JPWO2015182657A1 - Adhesive film forming agent for aluminum oxide or aluminum substrate - Google Patents

Abstract

Provided is an adhesive film forming agent for aluminum oxide or aluminum substrate, which can be formed by a wet coating method. 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 oxide or aluminum substrate adhesive film forming agent containing an aluminum salt . (Chemical Formula 1) Si (OR1) 4 (I) (Chemical Formula 2) R2mSi (OR3) 4-m (II) R1 and R3 each independently represent an alkyl group having 1 to 5 carbon atoms, and R2 represents , Represents a hydrogen atom or the like, and m represents an integer of 1 to 3.

Description

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

Sapphire glass is a single crystal aluminum oxide and has excellent properties of being extremely hard and transparent, resistant to heat and insoluble in chemicals. Due to its high hardness and resistance to scratches, sapphire glass is used for watch cover glass (windshield), camera lens cover glass, and touch panel substrates for smartphones and tablets.
Also known is a technology for applying antifouling agents such as fluorine compounds and silicon compounds to the surface of members such as glass in order to increase the scratch resistance, which is the resistance to scratching when other substances are rubbed against the substrate. It has been. By applying an antifouling agent, the slipperiness of the surface is improved, and even if an impact is applied, the impact can be softened by the slipperiness and excellent scratch resistance can be obtained. In addition, the application of the antifouling agent also provides an effect that water repellency, oil repellency, and fingerprints are difficult to stick.

If antifouling agent is applied to sapphire glass, it can be expected that remarkably excellent scratch resistance can be obtained due to the high hardness of sapphire glass and the sliding effect of the antifouling layer. However, aluminum oxide such as sapphire glass generally has poor adhesion to an antifouling agent, and the expected scratch resistance cannot be obtained. In order to avoid this problem, a method of forming an adhesion auxiliary layer of aluminum oxide (Al ₂ O ₃ ) and silicon dioxide (SiO ₂ ) by a dry coating method under vacuum has been reported. (Patent Document 1)

Further, a technique has been reported in which silicon oxide (SiO ₂ ) and silicon nitride (SiNx) are formed on a sapphire glass by sputtering and then an antifouling layer is formed. (Patent Document 2) Film formation by a dry coating method such as sputtering, PVD (Physical Vapor Deposition), or CVD (Chemical Vapor Deposition) is performed in a vacuum vessel, which requires an expensive and large-scale apparatus. There is also a problem that the size and shape of the base material on which the film can be formed are limited.

  On the other hand, film formation by wet coating methods such as flexographic printing, spin coating, ink jet, slit coating, bar coating, and spraying is inexpensive and can form a film at high speed. However, there is no known wet-coating method that sufficiently adheres to aluminum oxide, and in order to apply an antifouling agent, it was necessary to perform film formation by a high-cost dry coating method.

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

  The purpose of the present invention is to provide a functional film such as an antifouling agent on aluminum oxide such as sapphire glass or an aluminum substrate. An object of the present invention is to provide an adhesive film forming agent for aluminum oxide or aluminum substrate that can be formed into a film.

As a result of intensive studies to achieve the above object, the present inventor has completed the present invention having the following gist.
1. An adhesive film-forming agent for an aluminum oxide or aluminum substrate, comprising a hydrolyzed / condensed product of alkoxysilane and an aluminum salt.
2. 2. The adhesion according to 1 above, wherein the hydrolysis / condensation product of 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): Film forming agent.
(Chemical formula 1)
Si (OR ¹ ) ₄ (I)
(Chemical formula 2)
R ² _m Si (OR ³ ) _4-m (II)
In the above formulas (I) and (II), R ¹ and R ³ each independently represent an alkyl group having 1 to 5 carbon atoms, and R ² represents a halogen atom, a vinyl group, a methacryloxy group, an acryloxy 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 styryl group, a phenyl group, and a cyclohexyl group, and may have a hetero atom, a hydrogen atom, a halogen atom Atom, vinyl group, methacryloxy group, acryloxy group, styryl group, phenyl group, cyclohexyl group, amino group, glycidoxy group, mercapto group, isocyanate group or ureido group are represented. m represents an integer of 1 to 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. 3. The adhesion film forming agent according to 1 or 2 above, which is a seed.
4). 4. The adhesive film forming agent according to any one of 1 to 3 above, wherein the aluminum salt is an aluminum nitrate salt.
5). The above-mentioned 1-4, wherein the molar ratio (Al / (Si + Al)) of aluminum atoms to the total number of moles of silicon atoms (Si) and moles of aluminum atoms (Al) is 0.1 to 0.5. The adhesive film forming agent according to any one of the above items.
6). As the precipitation inhibitor, N-methyl-pyrrolidone, ethylene glycol, dimethylformamide, dimethylacetamide, diethylene glycol, propylene glycol, hexylene glycol, and at least one selected from the group consisting of these derivatives, The adhesive film forming agent according to any one of the above items.

7). The film obtained using the contact | glue film forming agent of any one of said 1-6.
8). 8. An aluminum oxide or aluminum substrate having the adhesion film according to 7 above.
9. 8. A touch panel having the adhesion film according to 7 above.
10. The formation method of the adhesion film for aluminum oxide or an aluminum substrate which bakes the coating film which apply | coated the adhesion film formation agent of any one of said 1-6 to an aluminum oxide substrate or an aluminum substrate at 100-600 degreeC.

  The adhesive film forming agent of the present invention is applied to an aluminum oxide or aluminum substrate such as sapphire glass by coating or the like to form a film, and a functional film such as an antifouling agent is formed thereon, Properties such as excellent scratch resistance can be imparted. For example, according to the present invention, a cover glass for a touch panel having excellent antifouling properties and scratch resistance can be obtained. Since the surface of metal aluminum is oxidized in the air to form an aluminum oxide film, the adhesive film forming agent of the present invention can also be used for a metal aluminum substrate.

It is typical sectional drawing of the cover glass for touchscreens which is a typical example of the aluminum oxide board | substrate obtained using the contact | glue film forming agent of this invention.

  The adhesive film forming agent of the present invention contains a hydrolyzed / condensed product of alkoxysilane as the component (A) and an aluminum salt as the component (B).

<(A) component>
The hydrolysis / condensation product of the alkoxysilane that is the component (A) is a hydrolysis / condensation product of an alkoxysilane component that includes at least one selected from alkoxysilanes represented by the following formulas (I) and (II). is there.

(Chemical 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 a 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. Is mentioned.
The alkoxysilane represented by the formula (I) is preferably 40 mol% or more because sufficient hardness may not be obtained at 40 mol% or less in all alkoxysilanes. More preferably, it is 50 mol% or more. More preferably, it is 80 mol% or more.

(Chemical 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, and has a heteroatom. C1-C20 hydrocarbon group, hydrogen atom, halogen atom, vinyl group, methacryloxy group, acryloxy group, styryl group, phenyl group, cyclohexyl group, amino group, glycidoxy group, mercapto group, isocyanate group or ureido group Represents. In addition, when R < ¹ >, R < ² > and R < ³ > become plural, R < ¹ >, R < ² > and R < ³ > represent the said definition each independently.

R ³ represents an alkyl group having 1 to 5 carbon atoms, and m represents an integer of 1 to 3. In the case where R ³ is more, R ³ are each independently, represent a defined above. 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 a formula (II) is given, it is not limited to these. For example, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxy Silane, acryloxyethyltrimethoxysilane, acryloxyethyltriethoxysilane, styrylethyltrimethoxysilane, styrylethyltriethoxysilane, 3- (N-styrylmethyl-2-aminoethylamino) propyltrimethoxysilane, 4- ( Trimethoxysilyl) styrene, vinyltrimethoxysilane, vinyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3-chloropropyltriethoxysilane 3-bromopropyltriethoxysilane, dimethyldiethoxysilane, dimethyldimethoxysilane, diethyldiethoxysilane, diethyldimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane trimethylethoxysilane, trimethylmethoxysilane, 3- (2-aminoethylamino Propyl) trimethoxysilane, 3- (2-aminoethylaminopropyl) triethoxysilane, 2-aminoethylaminomethyltrimethoxysilane, 2- (2-aminoethylthioethyl) triethoxysilane, 2- (3,4 -Epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxy Propyltriethoxysilane, 3-mercaptopropyltriethoxysilane, mercaptomethyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropyldimethyl Examples include ethoxysilane, γ-ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, and γ-ureidopropyltripropoxysilane.

The alkoxysilane hydrolyzate / condensate contained in the adhesive film-forming agent of the present invention is preferably a pentamer or less from the viewpoint of storage stability and hardness during low-temperature firing. A monomer is more preferable.
This alkoxysilane hydrolyzed / condensed product can be condensed in the presence of a base and water. The amount of the base present is preferably 0.01 to 2 moles, more preferably 0.05 to 1 moles with respect to the alkoxysilane. The amount of water present is preferably 0.5 times to 10 times moles, more preferably 1 time to 5 times moles relative to the alkoxysilane.

<(B) component>
Examples of the aluminum salt contained in the adhesive 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 the like. A hydrate, a hydrated salt, or a basic salt is mentioned.
Among these, an aluminum nitrate salt is particularly preferable from the viewpoint of availability and storage stability of the film forming agent.

<Precipitating agent>
The adhesion film forming agent of the present invention preferably contains a precipitation inhibitor from the viewpoint of storage stability. The precipitation inhibitor is used to prevent the aluminum salt from being precipitated in the coating film when the coating film is formed from the adhesive film forming agent of the present invention.
Examples of the precipitation inhibitor include N-methyl-pyrrolidone, ethylene glycol, dimethylformamide, dimethylacetamide, diethylene glycol, propylene glycol, hexylene glycol, and derivatives thereof. These may be used alone or in combination. can do.

<Organic solvent>
The adhesive film forming agent of the present invention usually contains an organic solvent that dissolves or disperses the components (A) and (B). It is preferable that this organic solvent forms a coating film of the adhesive film forming agent, dissipates when the coating film is heated to obtain an adhesive film, and does not remain in the formed adhesive film. For this reason, as such an organic solvent, those having the above components (A) and (B) dissolved or dispersed well and having a boiling point of preferably 60 to 250 ° C., more preferably 75 to 200 ° C. are suitable. .
Examples of the organic solvent include alcohols such as methanol, ethanol, propanol and butanol, esters such as ethyl acetate, glycols such as ethylene glycol and ether derivatives thereof, ester derivatives, ethers such as diethyl ether, acetone, Examples thereof include ketones such as methyl ethyl ketone and cyclohexanone, and aromatic hydrocarbons such as benzene and toluene. Of these, ethanol, propanol, or propylene glycol monomethyl ether is preferred from the viewpoints of solvent persistence and coatability.

<Other ingredients>
As long as the effect of the present invention is not impaired, the adhesive film forming agent of the present invention is a component other than those described above, for example, inorganic fine particles, metalloxane monomers, metalloxane oligomers, metalloxane polymers, crosslinking agents, organic polymers, leveling agents, Components such as a surfactant may be included.

<Manufacture of adhesive film forming agent>
The adhesive film forming agent of the present invention is at least one selected from the alkoxysilanes represented by the formulas (I) and (II), which is the component (A), and an aluminum salt that is the component (B). It is produced by mixing in an organic solvent containing water. The alkoxysilane represented by the formulas (I) and (II) is hydrolyzed / condensed by contact with water to be converted into a hydrolyzed / condensed product. Thereby, the adhesive film forming agent of the present invention is obtained in the form of a composition containing a hydrolyzed / condensed alkoxysilane and an aluminum salt dissolved or dispersed in an organic solvent.
The organic solvent used here can be the same as the above-mentioned organic solvent contained in the adhesive film forming agent of the present invention, including preferable characteristics.

  Regarding the content of each component in the adhesive film forming agent of the present invention, (A) the alkoxysilane hydrolysis / condensation product and (B) component aluminum salt are both solid metal oxides. When converted as a minute, 0.1 to 20% by mass is preferable, and 0.5 to 6% by mass is more preferable. When the content exceeds 20% by mass, the storage stability of the composition is deteriorated and it is difficult to control the thickness of the protective film to be formed. On the other hand, when the content is 0.1% by mass or less, the thickness of the protective film to be obtained becomes thin, and it is necessary to form a coating film many times in order to obtain a predetermined film thickness. .

The amount of water used for the hydrolysis of the alkoxysilane as the component (A) is preferably 0.5 or more in molar ratio (amount of water (mol)) / total mole of alkoxysilane used). ~ 5 is more preferred. When this molar ratio is 0.5 or more, the above-described alkoxysilane is sufficiently hydrolyzed to improve the film formability and increase the strength of the resulting adhesive coating.
In the above hydrolysis, when the hydrated salt of the aluminum salt as component (B) coexists, the moisture content is involved in the reaction, so the moisture content of the metal salt relative to the amount of water used for the hydrolysis. Must be included.

  It is preferable that the temperature at the time of hydrolysis of alkoxysilane is 20 to 100 degreeC. Among these, the range of 25 to 80 ° C. is more preferable from the viewpoint of obtaining a condensate having an appropriate molecular weight. The hydrolysis time is preferably 30 minutes to 48 hours, more preferably 30 minutes to 24 hours, from the viewpoint of obtaining a condensate having an appropriate molecular weight.

The precipitation inhibitor may be added when the alkoxysilane undergoes hydrolysis / condensation reaction in the presence of an aluminum salt, or may be added after completion of the hydrolysis / condensation reaction.
The precipitation inhibitor is preferably such that the aluminum salt of the aluminum salt is converted to aluminum oxide and the weight ratio of (precipitation inhibitor / aluminum oxide) is 1 or more, more preferably 2-20. When this ratio is less than 1, the effect of preventing precipitation of the metal salt during coating film formation is reduced.

  The content ratio of the hydrolysis / condensation product of the alkoxysilane as the component (A) and the aluminum salt as the component (B) contained in the adhesion film forming agent of the present invention is the total number of moles of silicon atoms (Si). The molar ratio (Al / (Si + Al)) of aluminum atoms to the total number of aluminum atoms and the number of moles of aluminum atoms (Al) is preferably 0.1 to 0.5, more preferably 0.2 to 0.4. When this molar ratio is 0.1 or more, or 0.5 or less, the desired adhesion characteristics can be improved.

<Adhesion film>
The adhesion film-forming agent of the present invention is applied to a substrate whose surface is covered with aluminum oxide, such as aluminum oxide or an aluminum substrate, and baked to obtain an adhesion film on the substrate surface.
As a method for forming the coating film on the substrate surface using the adhesive film forming agent of the present invention, various coating methods can be applied. For example, a dip coating method, a spin coating method, a spray coating method, a brush coating method, a roll transfer method, a screen printing method, an ink jet method, a flexographic printing method, and the like can be used.

The coating film formed on the substrate surface is then heated at a temperature of, for example, 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. Preferably, an adhesive film having a dense film structure can be obtained by baking at a temperature of 300 to 600 ° C. for 10 minutes or more, preferably 0.5 to 2 hours. These heat treatments can be performed using an apparatus such as an oven furnace or a hot plate. In addition, it is also possible to abbreviate | omit said heating for drying a coating film.
As described above, a film is formed on the aluminum oxide substrate from the adhesion film forming agent of the present invention. This adhesion film can function as an adhesion auxiliary layer for forming a coating agent for forming various characteristic films on the surface. For example, when an antifouling agent is used as the coating agent, an aluminum oxide substrate having an excellent scratch-resistant film on the surface can be obtained.

<Aluminum oxide substrate>
The adhesive film forming agent of the present invention is used to form an adhesive 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 a functional film obtained from a specific coating agent is formed on the surface of the adhesion film. The adhesion film is directly formed on the surface of the aluminum oxide substrate from the above-described adhesion film forming agent of the present invention.

An example of the functional film is an antifouling layer. The antifouling layer can be formed by applying an antifouling agent and baking it. Excellent scratch resistance is obtained by using sapphire glass as the substrate, forming a film obtained from the adhesive film forming agent of the present invention on the substrate, and subsequently forming a film 2 obtained from the antifouling agent.
The thickness of the adhesion coating or the functional film is preferably 5 to 1000 nm, more preferably 10 to 400 nm.

The adhesive film forming agent of the present invention is also effective for aluminum oxide having 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.
In addition, since the surface of the metal aluminum is oxidized in the air to form an aluminum oxide film, the adhesive film forming agent of the present invention can be used for a structure composed of a metal aluminum substrate.
In the present invention, the functional film provided on the adhesion coating is not particularly limited. Specific examples include coatings obtained from antifouling agents, paints, adhesives, antireflective agents, water repellents, hydrophilic agents, oil repellents, lipophilic agents, hard coat agents, antiskid materials, and the like.

<Touch glass for touch panel>
As a typical example of an aluminum oxide substrate obtained using the adhesive film forming agent of the invention, there is a cover glass for a touch panel shown in FIG. FIG. 1 is a schematic cross-sectional view of a cover glass for a touch panel. The cover glass 1 for a touch panel has a functional film 2 through an adhesion coating 3 on the surface of the sapphire glass 4. The adhesion film 3 is a film directly formed on the surface of the sapphire glass using the adhesion film forming agent of the present invention. An example of the functional film 2 is an antifouling layer. The antifouling layer can be formed by applying an antifouling agent and baking it.
By forming an adhesion film obtained from the film-forming agent of the present invention on the sapphire glass, and subsequently forming an antifouling film, the antifouling agent is maintained on the sapphire glass even when the finger or substance is rubbed. be able to. As a result, it is possible to prevent problems such as deterioration of scratch resistance, water repellency and oil repellency, and fingerprint adhesion when using the touch panel.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not construed as being limited to the following examples.
[Compounds and their abbreviations]
TEOS: Tetraethoxysilane AN: Aluminum nitrate nonahydrate 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>
Into a four-necked reaction flask, EtOH (22.49 g), water (7.42 g), and AN (12.88 g) were added and stirred. Next, 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.
This solution (30 g) was mixed with HG (14 g), PB (10.5 g), BCS (10.5 g), and PGME (35 g) to obtain an adhesive film forming agent.

<Example 2>
EtOH (22.93 g), water (6.6 g), and AN (19.62 g) were added to a four-neck reaction flask and stirred. Next, EtOH (25.43 g) and TEOS (25.43 g) were added and stirred in a water bath for 1 hour to prepare a solution.
This solution (30 g) was mixed with HG (14 g), PB (10.5 g), BCS (10.5 g), and PGME (35 g) to obtain an adhesive film forming agent.

<Comparative Example 1>
In a four-necked reaction flask equipped with a reflux tube, EtOH (33.87 g) and TEOS (34.72 g) as alkoxysilane were added and stirred. Next, EtOH (16.94 g), water (13.6 g), and an aqueous solution containing nitric acid 60 wt% (0.88 g) were added dropwise for 30 minutes and stirred. The solution was then refluxed for 3 hours and allowed to cool to room temperature to prepare a solution.
This solution (30 g) was mixed with HG (14 g), PB (10.5 g), BCS (10.5 g), and PGME (35 g) to obtain an adhesive film forming agent.

[Production of sapphire glass with antifouling agent film]
Using a spin coater, the adhesive film forming agents of Examples 1 and 2 and Comparative Example 1 described above were each applied to sapphire glass having a thickness of 0.7 mm (single crystal sapphire glass, surface roughness: 1 mm or less), Drying was performed at 80 ° C. for 3 minutes on a hot plate. Then, the adhesion film of the Example and comparative example of thickness 50-100nm was obtained by heating for 30 minutes at 150 degreeC or 300 degreeC in clean oven.
Next, an antifouling agent, which is an agent as a coating for forming a functional film, was applied to a substrate with an adhesion coating obtained from Examples and Comparative Examples using a spin coater. Then, it was dried at 80 ° C. for 3 minutes on a hot plate, and then heated at 170 ° C. for 20 minutes in a clean oven to produce a sapphire glass having an antifouling film on the surface.
In Comparative Example 2, a substrate in which the antifouling agent film was directly formed on the sapphire glass substrate was prepared without coating the adhesion film forming agents of Examples and Comparative Examples.

[Abrasion resistance evaluation: Steel wool scratch resistance test]
On the surface of the sapphire glass substrate produced in the above-mentioned examples and comparative examples held on the table of a reciprocating scratch resistance tester (manufactured by Daiei Kagaku Seiki Seisakusho), steel wool of # 0000 grade (Japan) Steel Wool Co., Ltd. (registered trademark: Bonster) was placed in contact with a square pad with an area of 2 cm ² , and the pad was rubbed from 0 reciprocations to 1000 reciprocations at an applied load of 1,000 g and a speed of 25 reciprocations per minute. . The contact angle of water with a liquid volume of 3 μL was measured using a contact angle meter (DM-701, manufactured by Kyowa Interface Science Co., Ltd.) every 200 reciprocations of friction. The measurement results are summarized in Table 1.

As shown in Table 1, the sapphire-coated sapphire glass substrates of Examples 1 and 2 had a water contact angle of 90 ° or more and a change from the initial of 20 ° even when 800 round-trip steel wool friction was performed. It was confirmed that good scratch resistance was obtained.
On the other hand, the sapphire glass substrate with antifouling agent of Comparative Examples 1 and 2 had a water contact angle of less than 90 ° and decreased by 20 ° or more due to 800 reciprocating steel wool friction.

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

  In addition, the entire content of the specification, claims, drawings and abstract of Japanese Patent Application No. 2014-111610 filed on May 29, 2014 is cited here as disclosure of the specification of the present invention. Incorporated.

DESCRIPTION OF SYMBOLS 1 Cover glass for touchscreens 2 Functional film 3 Adhesion film layer 4 Sapphire glass substrate

Claims (10)

  An adhesive film-forming agent for an aluminum oxide or aluminum substrate, comprising a hydrolyzed / condensed product of alkoxysilane and an aluminum salt. The hydrolysis / condensation product of alkoxysilane is a hydrolysis / condensation product of alkoxysilane containing at least one selected from the group consisting of alkoxysilanes represented by the following formulas (I) and (II): The adhesive film forming agent described.
(Chemical formula 1)
Si (OR ¹ ) ₄ (I)
(Chemical formula 2)
R ² _m Si (OR ³ ) _4-m (II)
In the above formulas (I) and (II), R ¹ and R ³ each independently represent an alkyl group having 1 to 5 carbon atoms, and R ² represents a halogen atom, a vinyl group, a methacryloxy group, an acryloxy 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 styryl group, a phenyl group, and a cyclohexyl group, and may have a hetero atom, a hydrogen atom, a halogen atom Atom, vinyl group, methacryloxy group, acryloxy group, styryl group, phenyl group, cyclohexyl group, amino group, glycidoxy group, mercapto group, isocyanate group or ureido group are represented. m represents an integer of 1 to 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 adhesion film forming agent according to claim 1 or 2, which is a seed.   The adhesion film forming agent according to claim 1, wherein the aluminum salt is an aluminum nitrate salt.   The molar ratio (Al / (Si + Al)) of aluminum atoms to the total number of moles of silicon atoms (Si) and moles of aluminum atoms (Al) is 0.1 to 0.5. The adhesive film formation agent of any one of these.   The precipitation inhibitor 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. The adhesion film forming agent according to any one of -5.   The film obtained using the contact | glue film-forming agent of any one of Claims 1-6.   An aluminum oxide substrate or an aluminum substrate having the coating according to claim 7.   A touch panel having the coating according to claim 7.   The formation of the adhesion film for aluminum oxide or aluminum substrate which bakes the coating film which apply | coated the adhesion film formation agent of any one of Claims 1-6 to an aluminum oxide substrate or an aluminum substrate at 100-600 degreeC. Method.

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