JP6737271B2 - Hard member - Google Patents

Description

The present invention relates to a hard member used as a cover glass for a touch panel or the like.

2. Description of the Related Art In recent years, in devices such as mobile phones, digital cameras, PDAs (personal digital assistants), and notebook PCs, those equipped with a touch panel have become widespread. For these devices, a cover glass (hard member) made of a glass substrate is often used to protect the touch panel.

Further, an antifouling layer is often provided on the outermost layer of the cover glass in order to prevent adhesion of dirt. Patent Documents 1 to 5 disclose that an antifouling layer is provided in order to prevent adhesion of dirt.

JP, 2010-37115, A JP, 2004-170962, A JP-A-6-135745 JP-A-8-294755 JP-A-2-91603

The cover glass disclosed in the above-mentioned patent documents, because the scratch resistance is not sufficiently high, the present inventor has a hard layer made of zirconium oxide or aluminum oxynitride for the purpose of improving the scratch resistance of the cover glass. , It was considered to provide it on the glass substrate. As a result, they have found that when a hard layer is provided on a glass substrate, even if an antifouling layer is formed on the glass substrate, the adhesion is low and the film easily peels off. Also, when a hard substrate such as sapphire is used as the cover member, the adhesion is low even if an antifouling layer is formed on the cover member, and the problem is that it is easily peeled off.

An object of the present invention is to provide a hard member having good scratch resistance and excellent adhesion to an antifouling layer.

The hard member of the present invention includes a substrate, a hard layer provided on the substrate and having a thickness of 150 nm or more, and an adhesive material provided on the hard layer and made of an inorganic material containing silicon and having a thickness of 60 nm or less. And an antifouling layer which is provided on the adhesion layer and contains an organosilicon compound.

In the present invention, the thickness of the adhesion layer is preferably 1 nm or more.

The hardness of the hard layer is preferably 7 GPa or more.

The hard layer is zirconium oxide, aluminum oxide, aluminum nitride, aluminum oxynitride, titanium oxide, tantalum oxide, niobium oxide, hafnium oxide, tin oxide, zinc oxide, indium oxide, DLC (Diamond Like Carbon), diamond, boron nitride, It is preferable to contain at least one selected from carbon nitride.

The adhesion layer preferably contains at least one selected from silicon oxide, silicon nitride, and silicon oxynitride.

The antifouling layer preferably contains a fluorine-containing organosilicon compound.

The substrate is preferably a glass substrate.

A hard member according to another aspect of the present invention is a hard substrate having a hardness of 8 GPa or more, an adhesion layer provided on the hard substrate, made of an inorganic material containing silicon, and having a thickness of 60 nm or less. And an antifouling layer containing an organic silicon compound, which is provided on the layer.

The hard substrate is preferably a sapphire substrate.

According to the present invention, it is possible to provide a hard member having good scratch resistance and excellent adhesion to an antifouling layer.

FIG. 1 is a schematic sectional view showing a hard member according to a first embodiment of the present invention. FIG. 2 is a schematic cross-sectional view showing a hard member according to the second embodiment of the present invention.

Hereinafter, preferred embodiments will be described. However, the following embodiments are merely examples, and the present invention is not limited to the following embodiments.

(First embodiment)
FIG. 1 is a schematic sectional view showing a hard member according to a first embodiment of the present invention. As shown in FIG. 1, the hard member 1 of the present embodiment includes a substrate 2, a hard layer 3 provided on the substrate 2, an adhesive layer 4 provided on the hard layer 3, and an adhesive layer 4. And an antifouling layer 5 provided on the top. When the hard member 1 is used as a cover glass for a touch panel or the like, it is preferable that the hard member 1 has translucency. For example, the hard member 1 preferably has a transmittance of more than 0% in at least a part of the wavelength range of visible light (360 to 830 nm). The hard member 1 more preferably has a transmittance of more than 0% in the wavelength range of 450 to 650 nm, further preferably has a transmittance of more than 0% in the wavelength range of 400 to 700 nm, and a wavelength of 360 to 830 nm. Most preferably, it has a transmission of greater than 0% in the region. In addition to this, the average transmittance in the wavelength range of 360 to 830 nm is preferably 30% or more, more preferably 50% or more, and most preferably 80% or more. The substrate 2 is not particularly limited, and examples thereof include a glass substrate and a resin substrate. When the hard member 1 is used as a cover glass for a touch panel or the like, the substrate 2 is a translucent glass substrate made of soda lime glass, aluminosilicate glass, alkali-free glass, crystallized glass, or the like, and these glasses. It is preferably a tempered glass substrate obtained by physically or chemically strengthening the substrate. From the viewpoint of mechanical strength, a tempered glass substrate obtained by chemically strengthening an aluminosilicate glass substrate is preferable. Since the aluminosilicate glass substrate has high mechanical strength, its thickness can be reduced.

From the viewpoint of mechanical strength and weight reduction, the thickness of the substrate 2 is preferably 0.1 to 1.5 mm, more preferably 0.3 to 1.2 mm, and 0.5 to 1.0 mm. Is more preferable.

The hard layer 3 is provided to improve the scratch resistance of the hard member 1. Therefore, the hard layer 3 is preferably made of a hard material. The hardness of the hard layer 3 is preferably harder than that of the substrate 2. An example of the hardness evaluation method is a nanoindentation method. For example, the hardness measured by the nanoindentation method using a Berkovich type diamond indenter is preferably 7 GPa or more, more preferably 8 GPa or more, more preferably 9 GPa or more, and 10 GPa or more. More preferably, it is more preferably 11 GPa or more, still more preferably 13 GPa or more. The upper limit of hardness is not particularly set, but is generally 350 GPa, for example.

The hard layer 3 preferably has a large thickness from the viewpoint of improving scratch resistance. Specifically, the hard layer 3 has a thickness of 150 nm or more, preferably 200 nm or more, more preferably 300 nm or more, and further preferably 500 nm or more. If the thickness of the hard layer 3 is less than 150 nm, good scratch resistance cannot be obtained. If the hard layer 3 is too thick, the substrate 2 may warp due to the stress of the hard layer 3. From such a viewpoint, the thickness of the hard layer 3 is preferably 10000 nm or less, more preferably 5000 nm or less, and further preferably 3000 nm or less.

When used as a cover glass for a touch panel or the like, the hard layer 3 preferably has translucency.

Examples of the material of the hard layer 3 include zirconium oxide, aluminum oxide, aluminum nitride, aluminum oxynitride, titanium oxide, tantalum oxide, niobium oxide, hafnium oxide, tin oxide, zinc oxide, indium oxide, DLC (Diamond Like Carbon), diamond. , Boron nitride, carbon nitride and the like. Of these, zirconium oxide, aluminum oxide, aluminum oxynitride, and DLC are particularly preferable.

The hard layer 3 is preferably formed by a RAS (Radical Assisted Sputtering) method because it tends to be hard. The RAS method is a method in which a substrate is alternately passed through a zone for forming a thin metal film by sputtering and a zone for oxidizing, nitriding, oxynitriding, or carbonizing the thin metal film by a radical gun or the like. This is a method of forming an oxide film, a metal nitride film, a metal oxynitride film, or a metal carbide film.

The adhesion layer 4 is provided to enhance the adhesion between the hard layer 3 and the antifouling layer 5. Examples of the material of the adhesion layer 4 include inorganic materials containing silicon such as silicon oxide, silicon nitride and silicon oxynitride. Specific composition formulas of the adhesive layer 4 include, for example, SiO ₂ , Si ₃ N ₄ , and SiO _x N _y (0≦x, 0≦y).

In the present invention, the adhesion layer 4 has a thickness of 60 nm or less. When the thickness of the adhesive layer 4 exceeds 60 nm, the hardness characteristics of the adhesive layer 4 have a great influence on the scratch resistance of the hard member 1, while the hardness characteristics of the hard layer 3 therebelow are less than those of the hard member 1. The effect on the scratch resistance becomes small, and good scratch resistance may not be obtained. The thickness of the adhesive layer 4 is preferably 1 nm or more. By setting the thickness of the adhesive layer 4 to 1 nm or more, better adhesiveness can be obtained. Therefore, the thickness of the adhesion layer 2 is preferably in the range of 1 to 60 nm, more preferably in the range of 2 to 50 nm, more preferably in the range of 5 to 30 nm, and in the range of 10 to 20 nm. It is more preferable that there is.

The method for forming the adhesion layer 4 is not particularly limited, but the adhesion layer 4 can be formed by the RAS method like the hard layer 3.

The antifouling layer 5 preferably contains an organosilicon compound. By including the organic silicon compound, the adhesiveness with the adhesive layer 4 can be enhanced. As a result, even after long-term use, the antifouling layer 5 is less likely to peel off, and the antifouling property and slipperiness are less likely to deteriorate.

Examples of the organosilicon compound include one or more compounds selected from silane coupling agents, silicone oils, silicone resins, silicone rubbers, hydrophobic silicas, and fluorine-containing organosilicon compounds. Among these, the fluorine-containing organosilicon compound is preferable.

Examples of the fluorine-containing organosilicon compound include a polymer having a —O—Si—O— unit in the main chain and having a water-repellent functional group containing fluorine in the side chain. The fluorine-containing organosilicon compound can be synthesized, for example, by dehydration condensation of silanol. Examples of the fluorine-containing organosilicon compound include KY130 (manufactured by Shin-Etsu Chemical Co., Ltd.), Optool DSX (manufactured by Daikin Industries, Ltd.), TSL8257, TSL8233, TSL831 (above, manufactured by Momentive Performance Materials Japan LLC). , KBM7803 (manufactured by Shin-Etsu Chemical Co., Ltd.), AY43-158E (manufactured by Toray Dow Corning Co., Ltd.), and KP801M (manufactured by Shin-Etsu Chemical Co., Ltd.).

The thickness of the antifouling layer 5 is not particularly limited, but is preferably 1 nm or more, more preferably 1.5 nm or more, and particularly preferably 2 nm or more. If the thickness of the antifouling layer 5 is less than 1 nm, the antifouling effect may not be sufficiently obtained. If the antifouling layer 5 is too thick, the antifouling layer may be peeled off and then the reflectance and the color may be different from those of the non-peeled part, resulting in conspicuous unevenness. From such a viewpoint, the thickness of the antifouling layer 5 is preferably 30 nm or less, more preferably 25 nm or less, and further preferably 20 nm or less.

The raw material of the antifouling layer 5 is generally in a solution state. Therefore, the antifouling layer 5 can be formed by applying a solution for forming the antifouling layer 5 onto the adhesion layer 4 and then drying. The antifouling layer 5 can also be formed by a vacuum vapor deposition method in which a solution is impregnated into a porous ceramic, a metal fiber, a fine wire, etc., the solution is heated in a vacuum to evaporate, and deposited on the adhesion layer 4. ..

When the hardness of the surface of the hard member 1 on which the antifouling layer 5 is formed is measured by the above-mentioned nanoindentation method, the hardness is preferably 7 GPa or more.

In the present embodiment, since the adhesion layer 4 having a predetermined thickness is provided between the hard layer 3 having a predetermined thickness and the antifouling layer 5, the scratch resistance is good and the adhesion of the antifouling layer is good. It is possible to form a hard member having excellent heat resistance.

The hard member 1 is preferably a combination of a hard layer 3: zirconium oxide or aluminum oxynitride, an adhesion layer 4: silicon oxide, silicon nitride or silicon oxynitride, and an antifouling layer 5: a fluorine-containing organosilicon compound.

Further, in the present embodiment, the hard layer 3 is formed directly on the substrate 2, but a functional layer that imparts various functions to the hard member 1 may be provided between the substrate 2 and the hard layer 3. Good. As the functional layer, an optical filter layer that selectively transmits or reflects light of a specific wavelength by interference of light, a light absorption layer that absorbs light of a specific wavelength, a conductive layer having conductivity, and coloring the hard member 1 A decorative layer that imparts a drip pattern or an antiglare film having irregularities can be used.

(Second embodiment)
FIG. 2 is a schematic cross-sectional view showing a hard member according to the second embodiment of the present invention. As shown in FIG. 2, the hard member 11 of the present embodiment includes a hard substrate 12, an adhesion layer 14 provided on the hard substrate 12, and an antifouling layer 15 provided on the adhesion layer 14. There is. The hard substrate 12 is not particularly limited as long as the hardness is 8 GPa or more. In this embodiment, a sapphire substrate is used as the hard substrate 12. When used as a cover glass for a touch panel or the like, the hard substrate 12 preferably has a light-transmitting property. The sapphire substrate is manufactured by artificially growing high-purity alumina into a single crystal.

The hardness of the hard substrate 12 can be measured by the nanoindentation method using a Berkovich type diamond indenter as in the first embodiment. The hardness of the hard substrate 12 is preferably 10 GPa or more, more preferably 15 GPa or more, further preferably 20 GPa or more, and particularly preferably 25 GPa or more. The upper limit of hardness is not particularly set, but is generally 350 GPa, for example.

The adhesion layer 14 in the present embodiment can be formed by using the same material, the same thickness, and the same method as the adhesion layer 4 in the first embodiment. The antifouling layer 15 in this embodiment can be formed by using the same material, the same thickness, and the same method as those of the antifouling layer 5 in the first embodiment.

In the present embodiment, since the adhesion layer 14 having a predetermined thickness is provided between the hard substrate 12 and the antifouling layer 15, the hard layer has good scratch resistance and excellent adhesion to the antifouling layer. It can be a member.

The hard member 11 is preferably a combination of an adhesion layer 14: silicon oxide, silicon nitride or silicon oxynitride, and an antifouling layer 15: a fluorine-containing organosilicon compound.

Hereinafter, the present invention will be described with reference to specific examples. However, the following examples are merely examples, and the present invention is not limited to the following examples.

<Examples 1 to 6 and Comparative Examples 1 to 2>
The thickness of the adhesion layer 4 of the hard member 1 shown in FIG. 1 was changed, and the influence of the thickness of the adhesion layer 4 was examined.

(Example 1)
[Formation of Hard Layer 3]
A non-alkali glass substrate OA-10G manufactured by Nippon Electric Glass Co., Ltd. was used as the substrate 2, and a ZrO ₂ film as the hard layer 3 was formed on the substrate 2 by the RAS method. As the film forming conditions for the Zr film, the film forming pressure was 0.12 Pa, the flow rate of Ar gas as a carrier gas was 100 sccm, and the Zr target applied power was 5.5 kW. As a Zr film oxidation condition, a flow rate of oxygen gas as a carrier gas: 40 sccm and a radical gun applied power: 4.5 kW, a ZrO ₂ film was formed to a film thickness of 500 nm. The hardness of the substrate on which the ZrO ₂ film was formed was 11.1 GPa as a result of measurement by a nanoindentation method (maximum load: 1.225 mN) using a Berkovich diamond indenter. The hardness of the substrate (OA-10G) was 6.5 GPa. In addition, "ZrO ₂ "does not represent an actual composition ratio.

[Formation of adhesion layer 4]
A SiO ₂ film as the adhesion layer 4 was formed on the hard layer 3 by the RAS method. As the film forming conditions for the Si film, the film forming pressure was 0.12 Pa, the flow rate of Ar gas as a carrier gas was 100 sccm, and the Si target applied power was 5.0 kW. As the oxidation conditions for the Si film, the flow rate of oxygen gas as a carrier gas: 40 sccm, the electric power applied to the radical gun: 4.5 kW, and the SiO ₂ film was formed to have a film thickness of 2 nm. Note that "SiO ₂ "does not represent the actual composition ratio.

[Formation of antifouling layer 5]
The antifouling layer 5 was formed on the adhesion layer 4 as follows. The surface of the adhesion layer 4 was washed with a washing machine and treated with an atmospheric pressure plasma device. Thereafter, a fluorine-containing organosilicon compound solution (UF503: 0.1% by mass, manufactured by Daikin Industries, Ltd., Novec 7200: 99.9% by mass, manufactured by 3M) was applied using a spray device. The coating conditions were such that the substrate 2 was transported at a speed of 3 mm/sec, the coating amount was 10 ml/min, the air flow rate was 40 l/min, the spray nozzle reciprocating speed was 800 mm/sec, and the spray nozzle-substrate distance was 20 mm. After the fluorine-containing organosilicon compound solution is applied, it is heated at 150° C. for 60 minutes using a clean oven, and the applied surface is wiped off with a wiper soaked in alcohol to form an antifouling layer 5 on the adhesion layer 4. did. The film thickness of the antifouling layer 5 was 5 nm.

The hard member 1 of Example 1 was manufactured as described above.

(Example 2)
A hard member 1 was produced in the same manner as in Example 1 except that the thickness of the adhesive layer 4 was set to 15 nm.

(Example 3)
A hard member 1 was produced in the same manner as in Example 1 except that the thickness of the adhesive layer 4 was set to 20 nm.

(Example 4)
A hard member 1 was produced in the same manner as in Example 1 except that the thickness of the adhesive layer 4 was 30 nm.

(Example 5)
A hard member 1 was produced in the same manner as in Example 1 except that the thickness of the adhesive layer 4 was 40 nm.

(Example 6)
A hard member 1 was produced in the same manner as in Example 1 except that the thickness of the adhesive layer 4 was 50 nm.

(Comparative Example 1)
A hard member 1 was produced in the same manner as in Example 1 except that the antifouling layer 5 was directly formed on the hard layer 3 without forming the adhesion layer 4.

(Comparative example 2)
A hard member 1 was produced in the same manner as in Example 1 except that the thickness of the adhesive layer 4 was set to 80 nm.

[Evaluation of scratch resistance]
The scratch resistance of the hard member 1 produced in Examples 1 to 6 and Comparative Examples 1 to 2 was evaluated as follows.

The scratch resistance was evaluated by a rocking rubbing test. The rocking rubbing test was performed using Taber Oscillating Abrasion Tester 6160 manufactured by Taber Industries. 1300 g of sand (Colorado Silica Sand (Sieve Sizes 6/9) manufactured by PREMIER Silica) was put into the container of the apparatus together with the sample. The sample was taped to the bottom of the container and placed so that the sand covered it. The sample was in a state of being positioned about 1.5 cm below the surface of the sand. In this state, the container is rocked so that the sand in the container moves to rub the sample surface. The rocking stroke was 100 mm, the rocking speed was 200 reciprocations/minute, and the rocking frequency was 1000 reciprocations. The transmission haze was measured with a haze meter (NDH-5000 manufactured by Nippon Denshoku Industries Co., Ltd.) and evaluated by the difference in haze value (ΔH (%)) before and after the rocking rubbing test. The difference in haze value (ΔH(%)) was evaluated by distinguishing ⊚, ∘, and × based on the following criteria. The evaluation results are shown in Table 1.

⊚: 0.07 or less O: 0.08 to 0.14
X: 0.15 or more

[Evaluation of adhesion]
About the hard member 1 produced in Examples 1-6 and Comparative Examples 1-2, the adhesion of the antifouling layer was evaluated as follows.

The adhesion of the antifouling layer was evaluated by a steel wool rubbing test. The steel wool rubbing test is a 10 mm long × 10 mm wide Bonster commercial grade #0000 pressed against the surface of the antifouling layer (load 1000 gf), rubbing stroke 40 mm, rubbing speed 60 reciprocations/min, rubbing frequency It was carried out under the condition of 1,000 round trips. After the test, the contact angle with water on the surface of the antifouling layer was measured. The case where the contact angle was 90° or more was evaluated as ◯, and the case where the contact angle was less than 90° was evaluated as x. The evaluation results are shown in Table 1.

<Examples 7 to 8 and Comparative Example 3>
The film thickness of the hard layer 3 of Example 2 was changed and the influence of the film thickness of the hard layer 3 was examined.

(Example 7)
A hard member 1 was produced in the same manner as in Example 2 except that the film thickness of the hard layer 3 was 300 nm.

(Example 8)
A hard member 1 was produced in the same manner as in Example 2 except that the film thickness of the hard layer 3 was 200 nm.

(Comparative example 3)
A hard member 1 was produced in the same manner as in Example 2 except that the film thickness of the hard layer 3 was 100 nm.

[Evaluation of scratch resistance and adhesion]
The hard member 1 produced in Examples 7 to 8 and Comparative Example 3 was evaluated for scratch resistance and adhesion in the same manner as above. The evaluation results are shown in Table 1.

<Examples 9 to 10>
As the adhesion layer 4, a silicon nitride (SiN) film and a silicon oxynitride (SiON) film were used in place of the silicon oxide (SiO ₂ ) film. In addition, "SiN" and "SiON" do not show an actual composition ratio.

(Example 9)
The hard member 1 was produced in the same manner as in Example 2 except that a silicon nitride (SiN) film was formed as the adhesion layer 4 instead of the silicon oxide (SiO ₂ ) film. As the film forming conditions for the Si film, the film forming pressure was 0.12 Pa, the flow rate of Ar gas as a carrier gas was 100 sccm, and the Si target applied power was 5.0 kW. As a nitriding condition of the Si film, a flow rate of nitrogen gas as a carrier gas: 40 sccm and a radical gun applied power: 4.5 kW, a silicon nitride (SiN) film was formed to a film thickness of 15 nm.

(Example 10)
A translucent member was produced in the same manner as in Example 2 except that a silicon oxynitride (SiON) film was formed as the adhesion layer 4 instead of the silicon oxide (SiO ₂ ) film. As the film forming conditions for the Si film, the film forming pressure was 0.17 Pa, the flow rate of Ar gas as a carrier gas was 150 sccm, and the Si target applied power was 5.0 kW. As the oxynitriding conditions of the Si film, a flow rate of oxygen gas as a carrier gas: 10 sccm, a flow rate of nitrogen gas: 30 sccm, and a radical gun applied power: 4.5 kW, a silicon oxynitride (SiON) film was formed to a film thickness of 15 nm. Filmed

[Evaluation of scratch resistance and adhesion]
With respect to the hard member 1 produced in Examples 9 to 10, scratch resistance and adhesion were evaluated in the same manner as above. The evaluation results are shown in Table 1.

<Comparative example 4>
The scratch resistance and the adhesiveness when the hard layer 3 and the adhesive layer 4 were not formed were evaluated.

(Comparative Example 4)
A hard member 1 was produced in the same manner as in Example 2 except that the antifouling layer 5 was directly formed on the substrate 2 without forming the hard layer 3 and the adhesion layer 4.

[Evaluation of scratch resistance and adhesion]
The hard member 1 produced in Comparative Example 4 was evaluated for scratch resistance and adhesion in the same manner as above. The evaluation results are shown in Table 1.

<Example 11 and Comparative Example 5>
The hard member 11 shown in FIG. 2 was manufactured and evaluated using the hard substrate.

(Example 11)
As the hard substrate 12, a sapphire substrate having a thickness of 0.5 mm was used. The hardness of the sapphire substrate was 30.2 GPa when measured by the nanoindentation method (maximum load: 1.225 mN) using a Berkovich type diamond indenter. The adhesion layer 14 and the antifouling layer 15 were formed on the hard substrate 12 to prepare the hard member 11. The adhesion layer 14 and the antifouling layer 15 were formed in the same manner as the adhesion layer 4 and the antifouling layer 5 in Example 2.

(Comparative example 5)
A hard member 11 was produced in the same manner as in Example 11 except that the antifouling layer 15 was directly formed on the hard substrate 12 without forming the adhesion layer 14.

[Evaluation of scratch resistance and adhesion]
With respect to the hard member 11 produced in Example 11 and Comparative Example 5, scratch resistance and adhesion were evaluated in the same manner as above. The evaluation results are shown in Table 1.

<Examples 12 to 17 and Comparative Examples 6 to 7>
The hard layer 3 of the hard member 1 shown in FIG. 1 was changed to AlON, and the film thickness of the adhesive layer 4 was changed to examine the influence of the film thickness of the adhesive layer 4.

(Example 12)
[Formation of Hard Layer 3]
An aluminosilicate reinforced glass substrate T2X-1 manufactured by Nippon Electric Glass Co., Ltd. was used as the substrate 2, and an AlON film as the hard layer 3 was formed on the substrate 2 by the RAS method. As the film forming conditions for the Al film, the film forming pressure was 0.12 Pa, the flow rate of Ar gas as a carrier gas was 100 sccm, and the Al target applied power was 5.0 kW. As the oxynitriding conditions of the Al film, the flow rate of oxygen gas as a carrier gas: 2 sccm, the flow rate of nitrogen gas: 38 sccm, and the radical gun applied power: 4.5 kW, the AlON film was formed to a film thickness of 500 nm. The hardness of the substrate on which the AlON film was formed was measured by the nanoindentation method (maximum load: 1.225 mN) using a Berkovich type diamond indenter, and the result was 18.0 GPa. The hardness of the substrate (T2X-1) was 7.3 GPa. Note that "AlON" does not represent the actual composition ratio.

The method for forming the adhesion layer 4 and the method for forming the antifouling layer 5 are the same as in Example 1.

(Example 13)
Hard member 1 was produced in the same manner as in Example 12 except that the thickness of adhesion layer 4 was set to 15 nm.

(Example 14)
A hard member 1 was produced in the same manner as in Example 12 except that the thickness of the adhesive layer 4 was 20 nm.

(Example 15)
A hard member 1 was produced in the same manner as in Example 12 except that the thickness of the adhesive layer 4 was 30 nm.

(Example 16)
A hard member 1 was produced in the same manner as in Example 12 except that the thickness of the adhesive layer 4 was 40 nm.

(Example 17)
A hard member 1 was produced in the same manner as in Example 12 except that the thickness of the adhesive layer 4 was 50 nm.

(Comparative example 6)
A hard member 1 was produced in the same manner as in Example 12 except that the antifouling layer 5 was directly formed on the hard layer 3 without forming the adhesion layer 4.

(Comparative Example 7)
A hard member 1 was produced in the same manner as in Example 12 except that the thickness of the adhesive layer 4 was set to 80 nm.

[Evaluation of scratch resistance and adhesion]
With respect to the hard member 1 produced in Examples 12 to 17 and Comparative Examples 6 to 7, scratch resistance and adhesion were evaluated in the same manner as above. The evaluation results are shown in Table 1.

<Examples 18 to 19 and Comparative Example 8>
The film thickness of the hard layer 3 was changed and the influence of the film thickness of the hard layer 3 was examined.

(Example 18)
A hard member 1 was produced in the same manner as in Example 13 except that the film thickness of the hard layer 3 was 300 nm.

(Example 19)
A hard member 1 was produced in the same manner as in Example 13 except that the film thickness of the hard layer 3 was 200 nm.

(Comparative Example 8)
A hard member 1 was produced in the same manner as in Example 13 except that the film thickness of the hard layer 3 was 100 nm.

[Evaluation of scratch resistance and adhesion]
With respect to the hard member 1 produced in Examples 18 to 19 and Comparative Example 8, scratch resistance and adhesion were evaluated in the same manner as above. The evaluation results are shown in Table 1.

<Examples 20 to 21>
As the adhesion layer 4, a silicon nitride (SiN) film and a silicon oxynitride (SiON) film were used in place of the silicon oxide (SiO ₂ ) film. In addition, "SiN" and "SiON" do not show an actual composition ratio.

(Example 20)
The hard member 1 was manufactured in the same manner as in Example 13 except that a silicon nitride (SiN) film was formed as the adhesion layer 4 instead of the silicon oxide (SiO ₂ ) film. As the film forming conditions for the Si film, the film forming pressure was 0.12 Pa, the flow rate of Ar gas as a carrier gas was 100 sccm, and the Si target applied power was 5.0 kW. As a nitriding condition of the Si film, a flow rate of nitrogen gas as a carrier gas: 40 sccm and a radical gun applied power: 4.5 kW, a silicon nitride (SiN) film was formed to a film thickness of 15 nm.

(Example 21)
As the adhesion layer 4, a translucent member was produced in the same manner as in Example 13 except that a silicon oxynitride (SiON) film was formed instead of the silicon oxide (SiO ₂ ) film. As the film forming conditions for the Si film, the film forming pressure was 0.17 Pa, the flow rate of Ar gas as a carrier gas was 150 sccm, and the Si target applied power was 5.0 kW. As the oxynitriding conditions of the Si film, a flow rate of oxygen gas as a carrier gas: 10 sccm, a flow rate of nitrogen gas: 30 sccm, and a radical gun applied power: 4.5 kW, a silicon oxynitride (SiON) film was formed to a film thickness of 15 nm. Filmed

[Evaluation of scratch resistance and adhesion]
With respect to the hard member 1 produced in Examples 20 to 21, scratch resistance and adhesion were evaluated in the same manner as above. The evaluation results are shown in Table 1.

<Comparative Example 9>
The scratch resistance and the adhesiveness when the hard layer 3 and the adhesive layer 4 were not formed were evaluated.

(Comparative Example 9)
A hard member 1 was produced in the same manner as in Example 13 except that the antifouling layer 5 was directly formed on the substrate 2 without forming the hard layer 3 and the adhesion layer 4.

[Evaluation of scratch resistance and adhesion]
The hard member 1 produced in Comparative Example 9 was evaluated for scratch resistance and adhesion in the same manner as above. The evaluation results are shown in Table 1.

As is clear from the results of Examples 1 to 6 and Comparative Examples 1 to 2, and Examples 12 to 17 and Comparative Examples 6 to 7, an adhesion layer made of a silicon oxide (SiO ₂ ) film having a thickness of 50 nm or less was provided. In Examples 1 to 6 and Examples 12 to 17, good adhesion was obtained as compared with Comparative Example 1 and Comparative Example 6 in which the adhesion layer was not provided. Further, in Examples 1 to 6 and Examples 12 to 17, good scratch resistance was obtained as compared with Comparative Example 2 and Comparative Example 7 in which the adhesion layer having a thickness of 80 nm was provided. Therefore, it is understood that Examples 1 to 6 and Examples 12 to 17 according to the present invention have good scratch resistance and excellent adhesion to the antifouling layer.

As is clear from the results of Examples 2, 7 to 8 and Comparative Example 3, and Examples 13, 18 to 19 and Comparative Example 8, Examples 2, 7 to 8 provided with a hard layer having a thickness of 200 nm or more, and In Examples 13 and 18 to 19, good scratch resistance was obtained as compared with Comparative Examples 3 and 8 in which a hard layer having a thickness of 100 nm was provided.

As is clear from the results of Examples 2, 9 to 10 and Examples 13, 20 to 21, instead of the silicon oxide (SiO ₂ ) film, the silicon nitride (SiN) film or the silicon oxynitride (SiON) was used as the adhesion layer 4. It can be seen that even when a film is used, the effect of the present invention that the scratch resistance is good and the adhesion of the antifouling layer is excellent can be obtained.

From the results of Comparative Example 4 and Comparative Example 9, it can be seen that the scratch resistance is low when the hard layer 3 and the adhesion layer 4 are not formed.

The hard member of the present invention can be used not only as a cover glass or cover member for various devices, but also as a window material, a top plate of a cooker, or the like.

DESCRIPTION OF SYMBOLS 1... Hard member 2... Substrate 3... Hard layer 4... Adhesion layer 5... Antifouling layer 11... Hard member 12... Hard substrate 14... Adhesion layer 15... Antifouling layer

Claims (5)

A glass substrate,
A hard layer provided on the glass substrate, made of metal oxide, metal nitride, or metal oxynitride and having a thickness of 150 nm or more and 10000 nm or less (excluding aluminum oxide and sapphire);
An adhesion layer which is directly provided on the hard layer, is made of at least one selected from silicon oxide, silicon nitride, and silicon oxynitride, and has a thickness of 60 nm or less,
A hard member, which is provided directly on the adhesion layer and includes an antifouling layer containing an organosilicon compound. The hard member according to claim 1, wherein the adhesion layer has a thickness of 1 nm or more. The hard member according to claim 1 or 2, wherein the hardness of the hard layer is 7 GPa or more. The hard layer, zirconium oxide, aluminum nitride, aluminum oxynitride, titanium oxide, tantalum oxide, niobium oxide, hafnium oxide, tin oxide, zinc oxide, containing at least one selected et or oxide indium arm, according to claim 1 The hard member according to any one of 3 above. The hard member according to any one of claims 1 to 4, wherein the antifouling layer contains a fluorine-containing organosilicon compound.

Images