JPH08238683A - Hard coating agent and article formed with hard coating film - Google Patents

Abstract

PURPOSE: To prevent the problem of yellowing by incorporating hard coating agent which contains silane compound and/or its hydrolysate, surface modifying titanium oxide fine particles, and aluminum perchloride. CONSTITUTION: A hard coating agent comprises silane compound and/or its hydrolysate of R<1> m R<2> n Si(0R<3> )4-m-n (R<1> is organic group having 1-10C alkyl group, aryl group, alkyl halide group, aryl halide group, alkenyl group or epoxy group, (meth)acryloxide group, mercapto group, amino group or cyano group, R<3> is 1-6C alkyl group, aryl group, alkenyl group, alkoxyalkyl group or acyl group, m and n are 0, 1 or 2, and m+n is 0, 1 or 2), surface modifying titanium oxide fine particles, and aluminum perchlorate.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a plastic product such as a plastic lens for spectacles, a hard coating agent used for forming a transparent hard coat film on the surface of other articles, and an article having the hard coat film formed thereon.

[0002]

2. Description of the Related Art Conventionally, a hard coating film is formed by treating the surface of a plastic product with a hard coating agent in order to supplement the defects such as scratch resistance and solvent resistance of plastic products. Is being done.
In particular, in the field of optical articles typified by eyeglasses and glass substitute materials that require weather resistance, silicone-based hard coating agents using various silicone compounds as binders are becoming more prominent.

It has been proposed to add various inorganic fine particles to the hard coating agent as an aggregate for the purpose of increasing the hardness of the coating film. Among them, as an example of using colloidal silica as an aggregate, There are many proposals for combination with a curing catalyst, for example, an example using an aluminum chelate compound (Japanese Patent Publication No. 57-2735), an example using ammonium perchlorate (Japanese Patent Publication No. 62-9266), perchloric acid. Example using aluminum (JP-A-2-
No. 189380) can be cited as a specific example. However, those using these colloidal silica have a low refractive index of the cured film, and therefore when applied to a material exhibiting a high refractive index of 1.55 to 1.70, the refractive index difference is too large, There is a drawback that interference fringes are generated.

A system using antimony oxide sol as an aggregate has also been proposed (Japanese Patent Publication No. 61-54331). Although the refractive index of the cured coating of this system is slightly higher than that of the silica type, it has not reached a satisfactory level.

Further, a system using tin oxide sol as an aggregate has also been proposed (Japanese Patent Publication No. 3-51733 and Japanese Patent Laid-Open No. 24746/1994). Even in this system, the improvement of the refractive index of the coating is insufficient, the stability of the hard coating liquid itself is insufficient, and further, an antireflection layer made of an inorganic oxide provided on this cured layer, especially a silicon oxide layer Lacks in adhesion. Further, the surface hardness after vapor deposition of the antireflection layer is considerably lower than that of colloidal silica, and the prevention of interference fringes is not perfect.

A system utilizing composite particles of titanium oxide-iron oxide has also been proposed (Japanese Patent Laid-Open No. 2-178219, 3).
However, since this system contains iron oxide, it tends to yellow and lacks weather resistance, and cannot be used for optical articles.

A system utilizing titanium oxide sol has also been proposed (Japanese Patent Laid-Open No. 3-68901, Japanese Patent Laid-Open No. 6-901).
3-185820). This uses fine particles in which the surface of titanium oxide is coated with silicon oxide or zirconia, is excellent in dispersibility in an organic solvent, the stability of the hard coating solution is good, and the refractive index is improved. Yellowing is not completely solved, the adhesion to the antireflection layer is insufficient, and the surface hardness is insufficient, which is not satisfactory and the prevention of interference fringes is not perfect. .

Further, a system utilizing composite fine particles of cerium oxide and titanium oxide has also been proposed (JP-A-2-26).
4902 and 4-214028), this system has reached a good level of yellowing, but it does not have the same drawbacks as the above-mentioned modified titanium oxide sol.

The present invention has been made in order to improve the above-mentioned circumstances, has no problem of yellowing, has good adhesion to an antireflection film, and can prevent interference fringes from being generated. An object of the present invention is to provide a hard coating agent having excellent scratch resistance and an article on which a hard coat film is formed.

[0010]

Means and Action for Solving the Problems The present inventors have
As a result of intensive studies to achieve the above object, the following general formula (I) R ¹ _m R ² _n Si (OR ³ ) _4-mn ... (I) (wherein R ¹ is ¹ to 10 carbon atoms) 10 alkyl groups,
It represents an organic group having an aryl group, a halogenated alkyl group, a halogenated aryl group, an alkenyl group, or an epoxy group, a (meth) acryloxy group, a mercapto group, an amino group or a cyano group, and R ² represents 1 to 1 carbon atoms. 10 represents an alkyl group or an aryl group, R ³ represents an alkyl group having 1 to 6 carbon atoms, an aryl group, an alkenyl group, an alkoxyalkyl group or an acyl group, m and n are 0, 1 or 2, m + n is 0, 1 or 2. )
A surface-modified titanium oxide fine particles obtained by surface-coating titanium oxide fine particles as a binder with silicon oxide and zirconium oxide or silicon oxide, zirconium oxide and aluminum oxide, using a silane compound and / or a hydrolyzate thereof as a binder. In particular, a surface of fine particles of titanium oxide coated with two layers of an inorganic oxide whose main layer is silicon oxide as a main component, and an outer layer of which is an inorganic oxide whose main components are silicon oxide and zirconium oxide or silicon oxide, zirconium oxide and aluminum oxide. By using modified titanium oxide fine particles and aluminum perchlorate as a curing catalyst, it is possible to increase the refractive index of the cured film, and it is possible to form a film without interference fringes on the high refractive index substrate. In addition, the weather resistance is good, the coating does not turn yellow, the curability is excellent, the hardness is high and the scratch resistance is high. It is possible to form a film excellent, yet the case of forming the anti-reflection layer made of multiple layers of an inorganic oxide layer comprising SiO ₂ layer on the film, and found that excellent adhesion to the said layer, the present invention Came to make.

Therefore, the present invention comprises (1) the silane compound of the formula (I) and / or a hydrolyzate thereof, (2) the surface-modified titanium oxide fine particles, and (3) aluminum perchlorate. Provided are a hard coating agent contained, and an article such as a plastic lens for spectacles on which a hard coat film is formed by the hard coating agent.

The present invention will be described in more detail below. The hard coating agent of the present invention is used to form a hard cured film (hard coat film) on various substrates, and the first component thereof is following general formula _{^{(I) R 1 m R 2}} n Si (OR 3) 4-mn ... (I) ( wherein R ¹ is an alkyl group having 1 to 10 carbon atoms,
It represents an organic group having an aryl group, a halogenated alkyl group, a halogenated aryl group, an alkenyl group, or an epoxy group, a (meth) acryloxy group, a mercapto group, an amino group or a cyano group, and R ² represents 1 to 1 carbon atoms. 10 represents an alkyl group or an aryl group, R ³ represents an alkyl group having 1 to 6 carbon atoms, an aryl group, an alkenyl group, an alkoxyalkyl group or an acyl group, m and n are 0, 1 or 2, m + n is 0, 1 or 2. )
Is a silane compound and / or a hydrolyzate thereof.

Specific examples of R ¹ include an alkyl group such as a methyl group, an ethyl group, a propyl group, a hexyl group, a decyl group and a cyclohexyl group, an aryl group such as a phenyl group and a phenethyl group, and 3-chloro. Propyl group, 3,
3,3-trifluoropropyl group, 3,3,4,4
Halogenated alkyl groups such as 5,5,6,6,6-nonafluorohexyl groups, halogenated aryl groups such as p-chlorophenyl groups, vinyl groups, allyl groups, 9-decenyl groups, p-vinylbenzyl groups, etc. Epoxy group-containing organic groups such as alkenyl groups, 3-glycidoxypropyl groups, β- (3,4-epoxycyclohexyl) ethyl groups, and 9,10-epoxydecyl groups, γ-methacryloxypropyl groups, γ-acryloxy Groups such as (meth) acryloxy group-containing organic groups, γ-mercaptopropyl group-containing organic groups, p-mercaptomethylphenylethyl groups and other mercapto groups, γ-aminopropyl groups, (β-aminoethyl) -γ-amino Examples thereof include amino group-containing organic groups such as propyl group and cyano group-containing organic groups such as β-cyanoethyl group.

R ² is a methyl group, an ethyl group,
Alkyl groups such as propyl group, hexyl group, decyl group,
An aryl group such as a phenyl group can be exemplified. As R ³ , an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group and a hexyl group, an aryl group such as a phenyl group, an alkenyl group such as an isopropenyl group, an alkoxyalkyl group such as a methoxyethyl group, Examples thereof include an acyl group such as an acetyl group.

M and n are 0, 1 or 2, and m + n is 0, 1 or 2. That is, since the silane compound used in the present invention has a property of acting as an adhesive binder, the hydrolyzable group is 0 or 1, that is, (m + n) is 3
Or it is not preferable to use the compound of 4.

Specific examples of the silane compound satisfying these conditions include methyltrimethoxysilane, methyltriethoxysilane, methyltrimethoxyethoxysilane, methyltriacetoxysilane, methyltripropoxysilane, methyltriisopropenoxysilane, and methyltriisopropenoxysilane. Tributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxyethoxysilane, vinyltriisopropenoxysilane, phenyltrimethoxysilane, phenyltriethoxy. Silane, phenyltriacetoxysilane,
γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropyltripropoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glyce Sidoxypropyltriethoxysilane, γ-glycidoxypropyltriisopropenoxysilane, γ- (β-glycidoxyethoxy) propyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β -(3,4-epoxycyclohexyl) ethyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ- Mercap Trimethoxysilane, .gamma.-mercaptopropyl triethoxysilane, N
Tri-alkoxy or triacyloxysilanes such as-(β-aminoethyl) -γ-aminopropyltrimethoxysilane and β-cyanoethyltriethoxysilane and dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldiethoxysilane, phenylmethyldiethoxy. Silane, diphenyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylphenyldimethoxysilane, γ-glyce Sidoxypropylphenyldiethoxysilane, γ-glycidoxypropylmethyldiisopropenoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropylmethyldiethoxysilane, Dimethyldiacetoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-acryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane,
Examples of dialkoxysilanes or diacyloxysilanes such as γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, methylvinyldimethoxysilane, and methylvinyldiethoxysilane, and tetraalkoxysilanes are methyl silicate and ethyl. Examples thereof include silicate, n-propyl silicate, isopropyl silicate, n-butyl silicate, sec-butyl silicate and t-butyl silicate.

Further, these silane compounds may be partially or completely hydrolyzed as long as they can function as a binder.

These silane compounds and their hydrolyzates can be used alone or as a mixture of two or more kinds.

The second component of the present invention is surface-modified titanium oxide fine particles obtained by surface-coating titanium oxide fine particles with silicon oxide and zirconium oxide or with silicon oxide, zirconium oxide and aluminum oxide. By using the fine titanium oxide fine particles, the refractive index of the coating film can be increased, the hardness of the coating film as an aggregate can be increased, and the adhesion of the antireflection film can be increased.

In this case, in the present invention, it is effective that the surface-modified titanium oxide fine particles to be used have a structure in which the surface of the titanium oxide fine particles is firmly covered with two different layers. It is recommended to first coat silicon with silicon oxide, and then coat the upper layer with an inorganic oxide containing a mixture of silicon oxide and zirconium oxide or a mixture of silicon oxide, zirconium oxide and aluminum oxide as the main component. To be done.
The following advantages are brought about by adopting this two-layer structure. That is, as a first point, since titanium oxide is used as a nucleus, a high refractive index can be achieved. Secondly, since the particles are firmly coated with silicon oxide, the strength of the particles is increased, and as a result, the hardness of the coating film after curing and the coating film after the formation of the antireflection film are increased. A third point is that since the upper layer contains zirconia or zirconia and aluminum oxide, it has the effect of absorbing and dispersing the energy of the titanium atoms excited by light and stabilizing it, and it is possible to prevent yellowing. . If these atoms are contained in the titanium oxide fine particles or in the inner layer, the bond distance may be different, which may reduce the particle strength. Fourthly, since the outer layer contains silicon oxide, the adhesion is significantly improved when an antireflection layer is provided, the reactivity with the silane compound that functions as a binder is high, and the hardness of the coating can be increased. . Fifth, since the surface of titanium particles is completely protected by other inorganic oxides, the stability of the surface-modified titanium oxide particles of the present invention in a solution is high, and in connection therewith, a hard coating agent. The stability of is also improved. In this case, if the surface of the titanium oxide fine particles is covered with only one layer of silicon oxide, it is difficult to prevent yellowing and it cannot be applied to optical parts. In addition, since the surface coating is not completely achieved, there is a disadvantage that the stability is poor. Further, in a system in which the surface treatment is performed only with silicon oxide or zirconium oxide, the strength of the particles is weakened, so that satisfactory film hardness and film hardness after formation of the antireflection film cannot be obtained. Also, because the surface protection is incomplete,
The stability in solution and the stability of the hard coating agent are still insufficient.

The proportion of each component contained in the surface-modified titanium oxide fine particles in the present invention is as follows: TiO ₂ 55-96.9 wt% SiO ₂ 3-35 wt% ZrO ₂ 0.1-10 wt% Al ₂ O ₃ is preferably in the range of 0 to 10% by weight.

If the content of titanium oxide is lower than this range, it may not be possible to expect a sufficient improvement in the refractive index.
If it exceeds this range, yellowing prevention, hardness improvement and stability may not be satisfied. The titanium oxide content is more preferably 60 to 94.9% by weight.

When the content of silicon oxide is less than the above range, the hardness of the cured coating tends to be low, the stability of the sol and the hard coating agent solution tends to be insufficient, and the adhesion of the antireflection coating tends to be low. However, if it exceeds the above range, the content of titanium oxide decreases, so that the improvement of the refractive index may not be expected in some cases. The blending amount of silicon oxide is more preferably 5 to 35% by weight.

When the content of zirconium oxide is lower than the above range, prevention of yellowing of the hardened film is lowered, and when it exceeds the above range, there arises a problem due to the lower contents of titanium oxide and silicon oxide. The zirconium oxide content is more preferably 0.1 to 5% by weight.

When aluminum oxide is blended, an excessively large amount thereof causes a problem due to a decrease in the content of titanium oxide and silicon oxide. Therefore, the amount is preferably below the above range, more preferably 0 to 5% by weight. is there.

The ratio of the inner SiO ₂ layer in the surface-modified titanium oxide fine particles of the present system is preferably 1 to 25% by weight. When the content of silicon oxide is less than this range, the strength of the cured film is lowered, the stability of the sol and the hard coating agent solution is insufficient, and the adhesion of the antireflection film tends to be lowered, which is not preferable. On the other hand, if it exceeds this range, the content of titanium oxide, which is the mother nucleus, decreases, and it may not be possible to expect an improvement in the refractive index. It is more preferably 1 to 20% by weight.

The surface-modified titanium oxide fine particles can be obtained by subjecting the surface of the titanium oxide fine particles to a two-layer coating treatment with silicon oxide, zirconium oxide, and optionally aluminum oxide. The method of coating treatment is to include Si, Zr in an aqueous solution containing titanium oxide fine particles.
And Al compound are added / dispersed, and the whole system is further heated to adsorb / deposit the metal compound having a hydroxyl group dispersed in water on titanium oxide microparticles which is a mother nucleus, and finally chemically reacts on the titanium particle surface. Just combine them. Such a coating method can be carried out according to various conventionally known methods (for example, see JP-A-63-185820). In particular, when the inner layer is surface-coated with two layers of silicon oxide and the outer layer is silicon oxide and zirconium oxide or silicon oxide and zirconium oxide and aluminum oxide, a silicon compound is first added to the titanium oxide sol or its precursor solution. Then, the silicon compound, the zirconia compound and, if necessary, the aluminum compound may be added and allowed to act.

As the silicon compound to act, any one can be used as long as it can be dispersed in water and has a hydroxyl group capable of undergoing a condensation reaction in water, such as silica gel, silica sol, silicic acid solution and silicon. Alkoxides and the like can be used. For the purpose of forming a uniform and dense film with a small amount of use, it is preferable to use a material having a low molecular weight such as a hydrolyzate of a silicate or a silicon alkoxide and having a high condensation / curability.

The zirconia compound and the aluminum compound are each sol or each chloride, sulfate,
It can act in the form of an aqueous solution of a chloride such as carbonate.

In order to accelerate the coating action, heating may be performed, and it is preferable to heat at 60 ° C. or higher for treatment.

It is to be noted that some aggregates of titanium oxide fine particles coated with these inorganic oxides in the above treatment may be used as long as they do not adversely affect the characteristics of the cured coating. Further, an aqueous solution or dispersion of low molecular weight titanic acid which is a precursor of titanium oxide fine particles / sol may be used as a starting material as long as it does not adversely affect the cured film. In this case, since the precursor low-molecular-weight titanic acid grows into titanium oxide fine particles and is coated with silicon oxide at the same time, finer particles can be obtained.

Water is generally used as the dispersion medium, but methanol, ethanol, butanol, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, T
It is also possible to use organic solvents such as HF and dioxane.

As long as the characteristics of the cured coating are not adversely affected, the titanium oxide fine particles of the mother nucleus contain Si, Sn, Ce,
It may be contained in the form of being doped with a metal oxide such as Fe or a rare earth element, or in the form of a partially mixed crystal.

The preferable average particle size of the surface-modified titanium oxide fine particles is in the range of 1 to 300 μm.

The ratio of the surface-modified titanium oxide fine particles contained in the hard coating agent is 5 to 80 in the cured film.
It is preferably contained in a weight percentage. If it is lower than this range, the refractive index of the cured film may not be improved to a desired level, and if it exceeds this range, the ratio of the silane compound as a binder component becomes too low and the film is not formed or cracks occur. In some cases, the transparency may be reduced. It is more preferably 10 to 70% by weight.

In the hard coating agent of the present invention, aluminum perchlorate is used as a curing catalyst for the third component. That is, various curing catalysts for silicone-based hard coating agents have been conventionally known. For example, organic carboxylic acid, chromic acid, hypochlorous acid, boric acid, bromic acid, selenious acid, thiosulfuric acid, nitrous acid,
Examples thereof include metal salts such as thiocyanic acid and aluminate, bases such as amine compounds, alkoxides or complex compounds of aluminum, zirconium and titanium. However, even if these catalysts are applied to the present system, the curability is insufficient, so that the occurrence of interference fringes cannot be suppressed and the whitening of the coating cannot be prevented. On the other hand, these drawbacks can be avoided only when aluminum perchlorate is used as a catalyst.

Here, the amount of aluminum perchlorate used is a catalytic amount, and the amount of the catalyst contained in the cured coating film (solid content) is usually 0.01 to 10% by weight, more preferably 0. It is from 01 to 5% by weight.

As the hard coating agent of the present invention, if necessary, organic resin such as epoxy resin and acrylic resin, methanol, ethanol, isobutanol, diacetone alcohol, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, ethyl cellosolve, etc. The organic solvent, benzophenone-based, benzotriazole-based, phenol-based or other UV absorbers, polyether-modified silicone oil, fluorine-based surfactants and the like can be added.

The hard coating agent of the present invention forms a hard coat film on various substrates. In this case, a known method may be used as the coating method, and a method such as a dipping method, a spin method, or a spray method can be applied, but the dipping method and the spin method are particularly preferable in terms of surface accuracy. Before applying the hard coating agent to the substrate, the substrate is cured by chemical treatment with acid, alkali, various organic solvents, physical treatment with plasma, etc., or primer treatment with each resin. Adhesion with the film can be improved.

As curing conditions, heat curing can be carried out at 50 to 200 ° C., preferably hot air heating at 80 to 150 ° C. or far infrared heating can be adopted.

When a hard coating film is formed using the hard coating agent of the present invention, its thickness is 0.1 to 20.
μm is preferable, and more preferably 0.5 to 10 μm. If it is too thin, sufficient hardness cannot be obtained, and if it is too thick, cracks are likely to occur and the adhesion may be reduced.

The hard coating agent of the present invention is suitably applied to various plastic materials, particularly polycarbonate, polystyrene, polyester, modified acrylic resin,
Urethane resin, thiourethane resin, polycondensate of halogenated bisphenol A and ethylene glycol, acrylic urethane resin, halogenated aryl group-containing acrylic resin,
It is most suitable for a high refractive index base material having a refractive index of 1.55 to 1.75 such as a sulfur-containing resin. When the hard coating agent of the present invention is applied to these high refractive index substrates, interference fringes do not occur and a coat film is formed with a good appearance.

Further, the cured film obtained with the coating agent of the present invention can be dyed with a disperse dye. When dyeing, the dyeing conditions can be arbitrarily determined by the concentration of various disperse dyes, temperature, time and the like.

The hard coating agent of the present invention is effective for forming a hard coat film on a spectacle lens, a camera lens, an automobile window glass, an optical filter for a liquid crystal display, and the like, particularly a spectacle lens.

In this case, an antireflection film, especially a multilayer antireflection film, can be formed on the hard coat film, if necessary.

The multilayer antireflection film provided on the hard coating cured film of the present invention can be formed by alternately laminating a low refractive index film and a high refractive index film. It can be formed by vaporizing under vacuum with an oxide and an electron beam, and depositing it on a substrate. As the low refractive index film, a silicon dioxide film,
Although a magnesium fluoride film and the like can be mentioned, a silicon dioxide film is particularly preferably used from the viewpoint of scratch resistance and heat resistance. Further, examples of the high refractive index film include a titanium oxide film, an aluminum oxide film, a tantalum oxide film, a zirconium oxide film, and an oxide film such as a rare earth element.

[0047]

The hard coating agent of the present invention has the following advantages. (A) The cured coating has excellent weather resistance and does not yellow. (B) Excellent adhesion to the antireflection layer. (C) The curability is excellent, the denseness of the cured film is high, and the generation of interference fringes can be prevented. (D) The surface hardness is high, and the surface hardness after the antireflection layer is installed is also high. (E) The cured film can have a high refractive index and can be applied to a component having a high refractive index of the base material.

Therefore, it is excellent as a hard coating agent for improving the insufficient abrasion resistance while maintaining good optical characteristics of plastic parts such as light weight and excellent workability.

[0049]

EXAMPLES Hereinafter, the present invention will be specifically described by showing production examples, examples and comparative examples, but the present invention is not limited to the following examples.

[Production Example 1] Method for producing surface-modified sol Neutralization was carried out by adding 10% ammonia water to a 1.0% by weight titanium sulfate aqueous solution until the pH reached 8.5, and the produced titanium oxide gel was filtered off. did. The gel thus obtained was dispersed in pure water, 33% hydrogen peroxide solution was added at a ratio such that H ₂ O ₂ / TiO ₂ = 4 (weight ratio), and the mixture was heated at 80 ° C. for 5 hours to obtain TiO 2. ₂ to obtain a homogeneous solution containing 2% by weight. Since the titanium oxide particles in this aqueous solution were extremely fine, they were transparent in appearance.

Separately from this, the sodium component was removed by treating the aqueous solution of sodium silicate with a cation exchange resin to prepare an aqueous solution of silicic acid having a SiO ₂ concentration of 3.0% by weight.

The above TiO ₂ sol liquid and silicic acid aqueous solution were mixed so as to have a ratio of SiO ₂ / TiO ₂ = 13/72 and heated at 95 ° C. for 40 hours. The coating of the first layer was completed. The obtained liquid became a milky white transparent colloidal solution and was a liquid excellent in stability over time.

In order to further coat a second layer of (SiO ₂ + ZrO ₂ ) thereon, the above aqueous solution of silicic acid, an aqueous solution of zirconyl ammonium carbonate having a ZrO ₂ concentration of 0.5% by weight, and the above aqueous solution of silicic acid are used. ZrO ₂ / SiO ₂ = 1 /
The mixture of the mixture of 4 was added to the above-mentioned silicon oxide-coated titanium oxide sol solution with a solid content ratio (dropping side / modified titanium.
The sol side was added at a ratio of 15/85) in the same manner as above, and the surface was coated.

This aqueous solution was subjected to vacuum deposition to obtain a solid content concentration of 20.
After concentrating to wt%, convert the solvent to methanol,
A methanol solution having a solid content of 20% by weight was obtained.

[Production Example 2] Ferric sulfate was added to TiO ₂ / Fe ₂ O ₃ = 97.5 / when preparing titanium oxide particles as a mother nucleus.
The surface-modified sol was synthesized in the same manner as in Production Example 1 above, in such a manner that the ratio was 2.5 (weight ratio).

Other surface-modified sols described later were also produced according to the above Production Example 1.

Example 1 300 g of γ-glycidoxypropyltrimethoxysilane, 200 g of γ-glycidoxypropylmethyldiethoxysilane, 20 g of tetramethoxysilane and 150 g of isobutyl alcohol were placed in the flask in order. 114 g of 0.05 N dilute hydrochloric acid water was slowly added dropwise over 30 minutes while stirring under ice cooling. Further, the titanium oxide fine particle sol (TiO ₂ = 72% by weight, SiO ₂ (inner layer) = 13% by weight) obtained in Production Example 1 in which the inner layer was covered with two layers of SiO ₂ layer and outer layer was (SiO ₂ + ZrO ₂ ). , SiO ₂ (outer layer) = 12% by weight, ZrO ₂ = 3% by weight, 20% by weight methanol solution 7 of Catalyst Kasei Co., Ltd.
After adding 00 g and aging at 20 ° C. for 16 hours, 1 g of silicone-based surfactant and 200 of diacetone alcohol
g, and 5 g of aluminum perchlorate hexahydrate was added thereto to prepare a coating liquid. The proportion of the surface-modified sol contained in the coating obtained by curing the coating liquid was 25.4% by weight (theoretical value).

Next, a lens made of a resin having a refractive index of 1.60 is coated with this coating solution by a dipping method,
It was cured at 120 ° C. for 60 minutes (this surface-hard-coated lens is hereinafter referred to as A-1).

An antireflection film was formed on this hard-coated lens by the following procedure. Using an electron beam heating type vacuum vapor deposition apparatus, a SiO ₂ sintered body was used as a vapor deposition material for a low refractive index film (ZrO ₂ + Ta ₂ O ₅
A mixed sintered body of + Y ₂ O ₃ ) was used, and an antireflection film made of a multilayer inorganic oxide was provided. However, the innermost layer is a SiO ₂ layer (this multi-coated surface-treated lens is hereinafter referred to as A-2).

Example 2 100 g of γ-glycidoxypropylmethyldiethoxysilane, 50 g of tetramethoxysilane, an inner layer of SiO ₂ layer and an outer layer of (SiO ₂ + ZrO ₂ ).
₂ ) Titanium oxide fine particle sol (Ti)
O ₂ = 84% by weight, SiO ₂ = 15% by weight, ZrO ₂ = 1
A coating liquid was prepared in the same manner as in Example 1 except that 1500 g of a 20% by weight) methanol solution was used. The proportion of the surface-modified sol contained in the cured coating in this system was 49.8% by weight (theoretical value).

In the same manner as in Example 1, a resin lens (B-1) having a refractive index of 1.66 which was hard-coated and a lens (B-2) which had been multi-coated were prepared.

[Example 3] Oxidation in which the surface-modified titanium oxide fine particle sol of Example 1 was replaced with _two layers of an inner layer of SiO ₂ and an outer layer of (SiO ₂ + ZrO ₂ + Al ₂ O ₃ ). Titanium fine particle sol (TiO ₂ = 64% by weight, SiO ₂
= 30 wt%, ZrO ₂ = 5 wt%, Al ₂ O ₃ = 1 wt%) A coating solution was prepared in the same manner as in Example 1 except that 800 g of a 20 wt% methanol solution was used.
The proportion of the surface-modified titanium oxide sol contained in the cured coating in this system was 28.0% by weight (theoretical value).

In the same manner as in Example 1, a resin lens (C-1) having a refractive index of 1.60 which was hard-coated and a lens (C-2) which had been multi-coated were prepared.

Example 4 A resin lens (D-1) and a multi-coated lens (D-) were used in the same manner as in Example 2 except that the surface-modified titanium oxide sol obtained in Production Example 2 was used.
2) was created respectively.

Example 5 Instead of the surface-modified titanium oxide fine particle sol of Example 1, a titanium oxide fine particle sol (TiO ₂ = 72) in which an inner layer was covered with two layers of SiO ₂ layer and an outer layer was ZrO ₂ layer % By weight, SiO ₂ = 25% by weight, ZrO
_A coating solution was prepared in the same manner as in Example 1 except that 700 g of a 20% by weight methanol solution ( ₂ = 3% by weight) was used.

In the same manner as in Example 1, a resin lens (E-1) having a refractive index of 1.60 which was hard-coated and a lens (E-2) which had been multi-coated were prepared.

Example 6 Instead of the surface-modified titanium oxide fine particle sol of Example 1, 30% by weight of SiO ₂ / ZrO _{2 was used.}
A coating liquid was prepared in the same manner as in Example 1 except that 800 g of a 20 wt% methanol solution of titanium oxide fine particle sol in which one layer of 5 wt% / Al ₂ O ₃ was coated on the titanium oxide particles was used. The proportion of the surface-modified titanium oxide sol contained in the cured coating in this system was 28.0% by weight (theoretical value).

In the same manner as in Example 1, a resin lens (F-1) having a refractive index of 1.60 which was hard-coated and a lens (F-2) which had been multi-coated were prepared.

Comparative Example 1 Instead of the surface-modified titanium oxide fine particle sol of Example 2, a titanium oxide fine particle sol coated with only a SiO ₂ layer (TiO ₂ = 85 wt%, SiO ₂
= 15% by weight) in 20% by weight methanol solution 1500 g
A coating liquid was prepared in the same manner as in Example 2 except that was used. The proportion of the titanium oxide fine particle sol contained in the cured coating in this system was 49.8% by weight (theoretical value).

In the same manner as in Example 2, a resin lens (G-1) having a refractive index of 1.66 which was hard-coated and a lens (G-2) which had been multi-coated were prepared.

Comparative Example 2 A coating solution was prepared in the same manner as in Example 2 except that 5 g of aluminum / acetylacetonate complex was used instead of aluminum perchlorate in Example 2.

In the same manner as in Example 2, a resin lens (H-1) having a refractive index of 1.66 which was hard-coated and a lens (H-2) which had been multi-coated were prepared.

Comparative Example 3 Instead of the surface-modified titanium oxide fine particle sol of Example 2, a titanium oxide fine particle sol coated with only a ZrO ₂ layer (TiO ₂ = 85% by weight, ZrO ₂
= 15% by weight) in 20% by weight methanol solution 1500 g
A coating liquid was prepared in the same manner as in Example 2 except that was used.

In the same manner as in Example 2, a resin lens (I-1) having a refractive index of 1.66 which was hard-coated and a lens (I-2) which had been multi-coated were prepared.

[Comparative Example 4] A sol in which the surface of fine composite oxide particles comprising 80% by weight of titanium oxide and 20% by weight of cerium oxide was coated with silicon oxide (TiO ₂ = 68% by weight,
A coating solution was prepared in the same manner as in Example 1 except that a 20 wt% methanol solution of CeO ₂ = 17 wt% and SiO ₂ = 15 wt%) was used. The ratio of the surface-modified titanium oxide sol contained in the cured coating in this system is 25.4.
It was weight% (theoretical value).

In the same manner as in Example 1, a resin lens (J-1) having a refractive index of 1.60 which was hard-coated and a lens (J-2) which had been multi-coated were prepared.

The composition of each sol used above is shown in Table 1.

[0078]

[Table 1]

Next, the characteristics of the surface-treated lens obtained by the above method were examined by the following methods. Table 2 shows the results. (A) Presence or absence of interference fringes The cured film on the lens surface was visually evaluated under a fluorescent lamp. (B) Scratch resistance Under a load of 500 g, the surface of the cured coating was rubbed 10 times with steel wool # 0000, and the appearance of scratches was visually determined. (C) Adhesion According to JIS K-5400, Item 6.15, the cured film was cross-cut at 1 mm intervals for 100 meshes and subjected to a peeling test using cellophane tape (manufactured by Nichiban Co., Ltd.). I checked the number. (D) Solvent resistance The cured film was lightly rubbed 100 times with absorbent cotton impregnated with acetone, and the transparency was visually evaluated. (E) Weather resistance The surface-treated lens is put in a xenon weather meter for 20 minutes.
After irradiation with light for 0 hours, the change in appearance was visually examined.

[0080]

[Table 2]

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Claims (6)

[Claims] (1) The following general formula (I) R ¹ _m R ² _n Si (OR ³ ) _4-mn (I) (wherein R ¹ is an alkyl group having 1 to 10 carbon atoms,
It represents an organic group having an aryl group, a halogenated alkyl group, a halogenated aryl group, an alkenyl group, or an epoxy group, a (meth) acryloxy group, a mercapto group, an amino group or a cyano group, and R ² represents 1 to 1 carbon atoms. 10 represents an alkyl group or an aryl group, R ³ represents an alkyl group having 1 to 6 carbon atoms, an aryl group, an alkenyl group, an alkoxyalkyl group or an acyl group, m and n are 0, 1 or 2, m + n is 0, 1 or 2. )
A silane compound represented by and / or a hydrolyzate thereof,
(2) Surface-modified titanium oxide fine particles obtained by surface-treating titanium oxide fine particles with silicon oxide and zirconium oxide or with silicon oxide, zirconium oxide and aluminum oxide, and (3) aluminum perchlorate. Hard coating agent. 2. The surface-modified titanium oxide fine particles are composed of titanium oxide fine particles, the inner layer of which is an inorganic oxide containing silicon oxide as a main component, and the outer layer of which contains silicon oxide and zirconium oxide or silicon oxide, zirconium oxide and aluminum oxide as main components. The hard coating agent according to claim 2, wherein the hard coating agent is surface-coated with two layers of inorganic oxides. 3. The ratio of each component constituting the surface-modified titanium oxide fine particles is such that TiO _{2 is} 55 to 96.9% by weight, and SiO _{2 is}
3 to 35% by weight, ZrO ₂ 0.1 to 10% by weight, Al ₂ O
The hard coating agent according to claim 1, which is in a range of _{30 to} 10% by weight. 4. The ratio of the surface-modified titanium oxide fine particles contained in the coating film obtained by curing the hard coating agent is 5 to 5.
80% by weight, 4.
The hard coating agent described. 5. An article on which a hard coat film is formed by the hard coating agent according to any one of claims 1 to 4. 6. A plastic lens for spectacles having a hard coat film formed by the hard coating agent according to claim 1.