JP2002187738A - Method for forming hard coat film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hard coat film which has high pencil hardness, high refractive index and high adhesion property with a base material although the film is amorphous, and which is useful as a surface protective film or an antidazzle thin film of various kinds of transparent members. SOLUTION: In the method for forming a hard coat film, a sol liquid containing an inorganic compound of at least one kind of element selected from the group of silicon, aluminum, zirconium and hafnium prepared by a sol-gel method is applied on a base material and heat treated at a temperature no exceeding 200 deg.C and irradiated with UV rays of at most 100 mJ/cm2 energy.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for forming a hard coat film, and more particularly, to a method for forming a hard coat thin film capable of forming a metal oxide thin film having a high pencil hardness in an amorphous state.

[0002]

2. Description of the Related Art Conventionally, a silicone hard coat film is prepared by applying a solution in which a silicon-containing polymer is dissolved on a substrate, drying the solution, and then heating (curing) it to 100 to 300 ° C.
It was formed by doing.

However, since the silicone hard coat film has a pencil hardness of about 3H, there is a problem that the surface is easily damaged when subjected to an impact.

Further, since the refractive index of the silicone hard coat film is about 1.4, it requires a high refractive index.
There is a problem that it cannot be used for a low reflection film or a high reflection film utilizing optical interference.

Generally speaking, a material called "hard coat film" has a hardness as high as possible, and there is no need to select the type of substrate, and the adhesion to the substrate is as large as possible. Therefore, it is desired to manufacture it by a simple process at a low cost.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to have a pencil hardness much higher than 3H, to have a high adhesion to a substrate, and to form it only on a specific substrate. It is an object of the present invention to provide a method for forming a hard coat film, which can relax the restriction described above and can be manufactured at a low cost by a simple manufacturing method.

Another object of the present invention is to provide a method for forming a hard coat film which can easily produce a hard coat film which is amorphous but has high hardness and excellent adhesion to a substrate. Is to do.

[0008]

According to the present invention, there is provided a method for manufacturing a semiconductor device, comprising: forming at least one element selected from the group consisting of silicon, aluminum, zirconium, and hafnium; A sol solution containing an inorganic compound of
A method for forming a hard coat film, which comprises irradiating ultraviolet rays of at most 100 mJ / cm ² while performing a heat treatment at a temperature not exceeding 00 ° C. In a preferred embodiment of the present invention, the base material is glass. And / or plastic, and the heat treatment is performed in an atmosphere having a relative humidity of 70% or more. In another preferred embodiment of the present invention, the inorganic compound is at least selected from the group consisting of zirconia and hafnia. As one type, in still another preferred embodiment of the present invention, the ultraviolet light source is a high-pressure mercury lamp or a low-pressure mercury lamp.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The hard coat film in the method of the present invention is formed by first applying a sol liquid prepared by a sol-gel method onto a substrate to form a gel film.

The sol solution contains, for example, an inorganic compound containing at least one element selected from the group consisting of silicon, aluminum, zirconium, and hafnium, in particular, at least one element selected from the group consisting of hafnium and zirconium. Any solution containing sol may be used. As a preferred example, a predetermined amount of the element, preferably, an inorganic compound of hafnium and / or zirconium is dissolved in a solvent, and water and an acid are further added. And a sol liquid obtained by the preparation.

Examples of the inorganic compound containing silicon include silicon halides including silicon chloride and silicon bromide, and tetramethoxysilane, tetraethoxysilane, tetra-i-propylsilane, and tetra-n-butoxysilane. And inorganic compounds of silicon selected from the group consisting of alkoxysilanes. However, these are merely examples, and other silicon-containing inorganic compounds are included in the scope of the present invention as long as the object of the present invention can be achieved.

As inorganic compounds containing aluminum, for example, aluminum halides containing aluminum chloride, for example, aluminum inorganic acid salts containing aluminum nitrate, ammonium sulfate and ammonium aluminum nitrate, for example, aluminum lactate, aluminum acetate,
And organic salts of aluminum, including aluminum laurate, such as aluminum methoxide, aluminum sec-
Examples include aluminum compounds selected from the group consisting of butoxide, aluminum alkoxides including aluminum isopropoxide, and aluminum complexes including, for example, aluminum acetylacetonate. However, these are merely examples, and other aluminum-containing inorganic compounds are included in the scope of the present invention as long as the object of the present invention can be achieved.

As the inorganic compound containing zirconium, for example, zirconium chloride octahydrate, zirconium halide containing zirconium chloride and zirconium bromide, for example, zirconium oxynitrate dihydrate and zirconium nitrate tetrahydrate Selected from the group consisting of zirconium inorganic acid salts including, for example, zirconium organic acid salts including zirconium acetate, zirconium alkoxides including zirconium tetra-n-butoxide and zirconium tetra-isopropoxide, and zirconium complexes including, for example, zirconium acetylacetonate. Zirconium compounds. However, these are merely examples, and other zirconium-containing inorganic compounds are included in the scope of the present invention as long as the object of the present invention can be achieved.

As an inorganic compound containing hafnium,
Hafnium halides, for example, hafnium chloride and hafnium bromide, for example, hafnium inorganic acid salts including hafnium nitrate, for example, hafnium alkoxides including hafnium tetramethoxide and hafnium tetraisopropoxide, and hafnium complexes including, for example, hafnium acetylacetonate And a hafnium compound selected from the group consisting of: However, these are merely examples, and other hafnium-containing inorganic compounds are included in the scope of the present invention as long as the object of the present invention can be achieved.

As the solvent, any solvent can be used as long as it can dissolve an inorganic compound containing at least one element selected from the group consisting of silicon, aluminum, zirconium and hafnium and can achieve the object of the present invention. Is not particularly limited, and for example, an alcohol solvent is preferable, and particularly, an alcohol solvent having 1 to 5 carbon atoms such as methanol, ethanol, n-propanol, n-butanol, and n-pentanol is preferable.

Specific examples of the acid include hydrochloric acid, nitric acid,
Inorganic acids such as nitrous acid, sulfuric acid, sulfurous acid, carbonic acid, chloric acid, chlorous acid, and iodic acid; and organic acids such as acetic acid, propionic acid, butyric acid, and lower monocarboxylic acids such as isobutyric acid. Can be mentioned.

The concentration of at least one element selected from the group consisting of silicon, aluminum, zirconium and hafnium in the sol solution is 1 to 3 in terms of oxide.
It is preferably 0%, particularly preferably 1 to 20%.

In the method of the present invention, a hard coat film is formed by applying the sol liquid on a predetermined base material to form a gel film and irradiating ultraviolet rays.

The substrate may be coated with a sol liquid, withstand the drying conditions when drying the sol liquid, or withstand the heating temperature if heating when irradiating ultraviolet rays. There is no particular limitation as long as the above condition is satisfied, and various materials can be adopted. As this substrate, for example, quartz glass, 96% quartz glass,
Soda-lime glass, aluminoborosilicate glass, borosilicate glass, aluminosilicate glass, and a substrate formed of glass including lead glass, and a plastic including polycarbonate and polyethylene terephthalate, and a heat softening temperature of 200 ° C. Substrates made of the following plastics, common steel, structural constant alloy steel, high-strength steel, heat-resistant steel, high chromium-based heat-resistant steel, alloy steels including high nickel-chromium-based heat-resistant steel, and stainless steel Steel material, etc.
Industrial pure aluminum, 5000 series alloy, Al-Mg
Aluminum alloys, including 6000 series aluminum alloys and 6000 series aluminum alloys, various copper alloys including silver-containing copper, tin-containing copper, chromium copper, chromium-zirconium copper, and zirconium copper, pure titanium, drag titanium alloy, and Substrates formed from metal materials such as titanium alloys including corrosion-resistant titanium alloys, and base materials formed from ceramic materials such as mullite porcelain, alumina porcelain, zircon porcelain, cordierite porcelain, and steatite porcelain And a coated metal substrate obtained by coating the surface of a substrate formed from the metal-based material with any one of enamel, glass lining, and ceramic coating.

The substrate formed from the glass material includes:
Examples include window glass of various structures including automobiles, railway vehicles, aircraft, and buildings, and glass requiring water repellency of head-up displays for automobiles and aircraft.

Examples of the base material formed of a metal material include an outer plate such as a power transmission line, a building, a sash, and an outer plate of a railway vehicle, for example.

Examples of the base material formed of a ceramic material include, for example, an insulator, an insulator tube, a ceramic style, and a roof tile.

Examples of the coated metal substrate include various tanks, reaction tanks, brewing tanks, and daily necessities such as cups, washbasins, and vases.

In addition to the above-mentioned base material, there can also be mentioned a painted surface in which a paint is applied to a metal or ceramic surface. As the painted surface, specifically, automobiles,
Examples include railcars and aircraft body surfaces.

The above-mentioned base material may further include an outer wall of a building such as a concrete wall, a terracotta tile wall, a mortar wall, and a plaster wall.

Examples of the substrate include paper, cloth, leather, and wood. Among the above-mentioned various substrates, a substrate formed of the glass, a substrate formed of the plastic, and a composite substrate thereof can be exemplified.

As a method of applying the sol liquid on the surface of the base material, for example, a dipping method in which the base material is immersed in the sol liquid and slowly pulled up, or the sol liquid is cast on the fixed base material surface A casting method, a continuous method in which a substrate is immersed in a sol liquid from one end of a tank in which a sol is stored, and a substrate is taken out from the other end of the tank, and the sol is dropped on a rotating substrate. Spinner method of casting the sol liquid on the substrate by centrifugal force acting on, a spray method of spraying the sol liquid on the surface of the substrate,
And flow coat.

The amount of the sol solution applied varies depending on the viscosity of the sol solution and other conditions. In the case where a thin film having a desired thickness cannot be obtained by one coating, the coating can be repeated several times.

The substrate to which the sol solution has been applied may be dried before being irradiated with ultraviolet rays, or may be irradiated immediately after the application.

The UV irradiation on the gel film obtained by applying the sol solution is performed at a temperature not exceeding 200 ° C., preferably 50 ° C.
Performing while heating to ~ 150 ° C. If the heating temperature is higher than 200 ° C., the object of the present invention cannot be achieved even by irradiating ultraviolet rays, and there is a problem that the plastic substrate is deformed.

The intensity of the irradiated ultraviolet light is at most 100 mJ / cm ² , preferably 50 to 100 mJ / c.
m ² . If the intensity of the ultraviolet light exceeds 100 mJ / cm ² , the object of the present invention cannot be achieved, and there is a problem that, for example, the plastic base material is deformed. A high-pressure mercury lamp and a low-pressure mercury lamp can be used as a light source of the ultraviolet light to be irradiated. When these mercury lamps are used, ultraviolet rays of the above intensity can be irradiated at low cost.

Furthermore, when the gel film is irradiated with ultraviolet rays according to the method of the present invention, an amorphous film made of the metal oxide is obtained. Normally, amorphous films are expected to have lower hardness than crystalline films. However, it is unexpected that amorphous films obtained according to the method of the present invention have higher pencil hardness.

The irradiation with ultraviolet rays is preferably performed in an atmosphere having a relative humidity of 70% or more. When UV light is irradiated on the gel film on the substrate in an atmosphere having a relative humidity of 80% or more,
A hard coat film having even higher hardness can be obtained.

The thickness of the obtained hard coat film can be determined according to the intended use.
The range from m to 1000 nm is preferred.

The hard coat film formed by the method according to the present invention is non-crystalline (amorphous), has a pencil hardness of 6H or more, and has extremely high adhesion to a substrate.

Due to such characteristics, the hard coat can be used for various uses. For example, surface protective film of plastic lens attached to spectacles, LC
D and other anti-reflection surface protective films for displays,
Alternatively, there are applications such as an antiglare protective film for preventing glare.

[0037]

EXAMPLES (Example 1) 1) Preparation of Hafnia sol solution 2.0 g of HfCl ₄ was dissolved in 15 ml of 99.5% ethanol under an N ₂ atmosphere (dry state). 0.17 g of H ₂ O and 60% HNO
₃ A mixed solution containing 3.32 g was added with stirring, and then heated at 50 ° C. for 2 hours to obtain a sol solution.

2) Coating and UV Irradiation The sol was applied to a soda-lime glass substrate by a spinner method. The applied gel film was irradiated with a high-pressure mercury lamp. The UV intensity, irradiation time and substrate temperature at that time are displayed.
Shown in 1. The unit of the ultraviolet intensity described in this specification is mJ / cm ² even if it is simply described as mJ.

[0039]

[Table 1]

All of the obtained hafnia films were scratched at 9H and were not scratched at 8H, so they were judged to have a pencil hardness of 8H or more, and the number of peeled grids was 0 in the grid peeling method. The structure of this hafnia film was examined by X-ray diffraction. At 2θ = 5 to 90 °, no peak was observed other than the broad peak attributed to amorphous near 2θ = 20 °, confirming that the hafnia film was amorphous. The refractive index of this hafnia film was 1.9. By the way, since the coating film was damaged at 6B, it was judged that the pencil hardness was 6B or less, and 100% was obtained by the cross-cut peeling method.
Peeled off.

Example 2 The same procedure as in Example 1 was carried out except that the glass substrate was changed to non-alkali glass and the substrate temperature was set to 150 ° C.

The resulting hafnia films all had a pencil hardness of 8
It was judged to be H or more, and the peeling was zero in the cross-cut peeling method. The structure of this hafnia film was examined by X-ray diffraction. At 2θ = 5 to 90 °, no peak was observed other than the broad peak attributed to amorphous near 2θ = 20 °, confirming that the hafnia film was amorphous. The refractive index of this hafnia film was 1.9. Incidentally, the pencil hardness of the coating film was judged to be H or less, and 100% was peeled off by the cross-cut peeling method.

Example 3 1) Preparation of Hafnia Sol Solution 2.0 g of HfCl ₄ was dissolved in 15 ml of 99.5% ethanol under a N ₂ atmosphere (dry state). 0.51 g of H ₂ O and 60% HNO
The mixed solution containing ₃ 0.33 g, after added with stirring to obtain a sol liquid was heated at 60 ° C. 1.5 hours.

2) Coating and UV Irradiation The sol was applied to a soda-lime glass substrate by a spinner method. The applied gel film was irradiated with a low-pressure mercury lamp.
Table 2 shows the UV intensity, irradiation time and substrate temperature at that time.

[0045]

[Table 2]

The pencil hardness of the obtained hafnia films was all 8
It was judged to be H or more, and the peeling was zero in the cross-cut peeling method. The structure of this hafnia film was examined by X-ray diffraction. At 2θ = 5 to 90 °, no peak was observed other than the broad peak attributed to amorphous near 2θ = 20 °, confirming that the hafnia film was amorphous. The refractive index of this hafnia film was 1.9. Incidentally, the pencil hardness of the coating film was judged to be 6B or less, and 100% was peeled off by the cross-cut peeling method.

Example 4 The procedure of Example 3 was repeated except that the substrate was quartz glass and the temperature of the substrate was 170 ° C.

The pencil hardness of all the obtained hafnia films was 8
It was judged to be H or more, and the peeling was zero in the cross-cut peeling method. The structure of this hafnia film was examined by X-ray diffraction. At 2θ = 5 to 90 °, no peak was observed other than the broad peak attributed to amorphous near 2θ = 20 °, confirming that the hafnia film was amorphous. The refractive index of this hafnia film was 1.9. Incidentally, the pencil hardness of the coating film was determined to be 6B or less, and 100% was peeled off by the cross-cut peeling method.

Example 5 The procedure of Example 1 was repeated except that the substrate was made of polycarbonate, the coating method was a dipping method, and the UV intensity, the UV irradiation time and the substrate temperature were set to the values shown in Table 3. It carried out similarly to each example in Example 1.

[0050]

[Table 3]

In Examples 3, 4, 7 and 8 in Table 3, since the substrate temperature was outside the range of the present invention, the polycarbonate substrate was yellowed and deformed. In the experiments indicated by other numbers, no change was observed in the substrate. The pencil hardness of all of the obtained hafnia films was judged to be 8H or more, and the peeling was zero in the crosscut peeling method. The structure of this hafnia film was examined by X-ray diffraction. 2θ =
At 5 to 90 °, no peak was observed other than the broad peak attributed to amorphous around 2θ = 20 °, confirming that the hafnia film was amorphous.
The refractive index of this hafnia film was 1.9. By the way, the pencil hardness of the coating film is determined to be 6B or less,
In the cross-cut peeling method, 100% peeling was performed.

Example 6 Example 6 was performed in the same manner as in Example 3 except that the coating film was placed in an atmosphere at a relative humidity of 75%.

The pencil hardness of the obtained hafnia films was 9
It was judged to be H or more, and the peeling was zero in the cross-cut peeling method. The structure of this hafnia film was examined by X-ray diffraction. At 2θ = 5 to 90 °, no peak was observed other than the broad peak attributed to amorphous near 2θ = 20 °, confirming that the hafnia film was amorphous. The refractive index of this hafnia film was 1.9. Incidentally, the pencil hardness of the coating film was judged to be 6B or less, and 100% was peeled off by the cross-cut peeling method.

Example 7 Example 6 was the same as Example 5 except that the coating film was placed in an atmosphere with a relative humidity of 85%.
The same was done. The pencil hardness of all of the obtained hafnia films was determined to be 9H or more, and the cross-cut peeling method was used for peeling.
Met. The structure of this hafnia film was examined by X-ray diffraction. At 2θ = 5 to 90 °, no peak was observed other than the broad peak attributed to amorphous near 2θ = 20 °, confirming that the hafnia film was amorphous. The refractive index of this hafnia film was 1.9. Incidentally, the pencil hardness of the coating film was judged to be 6B or less, and 100% was peeled off by the cross-cut peeling method.

(Example 8) 1) Preparation of zirconia sol solution 4.0 g of ZrOCl ₂ was dissolved in 54.96 g of 99.5% ethanol, and 1.49 g of acetic acid was added. 2.23 g of H ₂ O and 60% HNO ₃
After adding a mixed solution containing 3.91 g with stirring, the mixture was heated at 40 ° C. for 3 hours to obtain a sol solution.

2) Coating and UV Irradiation The sol was applied to a soda-lime glass substrate by a spinner method. The applied gel film was irradiated with a high-pressure mercury lamp. Table 4 shows the UV intensity, irradiation time and substrate temperature at that time.

[0057]

[Table 4]

The hardness of all the obtained zirconia films was 6H.
It was determined that the above was satisfied, and the peeling was zero in the crosscut peeling method. The structure of the zirconia film was examined by an X-ray diffraction method. At 2θ = 5 to 90 °, no peak was observed other than the broad peak attributed to amorphous around 2θ = 20 °, confirming that the zirconia film was amorphous. The zirconia film has a refractive index of 1.8.
Met. Incidentally, the pencil hardness of the coating film was judged to be 6B or less, and 100% was peeled off by the cross-cut peeling method.

Example 9 1) Preparation of Zirconia Sol Solution 4.0 g of ZrOCl ₂ was dissolved in 54.96 g of 99.5% ethanol. To this solution, a mixed solution containing 5.60 g of H ₂ O and 2.51 g of 60% HNO ₃ was added with stirring, and then heated at 60 ° C. for 1 hour to obtain a sol liquid.

2) Coating and UV Irradiation The sol was applied on a non-alkali glass substrate by a dipping method. The obtained gel film was irradiated with a low-pressure mercury lamp. Table 5 shows the UV intensity, irradiation time and substrate temperature at that time.

[0061]

[Table 5]

The hardness of all the obtained zirconia films was 6H.
It was determined that the above was satisfied, and the peeling was zero in the crosscut peeling method. The structure of the zirconia film was examined by an X-ray diffraction method. At 2θ = 5 to 90 °, no peak was observed other than the broad peak attributed to amorphous around 2θ = 20 °, confirming that the zirconia film was amorphous. The zirconia film has a refractive index of 1.8.
Met. Incidentally, the pencil hardness of the coating film was judged to be 6B or less, and 100% was peeled off by the cross-cut peeling method.

Example 10 In Example 8, the substrate was changed from soda lime glass to polycarbonate.
The same procedures were performed as in Examples 8 except that the substrate temperature was set to 50 ° C.

The hardness of all the obtained zirconia films was 6H.
It was determined that the above was satisfied, and the peeling was zero in the crosscut peeling method. The structure of the zirconia film was examined by an X-ray diffraction method. At 2θ = 5 to 90 °, no peak was observed other than the broad peak attributed to amorphous around 2θ = 20 °, confirming that the zirconia film was amorphous. The zirconia film has a refractive index of 1.8.
Met. Incidentally, the pencil hardness of the coating film was judged to be 6B or less, and 100% was peeled off by the cross-cut peeling method.

Example 11 1) Preparation of Alumina Sol Solution 15.0 g of Al (sec-C ₄ H ₉ ) ₃ was dissolved in 258.9 g of isopropanol. To this solution, 62.1 g of H ₂ O and 18.06 g of 60% HNO ₃
Was added with stirring, and then left at room temperature for 2 days to obtain a sol solution.

2) Coating and UV Irradiation The sol was applied to a soda-lime glass substrate by a flow method. The obtained gel solution was irradiated with a high-pressure mercury lamp. Table 6 shows the UV intensity, irradiation time and substrate temperature at that time.

[0067]

[Table 6]

The alumina films obtained were all judged to have a hardness of 6H or more, and the peeling was zero in the cross-cut peeling method. The structure of this alumina film was examined by an X-ray diffraction method.
At 2θ = 5 ° to 90 °, no peak was observed other than the broad peak attributed to amorphous around 2θ = 20 °, confirming that the alumina film was amorphous. The refractive index of this alumina film was 1.6. Incidentally, the pencil hardness of the coating film was judged to be 6B or less, and 100% was peeled off by the cross-cut peeling method.

Example 12 1) Preparation of Silica Sol Solution 6.50 g of Si (OC ₂ H ₅ ) ₄ was dissolved in 55 ml of 99.5% ethanol. To this solution, a mixed solution containing 1.13 g of H ₂ O and 0.86 g of 60% HNO ₃ was added with stirring, and then left at room temperature for 1 day to obtain a sol solution.

2) Coating and UV Irradiation The sol was applied to a soda-lime glass substrate by a dipping method. The obtained gel film was irradiated with a high-pressure mercury lamp. Table 7 shows the UV intensity, irradiation time and substrate temperature at that time.

[0071]

[Table 7]

The hardness of each of the obtained silica films was judged to be 6H or more, and the peeling was zero in the cross-cut peeling method.
The structure of this silica film was examined by an X-ray diffraction method. 2θ =
At 5 to 90 °, no peak was observed other than the broad peak attributed to amorphous around 2θ = 20 °, confirming that the silica film was amorphous. The refractive index of this silica film was 1.8. Incidentally, the pencil hardness of the coating film was determined to be 6B or less, and 100% was peeled off by the cross-cut peeling method.

Example 13 In Example 8, the coating film was placed in a container having a relative humidity of 80% and irradiated with ultraviolet light through quartz glass. Table 8 shows the UV intensity, irradiation time and substrate temperature.

[0074]

[Table 8]

The hardness of all the obtained zirconia films was 9H.
It was determined that the above was satisfied, and the peeling was zero in the crosscut peeling method. The structure of the zirconia film was examined by an X-ray diffraction method. At 2θ = 5 to 90 °, no peak was observed other than the broad peak attributed to amorphous around 2θ = 20 °, confirming that the zirconia film was amorphous. The zirconia film has a refractive index of 1.6.
Met. Incidentally, the pencil hardness of the coating film was judged to be 6B or less, and 100% was peeled off by the cross-cut peeling method.

Example 14 In Example 11, the coating film was placed in a container having a relative humidity of 90%. Ultraviolet light was irradiated through quartz glass. Table 9 shows the UV intensity, irradiation time and substrate temperature at that time.

[0077]

[Table 9]

The hardness of all the obtained alumina films was determined to be 7H or more, and the peeling was zero in the cross-cut peeling method. The structure of this alumina film was examined by an X-ray diffraction method.
At 2θ = 5 ° to 90 °, no peak was observed other than the broad peak attributed to amorphous around 2θ = 20 °, confirming that the alumina film was amorphous. The refractive index of this alumina film was 1.6. Incidentally, the pencil hardness of the coating film was judged to be 6B or less, and 100% was peeled off by the cross-cut peeling method.

Comparative Example 1 1) Preparation of Titania Sol Solution 200 ml of 99.5% ethanol was added to 28.4 g of titanium tetraisopropoxide. 1.8 g of H ₂ O and 60% HNO ₃
After adding a mixed solution containing 2.1 g with stirring, the mixture was allowed to stand at room temperature for 1 day to obtain a titania sol solution.

2) Coating and UV irradiation The sol was applied to a soda lime glass substrate by a spinner method. The obtained gel film was irradiated with a high-pressure mercury lamp. Table 10 shows the UV intensity, irradiation time and substrate temperature at that time.

[0081]

[Table 10]

The pencil hardness of the obtained titania film was all B
It was judged to be the following, and 70% was peeled off by the cross-cut peeling method. Incidentally, the pencil hardness of the coating film was judged to be 6B or less, and 100% was peeled off by the cross-cut peeling method.

[0083]

According to the method of the present invention, it is possible to produce a hard coat film, which is an amorphous metal oxide film having excellent adhesion, high pencil hardness and high refractive index, under mild conditions. it can.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (reference) // C09K 3/18 101 C09K 3/18 101 F term (reference) 4D075 BB26Z BB42Z BB46Z BB54Z BB91Z BB93Z BB94Z CA02 CA13 CA36 CB02 CB03 DA06 DB02 DB04 DB06 DB07 DB12 DB13 DB14 DC02 DC05 DC08 DC13 DC24 DC38 EA12 EB01 EB43 EB47 4F100 AA17A AA19A AA20A AA27A AG00B AK01B AT00B BA02 CC00A EH46A EH462 JEJA12J01A12J01A12A13J01A12A EA01 EA04 EA09 EB07 FA01 FA05 FA28 FB06 4H020 BA04

Claims (5)

[Claims] 1. A sol liquid formed by a sol-gel method and containing an inorganic compound of at least one element selected from the group consisting of silicon, aluminum, zirconium, and hafnium, is coated on a substrate, 100m at most while heating at a temperature not exceeding 200 ° C
A method for forming a hard coat film, which comprises irradiating ultraviolet rays of J / cm ² . 2. The method for forming a hard coat film according to claim 1, wherein said substrate is made of glass and / or plastic. 3. The method for forming a hard coat film according to claim 1, wherein the heat treatment is performed in an atmosphere having a relative humidity of 70% or more. 4. The method for forming a hard coat film according to claim 1, wherein said inorganic compound is at least one selected from the group consisting of zirconia and hafnia. 5. The method for forming a hard coat film according to claim 1, wherein the ultraviolet light source is a high-pressure mercury lamp or a low-pressure mercury lamp.