JPH0769481B2 - High refractive index hard coat film - Google Patents

Description

TECHNICAL FIELD The present invention relates to a high refractive index hard coat film having a high refractive index and being excellent in dyeability, weather resistance and the like. Further, it is preferably applied as a high refractive index layer used in forming an antireflection film.

[Prior Art] As a method for obtaining a high refractive index hard coat film, titanium,
A method of obtaining from an alcoholate such as tantalum and a melamine resin is disclosed in JP-A-57-37301.

Further, in JP-A-58-46301, JP-A-59-49501 and JP-A-63-225635, compositions comprising titanium alcoholate and colloidal silica, or colloidal titanium oxide and a silane coupling agent are disclosed. Techniques for things are disclosed.

On the other hand, JP-A-63-223701 discloses a high-refractive-index coating film comprising cerium oxide fine particles, a specific organosilicon compound and silica fine particles.

[Problems to be Solved by the Invention] However, the method disclosed in JP-A-57-37301 has problems that a sufficiently high refractive index cannot be obtained and that water resistance is not sufficient.

In addition, the methods disclosed in JP-A-58-46301 and JP-A-59-49501 also have problems of poor water resistance and yellowing of the coating film. Furthermore, there are drawbacks such as haze due to cloudiness of the coating film and poor weather resistance. In addition, JP-A-63
The technique according to Japanese Laid-Open Patent Publication No. 225635 also has a poor weather resistance, and in particular, it has a fatal defect that the adhesion of a coating film after a weather resistance test becomes poor.

Further, the technique according to JP-A-63-223701 using fine particles of cerium oxide also causes yellowing of the coating film when sufficient cerium oxide is used to obtain a sufficiently high refractive index, while improving yellowing of the coating film. There is a trade-off problem that a high refractive index cannot be obtained if the amount of addition is small.

Therefore, the present invention is intended to solve these problems, having a sufficiently high refractive index, excellent weather resistance, water resistance, and yellowing, there is no transparency deterioration due to haze, etc.,
An object is to provide a high refractive index hard coat film having an excellent appearance.

[Means for Solving the Problems] The present invention has the following configurations in order to achieve the above object.

“A high refractive index hard coat film comprising a cured product of a composition containing the following components A and B as main components.

A. Composed of a complex oxide of cerium oxide and titanium oxide,
The weight ratio of cerium oxide to titanium oxide is 0.1.
Or more, and 1.4 or less, and the average particle size is 1 mμ or more, 100
Fine particles of mμ or less.

B. BR ¹ _a SiX _3-a (I) or One or more selected from organosilicon compounds represented by and their hydrolysates.

(Here, R and R ¹ are organic groups having 1 to 10 carbon atoms. X
Is a hydrolyzable group, and a is 0 or 1. Y is an organic group having 2 to 40 carbon atoms. ) Here, the composite oxide composed of cerium oxide and titanium oxide, which are the components A, are fine particles of cerium oxide and titanium oxide, respectively, which are further aggregated or mixed in water and / or an organic solvent. It exists in the state of so-called sol dispersed in. There is no problem even if such cerium oxide and titanium oxide are mixed in the manufacturing stage, or they are mixed after they are individually manufactured. In particular, a method of mixing at the manufacturing stage is preferable in order to obtain a uniform mixed state.

The weight ratio of cerium oxide and titanium oxide in the composite oxide is 0.1 or more in the weight ratio of cerium oxide to titanium oxide (cerium oxide / titanium oxide),
It must be 1.4 or less. That is, if it is less than 0.1, a coating having good weather resistance cannot be obtained. Also 1.4
If it exceeds, there is a drawback that the film is colored yellowish brown.

Further, the average particle size of the composite oxide fine particles is 1 mμ or more and 100 mμ or less in both single and aggregate. The particle size means the maximum size of the particles either alone or in agglomeration. If the average particle size exceeds 100 mμ, a transparent film cannot be obtained. On the other hand, if it is less than 1 mμ, not only the stability of the fine particles is poor, but also the dyeability of the film is significantly lowered. The particle size in the present invention is a value measured by JEM-1200 manufactured by JEOL Ltd.,
The average particle diameter is the average of the particle diameters of at least 100 particles. Further, in the present invention, even after the composition is cured, the condition that the average particle diameter is 1 mμ or more and 100 mμ or less is satisfied.

Cerium oxide and titanium oxide are generally in the form of cerium dioxide and titanium dioxide, and a colloidal liquid dispersed in water or a solvent is easily available and easy to operate. However, any material may be used as long as it is cerium oxide or titanium oxide, and the state of existence thereof is not limited as described above. For example, it was obtained by a pulverization method or a gas phase synthesis method. It is also possible to uniformly disperse the substance in a dispersion medium and use it.

The component B of the present invention is selected from the group consisting of an organosilicon compound represented by the following general formula (I) and its hydrolyzate, and an organosilicon compound represented by the following general formula (II) and its hydrolyzate. At least one selected organosilicon compound and / or its hydrolyzate is used.

BR ¹ _a SiX _3-a (I) (Here, R and R ¹ are organic groups having 1 to 10 carbon atoms. X
Is a hydrolyzable group, and a is 0 or 1. Y is an organic group having 2 to 40 carbon atoms. ) First, the organosilicon compound represented by formula (I) and its hydrolyzate will be described.

In the formula represented by the general formula (I), R and R ^{1 each} have 1 carbon atom.
~ 10 organic groups, as a specific example thereof, a methyl group,
Hydrocarbon groups such as ethyl group, phenyl group, vinyl group, chloropropyl group, halogenated hydrocarbon groups such as 3,3,3-trifluoropropyl group, γ-glycidoxypropyl group,
Epoxy group-containing organic groups such as β- (3,4-epoxycyclohexyl) ethyl groups, γ-methacryloxypropyl groups, (meth) acryl group-containing organic groups such as γ-acryloxypropyl groups, other mercapto groups, cyano groups , Organic groups having various substituents such as amino groups, and the like. R and R ¹ may be the same or different.

X is not particularly limited as long as it is a functional group capable of being hydrolyzed, that is, a silanol group is formed by a hydrolysis reaction, and specific examples thereof include a methoxy group, an ethoxy group, and a methoxyethoxy group. Examples thereof include an acyloxy group such as an alkoxy group and an acetoxy group, a halogen group such as a chloro group and a bromo group, and an aryloxy group such as a phenoxy group.

Further, a is 0 or 1, but when a is 1, at least one of R and R ¹ is a reactive organic group such as an epoxy group-containing organic group or a (meth) acryloxy group-containing organic group. It is preferable from the viewpoint of improving the surface hardness.

Specific representative examples of these organosilicon compounds include:
Methyltrimethoxysilane, methyltriethoxysilane, methyltrimethoxyethoxysilane, methyltriacetoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane , Vinyltriacetoxysilane, vinyltrimethoxyethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane,
γ-chloropropyltriacetoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-mercaptopropyl Trimethoxysilane,
γ-mercaptopropyltrimethoxyethoxysilane,
γ-mercaptopropyltriethoxysilane, N-β-
(Aminoethyl) -γ-aminopropyltrimethoxysilane, β-cyanoethyltriethoxysilane, methyltriphenoxysilane, chloromethyltrimethoxysilane, chloromethyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltri Ethoxysilane, α-glycidoxyethyltrimethoxysilane, α-glycidoxyethyltriethoxysilane, β-
Glycidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane, α-glycidoxypropyltrimethoxysilane, α-glycidoxypropyltriethoxysilane, β-glycidoxypropyltrimethoxysilane, β- Glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane,
γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltripropoxysilane, γ-glycidoxypropyltributoxysilane, γ-glycidoxypropyltrimethoxyethoxysilane, γ-glycidoxypropyltriphenoxysilane , Α-glycidoxybutyltrimethoxysilane, α-glycidoxybutyltriethoxysilane, β-glycidoxybutyltrimethoxysilane, 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) ethyltrimethoxyethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriphenoxysilane, γ- (3,4-epoxycyclohexyl) propyltrimethoxysilane, γ- (3,4-epoxycyclohexyl) propyl Triethoxysilane, δ-
Trialkoxysilanes such as (3,4-epoxycyclohexyl) butyltrimethoxysilane and δ- (3,4-epoxycyclohexyl) butyltriethoxysilane, triacyloxysilanes or triphenoxysilanes or their hydrolysates and dimethyldimethoxysilane. , Phenylmethyldimethoxysilane, dimethyldiethoxysilane, phenylmethyldiethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropylmethyldiethoxysilane, dimethyldiacetoxysilane,
γ-methacryloxypropylmethyldimethoxysilane,
γ-methacryloxypropylmethyldiethoxysilane,
γ-methylcaptopropylmethyldimethoxysilane, γ
-Mercaptopropylmethyldiethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, glycidoxymethylmethyldimethoxysilane, glycidoxymethylmethyldiethyl Ethoxysilane, α-glycidoxyethylmethyldimethoxysilane, α-glycidoxyethylmethyldiethoxysilane, β-glycidoxyethylmethyldimethoxysilane, β-glycidoxyethylmethyldiethoxysilane, α-glycidoxy Propylmethyldimethoxysilane, α-glycidoxypropylmethyldiethoxysilane, β-glycidoxypropylmethyldimethoxysilane, β-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethane Cyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, γ-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethyldimethoxyethoxysilane, γ- Glycidoxypropylmethyldiphenoxysilane, γ-glycidoxypropylmethyldiacetoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane, γ-glycidoxypropylvinyldimethoxysilane , Γ-glycidoxypropylvinyldiethoxysilane, γ-glycidoxypropylphenyldimethoxysilane, γ-glycidoxypropylphenyldiethoxysilane, etc. dialkoxysilane, diphenoxysilane or diacyloxysilane Silanes or their hydrolysates are examples.

Next, another general formula (I
The organosilicon compound represented by I) and / or its hydrolyzate will be described.

In the general formula (II), R ¹ is the above-mentioned general formula (I).
An example similar to can be given. Y is an organic group having 2 to 40 carbon atoms. That is, Y is a functional group contained in the molecule through two Si atoms and a Si—C bond, and the functional group contains a heteroatom other than carbon and hydrogen such as an oxygen atom and a nitrogen atom. There is no problem. Moreover,
Within the range of 2 to 40 carbon atoms, the organic group may be chain-like or cyclic, and there is no problem even if an oxygen atom or the like is present as an epoxy ring or the like, It is preferable in that it contributes as a functional group during curing.

As a concrete example, And so on.

As the organosilicon compound represented by the above general formula (I) or (II), it is preferable to use an organosilicon compound containing an epoxy group or a glycidoxy group particularly for the purpose of imparting dyeability. In addition, an alkyl group having 1 to 4 carbon atoms or an alkoxyalkyl group is preferably used as X from the viewpoints of the curing rate and the ease of hydrolysis.

Among these organosilicon compounds and / or their hydrolysates, hydrolysates are preferable in order to lower the curing temperature and promote curing.

Hydrolysis is produced by adding pure water or an acidic aqueous solution such as hydrochloric acid, acetic acid, or sulfuric acid and stirring.
Furthermore, the degree of hydrolysis can be easily controlled by adjusting the amount of pure water or acidic aqueous solution added. At the time of hydrolysis, it is particularly preferable to add pure water or an acidic aqueous solution in an equimolar or more and 3 times or less molar amount with respect to the X group of the general formula (I) or (II) from the viewpoint of accelerating the curing.

During the hydrolysis, alcohol or the like is generated, so it is possible to perform the hydrolysis without a solvent.However, the hydrolysis is performed after mixing the organic silicon compound and the solvent for the purpose of making the hydrolysis more uniform. It is also possible. It is also possible to remove an appropriate amount of alcohol after hydrolysis under heating and / or reduced pressure for use depending on the purpose, and to add an appropriate solvent after that.

Examples of these solvents include alcohols, esters, ethers, ketones, halogenated hydrocarbons, aromatic hydrocarbons such as toluene and xylene, and solvents such as N, N-dimethylformamide. Further, these solvents can be used as a mixed solvent of two or more kinds, if necessary. Further, depending on the purpose, it is possible to accelerate the hydrolysis reaction and further heat it to room temperature or higher in order to proceed the reaction such as precondensation, or to lower the hydrolysis temperature to room temperature or lower in order to suppress precondensation. It goes without saying that it is possible to do it.

The addition ratio of the components A and B in the present invention should be appropriately optimized depending on the target refractive index and the substrate to which it is applied. In particular, the refractive index of the substrate is 1.55 or more, or more. When it has a refractive index, it is preferable that the component A is 25 to 30 parts by weight with respect to the component B 100 parts by weight. Particularly when both functions of high surface hardness and high refractive index are simultaneously satisfied, the range of 50 to 150 parts by weight is preferable.

In addition, it is generally known that an antireflection effect is achieved by laminating a plurality of coatings having different refractive indexes. Among them, a lower refractive index than a film having a certain refractive index is provided. It is known that, in the case of forming the coating film, the larger the difference, the higher the antireflection effect.
Therefore, when a film having a lower refractive index is formed on the film of the present invention, the film of the present invention has a high refractive index, and thus can also exhibit an excellent antireflection effect.

The performance of the coating film of the present invention can be improved or modified by adding components other than the components A and B.

For example, to improve dyeability, various epoxy resins other than component A,
It is preferable to use urethane resin or acrylic resin. Among them, the bisphenol A type epoxy resin is particularly preferable because it can greatly improve the dyeability without significantly reducing the refractive index of the coating.

Further, the coating composition used in forming the coating film of the present invention includes various surfactants for the purpose of improving the flow at the time of coating, improving the smoothness of the coating film, and decreasing the friction coefficient of the coating film surface. It is also possible to use, and particularly, a block or graft polymer of dimethylsiloxane and alkylene oxide, and a fluorine-based surfactant are effective. Also, disperse dyes and pigments and fillers, dissolve the organic polymer to color the coating film,
It is also possible to easily improve the practicality as a coating agent such as coatability, adhesion to a base material, and improvement of physical properties.

Further, for the purpose of improving the weather resistance, it is possible to easily add an ultraviolet absorber or an antioxidant as a heat deterioration improving method.

The coating film of the present invention is obtained by curing the coating composition, and the curing is performed by drying or heat treatment. The heating temperature can be used in a fairly wide range, and sufficiently good results can be obtained at 50 to 250 ° C.

Further, various curing agents can be used in combination for the purpose of accelerating curing and curing at low temperature. As the curing agent, various epoxy resin curing agents or various organic silicon resin curing agents are used. Specific examples of these curing agents include various organic acids and their acid anhydrides, nitrogen-containing organic compounds, various metal complex compounds or metal alkoxides, and various salts such as alkali metal organic carboxylates and carbonates. Can be mentioned. These curing agents can be used as a mixture of two or more kinds.

Among these curing agents, for the purpose of the present invention, stability of the paint, from the viewpoint of the presence or absence of coloring of the coating film after coating,
The aluminum chelate compounds shown below are particularly useful. The aluminum chelate compounds herein, for example, an aluminum chelate compound represented by the general formula AlX _n Y _3-n.

However, in the formula, X is OL (L is a lower alkyl group), Y is a ligand derived from a compound represented by the general formula M ¹ COCH ₂ COM ² (M ¹ and M ² are both lower alkyl groups), and General formula M ³ COCH ₂ C
It is at least one selected from the ligands derived from the compounds represented by OOM ⁴ (M ³ and M ⁴ are both lower alkyl groups), and n is 0, 1 or 2. Examples of the aluminum chelate compound represented by AlX _n Y _3-n include various compounds, but from the viewpoints of solubility in the composition, stability, effect as a curing catalyst, etc., aluminum acetylacetoacetate is particularly preferable. Nate, aluminum bisethylacetoacetate monoacetylacetonate, aluminum-
Examples include di-n-butoxide-monoethylacetoacetate and aluminum-di-iso-propoxide-monomethylacetoacetate. It is also possible to use a mixture of two or more of these.

The high-refractive-index hard coat film in the present invention is used by coating it on various types of substrates, and examples of applicable substrates include inorganic glass and various plastics. There is no problem whether these base materials are colorless or colored, and they may be transparent or opaque. However, since the coating film of the present invention is a film having a high surface hardness and a high refractive index, when applied to a plastic substrate having a high refractive index, specifically 1.55 or more, it does not generate reflection interference fringes. It is particularly effective from the point of view.

Particularly preferable plastic substrates to which the present invention is applied include, for example, acrylic resins, polycarbonates, diethylene glycol bisallyl carbonate polymers, di (meth) acrylate polymers of (halogenated) bisphenol A and copolymers thereof, and (halogenated) bisphenol A. Examples thereof include urethane-modified di (meth) acrylate polymers and copolymers thereof.

When applying the coating composition of the present invention comprising the fine particles of the composite oxide of cerium oxide and titanium oxide and the organosilicon compound and / or its hydrolyzate to various substrates, the cleaning and adhesion properties are improved. The substrate can be subjected to various pretreatments for the purpose of improvement, water resistance, and the like. Particularly effective means for the present invention include activated gas treatment and chemical treatment.

The activated gas treatment is ions, electrons or excited gas produced under normal pressure or reduced pressure. As a method of generating these activated gases, for example, corona discharge, high-voltage discharge by direct current under low pressure, low frequency, high frequency, or microwave is used.

Particularly, a treatment with a low temperature plasma obtained by high frequency discharge under reduced pressure is preferably used from the viewpoint of reproducibility and productivity.

The gas used here is not particularly limited, but specific examples include oxygen, nitrogen, hydrogen, carbon dioxide, sulfur dioxide, helium, neon, argon, freon, water vapor,
Examples thereof include ammonia, carbon monoxide, chlorine, nitric oxide, and nitrogen dioxide. These can be used not only as one kind but also as a mixture of two or more kinds. Among the above, preferable gases include those containing oxygen, and those existing in nature such as air may be used. More preferably, pure oxygen gas is effective for improving adhesion. Further, for the same purpose, it is possible to raise the temperature of the substrate to be treated during the treatment.

On the other hand, specific examples of the chemical treatment include alkali treatment with pseudo-sodium, acid treatment with hydrochloric acid, sulfuric acid, potassium permanganate, potassium dichromate, treatment with an organic solvent having an aromatic ring, and the like.

The above pretreatments can be carried out continuously or in stages in combination.

As a means for applying the coating composition of the present invention to various substrates, commonly used coating methods such as brush coating, dip coating, roll coating, spray coating, spin coating and flow coating can be easily applied.

The film thickness of the coating film in the present invention is not particularly limited. However, from the viewpoint of maintaining adhesive strength and hardness, 0.1-2
It is preferably used between 0 μm. More preferably 0.4
~ 8.0 μm. Further, in coating the coating film, it is used by diluting it with various solvents from the standpoint of workability, adjustment of the film thickness, etc. Examples of the diluting solvent include water, alcohol,
Various kinds of esters, ethers, halogenated hydrocarbons, dimethylformamide, dimethylsulfoxide and the like can be used according to the purpose, and a mixed solvent can be used if necessary.

The high-refractive-index hard coat film obtained by the present invention has a high refractive index, is excellent in weather resistance, has a durable high-hardness surface, and is capable of being dyed, so that spectacle lenses and various It is preferably applied to optical lenses, CRT filters, show windows, light covers for automobiles, and the like.

[Examples] Examples will be described below, but the present invention is not limited thereto.

Example 1 (1) Preparation of coating composition (a) Preparation of γ-glycidoxypropyltrimethoxysilane hydrolyzate 63.5 g of γ-glycidoxypropyltrimethoxysilane was charged into a reactor equipped with a rotor. The solution was maintained at 10 ° C., and 14.5 g of 0.01N hydrochloric acid aqueous solution was gradually added dropwise while stirring with a magnetic stirrer. Stop cooling after the dropping,
A hydrolyzate of γ-glycidoxypropyltrimethoxysilane was obtained.

(B) Preparation of Hydrolyzate Concentrate The silane hydrolyzate was rotovapped.
The mixture was concentrated at an external temperature of 95 ° C for 2 hours to obtain 50.0 g of a concentrate.

(C) Preparation of coating composition 3.5 g of the concentrate of (b) above was sampled, 12.6 g of phenethyl alcohol and 0.1 g of silicone surfactant were added and mixed,
Furthermore, N, N-dimethylformamide dispersion colloidal cerium / titanium oxide sol (weight ratio of cerium oxide / titanium oxide 1.0, average particle size: about 10 mμ, solid content 10%) 8
8.0 g and aluminum acetylacetonate 0.6 g were added and sufficiently stirred to obtain a coating composition.

(2) Preparation of plastic substrate Tetrabrom bisphenol A ethylene oxide 2
70 parts of a monomer containing a polyfunctional acrylate monomer to which 0.9 mol of hexamethylene diisocyanate has been added and 30 parts of styrene are isopropyl peroxide to 1 mol of a hydroxyl group-containing compound obtained by condensing 1 mol of acrylic acid to a mol addition product by esterification. The base material which was cast-polymerized using as a polymerization initiator was subjected to low temperature plasma treatment to obtain a surface-treated base material. The refractive index of the obtained resin was 1.609.

(3) Coating and curing The coating composition prepared in (1) above is pulled up on the plastic substrate obtained in (2) above at a rate of 10
Dip coated on plastic substrate at cm / min, then 9
Precured for 12 minutes at 3 ° C. After the pre-curing was taken out and the temperature of the plastic substrate reached room temperature, the above-mentioned coating and pre-curing were repeated 3 times and then heated at 100 ° C. for 2 hours to obtain a high refractive index hard coat film. Thus, a plastic substrate having a high-refractive-index hard coat layer having an excellent transparency was obtained. The refractive index of this high refractive index hard coat film is 1.
It was 778. In addition, various performances were measured. The evaluation method is shown below, and the results are shown in Table 1.

(Evaluation method) (a) Appearance A lens having good transparency and no coloration with the naked eye was evaluated as ◯.

(B) High refractive index performance Diethylene glycol bisallyl carbonate polymer lens (diameter 71m
m, thickness 2.1 mm, CR-39 plano lens) in Example 1-
The total light transmittance of the coating and cured by the method of (3) is calculated by SM color computer (Suga Test Instruments Co., Ltd.).
The refractive index calculated by subtracting the measurement result from 100 and subtracting the measurement result from 100 is 1.57 or more.
And

(C) Adhesion Adhere 100 pieces of crevices reaching the base material of 1 mm on the surface of the coating with a steel knife and firmly attach cellophane adhesive tape (trade name "Cellotape" manufactured by Nichiban Co., Ltd.) 90 Those that were peeled off rapidly in the direction of degree and did not peel off the coating film were rated as ◯.

(D) Dyeability It was immersed in a disperse dye (a mixture of three colors of red, blue and yellow) at 93 ° C for 15 minutes, and showed an extinction rate of 20% or more using an SM color computer (manufactured by Suga Test Instruments Co., Ltd.). The case was marked as ○.

(E) Weather resistance The obtained lens was exposed outdoors for 2 months, and the adhesion of the coating film was evaluated in the same manner as in (c) above.

Examples 2 and 3 In Example 1, except that the weight ratio of the cerium oxide and titanium oxide (component A), which are complex oxide sols, and the hydrolysis concentrate (component B) was changed as shown in Table 1. In the same manner as in Example 1, a high refractive index hard coat film was obtained, and the same substrate was coated and cured. The performance was measured in the same manner as in Example 1, and the evaluation results are shown in Table 1.

Examples 4, 5 and Comparative Examples 2, 3 (1) Preparation of Plastic Base Material Having Hard Coat Layer In Example 2, the weight ratio of cerium oxide / titanium oxide as the component A was changed as shown in Table 2. Except for
Various lenses were prepared in the same manner as in Example 2. Various performances were measured in the same manner as in Example 2. The results are shown in Table 2.

Further, for the obtained lens, a coating film comprising the following coating composition was further formed on the high refractive index hard coat film, and its antireflection performance was also measured.

(2) Preparation of coating composition for antireflection processing (a) Preparation of hydrolyzate 4.8 g of γ-glycidoxypropyltrimethoxysilane in a reactor equipped with a rotor, 3,3,3-trifluoropropyl 3.7 g of trimethoxysilane was charged, the liquid temperature was kept at 10 ° C., and 2.0 g of 0.01N hydrochloric acid aqueous solution was gradually added dropwise while stirring with a magnetic stirrer. After completion of dropping, cooling was stopped to obtain a hydrolyzate.

(B) Preparation of paint The silane hydrolyzate was added to n-propyl alcohol 82.3
g, distilled water 35.3 g, ethyl cellosolve 11.3 g, and methanol-dispersed colloidal silica (average particle size 12 ±
1mμ, solid content 30%) 8.3g, 1.8g of silicone surfactant prepared in advance to 5wt% with n-propyl alcohol
And 0.5 g of aluminum acetylacetonate were added and sufficiently stirred to obtain a coating composition.

(3) Preparation of antireflection article The coating composition prepared in (2) above was spin-coated on the plastic substrate having the hard coat layer obtained in (1) above under the following conditions. After coating, pre-cure at 82 ℃ / 12 minutes, then 100 ℃ / 4
After heating and curing for an hour, an antireflection cured article was obtained.

Spin coating conditions Rotation speed: 3500 rpm Rotation time: 30 seconds The antireflection property of the obtained antireflection article is that the total light transmittance measured by a haze computer (manufactured by Suga Test Instruments Co., Ltd.) is 96.5% or more. , ○.

Example 6 (1) Preparation of coating composition (a) Dissolution of epoxy resin 15.0 g of a bromine-containing epoxy resin (Epiclone 152, manufactured by Dainippon Ink and Chemicals, Inc.) was weighed, and acetylacetone 9.
It was dissolved in 6 g to obtain 24.6 g of a lysate.

(B) Preparation of paint To 17.1 g of the concentrate of Example 1- (b), the dissolved product of (a) was added, 5.6 g of phenethyl alcohol and 0.6 g of a silicone-based surfactant were added and mixed, and N, N was further added. -Dimethylformamide dispersion colloidal cerium oxide / titanium oxide sol (weight ratio of cerium oxide / titanium oxide 1.0, average particle size: about 10 mμ, solid content 20%) 149.9 g, and aluminum acetylacetonate 3.0 g were added and sufficiently stirred. A coating composition was prepared.

(2) Coating and curing The coating composition prepared in the above (1) was dip-coated on the plastic substrate obtained in Example 1- (2) at a pulling rate of 10 cm / min, and then 82 Preliminary curing was performed at 12 ° C for 12 minutes, and heating was further performed at 100 ° C for 2 hours to obtain a high refractive index hard coat film. The lens thus obtained had excellent transparency.
The refractive index was 1.699. Various performances were measured in the same manner as in Example 1, and the results are shown in Table 3. In addition, this film was treated with a plasma device for surface treatment (PR501A Yamato Scientific Co., Ltd.) with an oxygen flow rate of 100 ml / min and an output of 50.
Treatment with W for 1 minute.

Further, the obtained lens was coated with the coating composition for antireflection treatment in the same manner as in Example 4 to prepare an antireflection article. The performance results are shown in Table 3.

[Effects of the Invention] The high refractive index hard coat film obtained by the present invention comprises:
It has the following effects.

(1) It has a sufficiently high refractive index.

(2) Excellent weather resistance.

(3) It has excellent dyeability.

(4) It is also applicable as an antireflection film.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display area C09D 183/04 LRX 183/14 G02B 1/11

Claims (1)

[Claims] 1. A high refractive index hard coat film comprising a cured product of a composition containing the following components A and B as main components. A. Composed of a complex oxide of cerium oxide and titanium oxide,
The weight ratio of cerium oxide to titanium oxide is 0.1.
Or more, and 1.4 or less, and the average particle size is 1 mμ or more, 100
Fine particles of mμ or less. B. BR ¹ _a SiX _3-a (I) or One or more selected from organosilicon compounds represented by and their hydrolysates. (Here, R and R ¹ are organic groups having 1 to 10 carbon atoms. X
Is a hydrolyzable group, and a is 0 or 1. Y is an organic group having 2 to 40 carbon atoms. )