass container provided with a magnetic stirrer, 74.2 parts by weight of γ-glycidoxypropyltrimethoxysilane and γ-glycidoxypropylmethyldimethoxysilane 31 corresponding to the aforementioned component A were added. Then, 36.8 parts by weight of 0.01 N hydrochloric acid was added dropwise with stirring over 3 hours while maintaining the liquid temperature at 5 to 10 ° C. After completion of the dropwise addition, the mixture was stirred for 0.5 hour to obtain a partial hydrolyzate of γ-glycidoxypropyltrimethoxysilane and γ-glycidoxypropylmethyldimethoxysilane. Next, 397.8 parts by weight of titanium oxide-tin oxide composite methanol sol (concentration in terms of TiO ₂ + SnO ₂ of 30.5% by weight) obtained in Reference Example 2 described above, 65 parts by weight of butyl cellosolve,
Further, 4.2 parts by weight of aluminum acetylacetonate as a curing agent was added to 142.1 parts by weight of the above-mentioned partial hydrolyzate of γ-glycidoxypropyltrimethoxysilane and γ-glycidoxypropylmethyldimethoxysilane, and After stirring, the mixture was filtered to prepare a coating liquid.

Example 5 In a glass container equipped with a magnetic stirrer, 37.1 parts by weight of γ-glycidoxypropyltrimethoxysilane corresponding to the above-mentioned component A, and γ-glycidoxypropylmethyldimethoxysilane 37 .1 part by weight and 23.7 parts by weight of tetraethoxysilane, and
Keep at 0 ° C. and stir with stirring.
Parts by weight were added dropwise over 3 hours. After completion of the dropwise addition, the mixture was stirred for 0.5 hour to obtain a partial hydrolyzate of γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, and tetraethoxysilane. Next, the titanium oxide-tin oxide composite methanol sol obtained in the above-mentioned Reference Example 2 (concentration in terms of TiO ₂ + SnO ₂ is 30.
397.8 parts by weight), 65 parts by weight of butyl cellosolve and 4.2 parts by weight of aluminum acetylacetonate as a curing agent were added to the above-mentioned γ-glycidoxypropyltrimethoxysilane and γ-glycidoxypropylmethyldimethoxy. It was added to 134.7 parts by weight of a partial hydrolyzate of silane and tetraethoxysilane, and after sufficiently stirring, filtration was performed to prepare a coating liquid.

Comparative Example 1 105.3 parts by weight of γ-glycidoxypropyltrimethoxysilane corresponding to the above-mentioned component A was added to a glass container equipped with a magnetic stirrer, and the liquid temperature was adjusted to 5-1.
Keep at 0 ° C. and stir with stirring.
Parts by weight were added dropwise over 3 hours. After completion of the dropwise addition, the mixture was stirred for 0.5 hour to obtain a partial hydrolyzate of γ-glycidoxypropyltrimethoxysilane. Next, the titanium oxide methanol sol obtained in Reference Example 3 (TiO ₂ concentration was 20.2
600.6 parts by weight), 65 parts by weight of butyl cellosolve, 4.2 parts by weight of aluminum acetylacetonate as a curing agent, 142.1 parts by weight of the above-mentioned partial hydrolyzate of γ-glycidoxypropyltrimethoxysilane After sufficiently stirring, the mixture was filtered to prepare a coating liquid.

Comparative Example 2 To a glass container equipped with a magnetic stirrer, 105.3 parts by weight of γ-glycidoxypropyltrimethoxysilane corresponding to the above-mentioned component A was added, and the liquid temperature was adjusted to 5-1.
Keep at 0 ° C. and stir with stirring.
Parts by weight were added dropwise over 3 hours. After completion of the dropwise addition, the mixture was stirred for 0.5 hour to obtain a partial hydrolyzate of γ-glycidoxypropyltrimethoxysilane. Next, colloidal particles of tin oxide having a particle diameter of 7.2 nm are used as nuclei, and the surface thereof has a WO ₃ / SnO ₂ weight ratio of 5.12 and a particle diameter of 5 nm.
Particle diameter of about 18 n formed by coating with tungsten oxide-tin oxide composite colloidal particles
m modified tin oxide methanol sol [(WO ₃ + SnO ₂ )
/ SnO ₂ weight ratio 0.46, containing 30.0% by weight of total metal oxides in terms of WO ₃ + SnO ₂ ] 433.3
Parts by weight, 65 parts by weight of butyl cellosolve, and 4.2 parts by weight of aluminum acetylacetonate as a curing agent.
It was added to 142.1 parts by weight of the above-mentioned partial hydrolyzate of γ-glycidoxypropyltrimethoxysilane, sufficiently stirred, and then filtered to prepare a coating liquid.

Comparative Example 3 To a glass container equipped with a magnetic stirrer, 105.3 parts by weight of γ-glycidoxypropyltrimethoxysilane corresponding to the above-mentioned component A was added, and the liquid temperature was adjusted to 5-1.
Keep at 0 ° C. and stir with stirring.
Parts by weight were added dropwise over 3 hours. After completion of the dropwise addition, the mixture was stirred for 0.5 hour to obtain a partial hydrolyzate of γ-glycidoxypropyltrimethoxysilane. Next, colloidal silica methanol sol (solid content: 20%, average particle size: 15 nm) 6
50.0 parts by weight, 65 parts by weight of butyl cellosolve, and 4.2 parts by weight of aluminum acetylacetonate as a curing agent were added to 142.1 parts by weight of the above-mentioned partial hydrolyzate of γ-glycidoxypropyltrimethoxysilane, After sufficiently stirring, filtration was performed to prepare a coating liquid.

(Formation of Cured Film) Commercially available refractive index n _D = 1.
A polycarbonate plate of No. 59 was prepared, and the coating composition obtained in each of Examples 1 to 5 and Comparative Examples 1 to 3 was applied thereto by spin coating, followed by heat treatment at 120 ° C. for 2 hours. The coating film was cured to prepare a test sample (optical member).

The following tests were carried out on films on the polycarbonate comprising the coating compositions obtained in Examples 1 to 5 and Comparative Examples 1 to 3 as Example Films 1 to 5 and Comparative Examples 1 to 3, respectively. The results are shown in Tables 1 and 2. (Scratch resistance test) The test sample of the above optical member was rubbed with steel wool # 0000, and the degree of scratch resistance was visually determined. The criteria were as follows.

A: hardly scratched even when strongly rubbed B: considerably scratched when strongly rubbed C: scratched as well as optical substrate (test for presence of interference fringes) Fluorescent lamp The test sample of the above optical member was visually judged below. The criteria are as follows.

A: almost no interference fringes B: slightly visible C: fairly visible (adhesion test) 100 cross-cuts were made on the test sample of the optical member at 1 mm intervals. Where the adhesive tape (trade name Cellotape, Nichiban Co., Ltd.)
Product), then peel off the adhesive tape quickly,
The presence or absence of peeling of the cured film after peeling off the adhesive tape was examined. If the cured film did not peel off, it was judged as good, and if the peeling occurred, it was regarded as bad.

(Warm Water Resistance Test) A test sample of the above optical member was immersed in hot water of 80 ° C. for 2 hours, and the same adhesion test as described above was performed. (Transparency test) In a dark room, under a fluorescent lamp, a test sample of the optical member was visually inspected for cloudiness. The criteria are as follows.

A: Fogging is hardly visible. B: Somewhat visible. C: It looks pretty. (Weather resistance test) A test sample (optical member) further provided with an antireflection film made of a vapor-deposited film of an inorganic oxide on the cured film of the test sample of the above optical member was exposed outdoors for one month. A change in the appearance of the test sample (optical member) was judged by visual observation.

[0080]

Table 1 Example 1 Film scratch resistance Interference fringe adhesion Hot water resistance Transparency Weather resistance 1 A A good good A no abnormality 2 A A good good A no abnormality 3 A A good good A no abnormality 4 A A Good Good A No abnormality 5 A A Good Good A No abnormality

[0081]

[Table 2] Comparative Example 2 Film Scratch Resistance Interference Fringe Adhesion Resistance to Hot Water Transparency Weather Resistance 1 A A Good Peeling A Blue discoloration 2 A A Good Partial peeling A Slight yellowing 3 A C Good Good A No abnormality For the optical member having the cured film made of the coating composition of the present invention, good results were obtained in the above test.

On the other hand, when titanium oxide particles are used in place of the titanium oxide-tin oxide composite colloid particles for the component (B), the water resistance is inferior, the cured film turns blue due to sunlight, and the weather resistance is reduced. Poor sex. When the component (B) is replaced with titanium oxide-tin oxide composite colloidal particles and modified tin oxide colloidal particles whose surfaces are covered with colloidal particles of tungsten oxide-tin oxide composite are used as colloidal particles of tin oxide. Inferior in warm water resistance, the cured film is yellowed by sunlight, and is inferior in weather resistance.

When the silica colloid particles are used in place of the titanium oxide-tin oxide composite colloid particles for the component (B), the cured film has a low refractive index, which causes a difference in the refractive index between the cured film and the plastic substrate. Therefore, interference fringes are generated on the surface of the optical member, which is not preferable.

[0084]

The cured film obtained by the coating composition of the present invention is a coating layer having improved scratch resistance, surface hardness, abrasion resistance, transparency, heat resistance, light resistance, weather resistance and, in particular, improved water resistance. Becomes Further, the adhesiveness with an antireflection film (such as an inorganic oxide or a fluoride) and a metal vapor-deposited film formed on the coating layer is also good.

The optical member of the present invention is excellent in scratch resistance, surface hardness, abrasion resistance, transparency, heat resistance, light resistance, weather resistance, and especially water resistance, and has a refractive index of 1. 54
An optical member having high transparency and good appearance without interference fringes even when coated on the above-mentioned member having a high refractive index. Optical member having a cured film comprising the coating composition of the present invention, in addition to eyeglass lenses, camera lenses, automotive window glass,
It can be used for optical filters attached to liquid crystal displays, plasma displays, and the like.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Neko Iijima 722-1, Tsuboi-cho, Funabashi-shi, Chiba Pref. Nissan Chemical Industry Co., Ltd.

Claims (5)

[Claims] 1. The following components (A) and (B); component (A): general formula (I) (R ¹ ) _a (R ³ ) _b Si (OR ² ) _{4- (a + b)} (I (Where R ¹ and R ³ are an alkyl group, an aryl group, a halogenated alkyl group, a halogenated aryl group, an alkenyl group, or an epoxy group, an acryloyl group, a methacryloyl group, a mercapto group, an amino group, or a cyano group, respectively) Wherein R ² is an organic group having a bond with a silicon atom through a Si—C bond, and R ² is an alkyl group having 1 to 8 carbon atoms, an alkoxyalkyl group, or an acyl group;
a and b are each an integer of 0, 1, or 2, and a +
b is an integer of 0, 1, or 2. ) And the general formula (I
I) [(R ⁴ ) _c Si (OX) _{3 -c} ] ₂ Y (II) (where R ⁴ represents an alkyl group having 1 to 5 carbon atoms, and X represents an alkyl group having 1 to 4 carbon atoms or acyl) Y is a methylene group or an alkylene group having 2 to 20 carbon atoms, and c is an integer of 0 or 1.), and an organic silicon compound represented by the formula: A coating composition comprising at least one silicon-containing substance, and component (B): titanium oxide-tin oxide composite colloid particles having a primary particle diameter of 2 to 20 nm. 2. The composition according to claim 1, wherein the component (A) is at least one silicon-containing substance selected from the group consisting of an organosilicon compound represented by the general formula (I) and a hydrolyzate thereof. Coating composition. 3. The coating composition according to claim 1, wherein the component (C) contains at least one metal compound selected from the group consisting of metal salts, metal alkoxides and metal chelates as a curing catalyst. Stuff. 4. An optical member having a cured film made of the coating composition according to claim 1 on a surface. 5. An optical member having on its surface a film obtained by laminating a cured film comprising the coating composition according to claim 1 and an antireflection film.