CN106536651B - Adhesive coating forming agent for alumina substrate or aluminum substrate - Google Patents

Adhesive coating forming agent for alumina substrate or aluminum substrate Download PDF

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Publication number
CN106536651B
CN106536651B CN201580040161.6A CN201580040161A CN106536651B CN 106536651 B CN106536651 B CN 106536651B CN 201580040161 A CN201580040161 A CN 201580040161A CN 106536651 B CN106536651 B CN 106536651B
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aluminum
alumina substrate
forming agent
substrate
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CN106536651A (en
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大田政太郎
饭沼洋介
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Nissan Chemical Corp
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Nissan Chemical Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
    • B05D3/0254—After-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B18/00—Layered products essentially comprising ceramics, e.g. refractory products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C04B41/85—Coating or impregnation with inorganic materials
    • C04B41/87—Ceramics
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/28—Nitrogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means

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Abstract

Provided is an agent for forming an adhesion coating film for an alumina substrate or an aluminum substrate, which can form a film by a wet coating method. An adhesion coating forming agent for an alumina substrate or an aluminum substrate, comprising: comprises a hydrolysis condensate of at least 1 alkoxysilane component selected from alkoxysilanes represented by the following formulas (I) and (II), and an aluminum salt. (chemical formula 1) Si (OR)1)4(I) (chemical formula 2) R2 mSi(OR3)4‑m(II)，R1And R3Each independently represents an alkyl group having 1 to 5 carbon atoms, R2Represents a hydrogen atom or the like, and m represents an integer of 1 to 3.

Description

Adhesive coating forming agent for alumina substrate or aluminum substrate
Technical Field
The present invention relates to an adhesion coating forming agent for alumina substrates such as sapphire glass or for aluminum substrates.
Background
Sapphire glass is a single-crystal alumina having excellent properties such as being very hard, transparent, heat-resistant, and insoluble in chemicals. Due to the characteristics of high hardness and difficulty in scratching, the sapphire glass can be used for cover glass (windshield) of a clock, cover glass of a camera lens, and a touch panel substrate of a smart phone or a tablet computer.
In order to improve the scratch resistance of a base material which is not easily scratched when the base material is rubbed with another substance, a technique of coating an antifouling agent such as a fluorine-based compound or a silicon-based compound on the surface of a member such as glass is also known. By applying the antifouling agent, the smoothness of the surface is improved, and even if an impact is applied, the impact can be alleviated by utilizing the smoothness, and excellent scratch resistance can be obtained. In addition, the coating of the antifouling agent can also provide water-repellent, oil-repellent and fingerprint-resistant effects.
When the antifouling agent is applied to the sapphire glass, it is expected that the high hardness of the sapphire glass and the slip effect of the antifouling layer can provide remarkably excellent scratch resistance. However, alumina such as sapphire glass generally has poor adhesion to an antifouling agent, and thus expected abrasion resistance cannot be obtained. To avoid this problem, formation of alumina (Al) by a dry coating method under vacuum has been reported in the past2O3) With silicon dioxide (SiO)2) The method of (1) for adhesion of an auxiliary layer.
In addition, it is reported that silicon oxide (SiO) is sputtered on sapphire glass2) And a technique of forming a silicon nitride (SiNx) film and then forming an antifouling layer (patent document 2). Film formation by a dry coating method such as sputtering, PVD (Physical Vapor Deposition), CVD (Chemical Vapor Deposition) or the like is performed in a vacuum vessel, and requires expensive large-scale equipment. In addition, there is a problem that the size and shape of the substrate 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 spray can be performed at low cost and high speed. However, a wet coating method that can sufficiently adhere to alumina is not known, and a dry coating method is required to form a film at high cost in order to apply an antifouling agent.
Documents of the prior art
Patent document
Patent document 1: U.S. patent publication 2014/0087197A1
Patent document 2: japanese patent No. 5435168
Disclosure of Invention
Problems to be solved by the invention
An object of the present invention is to provide an adhesion coating film forming agent for an alumina substrate or an aluminum substrate, which can be formed by a wet coating method while exhibiting an effect of improving adhesion between an alumina substrate or an aluminum substrate such as sapphire glass when a functional film such as an antifouling agent is provided on the alumina substrate or the aluminum substrate.
Means for solving the problems
The present inventors have conducted intensive studies to achieve the above object, and as a result, have completed the present invention having the following gist.
1. An alumina substrate or an adhesion coating forming agent for an alumina substrate, characterized by containing a hydrolysis condensate of alkoxysilane and an aluminum salt.
2. The adhesive coating forming agent according to the above 1, wherein the hydrolysis condensate of the alkoxysilane is a hydrolysis condensate containing at least 1 alkoxysilane component selected from alkoxysilanes represented by the following formulas (I) and (II).
Si(OR1)4 (I)
R2 mSi(OR3)4-m (II)
In the above formulae (I) and (II), R1And R3Each independently represents an alkyl group having 1 to 5 carbon atoms, R2Represents an optionally selected halogen atom, vinyl group, methacryloxy groupAt least 1 kind of substituted hydrocarbyl of 1-20 carbon atoms in the group formed by acryloxy, styryl, phenyl and cyclohexyl and optionally have heteroatom, hydrogen atom, halogen atom, vinyl, methacryloxy, acryloxy, styryl, phenyl, cyclohexyl, amino, epoxy propoxy, sulfydryl, isocyanate group or ureido. m represents an integer of 1 to 3.
3. The adhesion coating forming agent according to the above 1 or 2, wherein the aluminum salt is at least 1 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.
4. An adhesion coating forming agent according to any one of the above 1 to 3, wherein the aluminum salt is an aluminum nitrate salt.
5. The adhesive coating forming agent according to any one of the above 1 to 4, wherein a molar ratio (Al/(Si + Al)) of aluminum atoms to a total of a total number of moles (Si) of silicon atoms and a number of moles (Al) of aluminum atoms is 0.1 to 0.5.
6. The adhesive coating forming agent according to any one of the above 1 to 5, further comprising at least 1 selected from the group consisting of N-methyl-pyrrolidone, ethylene glycol, dimethylformamide, dimethylacetamide, diethylene glycol, propylene glycol, hexylene glycol, and derivatives thereof as a precipitation inhibitor.
7. A coating film obtained by using the adhesive coating forming agent according to any one of the above 1 to 6.
8. An alumina substrate or an aluminum substrate having the adhesive coating film of the above 7.
9. A touch panel comprising the adhesive coating of claim 7.
10. A method for forming a sealing coating film for an alumina substrate or an aluminum substrate, wherein a coating film obtained by applying the sealing coating film-forming agent of any one of 1 to 6 above to an alumina substrate or an aluminum substrate is baked at 100 to 600 ℃.
ADVANTAGEOUS EFFECTS OF INVENTION
The adhesive coating forming agent of the present invention can be applied to an alumina substrate or an aluminum substrate such as sapphire glass by coating or the like to form a coating, and a functional film such as an antifouling agent is formed thereon, thereby imparting excellent characteristics such as scratch resistance. For example, according to the present invention, a cover glass for a touch panel having excellent stain resistance and scratch resistance can be obtained. Since the surface of the metal aluminum is oxidized in the air to form an aluminum oxide film, the adhesion film forming agent of the present invention can also be used for the application to a metal aluminum substrate.
Drawings
Fig. 1 is a schematic cross-sectional view of a cover glass for a touch panel, which is a typical example of an alumina substrate obtained by using the adhesive coating forming agent of the present invention.
Detailed Description
The adhesive coating forming agent of the present invention contains a hydrolysis-condensation product of alkoxysilane (a) and an aluminum salt (B).
< component (A) >
The hydrolysis-condensation product of the alkoxysilane as the component (a) is a hydrolysis-condensation product containing at least 1 alkoxysilane component selected from alkoxysilanes represented by the following formulae (I) and (II).
Si(OR1)4 (I)
R1Represents an alkyl group having 1 to 5 carbon atoms. From the viewpoint of reactivity, as OR1Preferably methoxy, ethoxy or propoxy.
Specific examples of the alkoxysilane represented by the formula (I) are mentioned, but the alkoxysilane is not limited to these. Examples thereof include tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetra-n-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra-tert-butoxysilane, and tetrapentyloxysilane.
When the alkoxysilane represented by the formula (I) is 40 mol% or less based on the total alkoxysilane, sufficient hardness may not be obtained, and therefore, it is preferably 40 mol% or more. More preferably 50 mol% or more. More preferably 80 mol% or more.
R2 mSi(OR3)4-m (II)
R2Represents a hydrocarbon group having 1 to 20 carbon atoms which is optionally substituted with at least 1 kind 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 which optionally has 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 ureido group. In addition, R is1、R2And R3When there are plural, R1、R2And R3The above definitions are expressed independently of one another.
R3Represents an alkyl group having 1 to 5 carbon atoms, and m represents an integer of 1 to 3. In addition, R is3When there are plural, R3The above definitions are expressed independently of one another. From the viewpoint of reactivity, as OR3Preferably methoxy or ethoxy.
Specific examples of the alkoxysilane represented by the formula (II) are mentioned, but the alkoxysilane is not limited to these. Examples thereof include 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, acryloxyethyltrimethoxysilane, acryloxyethyltriethoxysilane, styrylethyltrimethoxysilane, styrylethyltriethoxysilane, 3- (N-styrylmethyl-2-aminoethylamino) propyltrimethoxysilane, 4- (trimethoxysilyl) styrene, vinyltrimethoxysilane, vinyltriethoxysilane, 3,3, 3-trifluoropropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-chloropropyltriethoxysilane, 3-bromopropyltriethoxysilane, dimethyldiethoxysilane, dimethyldimethoxysilane, diethyldiethoxysilane, diethyldimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilyltrimethoxysilane, trimethylmethoxysilane, 3- (2-aminoethylaminopropyl) trimethoxysilane, 3- (2-aminoethylaminopropyl) triethoxysilane, 2-aminoethylaminomethyltrimethoxysilane, 2- (2-aminoethylthioethyl) triethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, di-ethyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-mercaptopropyltriethoxysilane, mercaptomethyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropyldimethylethoxysilane, gamma-ureidopropyltriethoxysilane, gamma-ureidopropyltrimethoxysilane, gamma-ureidopropyltripropoxysilane, etc.
From the viewpoint of storage stability and hardness at low-temperature baking, the hydrolysis condensate of the alkoxysilane contained in the adhesion coating forming agent of the present invention is preferably a 5-mer or less, and more preferably a 2-4-mer.
The hydrolytic condensate of the alkoxysilane can be condensed in the presence of a base and water. The amount of the base present is preferably 0.01 to 2 times by mol, more preferably 0.05 to 1 time by mol, based on the alkoxysilane. The amount of water present is preferably 0.5 to 10 times by mol, more preferably 1 to 5 times by mol, based on the alkoxysilane.
< ingredient (B) >
Examples of the aluminum salt contained in the adhesive coating 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, hydrates thereof, and hydrous or basic salts thereof.
Among them, aluminum nitrate is particularly preferable from the viewpoints of easiness of obtaining and storage stability of the film forming agent.
< precipitation preventing agent >
The adhesion coating forming agent of the present invention preferably contains a precipitation inhibitor from the viewpoint of storage stability. The precipitation preventing agent is used for preventing precipitation of an aluminum salt in a coating when the coating is formed by the adhesive coating forming agent of the present invention.
Examples of the precipitation preventing agent include N-methyl-pyrrolidone, ethylene glycol, dimethylformamide, dimethylacetamide, diethylene glycol, propylene glycol, hexylene glycol, and derivatives thereof, and 1 or 2 or more of them may be used or mixed.
< organic solvent >
The adhesive coating forming agent of the present invention generally contains an organic solvent for dissolving or dispersing the components (a) and (B). The organic solvent is preferably dispersed and not left in the formed adhesive coating when the adhesive coating is obtained by forming a coating of the adhesive coating forming agent and heating the coating. Therefore, as the organic solvent, a solvent having a boiling point of preferably 60 to 250 ℃, more preferably 75 to 200 ℃ and capable of dissolving or dispersing the components (a) and (B) well is 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, ether derivatives thereof, ester derivatives thereof, ethers such as diethyl ether, ketones such as acetone, methyl ethyl ketone, and cyclohexanone, and aromatic hydrocarbons such as benzene and toluene. Among them, ethanol, propanol, or propylene glycol monomethyl ether is preferable from the viewpoint of solvent residue and coatability.
< other ingredients >
The adhesive coating forming agent of the present invention may contain components other than the above-described components, for example, components such as inorganic fine particles, a metal siloxane (metaloxane) monomer, a metal siloxane oligomer, a metal siloxane polymer, a crosslinking agent, an organic polymer, a leveling agent, and a surfactant, within a range not to impair the effects of the present invention.
< production of adhesive coating Forming agent >
The adhesive coating forming agent of the present invention is produced by mixing at least 1 selected from alkoxysilanes represented by formulas (I) and (II) as the component (a) with an aluminum salt as the component (B) in an organic solvent containing water. The alkoxysilanes represented by the formulae (I) and (II) undergo hydrolysis/condensation by contact with water, and are converted into a hydrolysis condensate. Thus, the adhesive coating forming agent of the present invention can be obtained in the form of a composition containing a hydrolysis-condensation product of alkoxysilane and an aluminum salt dissolved or dispersed in an organic solvent.
The organic solvent used here may be the same as the organic solvent contained in the adhesive coating forming agent of the present invention, including preferable characteristics.
The content of each component in the adhesive coating forming agent of the present invention is preferably 0.1 to 20% by mass, more preferably 0.5 to 6% by mass, in terms of the solid content of the metal oxide, of both the hydrolysis-condensation product of the alkoxysilane as the component (a) and the aluminum salt as the component (B). When the content exceeds 20% by mass, the storage stability of the composition is deteriorated and the control of the film thickness of the protective film to be formed is difficult. On the other hand, if the amount is 0.1 mass% or less, the thickness of the obtained protective film becomes thin, and it is necessary to form a coating film a plurality of times in order to obtain a predetermined film thickness, which complicates the production of an adhesive coating film.
The amount of water used for hydrolysis of the alkoxysilane as the component (a) is preferably 0.5 or more, more preferably 1 to 5 in terms of a molar ratio (amount of water (mole))/total mole of the alkoxysilane used. When the molar ratio is 0.5 or more, the alkoxysilane is sufficiently hydrolyzed to improve the film forming property, and the strength of the obtained adhesive coating film is increased.
In the hydrolysis, when a water-containing salt of an aluminum salt as the component (B) coexists, the water content of the salt is involved in the reaction, and therefore, the water content of the metal salt needs to be calculated for the amount of water used in the hydrolysis.
The hydrolysis of the alkoxysilane is preferably carried out at a temperature in the range of 20 to 100 ℃. Among them, from the viewpoint of obtaining a condensate having an appropriate molecular weight, the temperature is more preferably in the range of 25 to 80 ℃. The hydrolysis time is preferably 30 minutes to 48 hours, and 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 in the hydrolysis/condensation reaction of alkoxysilane in the presence of an aluminum salt, or may be added after completion of the hydrolysis/condensation reaction.
The precipitation inhibitor is preferably 1 or more, more preferably 2 to 20, in terms of aluminum of the aluminum salt to alumina (precipitation inhibitor/alumina). When the ratio is less than 1, the effect of preventing the metal salt from being precipitated during the formation of a coating film is small.
The content ratio of the hydrolyzed condensate of the alkoxysilane as the component (a) and the aluminum salt as the component (B) contained in the adhesive coating forming agent of the present invention is preferably 0.1 to 0.5, more preferably 0.2 to 0.4, in terms of the molar ratio (Al/(Si + Al)) of aluminum atoms to the total of the total number of moles of silicon atoms (Si) and the number of moles of aluminum atoms (Al). When the molar ratio is 0.1 or more and 0.5 or less, the intended adhesion property can be improved.
< sealing coating film >
The adhesive coating forming agent of the present invention is applied to a substrate, such as an alumina substrate or an aluminum substrate, the surface of which is covered with alumina, and is baked, thereby obtaining an adhesive coating on the surface of the substrate.
The method of forming a coating film on a substrate surface using the adhesive coating forming agent of the present invention can be carried out by various coating methods. 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, or the like can be used.
Next, the coating film formed on the surface of the substrate is dried by heating at a temperature of, for example, 50 to 100 ℃, preferably 60 to 80 ℃, and then baked at a temperature of 100 ℃ or higher, preferably 100 to 600 ℃, more preferably 300 to 600 ℃ for 10 minutes or longer, preferably 0.5 to 2 hours, whereby a close-contact coating film having a dense film structure can be obtained. These heat treatments can be performed using an oven, a hot plate, or the like. The heating for drying the coating film may be omitted.
In the above-described manner, the coating is formed on the alumina substrate by the adhesive coating forming agent of the present invention. The adhesion coating film can function as an adhesion auxiliary layer for forming a coating agent for forming a coating film having various properties on the surface thereof. For example, when an antifouling agent is used as the coating agent, an alumina substrate having a coating film with excellent scratch resistance on the surface can be obtained.
< alumina substrate >
The adhesive coating forming agent of the present invention is used for forming an adhesive coating on the surface of an alumina substrate or an aluminum substrate. That is, an adhesive coating is formed on the surface of the alumina substrate, and then a functional film obtained from a specific coating agent is formed on the surface of the adhesive coating. The adhesive coating is formed directly on the surface of the alumina substrate by the adhesive coating 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. The substrate used was sapphire glass, on which the coating film obtained from the adhesive coating film forming agent of the present invention was formed, and then the coating film 2 obtained from the antifouling agent was formed, thereby obtaining excellent scratch resistance.
The thickness of the adhesion coating film and the functional film is preferably 5 to 1000nm, more preferably 10 to 400 nm.
The adhesive coating forming agent of the present invention is effective for alumina having various crystal structures. In addition to sapphire glass, which is a single crystal alumina, it can be used for polycrystalline or amorphous alumina.
Further, since the surface of the metal aluminum is oxidized in the air to form an aluminum oxide film, the adhesion film forming agent of the present invention can be used for a structure formed of a metal aluminum substrate.
In the present invention, the functional film provided on the adhesive coating is not particularly limited. Specific examples thereof include coatings obtained from antifouling agents, paints, adhesives, antireflection agents, water-repellent agents, hydrophilic agents, oil-repellent agents, hard coating agents, and anti-slip materials.
< cover glass for touch Panel >
As a typical example of the alumina substrate obtained by using the adhesive coating forming agent of the present invention, a cover glass for a touch panel shown in fig. 1 can be mentioned. 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 on the surface of a sapphire glass 4 with an adhesive coating 3 interposed therebetween. The adhesive coating 3 is a coating formed directly on the surface of the sapphire glass using the adhesive coating 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.
By forming an adhesive coating film obtained from the coating film forming agent of the present invention on sapphire glass and then forming a film of the antifouling agent, the antifouling agent can be maintained on the sapphire glass even by rubbing with fingers or objects. This can prevent deterioration of scratch resistance, water repellency, and oil repellency, and a problem of fingerprints when the touch panel is used.
Examples
The present invention will be specifically explained below with reference to examples, but the present invention is not to be construed as being limited thereto.
[ Compound and abbreviation ]
TEOS: tetraethoxysilane AN: aluminum nitrate nonahydrate
EtOH: ethanol PGME: propylene glycol monomethyl ether
HG: hexanediol PB: propylene glycol monobutyl ether
BCS: ethylene glycol monobutyl ether
Antifouling agent: p-5425-0.2 manufactured by FT-Net
< example 1 >
EtOH (22.49g), water (7.42g) and AN (12.88g) were put into a four-necked reaction flask and stirred. Subsequently, EtOH (28.60g) and TEOS (28.60g) were charged, and the mixture was stirred at 20 ℃ for 1 hour to prepare a solution.
This solution (30g) was mixed with HG (14g), PB (10.5g), BCS (10.5g) and PGME (35g) to obtain an adhesive film-forming agent.
< example 2 >
EtOH (22.93g), water (6.6g) and AN (19.62g) were put into a four-necked reaction flask and stirred. Subsequently, EtOH (25.43g) and TEOS (25.43g) were charged, and stirred in a water bath for 1 hour to prepare a solution.
This solution (30g) was mixed with HG (14g), PB (10.5g), BCS (10.5g) and PGME (35g) to obtain an adhesive film-forming agent.
< comparative example 1 >
EtOH (33.87g) and TEOS (34.72g) as an alkoxysilane were put into a four-necked reaction flask equipped with a reflux tube, and stirred. Subsequently, EtOH (16.94g), water (13.6g) and an aqueous solution (0.88g) containing 60 wt% nitric acid were added dropwise over 30 minutes, and the mixture was stirred. Then, it was refluxed for 3 hours and naturally cooled to room temperature to prepare a solution.
This solution (30g) was mixed with HG (14g), PB (10.5g), BCS (10.5g) and PGME (35g) to obtain an adhesive film-forming agent.
[ production of sapphire glass having antifouling agent film ]
The adhesive coating forming agents of examples 1 and 2 and comparative example 1 were applied to sapphire glasses (single crystal sapphire glass, surface roughness:below) was dried on a hot plate at 80 ℃ for 3 minutes. Then, the film was heated at 150 ℃ or 300 ℃ for 30 minutes in a dust-free oven to obtain a sealing film having a thickness of 50 to 100nm for each of examples and comparative examples.
Next, an antifouling agent, which was a coating agent for forming a functional film, was applied to the substrate with the adhesive coating film obtained in examples and comparative examples using a spin coater. Then, the glass was dried on a hot plate at 80 ℃ for 3 minutes, and then heated in a dust-free oven at 170 ℃ for 20 minutes, thereby producing a sapphire glass having an antifouling agent film on the surface.
In comparative example 2, a substrate in which an antifouling agent film was directly formed on a sapphire glass substrate was produced without performing coating using the adhesive coating forming agent of the examples and comparative examples.
[ abrasion resistance evaluation: steel wool scratch resistance test
The surface of the sapphire glass substrate produced in the above examples and comparative examples, which was held on the stage of a reciprocating scratch resistance tester (manufactured by Daorhiki Seisaku Seisakusho Co., Ltd.), was bonded to a glass substrate having an area of 2cm2Square pad jointA steel wool of #0000 grade (BON STAR, registered trademark, manufactured by Nippon Steel wool Co., Ltd.) was placed on the pad in a touching manner, and the pad was rubbed from 0 to 1000 reciprocations at a speed of 1000g applied load and 25 reciprocations per minute. The contact angle of water was measured at a liquid volume of 3. mu.L using a contact angle meter (DM-701, manufactured by Kyowa Kagaku K.K.) for every 200 cycles of rubbing. The measurement results are shown in table 1.
[ Table 1]
As shown in table 1, the sapphire glass substrates with an antifouling agent of examples 1 and 2 had a water contact angle of 90 ° or more and a change from the initial value of less than 20 ° even when they were subjected to 800 reciprocal steel wool rubs, and it was confirmed that good scratch resistance was obtained.
On the other hand, the sapphire glass substrates with the antifouling agents of comparative examples 1 and 2 had a water contact angle of less than 90 ° and decreased by 20 ° or more due to 800-time reciprocal steel wool rubbing.
Industrial applicability
The alumina substrate having an antifouling film as a functional film formed by sandwiching a coating film obtained from the adhesive coating film forming agent of the present invention has excellent abrasion resistance, and can be used as a cover glass (windshield) for a timepiece, a cover glass for a camera lens, a touch panel substrate for a smartphone, a tablet computer, or the like.
The entire contents of the specification, claims, drawings and abstract of the specification of japanese patent application 2014-111610, which is filed on 5/29/2014, are incorporated herein as the disclosure of the present invention.
Description of the reference numerals
1 cover glass for touch Panel 2 functional film
3 sealing coating layer 4 sapphire glass substrate

Claims (6)

1. An alumina substrate characterized by having a coating film obtained from an adhesion coating film-forming agent containing a hydrolysis condensate of alkoxysilane and an aluminum salt, and a functional film obtained from an antifouling agent, wherein the molar ratio (Al/(Si + Al)) of aluminum atoms to the total of the total number of moles (Si) of silicon atoms and the number of moles (Al) of aluminum atoms is 0.2 ~ 0.4.4.
2. The alumina substrate according to claim 1, wherein the hydrolytic condensate of an alkoxysilane is a hydrolytic condensate of an alkoxysilane containing at least 1 selected from the group consisting of alkoxysilanes represented by the following formulae (I) and (II),
Si（OR1）4 （I）
R2 mSi（OR3）4-m （II）
in the above formulae (I) and (II), R1And R3Each independently represents an alkyl group having 1 ~ 5 carbon atoms, R2Represents a hydrocarbon group of carbon number 1 ~ 20 optionally substituted with at least 1 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 optionally having 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 ureido group, and m represents an integer of 1 ~ 3.
3. The alumina substrate according to claim 1 or 2, wherein the aluminum salt is at least 1 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.
4. The alumina substrate according to claim 1 or 2, wherein the aluminum salt is an aluminum nitrate salt.
5. The alumina substrate according to claim 1 or 2, wherein the adhesion coating film forming agent further contains at least 1 selected from the group consisting of N-methyl-pyrrolidone, ethylene glycol, dimethylformamide, dimethylacetamide, diethylene glycol, propylene glycol, hexylene glycol, and derivatives thereof as a precipitation preventing agent.
6. The method for producing an alumina substrate according to claim 1 ~ 5, wherein the method comprises applying the adhesive coating forming agent to a coating film formed on the alumina substrate and baking the coating film at 100 ~ 600 ℃.
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