JP3031571B2 - Hard coat film and substrate with hard coat film - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hard coat film formed on the surface of a substrate such as glass and plastic, and more particularly, to a high refractive index, excellent transparency, hot water resistance, weather resistance, and the like. The present invention relates to a hard coat film having excellent scratch resistance, abrasion resistance, and dyeability, and also having excellent adhesion to a substrate.

[0002] The present invention further relates to a substrate with a hard coat film having such an excellent hard coat film formed on the surface.

[0003]

BACKGROUND OF THE INVENTION For the purpose of forming a hard coat film having a high refractive index on the surface of a substrate such as a transparent plastic or glass, various hard coat films and methods for forming these hard coat films are available. Proposed.

For example, Japanese Patent Application Laid-Open No. 63-247702 discloses a coating film containing titanium oxide particles and a specific organosilicon compound. In addition, Japanese Unexamined Patent Application Publication No.
Japanese Patent Application Publication No. 264902 discloses a hard coat film composed of composite oxide fine particles of cerium oxide and titanium oxide and an organosilicon compound. Further, JP-A-3-68
No. 901 discloses a hard coat film composed of fine particles obtained by treating titanium oxide-based fine particles with silica and / or an organic silicon compound and an organic silicon compound.

However, Japanese Patent Application Laid-Open No. 63-247702 discloses
The coating film described in Japanese Patent Publication No.
There is a problem that the film discolors over time and the adhesion to the substrate is not good. Further, the hard coat films described in JP-A-2-264902 and JP-A-3-68901 have somewhat better weather resistance than the coating films described in JP-A-63-247702. However, there is a problem that the scratch resistance and the abrasion resistance are not practically sufficient.

[0006]

SUMMARY OF THE INVENTION The object of the present invention is to solve the above-mentioned problems in the prior art, and has a high refractive index, excellent transparency, and furthermore, hot water resistance, weather resistance, abrasion resistance, and the like. Provided is a hard coat film having excellent abrasion resistance and dyeing properties, and excellent adhesion to a substrate, and a substrate with a hard coat film having a hard coat film having such excellent characteristics formed on the surface. It is intended to be.

[0007]

SUMMARY OF THE INVENTION The first hard coat film according to the present invention comprises:
A coating liquid for forming a hard coat film containing a hydrolyzable organosilicon compound capable of forming a matrix and composite oxide particles is applied to the surface of the substrate, dried, and heated to a temperature lower than the heat resistance temperature of the substrate.
A hard coat film hardened and cured , wherein the composite oxide particles comprise an iron oxide component and a titanium oxide component,
Iron oxide component amount terms of Fe ₂ O _3, the weight ratio Fe ₂ O ₃ / TiO ₂ when converted to the amount of titanium oxide component TiO ₂ is 0.0
A composite oxide in which iron oxide and titanium oxide are chemically bonded, wherein the average particle diameter of the composite oxide particles is in the range of 1 to 100 μm, Alternatively, it is a solid solution comprising an oxide of iron and titanium, or a mixture thereof.

The second hard coat film according to the present invention is obtained by applying a coating solution for forming a hard coat film containing a hydrolyzable organosilicon compound capable of forming a matrix and composite oxide particles to the surface of a substrate, followed by drying. , Heating below the heat resistant temperature of the substrate
A hard coat film cured by heating , wherein the composite oxide particles are composed of an iron oxide component, a titanium oxide component, and a silica component, the amount of the iron oxide component is converted to Fe ₂ O ₃ , and the amount of the titanium oxide component is reduced. When converted to TiO ₂ and the amount of silica component was converted to SiO ₂ , the weight ratio Fe ₂ O ₃ / TiO ₂ was 0.005 to 0.005.
1.0 and the weight ratio of SiO ₂ / (Fe ₂ O ₃ + Ti
O ₂ ) is in the range of 0.001 to 1.0, the average particle diameter of the composite oxide particles is in the range of 1 to 100 μm, and the composite oxide particles are composed of iron oxide, titanium oxide, and silica. It is characterized in that it is a composite oxide which is chemically bonded, a solid solution composed of an oxide of iron, titanium and silicon, or a mixture thereof.

In the first and second hard coat films according to the present invention, the composite oxide particles are preferably surface-modified with an organic silane compound. The substrate with a hard coat film according to the present invention is characterized in that the first or second hard coat film according to the present invention is formed on the surface of the substrate.

[0010]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, a first hard coat film (1) and a second hard coat film (2) according to the present invention,
Further, the first base material with a hard coat film (A) and the second base material with a hard coat film (B) according to the present invention having such a hard coat film formed on the surface will be specifically described.

Hard Coat Film (1) First, the first hard coat film (1) according to the present invention will be specifically described. This hard coat film (1) is coated with a coating liquid for forming a hard coat film containing a hydrolyzable organosilicon compound capable of forming a matrix and composite oxide particles on the surface of the substrate, and dried. Heat below
After being cured , the composite oxide particles are composed of an iron oxide component and a titanium oxide component.

[0012] As the composite oxide, the following (a) ~ (c)
Means either. (A) a composite oxide in which iron oxide and titanium oxide are chemically bonded; (b) a solid solution composed of an oxide of iron and titanium; (c) a mixture of the above (a) and (b) .

Further, the above iron oxide or titanium oxide is
Any of them may be a hydrate or a hydroxide. Since the iron oxide has a longer wavelength region of ultraviolet absorption than cerium oxide, the hard coat film (1) is a conventional hard coat film containing composite oxide particles of cerium oxide and titanium oxide. Excellent in weather resistance in comparison.

The average particle diameter of the composite oxide particles contained in the hard coat film (1) is in the range of 1 to 100 μm, preferably 2 to 60 μm. Hard coat films containing composite oxide particles having an average particle size of more than 100 μm tend to be cloudy and opaque, and hard coat films containing composite oxide particles having an average particle size of less than 1 μm have poor hardness. There is a tendency that the refractive index is not sufficiently high at the same time as the scratch resistance is insufficient.

The composite oxide contained in the hard coat film (1) has a weight ratio of Fe ₂ O ₃ when the amount of iron oxide is converted to Fe ₂ O ₃ and the amount of titanium oxide is converted to TiO _2.
/ TiO ₂ is 0.005 to 1.0, preferably 0.01
０．７0.70. In the present specification, the ratio of Fe ₂ O ₃ / TiO ₂ in the composite oxide particles is determined based on the iron compound used as a raw material and Fe ₂ O ₃ and Ti, respectively.
It is a value calculated by converting to O ₂ .

If the weight ratio is less than 0.005, a hard coat film having good weather resistance cannot be obtained, and if it exceeds 1.0, the hard coat film turns yellow and a hard coat film having excellent transparency can be obtained. Tend to not exist.

In preparing the coating solution for forming the hard coat film (1), for example, a sol (iron oxide / titanium oxide ) in which the composite oxide particles (a) to (c) are dispersed in water or an organic solvent is used. (A composite oxide sol) is preferably used.

Such an iron oxide / titanium oxide composite oxide sol can be produced by the method described in JP-A-2-178219. More specifically, it is as follows.

A composite hydrated oxide of iron and titanium and / or a mixture of hydrated iron oxide and hydrated titanium oxide obtained by hydrolyzing a mixed aqueous solution containing a titanium compound and an iron compound in the above ratio. Hydrogen peroxide is added to the dispersion containing, preferably, H ₂ O ₂ / (Fe ₂ O ₃ + TiO ₂ ) (weight ratio) of 4 to 7, preferably at a temperature of 50 ° C. or more and about 0. The mixture is heated for 5 to 8 hours to dissolve or peptize the hydrated oxide contained in the dispersion. At this time, the concentration of the hydrated oxide contained in the liquid is (Fe ₂ O ₃ + TiO ₂ )
The amount is usually adjusted to about 6% by weight or less, preferably about 4% by weight or less.

Next, when the obtained solution is heated to 60 ° C. or more, preferably 80 ° C. or more, the hydrogen peroxide-soluble compound in the solution is hydrolyzed to obtain an iron oxide / titanium oxide composite oxide sol.

The iron oxide / titanium oxide composite oxide sol thus obtained is formed into a matrix (substrate component) .
Hydrolysis that can form a solution or matrix in which a soluble hydrolyzable organosilicon compound is dissolved in an organic solvent
The coating liquid for forming the hard coat film (1) is prepared by mixing with a dispersion in which the reactive organosilicon compound is uniformly dispersed.

At this time, the iron oxide / titanium oxide composite oxide sol may be directly mixed with the above solution or dispersion, but an organic solvent is mixed with the iron oxide / titanium oxide composite oxide sol, or Mixing may be performed after replacing the solvent of the sol with an organic solvent.

As the organic solvent used for mixing with the iron oxide / titanium oxide composite oxide sol or replacing the solvent of the sol, specific examples thereof include alcohols such as methanol, ethanol and isopropyl alcohol. , Methyl cellosolve, ethyl cellosolve, glycols such as ethylene glycol, esters such as methyl acetate and ethyl acetate, ethers such as diethyl ether and tetrahydrofuran, ketones such as acetone and methyl ethyl ketone, halogenated hydrocarbons such as dichloroethane, Examples include aromatic hydrocarbons such as toluene and xylene, and N, N-dimethylformamide.
These solvents may be used as a mixture of two or more kinds.

In preparing the coating solution for forming the hard coat film (1), it is preferable to use the iron oxide / titanium oxide composite oxide sol as described above, but it is composed of an iron oxide component and a titanium oxide component. Fine particles in a state other than a sol may be used as long as the composite oxide particles can be dispersed in the coating solution in a monodispersed or nearly monodispersed state.

As the hydrolyzable organosilicon compound capable of forming a matrix used in the coating solution for forming the hard coat film (1), for example, a silane compound represented by the following general formula (I) is used.

[0026]

Embedded image

(Where a and b are integers of 0 to 2, a + b is 1 to 3. R ¹ is an alkyl group, an alkenyl group, a phenyl group or a halogenated hydrocarbon group. R ² is an epoxy group, an amino group, an amide group, a mercapto group, a methacryloxy group, a cyano group, a vinyl group, an organic group containing an aromatic ring whose nucleus is substituted by halogen, and X is a hydrolyzable group. Examples thereof include a halogen atom or an alkoxyl group, an alkoxyalkoxyl group, and an acyloxy group.) Examples of the silane compound represented by the formula (I) include tetrafunctional silanes such as tetramethoxysilane and tetraethoxysilane; Methyltrimethoxysilane, methyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxy Silane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, N-, β- (aminoethyl) -γ-aminopropyltri Trifunctional silanes such as methoxysilane, γ-ureidopropyltrimethoxysilane, γ-cyanopropyltrimethoxysilane, γ-morpholinopropyltrimethoxysilane, and N-phenylaminopropyltrimethoxysilane;
Examples include bifunctional silanes in which a part is substituted with a methyl group, an ethyl group, or a vinyl group. These organosilicon compounds may be used as a mixture of two or more.

These organosilicon compounds may be used as they are, hydrolyzed, or partially condensed. A hard coat film (1) forming coating solution, in order to accelerate the curing of the coating formed by an organic silicon compound, may contain a curing catalyst further.

Specific examples of such a curing catalyst include amines such as n-butylamine, triethylamine and guanidine, amino acids such as glycine, 2-methylimidazole, 2,4-diethylimidazole, 2-phenylimidazole and the like. Metal acetylacetonates such as imidazole, aluminum acetylacetonate, titanium acetylacetonate chromium acetylacetonate, organic acid metal salts such as sodium acetate, zinc naphthenate, tin octylate, SnCl ₄ , TiCl ₄ , ZnCl
_And Lewis acids such as _2, magnesium perchlorate, and the like.

Specific examples of the organic solvent used for the coating solution for forming the hard coat film (1) include alcohols such as methanol, ethanol and isopropyl alcohol, ketones such as acetone and methyl ethyl ketone, methyl cellosolve and ethyl cellosolve. And formamides such as N, N-dimethylformamide, water, and freon. These solvents may be used as a mixture of two or more kinds.

Further, the coating liquid for forming the hard coat film (1) may contain a surfactant or an ultraviolet ray depending on the purpose of forming the hard coat film (1), the use of the substrate on which the hard coat film (1) is formed, and the like. Absorbent, antioxidant, thixotropic agent,
Pigments, dyes, antistatic agents, conductive substances, and the like may be added. Maleic acid, maleic anhydride, itaconic acid,
When a polycarboxylic acid such as itaconic anhydride is added, the dyeability, heat resistance, hot water resistance, and abrasion resistance of the hard coat film are improved.

The iron oxide / titanium oxide composite oxide particles in the coating solution for forming the hard coat film (1) have an iron oxide component amount of F
and expressed as the weight of e ₂ O ₃ ,
When expressed in terms of the weight of iO ₂ , the matrix 10
20 to 500 parts by weight, preferably 60 parts by weight per 0 parts by weight
It is prepared in the range of ~ 300 parts by weight.

The hard coat film (1) according to the present invention is obtained by dipping, spinning, spraying, or applying a coating solution for forming the hard coat film (1) on a substrate surface such as glass or plastic. Coating and drying by a method such as flexographic printing or the like, and then the coating thus formed on the surface of the substrate is cured by heating to a temperature lower than the heat resistant temperature of the substrate.

The thickness of the hard coat film (1) thus obtained is usually 0.1 to 20 μm, preferably 1 to 20 μm.
７7 μm. Hard coat film (2) Next, the hard coat film (2) according to the present invention will be described.

The hard coat film (2) according to the present invention is obtained by applying and drying a coating solution for forming a hard coat film containing a hydrolyzable organosilicon compound capable of forming a matrix and composite oxide particles on the surface of a substrate. , Heating below the heat resistant temperature of the substrate
Becomes cured Te, iron oxide component as a composite oxide particles,
It contains a titanium oxide component and a silica component.

The composite oxide component includes the following (a) to
(C) . (A) a composite oxide in which iron oxide, titanium oxide and silica are chemically bonded; (b) a solid solution composed of an oxide of iron, titanium and silicon; (c) a mixture of (a) and (b) .

The above-mentioned iron oxide, titanium oxide and silica can each take the state described in the section of the hard coat film (1). That is, for example, silica means silicic anhydride or a hydrate thereof.

The range of the particle size of the composite oxide particles contained in the hard coat film (2) is the same as that of the composite oxide particles contained in the hard coat film (1). The amount of the iron oxide component in the composite oxide particles contained in the hard coat film (2),
When the amounts of the titanium oxide component and the silica component are each expressed by the weight of Fe ₂ O ₃ , TiO ₂ and SiO ₂ , the ratio of Fe ₂ O ₃ / TiO ₂ is 0.005 to 1.0, preferably In the range of 0.01 to 0.7 and SiO
_{2 / (Fe 2 O 3 +} TiO 2) ratio is 0.001.
0, preferably in the range of 0.005 to 1.0. Si
When the O ₂ / (Fe ₂ O ₃ + TiO ₂ ) ratio exceeds 1.0, the refractive index of the hard coat film decreases, and when the ratio is less than 0.001, the effect of containing the silica component is hardly obtained.

When the silica component is contained in the composite oxide particles, the weather resistance of the hard coat film and the long-term stability of the coating solution tend to be improved. In preparing the coating solution for forming the hard coat film (2), an iron oxide / titanium oxide / silica composite oxide sol is preferably used, and the iron oxide / titanium oxide / silica composite oxide sol has already been described. As in the case of the prepared iron oxide / titanium oxide composite oxide sol,
It can be produced by the method described in JP-A-178219.

The coating solution for forming the hard coat film (2) is the same as that for forming the hard coat film (1) except that an iron oxide / titanium oxide / silica composite oxide sol is used instead of the iron oxide / titanium oxide composite oxide sol. It is prepared in the same manner as the coating solution.

Also, the hard coat film (2) is replaced with a hard coat film (2) instead of the coating solution for forming the hard coat film (1).
It can be formed on the surface of a base material such as a plastic in the same manner as in the hard coat film (1) except that the forming coating solution is used.

The composite oxide particles contained in the hard coat films (1) and (2) can be surface-modified with an organic silane compound. When the surface of the composite oxide particles is modified with an organosilane compound, the reactivity and affinity between the composite oxide particles and the matrix and the affinity between the composite oxide particles and the solvent in the coating liquid for forming a hard coat film are further improved. improves.

When the surface of the composite oxide particles is modified with an organic silane compound as described above, an organic silane compound which is generally used as a silane coupling agent is used. It is appropriately selected according to the type of the solvent of the coating liquid for use. Specific examples of such a surface-modifying organosilane compound include tetraethoxysilane, methyltrimethoxysilane, trimethylchlorosilane, vinyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ
-Glycidoxypropylmethyldiethoxysilane.

The surface modification of the composite oxide particles can be carried out, for example, by immersing the composite oxide particles in an alcohol solution of the above-mentioned organic silane compound for a certain period of time and then removing the solvent, or by combining with the above-mentioned organic silane compound in an alcohol solution. This is carried out by mixing an oxide sol and, after a certain period of time, separating and concentrating water in the mixed solution by a method such as ultrafiltration.

The amount of the organic silane compound used at this time is appropriately set according to the amount of hydroxyl groups present on the surfaces of the composite oxide particles. Substrate with hard coat film (A), (B) Next , substrate with hard coat film (A), (B) according to the present invention
Will be described.

The substrates (A) and (B) with a hard coat film according to the present invention comprise a hard coat film (1),
(2) is formed. As the substrate on which such hard coat films (1) and (2) are formed, various substrates made of glass, plastic, and the like are used. Specifically, various optical lenses such as spectacle lenses and cameras, and CRTs Front panel, filter, show window case, window glass,
Examples include a contact glass used for a copying machine and a light cover used for an automobile.

[0047]

Since the hard coat film according to the present invention has a high refractive index, when the hard coat film according to the present invention is formed on the surface of a plastic lens, interference fringes based on light interference between the plastic lens and the hard coat film are generated. Can be erased.

Further, the hard coat film according to the present invention comprises:
It is preferably applied to various optical lenses such as spectacle lenses and cameras because it has excellent weather resistance and high surface hardness, and therefore has excellent scratch resistance and abrasion resistance and excellent dyeability. .

Further, since the hard coat film according to the present invention has a high refractive index, when the hard coat film according to the present invention is formed on the surface of a base material, for example, a spectacle lens or a camera lens, the anti-reflection of the base material surface is prevented. Is made. For this reason, an imaging device such as a camera using a lens having a hard coat film formed on the surface according to the present invention has a smaller light amount than an imaging device using a lens having no hard coat film formed on the surface. It has features such as clear imaging.

When formed on the surface of a CRT front panel, a filter, a show window, a window glass, or the like, a base material having excellent transparency can be obtained, and the life and appearance of these base materials can be improved. .

Further, the hard coat film according to the present invention comprises:
Not only glass base material but also polycarbonate resin, acrylic resin, polystyrene resin, polyester resin,
It is also suitable as a film formed on the surface of a plastic substrate such as a polyurethane resin.

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples.

[0053]

Example 1 Preparation of iron oxide / titanium oxide composite oxide sol 2 g of ferric chloride in terms of Fe ₂ O ₃ and 98 g of titanium tetrachloride in terms of TiO ₂ were dissolved in pure water. 10 kg
Was prepared. 15% aqueous ammonia was gradually added to the mixed aqueous solution until the pH reached 9.0, to obtain a coprecipitated gel of hydrated iron oxide and hydrated titanium oxide.

The coprecipitated gel thus obtained was dehydrated and washed, and 1,100 g of the coprecipitated gel were added with 1,150 g of 35% hydrogen peroxide and 250 g of pure water, and then heated to 80 ° C. As a result, 2,500 g of a reddish brown solution was obtained. The pH of this solution was 7.8. The concentration of iron and titanium oxides contained in this solution is (TiO 2
After diluting with pure water to 1.0% by weight in terms of ( ₂ + Fe ₂ O ₃ ), the mixture was heated at 200 ° C. for 96 hours.

Next, the water in the solution was replaced with methanol, and the solution was concentrated until the reduced concentration became 20% by weight. As a result, the average particle size was 11 μm, and Fe ₂ O ₃ / TiO ₂ (weight ratio) was used.
Was 2/98 to obtain an iron oxide / titanium oxide composite oxide sol (sol A ₁ ).

Preparation of coating solution for forming hard coat film γ-glycidoxypropyltrimethoxysilane
While maintaining the temperature of the reaction vessel containing 1 part by weight at 10 ° C., 64.2 parts by weight of 0.01N HCl aqueous solution was gradually added dropwise with stirring to hydrolyze γ-glycidoxypropyltrimethoxysilane. . To this solution was added ethanol 100.
2 parts by weight and 215 parts by weight of isopropanol were added to form a matrix.

The sol A ₁ was added to the liquid containing the matrix.
Was added thereto, and further, 10.03 parts by weight of aluminum acetylacetonate was added, and the mixture was mixed well to obtain a coating solution for forming a hard coat film.

Formation of Hard Coat Film A polycarbonate molded product (Iupilon U-4000 manufactured by Mitsubishi Gas Chemical Co., Ltd.) was immersed in a 13% NaOH aqueous solution at 47 ° C. for several minutes, and then sufficiently washed with water.

Next, the polycarbonate molded article was immersed in the coating solution, pulled up at a pulling rate of 80 mm / min, dried at 90 ° C. for 18 minutes, and heat-cured at 104 ° C. for 90 minutes to obtain a hard coat film of Example 1. Was formed.

Characteristics of Hard Coat Film The following characteristics were evaluated for the hard coat film of Example 1 thus obtained. (A) High refraction performance The case where the refractive index obtained from the analysis result of the reflection interference spectrum of the surface of the hard coat film is 1.58 or more was evaluated as ○. (B) Scratch resistance A steel wool of $ 000 was reciprocated 10 times on the surface of a 1 cm x 3 cm test piece having a hard coat film while applying a load of 2 kg, and the hard coat film was rubbed with the steel wool and damaged. The degree was visually classified and evaluated in the following stages.

A: Almost no scratch B: Slightly scratched C: Severely scratched (c) Appearance A substrate with a hard coat film having good transparency and extremely little coloration was evaluated as ○. (D) Dyeability Three kinds of disperse dyes of red, blue and yellow are dissolved9
The substrate with the hard coat film was immersed in hot water of 2 ° C. for 5 minutes,
The extinction ratio at a wavelength of 550 nm was measured using an M color computer (manufactured by Suga Test Instruments Co., Ltd.) and evaluated as follows.

…: Extinction ratio of 30% or more △: extinction ratio of 20% to less than 30% ×: extinction ratio of less than 20% (e) Weather resistance After a 400-hour exposure acceleration test was performed, the change in appearance was evaluated, and the degree of the change was evaluated in three grades of △, Δ, and ×. (F) Degree of clouding A base material with a hard coat film is installed between a black background and a three-wavelength daylight fluorescent lamp, and a pattern of light transmitted through the base material with the hard coat film and reflected on the background is visually observed, The degree of haze due to the hard coat film was evaluated on a three-point scale of △, Δ, and ×. (G) Long-term stability A coating solution for forming a hard coat film was applied at 10 ° C. for 25 days and 4 days.
After storage for 5 days, a hard coat film was formed as described above, and the above (a) to (d) and (f) were evaluated. The hard coat film formed immediately after preparing the coating liquid for forming a hard coat film And the difference was evaluated in three grades of ○, Δ, and ×.

Table 1 shows the results.

[0064]

Example 2 Fe ₂ O ₃ / TiO ₂ (converted weight ratio) was 40
Iron oxide / titanium oxide composite oxide sol (sol A ₂ ) having an average particle size of 9 μm in the same manner as in Example 1 except that the amounts of ferric chloride and titanium tetrachloride were adjusted so as to be / 60. I got

A coating solution for forming a hard coat film was prepared in the same manner as in Example 1 except that the sol A ₂ was used in place of the sol A ₁ , and this coating solution was used to prepare the hard coat film of Example 2. A film was formed, and the characteristics of the obtained hard coat film were evaluated.

Table 1 shows the results.

[0067]

Example 3 1,000 g of sol A ₁ was placed in a reaction vessel,
After heating to 63 ° C., 2 liters of a mixed solution of vinyltriethoxysilane and methanol was gradually added with stirring. After completion of the addition, the temperature of the solution is further maintained at 63 ° C. to ripen the iron oxide / titanium oxide composite oxide sol in the solution, and then the solution is concentrated to a concentration of 30.5% by weight of vinyltriethoxysilane. Thus, a methanol-dispersed sol (sol A ₃ ) of the iron oxide / titanium oxide composite oxide surface-modified with was obtained.

A coating solution for forming a hard coat film was prepared in the same manner as in Example 1 except that the sol A ₃ was used in place of the sol A _1. A film was formed, and the characteristics of the obtained hard coat film were evaluated.

Table 1 shows the results.

[0070]

Example 4 A methanol-dispersed sol of iron oxide / titanium oxide composite oxide surface-treated with methyltriethoxysilane (Sol A) in the same manner as in Example 3 except that vinyltriethoxysilane was replaced with methyltrimethoxysilane ₄ ) Got it.

A coating solution for forming a hard coat film was prepared in the same manner as in Example 1 except that the sol A ₄ was used in place of the sol A ₁ , and this coating solution was used to prepare the hard coat film of Example 4. A film was formed, and the characteristics of the obtained hard coat film were evaluated.

Table 1 shows the results.

[0073]

Fifth Embodiment A water glass aqueous solution was previously alkali-dehydrated with a cation exchange resin to 2,500 g of a reddish brown solution having a pH of 7.8 obtained in the preparation process of the iron oxide / titanium oxide composite oxide sol of the first embodiment. The obtained silicic acid solution (concentration in terms of SiO ₂ : 5% by weight) was mixed with an iron oxide component, a titanium oxide component and a silica component by Fe ₂ O ₃ , TiO ₂ and SiO ₂
Weight ratio SiO ₂ / (Fe ₂ O ₃ + Ti when converted as
O ₂ ) is mixed in such an amount as to be 15/100.
Heated at 70 ° C. for 10 hours.

Next, the water in this solution was replaced with methanol and concentrated until the concentration in terms of (Fe ₂ O ₃ + TiO ₂ + SiO ₂ ) became 20% by weight. As a result, iron oxide, titanium oxide and silica having an average particle size of 11 μm were obtained. A composite oxide sol (sol B ₁ ) was obtained.

A coating solution for forming a hard coat film was prepared in the same manner as in Example 1 except that this sol B ₁ was used in place of the sol A ₁ , and this coating solution was used to prepare a hard coat film of Example 5. A film was formed, and the characteristics of the obtained hard coat film were evaluated.

Table 1 shows the results.

[0077]

Except that the sol B ₁ and 1,577.0 parts by weight in the preparation process of Example 6 a hard coat film-forming coating solution, in the same manner as in Example 5, to prepare a hard coat film-forming coating solution The hard coat film of Example 6 was formed using this coating solution, and the characteristics of the obtained hard coat film were evaluated. The refractive index of this hard coat film (thickness: 1.5 μm) was 1.805 as a result of analyzing the reflection interference spectrum of the film surface.

Table 1 shows the results.

[0079]

Embodiment 7 The weight ratio of SiO ₂ / (Fe ₂ O ₃ + TiO ₂ ) when the iron oxide component, titanium oxide component and silica component were converted to Fe ₂ O ₃ , TiO ₂ and SiO ₂ respectively was 10/100. An iron oxide / titanium oxide / silica composite oxide sol (sol B ₂ ) having an average particle size of 12 μm was obtained in the same manner as in Example 5 except that the sol was prepared as described above.

A coating solution for forming a hard coat film was prepared in the same manner as in Example 1 except that the sol B ₂ was used in place of the sol A _1. A film was formed, and the characteristics of the obtained hard coat film were evaluated.

Table 1 shows the results.

[0082]

Embodiment 8 When the iron oxide component, the titanium oxide component and the silica component were converted to Fe ₂ O ₃ , TiO ₂ and SiO ₂ , respectively, the weight ratio Fe ₂ O ₃ / TiO ₂ was 5/95, and SiO ₂ / An iron oxide / titanium oxide / silica composite oxide sol (sol B ₃ ) having an average particle size of 10 μm was prepared in the same manner as in Example 5 except that (Fe ₂ O ₃ + TiO ₂ ) was adjusted to 43/100. Obtained.

A coating solution for forming a hard coat film was prepared in the same manner as in Example 1 except that this sol B ₃ was used in place of the sol A ₁ , and this coating solution was used to prepare the hard coat film of Example 8 A film was formed, and the characteristics of the obtained hard coat film were evaluated.

Table 1 shows the results.

[0085]

EXAMPLE 9 Using the sol B ₂ in place of the sol A _1, except for using tetraethoxysilane instead of vinyltriethoxysilane, the oxide surface-modified with tetraethoxysilane in the same manner as in Example 3 A methanol-dispersed sol (sol B ₄ ) of iron / titanium oxide / silica composite oxide was obtained.

A coating solution for forming a hard coat film was prepared in the same manner as in Example 1 except that this sol B ₄ was used in place of sol A ₁ , and this coating solution was used to prepare the hard coat film of Example 9 A film was formed, and the characteristics of the obtained hard coat film were evaluated.

Table 1 shows the results.

[0088]

Example 10 A methanol-dispersed sol of an iron oxide / titanium oxide / silica composite oxide surface-modified with trimethylchlorosilane in the same manner as in Example 9 except that trimethylchlorosilane was used instead of tetraethoxysilane. B ₅₎ was obtained.

A coating solution for forming a hard coat film was prepared in the same manner as in Example 1 except that this sol B ₅ was used in place of the sol A ₁ , and this coating solution was used to prepare the hard coat film of Example 10. A film was formed, and the characteristics of the obtained hard coat film were evaluated.

Table 1 shows the results.

[0091]

Example 11 Except that γ-glycidoxypropyltriethoxysilane was used instead of tetraethoxysilane,
In the same manner as in Example 9, a methanol-dispersed sol (sol B ₆ ) of iron oxide / titanium oxide / silica composite oxide surface-modified with γ-glycidoxypropyltriethoxysilane was obtained.

A coating solution for forming a hard coat film was prepared in the same manner as in Example 1 except that the sol B ₆ was used in place of the sol A _1. A film was formed, and the characteristics of the obtained hard coat film were evaluated.

Table 1 shows the results.

[0094]

Example 12 The surface was modified with γ-glycidoxypropylmethyldiethoxysilane in the same manner as in Example 9 except that γ-glycidoxypropylmethyldiethoxysilane was used instead of tetraethoxysilane. Methanol-dispersed sol of iron oxide / titanium oxide / silica composite oxide (Sol B
₇ ) Got it.

A coating solution for forming a hard coat film was prepared in the same manner as in Example 1 except that the sol B ₇ was used in place of the sol A _1. A film was formed, and the characteristics of the obtained hard coat film were evaluated.

The results are shown in Table 1.

[0097]

Example 13 Iron oxide / oxidation surface-modified with γ-methacryloxypropyltriethoxysilane in the same manner as in Example 9 except that γ-methacryloxypropyltriethoxysilane was used instead of tetraethoxysilane. A titanium-silica composite oxide methanol dispersion sol (sol B ₈ ) was obtained.

A coating solution for forming a hard coat film was prepared in the same manner as in Example 1 except that this sol B ₈ was used in place of the sol A ₁ , and this coating solution was used to prepare the hard coat film of Example 13. A film was formed, and the characteristics of the obtained hard coat film were evaluated.

Table 1 shows the results.

[0100]

Example 14 The weight ratio of Fe ₂ O ₃ / TiO ₂ was 40/60 when the iron oxide component, titanium oxide component and silica component were converted to Fe ₂ O ₃ , TiO ₂ and SiO ₂ , respectively.
Where SiO ₂ / (Fe ₂ O ₃ + TiO ₂ ) is 15/10
Except that it was prepared to be 0, in the same manner as in Example 1,
An iron oxide / titanium oxide / silica composite oxide sol having an average particle size of 11 μm was prepared, and this sol was then treated in the same manner as in Example 11 to obtain an iron oxide / surface modified with γ-glycidoxypropyltriethoxysilane. A methanol-dispersed sol of titanium oxide / silica composite oxide (Sol B ₉ ) was obtained.

A coating solution for forming a hard coat film was prepared in the same manner as in Example 1 except that this sol B ₉ was used in place of the sol A _1. A film was formed, and the characteristics of the obtained hard coat film were evaluated.

Table 1 shows the results.

[0103]

Comparative Examples 1 and 2 Same as Example 7 except that the sol B ₂ was replaced by a titanium oxide / cerium oxide composite oxide sol (Optreak 1130A, manufactured by Catalyst Chemical Industry Co., Ltd.) and an antimony oxide sol, respectively. The hard coat films of Comparative Examples 1 and 2 were formed using these coating solutions, and the properties of the obtained hard coat films were evaluated.

Table 1 shows the results.

[0105]

EXAMPLES 15 to 19 The amount of sol B ₂ respectively 2,05
A coating liquid for forming a hard coat film was prepared in the same manner as in Example 7, except that the amount was changed to 6.9 parts by weight and 2,374.5 parts by weight.
Each of these coating liquids was applied to the surface of a glass lens having a refractive index shown in Table 2 in the same manner as in Example 1;
Sixteen hard coat films were formed.

The amount of sol B ₄ was set to 1,34, respectively.
8.8 parts by weight, 1403.1 parts by weight and 1,55 parts
A coating solution for forming a hard coat film was prepared in the same manner as in Example 9 except that the amount was changed to 7.0 parts by weight, and these coating solutions were applied to the surfaces of glass lenses having the refractive indexes shown in Table 2 respectively. Similarly, hard coat films of Examples 17 to 19 were formed.

Whether or not interference fringes were formed on the surface of each hard coat film was visually observed under a fluorescent lamp. The scratch resistance of each hard coat film was evaluated in the same manner as in Example 1.

Table 2 shows the results.

[0109]

[Comparative Example 3] Sol B ₄ was converted to a titanium oxide / cerium oxide composite oxide sol (manufactured by Catalyst Chemical Industry Co., Ltd., Optolake 1).
A hard coat film of Comparative Example 3 was formed in the same manner as in Example 19, except for changing to 130A), and whether or not interference fringes were formed on the surface of the hard coat film was visually observed under a fluorescent lamp. The scratch resistance of the hard coat film was evaluated in the same manner as in Example 1.

Table 2 shows the results.

[0111]

[Table 1]

[0112]

[Table 2]

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-63-139302 (JP, A) JP-A-61-276832 (JP, A) JP-A-3-68901 (JP, A) (58) Field (Int.Cl. ⁷ , DB name) G02B 1/10-1/12

Claims (4)

(57) [Claims] 1. A coating solution for forming a hard coat film containing a hydrolyzable organosilicon compound capable of forming a matrix and composite oxide particles is applied to the surface of a substrate and dried, and the heat-resistant temperature of the substrate is increased.
A hard coat film cured by heating to a temperature of less than or equal to a temperature , wherein the composite oxide particles are composed of an iron oxide component and a titanium oxide component, and the amount of the iron oxide component is converted to Fe ₂ O ₃ , and the titanium oxide component Weight ratio Fe ₂ O ₃ / TiO ₂ when the amount is converted to TiO _2
2 is in the range of 0.005 to 1.0, the average particle size of the composite oxide particles is in the range of 1 to 100 mμ, and the composite oxide particles are chemically bonded with iron oxide and titanium oxide. A hard coat film comprising a composite oxide, a solid solution comprising an oxide of iron and titanium, or a mixture thereof. 2. A coating liquid for forming a hard coat film containing a hydrolyzable organosilicon compound capable of forming a matrix and composite oxide particles is applied to the surface of a substrate and dried, and the heat-resistant temperature of the substrate is increased.
A hard coat film cured by heating to a temperature equal to or less than a temperature , wherein the composite oxide particles are composed of an iron oxide component, a titanium oxide component, and a silica component, and the amount of the iron oxide component is converted into Fe ₂ O ₃ ; When the titanium oxide component amount is converted to TiO ₂ and the silica component amount is converted to SiO ₂ , the weight ratio Fe ₂ O ₃ / TiO ₂ is in the range of 0.005 to 1.0, and the weight ratio is SiO _2. / (Fe ₂ O ₃ + TiO ₂ ) is 0.001-1.
0, the average particle size of the composite oxide particles is in the range of 1 to 100 μm, and the composite oxide particles are a composite oxide in which iron oxide, titanium oxide, and silica are chemically bonded, or iron. And a solid solution comprising titanium and silicon oxides or a mixture thereof. 3. The hard coat film according to claim 1, wherein the composite oxide particles are surface-modified with an organic silane compound. 4. A substrate with a hard coat film, wherein the substrate according to claim 1 is formed on the surface of the substrate.