KR102462034B1 - Agent for forming adhesive coating for aluminum oxide or aluminum substrate - Google Patents

Abstract

An adhesive film forming agent for aluminum oxide or aluminum substrates, which can be formed by a wet coating method, is provided.
Adhesive film forming agent for aluminum oxide or aluminum substrates containing a hydrolysis/condensation product of an alkoxysilane component containing at least one selected from alkoxysilanes represented by the following formulas (I) and (II), and an aluminum salt .
(Formula 1)
Si(OR ¹ ) ₄ (I)
(Formula 2)
R ² _m Si(OR ³ ) _4-m (II)
R ¹ and R ³ each independently represent an alkyl group having 1 to 5 carbon atoms, R ² represents a hydrogen atom or the like, and m represents an integer of 1 to 3.

Description

Adhesive film former for aluminum oxide or aluminum substrates {AGENT FOR FORMING ADHESIVE COATING FOR ALUMINUM OXIDE OR ALUMINUM SUBSTRATE}

The present invention relates to an adhesive film forming agent for aluminum oxide such as sapphire glass or an aluminum substrate.

Sapphire glass is single-crystal aluminum oxide, and has excellent properties such as being very hard and transparent, strong in heat, and insoluble in chemicals. From the characteristic that it is hard to be scratched with high hardness, sapphire glass is used for the cover glass (windproof) of a watch, the cover glass of a camera lens, and the touch panel board|substrate of a smart phone and a tablet.

There is also known a technique of applying an antifouling agent such as a fluorine-based compound or a silicone-based compound to the surface of a member such as glass in order to improve abrasion resistance, which is a property that scratches when another substance is rubbed on a substrate. By applying the antifouling agent, the slipperiness of the surface becomes good, and even if an impact is applied, the impact can be mitigated by the slipperiness, and excellent scratch resistance can be obtained. Moreover, by application|coating of an antifouling agent, the effect that water repellency, oil repellency, and a fingerprint are not easily attached is also acquired.

When an antifouling agent is applied to sapphire glass, it can be expected that remarkably excellent scratch resistance is obtained due to the high hardness of the sapphire glass and the sliding effect of the antifouling layer. However, aluminum oxide, such as a sapphire glass, generally has bad adhesiveness with an antifouling|stain-resistant agent, and anticipation of abrasion resistance is not acquired. In order to avoid this problem, conventionally, the method of forming the _{close_contact} |adherence auxiliary|assistant layer _of aluminum oxide (Al2O3) and silicon dioxide (SiO2) by the dry coating method under vacuum is reported (patent document ₁ ).

Moreover, the technique of forming a silicon oxide (SiO2) and _a silicon nitride (SiNx) into a film by sputtering on sapphire glass, and forming an antifouling|stain-resistant layer into a film after that is reported (patent document 2). Film formation by dry coating methods, such as sputtering, PVD (Physical Vapor Deposition), and CVD (Chemical Vapor Deposition), is performed in a vacuum container, and an expensive large-scale apparatus is required. In addition, there is also a problem that the size and shape of the substrate that can be formed into a film is limited.

On the other hand, film formation by a wet coating method such as flexographic printing, spin coating, inkjet, slit coating, bar coating or spraying can form a film inexpensively and at high speed. However, a wet coating method capable of sufficiently adhering to aluminum oxide is not known, and in order to apply an antifouling agent, it is necessary to perform film formation by an expensive dry coating method.

US Patent Publication 2014/0087197 A1 Japanese Patent Publication No. 5435168

An object of the present invention is, when forming a functional film such as an antifouling agent on an aluminum oxide such as sapphire glass or an aluminum substrate, it is interposed between the two to fulfill a role of enhancing their adhesiveness, and furthermore, aluminum oxide that can be formed into a film by a wet coating method Or it exists in providing the close_contact|adherence film forming agent for aluminum substrates.

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching in order to achieve the said objective, this inventor completed this invention which has the following summary.

1. Adhesive film forming agent for aluminum oxide or aluminum substrates characterized by containing the hydrolysis/condensation product of an alkoxysilane, and an aluminum salt.

2. The adhesion film formation as described in said 1, wherein the hydrolysis/condensation product of an alkoxysilane is a hydrolysis/condensation product of an alkoxysilane component containing at least one selected from alkoxysilanes represented by the following formulas (I) and (II). My.

(Formula 1)

Si(OR ¹ ) ₄ (I)

(Formula 2)

R ² _m Si(OR ³ ) _4-m (II)

In the formulas (I) and (II), R ¹ and R ³ each independently represent an alkyl group having 1 to 5 carbon atoms, and R ² is a halogen atom, a vinyl group, a methacryloxy group, an acryloxy group, and a styryl group. A hydrocarbon group having 1 to 20 carbon atoms, a hydrogen atom, a halogen atom, a vinyl group, or a methacryloxy group which may be substituted with at least one selected from the group consisting of , a phenyl group and a cyclohexyl group and may have a hetero atom. , an acryloxy group, a styryl group, a phenyl group, a cyclohexyl group, an amino group, a glycidoxy group, a mercapto group, an isocyanate group or a ureide group. m represents the integer of 1-3.

3. The aluminum salt is at least one selected from the group consisting of aluminum chloride, aluminum nitrate, aluminum sulfate, aluminum acetate, aluminum oxalate, aluminum sulfamate, aluminum sulfonate, aluminum acetoacetate, aluminum acetylacetonate, and basic salts thereof. The adhesive film forming agent as described in said 1 or 2 which is a species.

4. The adhesive film forming agent according to any one of 1 to 3, wherein the aluminum salt is an aluminum nitrate salt.

5. In any one of 1 to 4 above, wherein the molar ratio (Al/(Si + Al)) of aluminum atoms to the sum of the total number of moles of silicon atoms (Si) and the number of moles of aluminum atoms (Al) is 0.1 to 0.5. The described adhesion film former.

6. As a precipitation inhibitor, containing at least one selected from the group consisting of N-methyl-pyrrolidone, ethylene glycol, dimethylformamide, dimethylacetamide, diethylene glycol, propylene glycol, hexylene glycol, and derivatives thereof , The adhesive film forming agent according to any one of 1 to 5 above.

7. A film obtained by using the adhesion film forming agent according to any one of 1 to 6.

8. The aluminum oxide or aluminum substrate which has an adhesive film as described in 7 above.

9. The touch panel which has an adhesive film as described in 7 above.

10. A method for forming an adhesion film for aluminum oxide or aluminum substrates, wherein the coating film obtained by applying the adhesion film forming agent according to any one of 1 to 6 to an aluminum oxide substrate or an aluminum substrate is baked at 100 to 600°C.

The adhesion film forming agent of the present invention forms a film by applying it to an aluminum oxide such as sapphire glass or an aluminum substrate or the like, and forming a functional film such as an antifouling agent thereon, so that excellent scratch resistance properties, etc. can be imparted. have. For example, according to this invention, the cover glass for touch panels which has the outstanding antifouling property and abrasion resistance is obtained. Since the surface of metallic aluminum is oxidized in air to form an aluminum oxide film, the adhesion film forming agent of the present invention can also be used for metallic aluminum substrates.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic sectional drawing of the cover glass for touch panels which is a representative example of the aluminum oxide board|substrate obtained using the close_contact|adherence film forming agent of this invention.

The adhesion film forming agent of this invention contains the aluminum salt as a hydrolysis/condensation product of an alkoxysilane as (A) component, and (B) component.

<(A) component>

(A) The hydrolysis/condensation product of the alkoxysilane component is a hydrolysis/condensation product of the alkoxysilane component containing at least 1 sort(s) selected from the alkoxysilane represented by following formula (I) and (II).

(Formula 3)

Si(OR ¹ ) ₄ (I)

R ¹ represents an alkyl group having 1 to 5 carbon atoms. From the viewpoint of reactivity, the OR ¹ group is preferably a methoxy group, an ethoxy group or a propoxy group.

Although the specific example of the alkoxysilane represented by Formula (I) is given, it is not limited to these. For example, tetramethoxysilane, tetraethoxysilane, tetra-iso-propoxysilane, tetra-n-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra-tert- Butoxysilane, tetrapentaethoxysilane, etc. are mentioned.

Since sufficient hardness may not be obtained at 40 mol% or less in the alkoxysilane represented by Formula (I) in all the alkoxysilanes, 40 mol% or more is preferable. More preferably, it is 50 mol% or more. More preferably, it is 80 mol% or more.

(Formula 4)

R ² _m Si(OR ³ ) _4-m (II)

R ² may be substituted with at least one selected from the group consisting of a halogen atom, a vinyl group, a methacryloxy group, an acryloxy group, a styryl group, a phenyl group, and a cyclohexyl group, or may have a hetero atom A hydrocarbon group having 1 to 20 carbon atoms, a hydrogen atom, a halogen atom, a vinyl group, a methacryloxy group, an acryloxy group, a styryl group, a phenyl group, a cyclohexyl group, an amino group, a glycidoxy group, a mercapto group, an isocyanate group or a ureide group represents the group. In addition, when R ¹ , R ² and R ³ are plural, R ¹ , R ² and R ³ each independently represent the above definition.

R ³ represents an alkyl group having 1 to 5 carbon atoms, and m represents an integer of 1 to 3. In addition, when R< ³ > becomes plural, R< ³ > represents the said definition each independently. From the viewpoint of reactivity, the OR ³ group is preferably a methoxy group or an ethoxy group.

Although the specific example of the alkoxysilane represented by Formula (II) is given, it is not limited to these. For example, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, 3-acryloxypropyltri Methoxysilane, 3-acryloxypropyltriethoxysilane, acryloxyethyltrimethoxysilane, acryloxyethyltriethoxysilane, styrylethyltrimethoxysilane, styrylethyltriethoxysilane, 3-(N -Styrylmethyl-2-aminoethylamino)propyltrimethoxysilane, 4-(trimethoxysilyl)styrene, vinyltrimethoxysilane, vinyltriethoxysilane, 3,3,3-trifluoropropyltri Methoxysilane, 3-chloropropyltriethoxysilane, 3-bromopropyltriethoxysilane, dimethyldiethoxysilane, dimethyldimethoxysilane, diethyldiethoxysilane, diethyldimethoxysilane, diphenyldimethoxysilane , Diphenyldiethoxysilanetrimethylethoxysilane, trimethylmethoxysilane, 3-(2-aminoethylaminopropyl)trimethoxysilane, 3-(2-aminoethylaminopropyl)triethoxysilane, 2-aminoethyl Aminomethyltrimethoxysilane, 2-(2-aminoethylthioethyl)triethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-Glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-mercaptopropyltriethoxysilane, mercaptomethyltrimethoxysilane , 3-isocyanatepropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropyldimethylethoxysilane, γ-ureidopropyltriethoxysilane, γ- Ureidopropyl trimethoxysilane, gamma -ureidopropyl tripropoxysilane, etc. are mentioned.

Moreover, it is preferable that it is pentamer or less from a viewpoint of storage stability and the hardness at the time of low-temperature baking, and, as for the hydrolysis/condensation product of the alkoxysilane contained in the adhesion-film forming agent of this invention, 2 - tetramer are more preferable.

The hydrolysis/condensation product of this alkoxysilane can be condensed in the presence of a base and water. 0.01 times mole - 2 times mole are preferable with respect to an alkoxysilane, and, as for the abundance of a base, 0.05 times mole - 1 times mole are more preferable. 0.5 times mole - 10 times mole are preferable with respect to an alkoxysilane, and, as for the abundance of water, 1 times mole - 5 times mole are more preferable.

<(B) component>

Examples of the aluminum salt contained in the adhesion film forming agent of the present invention include aluminum chloride, aluminum nitrate, aluminum sulfate, aluminum acetate, aluminum oxalate, aluminum sulfamate, aluminum sulfonate, aluminum acetoacetate, aluminum acetylacetonate, and hydrates thereof; A hydrous salt or a basic salt is mentioned.

Especially, an aluminum nitrate salt is especially preferable from the point of the ease of acquisition and the storage stability of a film forming agent.

<Precipitation inhibitor>

It is preferable that a precipitation inhibitor is contained in the adhesive film forming agent of this invention from a viewpoint of storage stability. A precipitation inhibitor is used in order to prevent the aluminum salt from precipitating in a film, when a film is formed with the adhesive film forming agent of this invention.

Examples of the precipitation inhibitor include N-methyl-pyrrolidone, ethylene glycol, dimethylformamide, dimethylacetamide, diethylene glycol, propylene glycol, hexylene glycol, and derivatives thereof. It can be used by mixing the above.

<Organic solvent>

The adhesion film forming agent of this invention contains the organic solvent which melt|dissolves or disperse|distributes the said (A) component and (B) component normally. It is preferable that this organic solvent forms a coating film of an adhesion film forming agent, is dispersed when heat-processing this coating film to obtain an adhesion film, and does not remain in the formed adhesion film. For this reason, as such an organic solvent, it is preferable that the said (A) component and (B) component are melt|dissolved or disperse|distributed favorably, A boiling point becomes like this. Preferably it is 60-250 degreeC, More preferably, it is 75-200 degreeC.

Examples of the organic solvent include alcohols such as methanol, ethanol, propanol and butanol, esters such as ethyl acetate ester, glycols such as ethylene glycol and ether derivatives thereof, ester derivatives, ethers such as diethyl ether, acetone, Ketones, such as methyl ethyl ketone and cyclohexanone, aromatic hydrocarbons, such as benzene and toluene, etc. are mentioned. Among them, ethanol, propanol, or propylene glycol monomethyl ether is preferable from the viewpoint of solvent survivability and applicability.

<Other ingredients>

The adhesion film forming agent of the present invention, as long as the effect of the present invention is not impaired, components other than the above, for example, inorganic fine particles, metaloxane monomers, metaloxane oligomers, metaloxane polymers, crosslinking agents, organic polymers, Components, such as a leveling agent and surfactant, may be contained.

<Production of adhesive film former>

The adhesion film forming agent of this invention is an organic solvent containing at least 1 sort(s) selected from the alkoxysilane represented by Formula (I) and (II) which is the said (A) component, the aluminum salt which is (B) component, and water. It is prepared by mixing in The alkoxysilane represented by Formula (I) and (II) is hydrolyzed and condensed by contact with water, and is converted into a hydrolysis/condensation product. Thereby, the adhesion film forming agent of this invention is obtained in the form of a composition containing the hydrolysis/condensation product of an alkoxysilane, and an aluminum salt melt|dissolving or disperse|distributing in an organic solvent.

As the organic solvent used herein, the same organic solvents as those contained in the adhesion film forming agent of the present invention can be used, including desirable properties.

About content of each component in the adhesion film forming agent of this invention, when converting both the hydrolysis/condensation product of the alkoxysilane which is (A) component, and the aluminum salt which is (B) component as solid content of a metal oxide, 0.1 -20 mass % is preferable, and 0.5-6 mass % is more preferable. When content exceeds 20 mass %, the storage stability of a composition will worsen, and also film thickness control of the protective film formed will become difficult. On the other hand, if it is 0.1 mass % or less, the thickness of the protective film obtained becomes thin, in order to obtain a predetermined|prescribed film thickness, multiple times of coating film formation is needed, and manufacture of an adhesion film will become complicated.

(A) The amount of water used for hydrolysis of the alkoxysilane, which is the component, is preferably 0.5 or more, more preferably 1 to 5 in a molar ratio (amount (mol) of water)/total moles of alkoxysilane used. When this molar ratio is 0.5 or more, the hydrolysis of the above-mentioned alkoxysilane becomes enough, film-forming property is improved, and the intensity|strength of the adhesive film obtained is increased.

In addition, in the above hydrolysis, when the water-containing salt of the aluminum salt as component (B) coexists, the water content is involved in the reaction, so it is necessary to include the water content of the metal salt with respect to the amount of water used for hydrolysis. .

It is preferable that the temperature at the time of hydrolysis of an alkoxysilane is implemented in the range of 20-100 degreeC. Especially, it is more preferable that it is the range of 25-80 degreeC from a viewpoint from which the condensate of suitable molecular weight is obtained. As time for hydrolysis, 30 minutes - 48 hours are preferable from a viewpoint of obtaining the condensate of suitable molecular weight, More preferably, they are 30 minutes - 24 hours.

The precipitation inhibitor may be added when an alkoxysilane hydrolyzes and carries out a condensation reaction in presence of an aluminum salt, and may be added after completion|finish of those hydrolysis and condensation reaction.

A precipitation inhibitor converts the aluminum of an aluminum salt into aluminum oxide, and it is preferable that the weight ratio of (precipitation inhibitor/aluminum oxide) is 1 or more, and 2-20 are more preferable. When this ratio is less than 1, the precipitation prevention effect of the metal salt at the time of coating-film formation becomes small.

The content ratio of the hydrolysis/condensation product of alkoxysilane as component (A) and aluminum salt as component (B), which are contained in the adhesion film forming agent of the present invention, is the total number of moles of silicon atoms (Si) and the number of moles of aluminum atoms. It is preferable that the molar ratio (Al/(Si+Al)) of the aluminum atom with respect to the sum total of (Al) is 0.1-0.5, and 0.2-0.4 is more preferable. When this molar ratio is 0.1 or more, or when it is 0.5 or less, the target adhesive property can be improved.

<Adhesive film>

The adhesion film forming agent of this invention is apply|coated to the board|substrate whose surface is covered with aluminum oxide like aluminum oxide or an aluminum substrate, and an adhesion film is obtained on the substrate surface by baking.

As a method of forming the coating film on the substrate surface using the adhesion film forming agent of this invention, it can apply and implement various application|coating methods. For example, the dip coating method, the spin coating method, the spray coating method, the brush coating method, the roll transfer method, the screen printing method, the inkjet method, the flexographic printing method etc. can be used.

The coating film formed on the surface of the substrate is then heated, for example, at a temperature of 50 to 100°C, preferably 60 to 80°C to dry the coating film, and then 100°C or more, preferably 100 to 600°C, more preferably is fired at a temperature of 300 to 600°C for 10 minutes or more, preferably for 0.5 to 2 hours, to obtain an adhesive film having a dense film structure. These heat processing can be performed using apparatuses, such as an oven and a hot plate. In addition, it is also possible to abbreviate|omit the said heating for drying a coating film.

As described above, on the aluminum oxide substrate, a film is formed with the adhesion film forming agent of the present invention. This adhesion film can function as an adhesion auxiliary|assistant layer for forming the coating agent which forms various characteristic films on the surface. For example, when an antifouling agent is used as a coating agent, an aluminum oxide substrate having an excellent scratch resistance coating film on the surface is obtained.

<Aluminum oxide substrate>

The adhesion film forming agent of this invention is used for forming an adhesion film on the surface of aluminum oxide or an aluminum substrate. That is, an adhesion film is formed on the surface of the aluminum oxide substrate, and then, on the surface of the adhesion film, a functional film obtained from a specific coating agent is formed. The adhesion film is directly formed on the surface of the aluminum oxide substrate from the adhesion film forming agent of this invention mentioned above.

An example of the functional film is an antifouling layer. An antifouling layer can be formed by apply|coating an antifouling agent and baking. The excellent scratch resistance is obtained by using sapphire glass as a board|substrate, forming the film obtained from the adhesive film forming agent of this invention on it, and forming the film 2 obtained from the antifouling|stain-resistant agent then.

As for the thickness of an adhesion film and a functional film, 5-1000 nm is preferable, More preferably, it is 10-400 nm.

The adhesion film forming agent of this invention is effective also about the aluminum oxide of various crystal structures. In addition to sapphire glass, which is single-crystal aluminum oxide, it can also be used for polycrystalline or amorphous aluminum oxide.

Moreover, since the surface of metallic aluminum is oxidized in air to form an aluminum oxide film, the adhesion film forming agent of this invention can be used also for the structure which consists of a metallic aluminum substrate.

In the present invention, the functional film formed on the adhesion film is not particularly limited. Specific examples include a coating film obtained from an antifouling agent, a paint, an adhesive, an antireflection agent, a water repellent agent, a hydrophilic agent, an oil repellent agent, an oil lipophilic agent, a hard coat agent, a lubricant, and the like.

<Cover glass for touch panel>

The cover glass for touch panels shown in FIG. 1 is mentioned as a representative example of the aluminum oxide board|substrate obtained using the adhesive film forming agent of this invention. BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic sectional drawing of the cover glass for touch panels. The cover glass 1 for touch panels has the functional film 2 through the adhesion film 3 on the surface of the sapphire glass 4 . The adhesion film 3 is a film formed directly on the surface of sapphire glass using the adhesion film forming agent of this invention. An example of the functional film 2 is an antifouling layer. An antifouling layer can be formed by apply|coating an antifouling agent and baking.

By forming the adhesion film obtained from the film forming agent of this invention on sapphire glass, and then forming the film|membrane of an antifouling agent, even if it rubs a finger or a substance, an antifouling agent can be hold|maintained on sapphire glass. Accordingly, it is possible to prevent deterioration of abrasion resistance, water repellency and oil repellency, and problems such as adhesion of fingerprints when the touch panel is used.

Example

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to the following Examples and the like to be interpreted.

[Compound and its abbreviation]

TEOS: Tetraethoxysilane AN: Aluminum nitrate hexahydrate

EtOH: ethanol PGME: propylene glycol monomethyl ether

HG: Hexylene glycol PB: Propylene glycol monobutyl ether

BCS: Ethylene glycol monobutyl ether

Antifouling agent: manufactured by FT-Net, P-5425-0.2

<Example 1>

In a 4-necked reaction flask, EtOH (22.49 g), water (7.42 g), and AN (12.88 g) were added and stirred. Subsequently, EtOH (28.60 g) and TEOS (28.60 g) were added, and the mixture was stirred at 20°C for 1 hour to prepare a solution.

An adhesion film former was obtained by mixing this solution (30g) with HG (14g), PB (10.5g), BCS (10.5g), and PGME (35g).

<Example 2>

In a 4-necked reaction flask, EtOH (22.93 g), water (6.6 g), and AN (19.62 g) were added and stirred. Then, EtOH (25.43 g) and TEOS (25.43 g) were added, and the solution was prepared by stirring in a water bath for 1 hour.

An adhesion film former was obtained by mixing this solution (30g) with HG (14g), PB (10.5g), BCS (10.5g), and PGME (35g).

<Comparative Example 1>

EtOH (33.87 g) and TEOS (34.72 g) as an alkoxysilane were put into a four-necked reaction flask equipped with a reflux tube and stirred. Subsequently, EtOH (16.94 g), water (13.6 g), and an aqueous solution containing 60 wt% of nitric acid (0.88 g) were added dropwise over 30 minutes, and stirred, and the mixture was stirred. Then, it refluxed for 3 hours, and it was made to cool to room temperature, and the solution was prepared.

An adhesion film former was obtained by mixing this solution (30g) with HG (14g), PB (10.5g), BCS (10.5g), and PGME (35g).

[Production of sapphire glass having an antifouling film]

Using a spin coater, the adhesion film formers of Examples 1 and 2 and Comparative Example 1 described above were applied to sapphire glass (single crystal sapphire glass, surface roughness: 1 Å or less) having a thickness of 0.7 mm, respectively, and a hot plate Drying was performed for 3 minutes at 80 degreeC on the top. Then, the close_contact|adherence film of the Example and the comparative example with a thickness of 50-100 nm was obtained by heating at 150 degreeC or 300 degreeC for 30 minute(s) in clean oven.

Next, an antifouling agent, which is a coating agent for forming a functional film, was applied to the substrate with an adhesion film obtained in Examples and Comparative Examples using a spin coater. Then, the sapphire glass which has an antifouling|stain-resistant film on the surface was manufactured by drying at 80 degreeC for 3 minutes on a hotplate, and heating at 170 degreeC for 20 minutes in a clean oven then.

In the comparative example 2, the board|substrate which formed the antifouling|stain-resistant film directly on the sapphire glass substrate without coating the adhesion film forming agent of an Example and a comparative example was also produced.

[Abrasion resistance evaluation: Steel wool scratch resistance test]

On the surface of the sapphire glass substrate produced in the above examples and comparative examples, held on the pedestal of a reciprocating abrasion resistance testing machine (manufactured by Daiei Science Seiki Seisakusho Co., Ltd.), grade #0000 steel wool (manufactured by Nippon Steel Wool Co., Ltd., registered) Trademark: Bonstar) was raised to contact a square pad having an area of 2 cm 2 , and this pad was rubbed from 0 to 1000 reciprocations at an applied load of 1,000 g and a speed of 25 reciprocations per minute. The contact angle of water in 3 ml of liquid volume was measured using the contact angle meter (made by Kyowa Interface Science, Ltd., DM-701) every 200 reciprocating friction. The measurement results are summarized and shown in Table 1.

As shown in Table 1, the sapphire glass substrates with the antifouling agent of Examples 1 and 2 had a water contact angle of 90° or more even after 800 rounds of steel wool rubbing, and the change from the initial stage was less than 20°, which was good. It was confirmed that scratch resistance was obtained.

On the other hand, in the sapphire glass substrates with antifouling agent of Comparative Examples 1 and 2, the water contact angle became less than 90 degrees by 800 reciprocating steel wool friction, and it fell 20 degrees or more.

An aluminum oxide substrate having an antifouling film as a functional film formed through a film obtained from the adhesion film forming agent of the present invention has excellent scratch resistance, so that the cover glass of a watch (windproof), the cover glass of a camera lens, a smartphone or tablet, etc. It can be used as a touch panel substrate of

In addition, the whole content of the specification of JP Patent application 2014-111610 for which it applied on May 29, 2014, a claim, drawing, and an abstract is referred here, and it takes in as an indication of the specification of this invention.

1: Cover glass for touch panel
2: functional film
3: Adhesive film layer
4: Sapphire glass substrate

Claims (10)

The molar ratio (Al/(Si+Al)) of the hydrolysis/condensation product of the alkoxysilane and the aluminum salt to the sum of the total number of moles of silicon atoms (Si) and the number of moles of aluminum atoms (Al) is 0.2 to 0.4 An aluminum oxide or aluminum substrate on which a functional film is formed through an adhesion film obtained from an adhesion film forming agent contained so as to become The method of claim 1,
An aluminum oxide or aluminum substrate wherein the hydrolysis/condensation product of an alkoxysilane is a hydrolysis/condensation product of an alkoxysilane containing at least one selected from the group consisting of alkoxysilanes represented by the following formulas (I) and (II).
Si(OR ¹ ) ₄ (I)
R ² _m Si(OR ³ ) _4-m (II)
In the formulas (I) and (II), R ¹ and R ³ each independently represent an alkyl group having 1 to 5 carbon atoms, R ² is a halogen atom, a vinyl group, a methacryloxy group, an acryloxy group, a styryl group, A hydrocarbon group having 1 to 20 carbon atoms which may be substituted with at least one selected from the group consisting of a phenyl group and a cyclohexyl group and may have a hetero atom, a hydrogen atom, a halogen atom, a vinyl group, a methacryloxy group, an acryloxy group, a styryl group, a phenyl group, a cyclohexyl group, an amino group, a glycidoxy group, a mercapto group, an isocyanate group, or a ureide group. m represents the integer of 1-3. The method of claim 1,
Oxidation wherein the aluminum salt is at least one selected from the group consisting of aluminum chloride, aluminum nitrate, aluminum sulfate, aluminum acetate, aluminum oxalate, aluminum sulfamate, aluminum sulfonate, aluminum acetoacetate, aluminum acetylacetonate, and basic salts thereof. aluminum or aluminum substrate. The method of claim 1,
An aluminum oxide or aluminum substrate wherein the aluminum salt is an aluminum nitrate salt. The method of claim 1,
As a precipitation inhibitor, it further contains at least one selected from the group consisting of N-methyl-pyrrolidone, ethylene glycol, dimethylformamide, dimethylacetamide, diethylene glycol, propylene glycol, hexylene glycol, and derivatives thereof. aluminum oxide or aluminum substrate. The method of claim 1,
An aluminum oxide or aluminum substrate wherein the aluminum oxide is sapphire glass. The method of claim 1,
An aluminum oxide or aluminum substrate wherein the functional film is a film of a fluorine-based compound or a silicon-based compound. A touch panel comprising the aluminum oxide or the aluminum substrate according to any one of claims 1 to 7, wherein the functional film is a film of an antifouling agent. In the method for producing an aluminum oxide or aluminum substrate according to any one of claims 1 to 7, the hydrolysis/condensation product of alkoxysilane and an aluminum salt are mixed with the total number of moles of silicon atoms (Si) and the number of moles of aluminum atoms ( A coating film obtained by coating aluminum oxide or an aluminum substrate with an adhesion film forming agent containing a molar ratio (Al/(Si+Al)) of aluminum atoms to the total of Al) is 0.2 to 0.4, and baking at 100 to 600°C. A method for producing an aluminum oxide or aluminum substrate, comprising forming an adhesion film and then forming a functional film on the adhesion film. delete

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