WO2013115333A1 - Coating solution for metal oxide film and metal oxide film - Google Patents
Coating solution for metal oxide film and metal oxide film Download PDFInfo
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- WO2013115333A1 WO2013115333A1 PCT/JP2013/052254 JP2013052254W WO2013115333A1 WO 2013115333 A1 WO2013115333 A1 WO 2013115333A1 JP 2013052254 W JP2013052254 W JP 2013052254W WO 2013115333 A1 WO2013115333 A1 WO 2013115333A1
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
- C23C18/1208—Oxides, e.g. ceramics
- C23C18/1212—Zeolites, glasses
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
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- 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
- C09D183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
- C23C18/1208—Oxides, e.g. ceramics
- C23C18/1216—Metal oxides
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
- C23C18/122—Inorganic polymers, e.g. silanes, polysilazanes, polysiloxanes
Definitions
- the present invention relates to a coating solution for metal oxide coating and a metal oxide coating obtained therefrom.
- the touch panel detects the contact position of the operation surface touched by a finger or a pen. Using this function, the touch panel is used as an input device.
- Examples of the contact position detection method include a resistance film method and a capacitance method.
- the electrostatic capacity method is mainly used from the viewpoints of durability, transmittance, cost, design and the like of the touch panel.
- the electrical wiring film and electrodes of the touch panel are required to have corrosion resistance, heat resistance, adhesion to the substrate, low resistance, high etching property, and the like.
- Cr, Mo, W, or the like can be considered as an element for forming a thin film wiring for an electronic component.
- a wiring material made of an alloy of a refractory metal has been proposed.
- thin film wiring for electronic parts using Mo—Nb alloy is mainly used at present, but it is not sufficient in terms of corrosion resistance (see Patent Document 1).
- the touch panel is incorporated in a display device such as a liquid crystal display device, and is used as a display device with a touch panel function capable of detecting a touch position. Since a person who operates the touch panel visually recognizes the display device through the touch panel, a member having excellent light transmission characteristics is used for the electrode. For example, an inorganic material such as ITO (Indium Tin Oxide) is used. As such a protective film for protecting the electric wiring film and electrodes of the touch panel, a sputtered film of SiO X has been used. However, it was expensive and problematic. Therefore, recently, a coating-type metal oxide film has been used. However, when a coating-type metal oxide film is used, there is a problem that Mo and Mo—Nb are easily corroded.
- ITO Indium Tin Oxide
- the object of the present invention is to provide a coating solution that can maintain the properties of the current metal oxide coating and obtain a metal oxide coating that has the ability to inhibit corrosion of Mo, and a metal oxide obtained from the coating solution. It is to provide a physical coating.
- the present inventor conducted extensive studies to solve the above problems, and found that the problems can be solved by introducing a certain amount or more of a silane coupling agent having a specific organic group and aluminum nitrate. .
- the present invention has the following gist.
- R 2 l M 2 (OR 3 ) 4-1 (II)
- M 2 represents silicon (Si)
- R 2 may be substituted with a hydrogen atom or a fluorine atom, and a halogen atom, a vinyl group, a methacryloxy group, an acryloxy group, a styryl group, a phenyl group, Alternatively, it represents a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a cyclohexyl group or the like and may have a hetero atom
- R 3 represents an alkyl group having 1 to 5 carbon atoms.
- the metal alkoxide represented by the formula (I) or the metal alkoxide represented by (II) is selected from the group consisting of silicon alkoxide, partial polycondensate of silicon alkoxide, titanium alkoxide and partial polycondensate of titanium alkoxide.
- the coating solution for a metal oxide film according to (1) which is at least one kind.
- the metal alkoxide represented by the formula (I) is contained in an amount of 0.5 to 61.5 mol% based on the total number of moles of the formula (I), the formula (II) and the formula (III) used.
- the metal alkoxide represented by the formula (II) is contained in an amount of 38 mol% or more based on the total number of moles of the formula (I), the formula (II) and the formula (III) used.
- the metal salt represented by the formula (III) is contained in an amount of 0.5 to 61.5 mol% based on the total number of moles of the formula (I), the formula (II) and the formula (III) used.
- the content of the precipitation inhibitor is converted into the metal oxide of the metal salt of the formula (III),
- the molar ratio of the total (M 1 + M 2 + M 3 ) of all metal atoms contained in the coating solution for metal oxide coating and the metal atom (M 3 ) of the metal salt is: [Equation 1] 0.01 ⁇ M 3 / (M 1 + M 2 + M 3 ) ⁇ 0.7
- the coating liquid for metal oxide films which can maintain the characteristic of the current metal oxide film, and can obtain the metal oxide film which has the corrosion inhibition ability of Mo, and a metal oxide film are provided.
- the reason why such a metal oxide film is obtained by the coating solution for metal oxide film of the present invention is not necessarily clear, but the following can be considered.
- a dense metal layer is formed in the lower layer of the coating due to the polycondensate having a specific organic group, and as a result, a coating that does not corrode Mo can be obtained. .
- a coating solution for metal oxide coating (hereinafter also referred to as coating solution) used to form a metal oxide coating is obtained by hydrolyzing and polycondensing a metal alkoxide in an organic solvent in the presence of a metal salt. It is obtained by adding a precipitation inhibitor.
- M 1 is silicon (Si), titanium (Ti), tantalum (Ta), zirconium (Zr), boron (B), aluminum (Al), magnesium (Mg), tin (Sn) and zinc (Zn And R 1 represents an alkyl group having 1 to 5 carbon atoms, and n represents a valence of M 1 ) and a formula (II), R 2 l M 2 (OR 3 ) 4-1 (II) (Wherein M 2 represents silicon (Si), R 2 may be substituted with a hydrogen atom or a fluorine atom, and a halogen atom, a vinyl group, a methacryloxy group, an acryloxy group, a styryl group, a phenyl group, Alternatively, it represents a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a cyclohexyl group or the like and may have
- M 3 represents a metal
- X represents chlorine, nitric acid, sulfuric acid, acetic acid, sfamic acid, sulfonic acid, acetoacetic acid, acetylacetonate or a basic salt thereof
- m represents the valence of M 3.
- It is a coating solution obtained by hydrolysis and polycondensation in an organic solvent in the presence of a metal salt represented by formula (III) or a metal oxalate used in formula (III), and further adding a precipitation inhibitor. .
- M 1 in formula (I) includes silicon (Si), titanium (Ti) tantalum (Ta), zirconium (Zr), boron (B), aluminum (Al), magnesium (Mg), zinc (Zn), and the like. Can be mentioned. Of these, silicon alkoxide, silicon alkoxide partial polycondensate, titanium alkoxide and titanium alkoxide partial polycondensate are selected from the viewpoint of availability and storage stability of the coating solution for metal oxide coatings. It is preferable that it is at least one kind.
- R 1 in the formula (I) is an alkyl group having 1 to 5 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms. Particularly preferred is an alkyl group having 1 to 3 carbon atoms.
- the metal alkoxide represented by the formula (I) is contained in an amount of 0.5 to 61.5 mol% based on the total number of moles of the formula (I), the formula (II) and the formula (III) used.
- the content is preferably 5.0 to 57.0 mol%, and more preferably.
- n represents the valence of M 1 but is preferably 2 to 5.
- R 2 in formula (II) may be substituted with a hydrogen atom or a fluorine atom, and may be substituted with a halogen atom, a vinyl group, a methacryloxy group, an acryloxy group, a styryl group, a phenyl group, or a cyclohexyl group.
- a hydrocarbon group having 1 to 20 carbon atoms which may have a hetero atom.
- a methacryloxy group or a hydrocarbon group having 1 to 20 carbon atoms substituted with an acryloxy group is preferable.
- the metal alkoxide represented by the formula (II) is contained in an amount of 38 mol% or more based on the total number of moles of the formula (I), the formula (II) and the formula (III) used. More preferably, it is 43 mol% or more. Among these, 45 to 99 mol% is more preferable.
- R 3 in the formula (II) is an alkyl group having 1 to 5 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms. Particularly preferred is an alkyl group having 1 to 3 carbon atoms.
- 1 in formula (II) is preferably 1 to 3.
- alkoxysilane represented by Formula (II) is not limited to these.
- metal alkoxide represented by the formula (II) used in the coating liquid of the present invention metal alkoxides having other functional groups can be used as long as the effects of the present invention are not impaired.
- other functional groups include amino groups, glycidoxy groups, mercapto groups, isocyanate groups, and ureido groups, and hydrophilic functional groups are preferred.
- Specific examples of the alkoxysilane represented by the formula (II) are given below, but the invention is not limited thereto.
- 3- (2-aminoethylaminopropyl) trimethoxysilane 3- (2-aminoethylaminopropyl) triethoxysilane, 2-aminoethylaminomethyltrimethoxysilane, 2- (2-aminoethylthioethyl) Triethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-mercaptopropyltriethoxysilane, mercaptomethyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyl
- the metal salt used in the coating solution of the present invention includes the following formula (III) M 3 (X) m (III) (In the formula, M 3 represents a metal, X represents chlorine, nitric acid, sulfuric acid, acetic acid, succinic acid, succinic acid, sulfonic acid, acetoacetic acid, acetylacetonate, or a basic salt thereof, and m represents the value of M 3 . Or a mixture of two or more of the metal oxalates used in formula (III). Of these, metal nitrates, metal chloride salts, metal oxalates and basic salts thereof are preferred, and metal nitrates are particularly preferred.
- metal forming the metal nitrate aluminum (Al), indium (In), zinc (Zn), zirconium (Zr), bismuth (Bi), lanthanum (La), tantalum (Ta), yttrium (Y) And cerium (Ce).
- metal salt represented by the formula (III) is contained in an amount of 0.5 to 61.5 mol% based on the total number of moles of the formula (I), the formula (II) and the formula (III) used. Preferably, it is contained in an amount of 5.0 to 57.0 mol%.
- the coating solution of the present invention contains a precipitation inhibitor.
- the precipitation inhibitor has an effect of preventing the metal salt from being precipitated in the coating film when the coating film is formed. Specifically, it is preferably 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 precipitation inhibitor is preferably used in a mass ratio of (precipitation inhibitor / metal oxide) ⁇ 1 when the metal of the metal salt represented by the formula (III) is converted into an oxide.
- this mass ratio is less than 1, the effect of preventing precipitation of the metal salt during formation of the coating film is reduced.
- In the mass ratio in terms of precipitation inhibitor and metal oxide preferably 1 ⁇ (precipitation inhibitor / metal oxide) ⁇ 199.
- Anti-precipitation agents are added when a metal alkoxide composed of a metal such as silicon, titanium, tantalum, zirconium, boron, aluminum, magnesium, tin, or zinc undergoes hydrolysis or polycondensation reaction in the presence of a metal salt. Alternatively, it may be added after completion of the hydrolysis / polycondensation reaction.
- Examples of the method for polycondensation of metal alkoxides in the present invention include, for example, metal alkoxides of formula (I) and formula (II) in a solvent such as alcohol or glycol in the presence of a metal salt of formula (III). Examples of the method include hydrolysis and polycondensation.
- acids such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, succinic acid, maleic acid, fumaric acid; alkalis such as ammonia, methylamine, ethylamine, ethanolamine, triethylamine;
- a catalyst such as a metal salt such as hydrochloric acid, sulfuric acid or nitric acid is used.
- the metal salt represented by the formula (III) has a function as a catalyst.
- reaction temperature is preferably in the range of 5 to 100 ° C, more preferably in the range of 10 to 80 ° C, and still more preferably in the range of 15 to 60 ° C.
- reaction time is preferably in the range of 5 minutes to 6 hours, more preferably in the range of 10 minutes to 5 hours.
- the polysiloxane polymerization solution (hereinafter also referred to as polymerization solution) obtained by the above method is a concentration obtained by converting silicon atoms of all alkoxysilanes charged as raw materials into SiO 2 (hereinafter referred to as SiO 2 conversion concentration). ) Is generally 20% by mass or less. By selecting an arbitrary concentration within this concentration range, gel formation can be suppressed and a homogeneous solution can be obtained. Also in the present invention, the polysiloxane concentration range is preferably 20% by mass or less in terms of SiO 2 , particularly preferably 0.5% by mass to 20% by mass.
- organic solvent used in the coating liquid of the present invention examples include alcohols such as methanol, ethanol, propanol and butanol; esters such as ethyl acetate; glycols such as ethylene glycol; or ether derivatives thereof; or ester derivatives thereof; And ethers such as diethyl ether; ketones such as acetone, methyl ethyl ketone, and cyclohexanone; aromatic hydrocarbons such as benzene and toluene; These may be used alone or in combination.
- alkylene glycols or monoethers thereof are included from the viewpoint of stabilizing the metal alkoxide component composed of metals such as titanium, tantalum, zirconium, boron, aluminum, magnesium, tin, and zinc to improve the storage stability of the coating solution. It is desirable.
- alkylene glycols or monoethers thereof examples include ethylene glycol, diethylene glycol, propylene glycol, hexylene glycol, or monomethyl, monoethyl, monopropyl, monobutyl, and monophenyl ether thereof.
- these glycols or monoethers thereof have a molar ratio of less than 1 with respect to a metal alkoxide composed of a metal such as titanium, tantalum, zirconium, boron, aluminum, magnesium, tin, and zinc, the stability of these metal alkoxides And the storage stability of the coating solution is deteriorated.
- using a large amount of glycols or monoethers thereof causes no problem.
- all of the organic solvents used in the coating solution for metal oxide coating may be the above-described glycols or monoethers thereof.
- metal alkoxides composed of a metal such as titanium, tantalum, zirconium, boron, aluminum, magnesium, tin, and zinc
- metal alkoxides and alkylene glycols or monoethers thereof are mixed and stabilized, metal alkoxides composed of metals such as titanium, tantalum, zirconium, boron, aluminum, magnesium, tin, and zinc are mixed with silicon alkoxide alone or silicon alkoxide, Hydrolysis and polycondensation in the presence of metal salts.
- the amount of water used for hydrolysis of silicon alkoxide and / or titanium alkoxide is preferably 1 to 24 in terms of molar ratio with respect to the total number of moles of silicon alkoxide and / or titanium alkoxide. More preferably, it is 1-20.
- the molar ratio (amount of water (mole) / (total number of moles of metal alkoxide)) is 1 or less, hydrolysis of the metal alkoxide becomes insufficient, resulting in reduced film formability or obtained metal. This is not preferable because the strength of the oxide film is lowered.
- the molar ratio is more than 24, polycondensation continues to proceed, which is not preferable because storage stability is lowered.
- the coexisting metal salt is a hydrate salt
- the moisture content is involved in the reaction, so the metal relative to the amount of water used for the hydrolysis. It is necessary to consider the moisture content of the salt.
- titanium, tantalum, zirconium, boron that has been stabilized by hydrolyzing silicon alkoxide in the presence of a metal salt and then mixing with glycols or monoethers thereof in advance. It is preferable to mix metal alkoxides made of metals such as aluminum, magnesium, tin, and zinc.
- the molar ratio of the sum of all metal atoms (M 1 + M 2 + M 3) contained in the coating liquid of the present invention, the metal atom of the metal salt (M 3) is [Equation 1] 0.01 ⁇ M 3 / (M 1 + M 2 + M 3 ) ⁇ 0.7 It is preferable to satisfy the relationship. If this value is less than 0.01, the mechanical strength of the resulting coating is not sufficient, which is not preferable. On the other hand, when it exceeds 0.7, the adhesion of the metal oxide film to a substrate such as a glass substrate or a transparent electrode is lowered. Furthermore, when fired at a low temperature of 450 ° C. or lower, the chemical resistance of the resulting metal oxide film tends to be reduced.
- the solid content concentration in the coating liquid of the present invention when the metal alkoxide represented by the formulas (I) and (II) and the metal salt represented by the formula (III) are converted as metal oxides, the solid content Is preferably in the range of 0.5 to 20% by mass.
- the solid content exceeds 20% by mass, the storage stability of the coating solution for metal oxide coating is deteriorated, and it becomes difficult to control the thickness of the metal oxide film.
- the solid content is 0.5% by mass or less, the thickness of the obtained metal oxide film becomes thin, and many coatings are required to obtain a predetermined film thickness.
- the solid content concentration is more preferably 1 to 10% by mass.
- the solid content in the coating solution means SiO2, TiO2, Al2O3, and mixtures and copolymers thereof.
- inorganic fine particles other components such as inorganic fine particles, metalloxane oligomers, metalloxane polymers, leveling agents, and surfactants may be included as long as the effects of the present invention are not impaired.
- inorganic fine particles fine particles such as silica fine particles, alumina fine particles, titania fine particles, and magnesium fluoride fine particles are preferable, and those in a colloidal solution state are particularly preferable.
- the colloidal solution may be a dispersion of inorganic fine particles in a dispersion medium, or a commercially available colloidal solution.
- the inorganic fine particles preferably have an average particle size of 0.001 to 0.2 ⁇ m, more preferably 0.001 to 0.1 ⁇ m. When the average particle diameter of the inorganic fine particles exceeds 0.2 ⁇ m, the transparency of the cured film formed using the prepared coating liquid may be lowered.
- Examples of the dispersion medium for the inorganic fine particles include water and organic solvents.
- the pH or pKa is preferably adjusted to 1 to 10, more preferably 2 to 7, from the viewpoint of the stability of the electrode protective film forming agent.
- Examples of the organic solvent used for the dispersion medium of the colloidal solution include alcohols such as methanol, propanol, butanol, ethylene glycol, propylene glycol, butanediol, pentanediol, hexylene glycol, diethylene glycol, dipropylene glycol, and ethylene glycol monopropyl ether; Ketones such as methyl ethyl ketone and methyl isobutyl ketone; aromatic hydrocarbons such as toluene and xylene; amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone; esters such as ethyl acetate, butyl acetate and ⁇ -butyrolact
- metalloxane oligomer or metalloxane polymer single or composite oxide precursors such as silicon, titanium, aluminum, tantalum, antimony, bismuth, tin, indium, and zinc are used.
- the metalloxane oligomer or metalloxane polymer may be a commercially available product or may be obtained from a monomer such as a metal alkoxide, nitrate, hydrochloride, carboxylate or the like by a conventional method such as hydrolysis. .
- metalloxane oligomers or metalloxane polymers include siloxane oligomers or siloxane polymers such as methyl silicate 51, methyl silicate 53A, ethyl silicate 40, ethyl silicate 48, EMS-485, and SS-101 manufactured by Colcoat.
- titanoxane oligomers such as titanium-n-butoxide tetramer manufactured by Kanto Chemical Co., Inc. You may use these individually or in mixture of 2 or more types.
- a leveling agent, surfactant, etc. can use a well-known thing, and since a commercial item is easy to acquire especially, it is preferable.
- the method of mixing the above-mentioned other components with polysiloxane may be simultaneous with or after polysiloxane, and is not particularly limited.
- a desired metal oxide film can be obtained by applying the coating liquid for a metal oxide film of the present invention to an electrode or a substrate with an electrode, followed by thermosetting.
- a well-known or well-known method can be employ
- a good coating film can be formed by spin coating, flexographic printing, slit coating, ink jet, spray coating, gravure coating, and the like.
- the substrate used is plastic; glass; glass with transparent electrodes such as ATO (antimony-containing tin oxide), FTO (fluorine-doped tin oxide), ITO, IZO (indium / zinc composite oxide); Mo (molybdenum) ), Metal wiring such as Mo / Al / Mo (molybdenum / aluminum / molybdenum), Mo—Nb / Al—Nd / Mo—Nb (molybdenum-niobium / aluminum-neodymium / molybdenum-niobium), etc .; Can be mentioned.
- Plastics include polycarbonate, poly (meth) acrylate, polyethersulfone, polyarylate, polyurethane, polysulfone, polyether, polyetherketone, polyolefin, polyethylene terephthalate, polyacrylonitrile, triacetylcellulose, diacetylcellulose, acetate butyratecellulose Etc.
- Examples of the shape include a plate and a film.
- the coating solution for metal oxide coating is generally filtered using a filter or the like before coating.
- the coating film formed on the substrate may be dried to such an extent that the uniformity of the coating film does not break during transportation.
- a method using a hot plate is preferable as a drying method.
- the drying temperature is preferably in the range of room temperature to 120 ° C.
- the time required for drying may be 30 seconds or more, but 10 minutes or less is sufficient.
- the coating film formed on the base material is thermally cured by firing.
- the firing temperature is preferably in the range of 100 to 300 ° C, and more preferably in the range of 150 to 250 ° C.
- thermosetting method by baking a method using a hot plate, a thermal circulation oven, an infrared oven or the like is preferable.
- the time required for thermosetting by firing can be selected as appropriate, but it may be 5 minutes or longer, more preferably 30 minutes or longer.
- the thickness of the metal oxide film is preferably 1 to 3000 nm, more preferably 10 to 2000 nm.
- the obtained metal oxide film has an ability to inhibit corrosion of Mo and is useful as a protective film for protecting electrical wiring films such as touch panels and electrodes.
- thermosetting It is also effective to irradiate energy rays (ultraviolet rays or the like) using a mercury lamp, a metal halide lamp, a xenon lamp, an excimer lamp or the like prior to thermosetting.
- energy rays ultraviolet rays or the like
- the curing temperature can be further lowered, or the hardness of the coating can be increased.
- the irradiation amount of the energy beam can be appropriately selected as necessary, but usually several hundred to several thousand mJ / cm 2 is appropriate, preferably 100 to 9000 mJ / cm 2 .
- TEOS tetraethoxysilane
- C18 octadecyltriethoxysilane
- ACPS acryloxypropyltrimethoxysilane
- MPMS methacryloxypropyltrimethoxysilane
- TIPT tetraisopropoxytitanium
- AN aluminum nitrate nonahydrate
- EG ethylene glycol
- HG 2-methyl -2,4-pentanediol (also known as hexylene glycol)
- BCS 2-butoxyethanol (also known as butyl cellosolve)
- a metal oxide film using the solution of the above synthesis example was produced as follows.
- [Film formation method] The solution of each synthesis example described above was pressure filtered through a membrane filter having a pore size of 0.5 ⁇ m, and a film was formed on a glass substrate on which Mo was deposited or a glass substrate on which a 2 ⁇ m acrylic film was formed by spin coating. The substrate was dried on a hot plate at 60 ° C.
- Examples 1 to 6 are metal oxide films (KL1 to KL6) obtained by forming the solutions of Synthesis Examples 1 to 6 (K1 to K6) by the film forming method described above.
- the metal oxide films (KM1 to KM3) obtained by forming the solutions of Synthesis Examples 7 to 9 (K7 to K9) by the above-described film formation method were used as Comparative Examples 1 to 3.
- Mo corrosion test Mo was vapor-deposited with a film thickness of 30 nm on a glass substrate. Using this substrate, a metal oxide film having a thickness of 100 nm was formed thereon by the film forming method. This substrate was aged in a constant temperature and humidity chamber oven at a temperature of 60 ° C. and a relative humidity of 90%. Mo corrosion was observed using an optical microscope. Evaluated as ⁇ when Mo corrosion was not observed after 480 hours, ⁇ when Mo corrosion was not observed after 240 hours, and x when Mo was observed after aging for 240 hours. did.
- An acrylic film having a thickness of 2 ⁇ m was formed on the glass substrate.
- the acrylic film was formed as follows. First, the acrylic material composition was filtered under pressure with a membrane filter having a pore diameter of 0.5 ⁇ m, and a coating film was formed on the entire surface of the glass substrate by a spin coating method. Next, the substrate was heated and dried for 2 minutes on a hot plate, then transferred to a 230 ° C. hot air circulation oven and baked for 30 minutes. As a result, an acrylic film was formed on the glass substrate. A solution (K1 to K9) was applied on the acrylic film by the above film forming method to form a metal oxide film with a thickness of 100 nm.
- the metal oxide films of Examples 1 to 6 and the metal oxide films of Comparative Examples 1 to 3 formed by the above film formation method are formed on the glass substrate on which the acrylic film is formed, and the metal oxide is formed.
- the film was evaluated for cracks.
- the evaluation criteria for crack evaluation in the metal oxide film on the substrate, those that do not cause cracks are evaluated as ⁇ , and those that do not occur in the surface but crack only in the edges are evaluated as ⁇ , and cracks occur on the entire surface. was evaluated as x.
- Table 1 shows the results of Mo corrosion test and crack evaluation of the obtained metal oxide coating.
- the metal oxide film obtained by using the coating solution for metal oxide film of the present invention has Mo corrosion inhibiting ability and crack inhibiting ability, and serves as a protective film for protecting electrical wiring films and electrodes such as touch panels. Useful.
- the entire contents of the specification, claims, and abstract of Japanese Patent Application No. 2012-019718 filed on February 1, 2012 are hereby incorporated by reference as the disclosure of the specification of the present invention. Is.
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Abstract
Description
接触位置の検出方式としては、例えば、抵抗膜方式や静電容量方式などがある。中でも、タッチパネルの耐久性、透過率、コスト、デザイン性などの面から、静電容量方式が主に用いられている。 The touch panel detects the contact position of the operation surface touched by a finger or a pen. Using this function, the touch panel is used as an input device.
Examples of the contact position detection method include a resistance film method and a capacitance method. Among these, the electrostatic capacity method is mainly used from the viewpoints of durability, transmittance, cost, design and the like of the touch panel.
通常、電子部品用薄膜配線を形成させる元素としては、Cr、Mo、W等が考えられるが、最近では高融点金属の合金による配線材質が提案されている。そのなかでも、現在はMo-Nb合金を用いた電子部品用薄膜配線が主に用いられているが、耐食性の面では充分ではない(特許文献1参照)。 The electrical wiring film and electrodes of the touch panel are required to have corrosion resistance, heat resistance, adhesion to the substrate, low resistance, high etching property, and the like.
Usually, Cr, Mo, W, or the like can be considered as an element for forming a thin film wiring for an electronic component. Recently, a wiring material made of an alloy of a refractory metal has been proposed. Among these, thin film wiring for electronic parts using Mo—Nb alloy is mainly used at present, but it is not sufficient in terms of corrosion resistance (see Patent Document 1).
このような、タッチパネルの電気配線膜及び電極を保護する為の保護膜としては、SiOXのスパッタ膜が使用されていた。しかし、コストが高く、問題となっていた。そこで最近、塗布型の金属酸化物被膜が用いられている。
しかしながら、塗布型の金属酸化物被膜を使用した場合、Mo及びMo-Nbが腐食しやすいという問題があった。 The touch panel is incorporated in a display device such as a liquid crystal display device, and is used as a display device with a touch panel function capable of detecting a touch position. Since a person who operates the touch panel visually recognizes the display device through the touch panel, a member having excellent light transmission characteristics is used for the electrode. For example, an inorganic material such as ITO (Indium Tin Oxide) is used.
As such a protective film for protecting the electric wiring film and electrodes of the touch panel, a sputtered film of SiO X has been used. However, it was expensive and problematic. Therefore, recently, a coating-type metal oxide film has been used.
However, when a coating-type metal oxide film is used, there is a problem that Mo and Mo—Nb are easily corroded.
本発明者は、上記の課題を解決する為に鋭意検討を重ねたところ、特定の有機基を有するシランカップリング剤と硝酸アルミニウムを一定量以上導入することで、課題を解決出来ることを見出した。かくして、本発明は、下記を要旨とするものである。 The present invention has been made in view of these points. That is, the object of the present invention is to provide a coating solution that can maintain the properties of the current metal oxide coating and obtain a metal oxide coating that has the ability to inhibit corrosion of Mo, and a metal oxide obtained from the coating solution. It is to provide a physical coating.
The present inventor conducted extensive studies to solve the above problems, and found that the problems can be solved by introducing a certain amount or more of a silane coupling agent having a specific organic group and aluminum nitrate. . Thus, the present invention has the following gist.
M1(OR1)n (I)
(式中、M1は珪素(Si)、チタン(Ti)、タンタル(Ta)、ジルコニウム(Zr)、ホウ素(B)、アルミニウム(Al)、マグネシウム(Mg)、錫(Sn)又は亜鉛(Zn)の金属を表し、R1は炭素数1~5のアルキル基を表し、nはM1の価数を表す。)で示される金属アルコキシド、
及び式(II)、
R2 lM2(OR3)4-l (II)
(式中、M2は珪素(Si)を表し、R2は、水素原子又はフッ素原子で置換されてもよく、且つ、ハロゲン原子、ビニル基、メタクリロキシ基、アクリロキシ基、スチリル基、フェニル基、又はシクロヘキシル基などで置換されていてもよく、且つ、ヘテロ原子を有していてもよい炭素数1~20の炭化水素基を表す。R3は、炭素数1~5のアルキル基を表す。lは1~3の整数を表す。)
で示される金属アルコキシドを、
下記式(III)、
M3(X)m (III)
(式中、M3は金属を表し、Xは塩素、硝酸、硫酸、酢酸、スファミン酸、スルホン酸、アセト酢酸、アセチルアセトナート又はこれらの塩基性塩を表し、mはM3の価数を表す。)
で示される金属塩又は式(III)で用いられる金属の蓚酸塩の存在下に、有機溶媒中で加水分解・重縮合し、さらに析出防止剤を添加して得られることを特徴とする金属酸化物被膜用塗布液。
(2)式(I)で示される金属アルコキシド又は(II)で示される金属アルコキシドが、シリコンアルコキシド、シリコンアルコキシドの部分重縮合物、チタンアルコキシド及びチタンアルコキシドの部分重縮合物からなる群から選ばれる少なくとも1種である上記(1)に記載の金属酸化物被膜用塗布液。
(3)式(I)で表される金属アルコキシドが、使用する式(I)、式(II)及び式(III)の総モル数に対して、0.5~61.5モル%含有される上記(1)又は(2)に記載の金属酸化物被膜用塗布液。
(4)式(II)で表される金属アルコキシドが、使用する式(I)、式(II)及び式(III)の総モル数に対して、38モル%以上含有される上記(1)~(3)のいずれかに記載の金属酸化物被膜用塗布液。
(5)式(III)で表される金属塩が、使用する式(I)、式(II)及び式(III)の総モル数に対して、0.5~61.5モル%含有される上記(1)~(4)のいずれかに記載の金属酸化物被膜用塗布液。
(6)式(II)中のR2が、メタクリロキシ基又はアクリロキシ基で置換された、炭素数1~20の炭化水素基である上記(1)~(5)のいずれかに記載の金属酸化物被膜用塗布液。
(7)析出防止剤が、N-メチル-ピロリドン、エチレングリコール、ジメチルホルムアミド、ジメチルアセトアミド、ジエチレングリコール、プロピレングリコール、ヘキシレングリコール及びこれらの誘導体よりなる群から選ばれる少なくとも1つである上記(1)~(6)のいずれかに記載の金属酸化物被膜用塗布液。 (1) The following formula (I),
M 1 (OR 1 ) n (I)
(Wherein M 1 is silicon (Si), titanium (Ti), tantalum (Ta), zirconium (Zr), boron (B), aluminum (Al), magnesium (Mg), tin (Sn) or zinc (Zn And R 1 represents an alkyl group having 1 to 5 carbon atoms, and n represents a valence of M 1 ).
And formula (II),
R 2 l M 2 (OR 3 ) 4-1 (II)
(Wherein M 2 represents silicon (Si), R 2 may be substituted with a hydrogen atom or a fluorine atom, and a halogen atom, a vinyl group, a methacryloxy group, an acryloxy group, a styryl group, a phenyl group, Alternatively, it represents a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a cyclohexyl group or the like and may have a hetero atom, and R 3 represents an alkyl group having 1 to 5 carbon atoms. l represents an integer of 1 to 3.)
A metal alkoxide represented by
The following formula (III),
M 3 (X) m (III)
(In the formula, M 3 represents a metal, X represents chlorine, nitric acid, sulfuric acid, acetic acid, sfamic acid, sulfonic acid, acetoacetic acid, acetylacetonate or a basic salt thereof, and m represents the valence of M 3. To express.)
A metal oxide obtained by hydrolysis / polycondensation in an organic solvent in the presence of a metal salt represented by formula (III) or a metal oxalate used in formula (III) and further adding a precipitation inhibitor Coating liquid for physical coating.
(2) The metal alkoxide represented by the formula (I) or the metal alkoxide represented by (II) is selected from the group consisting of silicon alkoxide, partial polycondensate of silicon alkoxide, titanium alkoxide and partial polycondensate of titanium alkoxide. The coating solution for a metal oxide film according to (1), which is at least one kind.
(3) The metal alkoxide represented by the formula (I) is contained in an amount of 0.5 to 61.5 mol% based on the total number of moles of the formula (I), the formula (II) and the formula (III) used. The coating solution for metal oxide coating according to (1) or (2) above.
(4) The metal alkoxide represented by the formula (II) is contained in an amount of 38 mol% or more based on the total number of moles of the formula (I), the formula (II) and the formula (III) used. The coating solution for a metal oxide film according to any one of (3) to (3).
(5) The metal salt represented by the formula (III) is contained in an amount of 0.5 to 61.5 mol% based on the total number of moles of the formula (I), the formula (II) and the formula (III) used. The metal oxide coating solution according to any one of (1) to (4) above.
(6) The metal oxide according to any one of the above (1) to (5), wherein R 2 in formula (II) is a hydrocarbon group having 1 to 20 carbon atoms substituted with a methacryloxy group or an acryloxy group Coating liquid for physical coating.
(7) The above (1), wherein the precipitation inhibitor is 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 coating solution for a metal oxide film according to any one of (6) to (6).
(析出防止剤/金属酸化物)≧1(質量比)である上記(1)~(7)のいずれかに記載の金属酸化物被膜用塗布液。
(9)金属酸化物被膜用塗布液に含まれる全金属原子の合計(M1+M2+M3)と、金属塩の金属原子(M3)とのモル比は、
[数1]
0.01≦M3/(M1+M2+M3)≦0.7
である上記(1)~(8)のいずれかに記載の金属酸化物被膜用塗布液。
(10)有機溶媒は、アルキレングリコール類又はそのモノエーテル誘導体を含む上記(1)~(9)のいずれかに記載の金属酸化物被膜用塗布液。
(11)ポリシロキサンの濃度が、SiO2換算で、20質量%以下である上記(1)~(10)のいずれかに記載の金属酸化物被膜用塗布液。
(12)上記(1)~(11)のいずれかに記載の金属酸化物被膜用塗布液から得られる金属酸化物被膜。
(13)厚さが、1~3000nmである上記(12)に記載の金属酸化物被膜。
(14)上記(13)又は(14)に記載の金属酸化物被膜を具備する保護膜。 (8) The content of the precipitation inhibitor is converted into the metal oxide of the metal salt of the formula (III),
The coating solution for a metal oxide film according to any one of the above (1) to (7), wherein (precipitation inhibitor / metal oxide) ≧ 1 (mass ratio).
(9) The molar ratio of the total (M 1 + M 2 + M 3 ) of all metal atoms contained in the coating solution for metal oxide coating and the metal atom (M 3 ) of the metal salt is:
[Equation 1]
0.01 ≦ M 3 / (M 1 + M 2 + M 3 ) ≦ 0.7
The coating solution for a metal oxide film according to any one of (1) to (8) above.
(10) The coating solution for a metal oxide film according to any one of (1) to (9), wherein the organic solvent contains an alkylene glycol or a monoether derivative thereof.
(11) The coating solution for a metal oxide film according to any one of (1) to (10) above, wherein the polysiloxane concentration is 20% by mass or less in terms of SiO 2 .
(12) A metal oxide film obtained from the coating liquid for metal oxide film according to any one of (1) to (11) above.
(13) The metal oxide film according to (12), wherein the thickness is 1 to 3000 nm.
(14) A protective film comprising the metal oxide film according to (13) or (14).
本発明の金属酸化物被膜用塗布液によって、何故にそのような金属酸化物被膜が得られるのかについては必ずしも明らかではないが、概ね以下のようなことが考えられる。
本発明の金属酸化物被膜用塗布液中、特定の有機基を有する重縮合体により、被膜下層に緻密な金属層が形成され、その結果、Moが腐食しない被膜を得ることが出来ると考えられる。 ADVANTAGE OF THE INVENTION According to this invention, the coating liquid for metal oxide films which can maintain the characteristic of the current metal oxide film, and can obtain the metal oxide film which has the corrosion inhibition ability of Mo, and a metal oxide film are provided. The
The reason why such a metal oxide film is obtained by the coating solution for metal oxide film of the present invention is not necessarily clear, but the following can be considered.
In the coating solution for metal oxide coating of the present invention, a dense metal layer is formed in the lower layer of the coating due to the polycondensate having a specific organic group, and as a result, a coating that does not corrode Mo can be obtained. .
金属酸化物被膜を形成するのに使用される金属酸化物被膜用塗布液(以下、塗布液とも言う)は、金属アルコキシドを金属塩の存在下に有機溶媒中で加水分解・重縮合し、さらに析出防止剤を添加して得られる。 <Coating liquid for metal oxide coating>
A coating solution for metal oxide coating (hereinafter also referred to as coating solution) used to form a metal oxide coating is obtained by hydrolyzing and polycondensing a metal alkoxide in an organic solvent in the presence of a metal salt. It is obtained by adding a precipitation inhibitor.
M1(OR1)n (I)
(式中、M1は珪素(Si)、チタン(Ti)、タンタル(Ta)、ジルコニウム(Zr)、ホウ素(B)、アルミニウム(Al)、マグネシウム(Mg)、錫(Sn)及び亜鉛(Zn)などの金属を表し、R1は炭素数1~5のアルキル基を表し、nはM1の価数を表す。)で示される金属アルコキシド
及び式(II)、
R2 lM2(OR3)4-l (II)
(式中、M2は珪素(Si)を表し、R2は、水素原子又はフッ素原子で置換されてもよく、且つ、ハロゲン原子、ビニル基、メタクリロキシ基、アクリロキシ基、スチリル基、フェニル基、又はシクロヘキシル基などで置換されていてもよく、且つ、ヘテロ原子を有していてもよい炭素数1~20の炭化水素基を表す。R3は、炭素数1~5のアルキル基を表す。lは1~3の整数を表す。)
で示される金属アルコキシドを、
下記式(III)、
M3(X)m (III)
(式中、M3は金属を表し、Xは塩素、硝酸、硫酸、酢酸、スファミン酸、スルホン酸、アセト酢酸、アセチルアセトナート又はこれらの塩基性塩を表し、mはM3の価数を表す。)で示される金属塩又は式(III)で用いられる金属の蓚酸塩の存在下に、有機溶媒中で加水分解・重縮合し、さらに析出防止剤を添加して得られる塗布液である。 More specifically, the following formula (I),
M 1 (OR 1 ) n (I)
(Wherein M 1 is silicon (Si), titanium (Ti), tantalum (Ta), zirconium (Zr), boron (B), aluminum (Al), magnesium (Mg), tin (Sn) and zinc (Zn And R 1 represents an alkyl group having 1 to 5 carbon atoms, and n represents a valence of M 1 ) and a formula (II),
R 2 l M 2 (OR 3 ) 4-1 (II)
(Wherein M 2 represents silicon (Si), R 2 may be substituted with a hydrogen atom or a fluorine atom, and a halogen atom, a vinyl group, a methacryloxy group, an acryloxy group, a styryl group, a phenyl group, Alternatively, it represents a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a cyclohexyl group or the like and may have a hetero atom, and R 3 represents an alkyl group having 1 to 5 carbon atoms. l represents an integer of 1 to 3.)
A metal alkoxide represented by
The following formula (III),
M 3 (X) m (III)
(In the formula, M 3 represents a metal, X represents chlorine, nitric acid, sulfuric acid, acetic acid, sfamic acid, sulfonic acid, acetoacetic acid, acetylacetonate or a basic salt thereof, and m represents the valence of M 3. It is a coating solution obtained by hydrolysis and polycondensation in an organic solvent in the presence of a metal salt represented by formula (III) or a metal oxalate used in formula (III), and further adding a precipitation inhibitor. .
式(I)のR1は、炭素数1~5のアルキル基であり、好ましくは炭素数1~4のアルキル基である。特に好ましくは、炭素数1~3のアルキル基である。
また、式(I)で表される金属アルコキシドは、使用する式(I)、式(II)及び式(III)の総モル数に対して、0.5~61.5モル%含有されることが好ましく、5.0~57.0モル%含有されることがより好ましい。
nはM1の価数を表すが2~5が好ましい。 M 1 in formula (I) includes silicon (Si), titanium (Ti) tantalum (Ta), zirconium (Zr), boron (B), aluminum (Al), magnesium (Mg), zinc (Zn), and the like. Can be mentioned. Of these, silicon alkoxide, silicon alkoxide partial polycondensate, titanium alkoxide and titanium alkoxide partial polycondensate are selected from the viewpoint of availability and storage stability of the coating solution for metal oxide coatings. It is preferable that it is at least one kind.
R 1 in the formula (I) is an alkyl group having 1 to 5 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms. Particularly preferred is an alkyl group having 1 to 3 carbon atoms.
The metal alkoxide represented by the formula (I) is contained in an amount of 0.5 to 61.5 mol% based on the total number of moles of the formula (I), the formula (II) and the formula (III) used. The content is preferably 5.0 to 57.0 mol%, and more preferably.
n represents the valence of M 1 but is preferably 2 to 5.
本発明の塗布液においては、式(II)で表される金属アルコキシドが、使用する式(I)、式(II)及び式(III)の総モル数に対して、38モル%以上含有されることが好ましく、より好ましくは43モル%以上である。なかでも、45~99モル%がさらに好ましい。
式(II)のR3は、炭素数1~5のアルキル基であり、好ましくは炭素数1~4のアルキル基である。特に好ましくは、炭素数1~3のアルキル基である。
式(II)のlは、1~3が好ましい。 R 2 in formula (II) may be substituted with a hydrogen atom or a fluorine atom, and may be substituted with a halogen atom, a vinyl group, a methacryloxy group, an acryloxy group, a styryl group, a phenyl group, or a cyclohexyl group. And a hydrocarbon group having 1 to 20 carbon atoms which may have a hetero atom. Among these, from the viewpoint of film formability, a methacryloxy group or a hydrocarbon group having 1 to 20 carbon atoms substituted with an acryloxy group is preferable. In particular, a methacryloxy group or a hydrocarbon group having 1 to 15 carbon atoms substituted with an acryloxy group is preferable.
In the coating liquid of the present invention, the metal alkoxide represented by the formula (II) is contained in an amount of 38 mol% or more based on the total number of moles of the formula (I), the formula (II) and the formula (III) used. More preferably, it is 43 mol% or more. Among these, 45 to 99 mol% is more preferable.
R 3 in the formula (II) is an alkyl group having 1 to 5 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms. Particularly preferred is an alkyl group having 1 to 3 carbon atoms.
1 in formula (II) is preferably 1 to 3.
このような式(II)で表されるアルコキシシランの具体例を挙げるが、これに限定されるものではない。例えば、3-(2-アミノエチルアミノプロピル)トリメトキシシラン、3-(2-アミノエチルアミノプロピル)トリエトキシシラン、2-アミノエチルアミノメチルトリメトキシシラン、2-(2-アミノエチルチオエチル)トリエトキシシラン、2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン、3-グリシドキシプロピルメチルジメトキシシラン、3-グリシドキシプロピルトリメトキシシラン、3-グリシドキシプロピルメチルジエトキシシラン、3-グリシドキシプロピルトリエトキシシラン、3-メルカプトプロピルトリエトキシシラン、メルカプトメチルトリメトキシシラン、3-イソシアネートプロピルトリエトキシシラン、3-メルカプトプロピルトリメトキシシラン、3-アミノプロピルメチルジエトキシシラン、3―アミノプロピルジメチルエトキシシラン、γ-ウレイドプロピルトリエトキシシラン、γ-ウレイドプロピルトリメトキシシラン及びγ-ウレイドプロピルトリプロポキシシラン等が挙げられる。
親水性の官能基を有する金属アルコキシドの含有量としては、30モル%以下が好ましく、さらに好ましくは25モル%以下である。 As the metal alkoxide represented by the formula (II) used in the coating liquid of the present invention, metal alkoxides having other functional groups can be used as long as the effects of the present invention are not impaired. Examples of other functional groups include amino groups, glycidoxy groups, mercapto groups, isocyanate groups, and ureido groups, and hydrophilic functional groups are preferred.
Specific examples of the alkoxysilane represented by the formula (II) are given below, but the invention is not limited thereto. For example, 3- (2-aminoethylaminopropyl) trimethoxysilane, 3- (2-aminoethylaminopropyl) triethoxysilane, 2-aminoethylaminomethyltrimethoxysilane, 2- (2-aminoethylthioethyl) Triethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-mercaptopropyltriethoxysilane, mercaptomethyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropylmethyldiethoxysilane, 3 ―A Examples include minopropyldimethylethoxysilane, γ-ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, and γ-ureidopropyltripropoxysilane.
As content of the metal alkoxide which has a hydrophilic functional group, 30 mol% or less is preferable, More preferably, it is 25 mol% or less.
M3(X)m (III)
(式中、M3は金属を表し、Xは塩素、硝酸、硫酸、酢酸、蓚酸、スファミン酸、スルホン酸、アセト酢酸、アセチルアセトナート又はこれらの塩基性塩を表し、mはM3の価数を表す。)又は式(III)中で用いられる金属の蓚酸塩のうち、1種又は2種以上の混合物が用いられる。その中でも、金属硝酸塩、金属塩化物塩、金属蓚酸塩及びその塩基性塩が好ましく、特に好ましいのは金属硝酸塩である。
上記、金属硝酸塩を形成する金属としては、アルミニウム(Al)、インジウム(In)、亜鉛(Zn)、ジルコニウム(Zr)、ビスマス(Bi)、ランタン(La)、タンタル(Ta)、イットリウム(Y)及びセリウム(Ce)などが挙げられる。この内、入手の容易性と、金属酸化物被膜用塗布液の貯蔵安定性の点から、アルミニウム、インジウム、セリウムなどの金属の硝酸塩が好ましい。
式(III)で表される金属塩は、使用する式(I)、式(II)及び式(III)の総モル数に対して、0.5~61.5モル%含有されることが好ましく、5.0~57.0モル%含有されることがより好ましい。 The metal salt used in the coating solution of the present invention includes the following formula (III)
M 3 (X) m (III)
(In the formula, M 3 represents a metal, X represents chlorine, nitric acid, sulfuric acid, acetic acid, succinic acid, succinic acid, sulfonic acid, acetoacetic acid, acetylacetonate, or a basic salt thereof, and m represents the value of M 3 . Or a mixture of two or more of the metal oxalates used in formula (III). Of these, metal nitrates, metal chloride salts, metal oxalates and basic salts thereof are preferred, and metal nitrates are particularly preferred.
As the metal forming the metal nitrate, aluminum (Al), indium (In), zinc (Zn), zirconium (Zr), bismuth (Bi), lanthanum (La), tantalum (Ta), yttrium (Y) And cerium (Ce). Of these, nitrates of metals such as aluminum, indium and cerium are preferred from the viewpoint of availability and storage stability of the coating solution for metal oxide coating.
The metal salt represented by the formula (III) is contained in an amount of 0.5 to 61.5 mol% based on the total number of moles of the formula (I), the formula (II) and the formula (III) used. Preferably, it is contained in an amount of 5.0 to 57.0 mol%.
析出防止剤は、珪素、チタン、タンタル、ジルコニウム、ホウ素、アルミニウム、マグネシウム、錫、亜鉛などの金属から成る金属アルコキシドが、金属塩の存在下で加水分解・重縮合反応する際に添加されていても良く、加水分解・重縮合反応の終了後に添加されていても良い。 The precipitation inhibitor is preferably used in a mass ratio of (precipitation inhibitor / metal oxide) ≧ 1 when the metal of the metal salt represented by the formula (III) is converted into an oxide. When this mass ratio is less than 1, the effect of preventing precipitation of the metal salt during formation of the coating film is reduced. On the other hand, even if a large amount of precipitation inhibitor is used, it does not affect the coating solution for metal oxide film. In the mass ratio in terms of precipitation inhibitor and metal oxide, preferably 1 ≦ (precipitation inhibitor / metal oxide) ≦ 199.
Anti-precipitation agents are added when a metal alkoxide composed of a metal such as silicon, titanium, tantalum, zirconium, boron, aluminum, magnesium, tin, or zinc undergoes hydrolysis or polycondensation reaction in the presence of a metal salt. Alternatively, it may be added after completion of the hydrolysis / polycondensation reaction.
本発明において金属アルコキシドを重縮合する方法としては、例えば、式(I)、及び式(II)の金属アルコキシドを、式(III)の金属塩の存在下で、アルコール又はグリコールなどの溶媒中で加水分解・重縮合する方法が挙げられる。
通常、加水分解・重縮合反応を促進する目的で、塩酸、硫酸、硝酸、酢酸、蟻酸、蓚酸、マレイン酸、フマル酸などの酸;アンモニア、メチルアミン、エチルアミン、エタノールアミン、トリエチルアミンなどのアルカリ;塩酸、硫酸、硝酸などの金属塩;などの触媒が用いられる。本発明においては、式(III)で表される金属塩が、触媒としての機能を有する。 <Manufacture of polysiloxane>
Examples of the method for polycondensation of metal alkoxides in the present invention include, for example, metal alkoxides of formula (I) and formula (II) in a solvent such as alcohol or glycol in the presence of a metal salt of formula (III). Examples of the method include hydrolysis and polycondensation.
Usually, for the purpose of promoting hydrolysis / polycondensation reaction, acids such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, succinic acid, maleic acid, fumaric acid; alkalis such as ammonia, methylamine, ethylamine, ethanolamine, triethylamine; A catalyst such as a metal salt such as hydrochloric acid, sulfuric acid or nitric acid is used. In the present invention, the metal salt represented by the formula (III) has a function as a catalyst.
上記の方法で得られたポリシロキサンの重合溶液(以下、重合溶液ともいう。)は、原料として仕込んだ全アルコキシシランのケイ素原子をSiO2に換算した濃度(以下、SiO2換算濃度と称す。)を20質量%以下とすることが一般的である。この濃度範囲において任意の濃度を選択することにより、ゲルの生成を抑え、均質な溶液を得ることができる。本発明においても、ポリシロキサンの濃度範囲は、SiO2換算で20質量%以下が好ましく、特に好ましいのは0.5質量%~20質量%である。 Moreover, it is also common to further promote hydrolysis / polycondensation reaction by heating a solution in which alkoxysilane is dissolved. At that time, the heating temperature and the heating time can be appropriately selected as desired. The reaction temperature is preferably in the range of 5 to 100 ° C, more preferably in the range of 10 to 80 ° C, and still more preferably in the range of 15 to 60 ° C. The reaction time is preferably in the range of 5 minutes to 6 hours, more preferably in the range of 10 minutes to 5 hours.
The polysiloxane polymerization solution (hereinafter also referred to as polymerization solution) obtained by the above method is a concentration obtained by converting silicon atoms of all alkoxysilanes charged as raw materials into SiO 2 (hereinafter referred to as SiO 2 conversion concentration). ) Is generally 20% by mass or less. By selecting an arbitrary concentration within this concentration range, gel formation can be suppressed and a homogeneous solution can be obtained. Also in the present invention, the polysiloxane concentration range is preferably 20% by mass or less in terms of SiO 2 , particularly preferably 0.5% by mass to 20% by mass.
特に、チタン、タンタル、ジルコニウム、ホウ素、アルミニウム、マグネシウム、錫、亜鉛などの金属から成る金属アルコキシド成分を安定化して塗布液の貯蔵安定性をよくする観点から、アルキレングリコール類又はそのモノエーテルを含むことが望ましい。 Examples of the organic solvent used in the coating liquid of the present invention include alcohols such as methanol, ethanol, propanol and butanol; esters such as ethyl acetate; glycols such as ethylene glycol; or ether derivatives thereof; or ester derivatives thereof; And ethers such as diethyl ether; ketones such as acetone, methyl ethyl ketone, and cyclohexanone; aromatic hydrocarbons such as benzene and toluene; These may be used alone or in combination.
In particular, alkylene glycols or monoethers thereof are included from the viewpoint of stabilizing the metal alkoxide component composed of metals such as titanium, tantalum, zirconium, boron, aluminum, magnesium, tin, and zinc to improve the storage stability of the coating solution. It is desirable.
これらのグリコール類又はそのモノエーテルは、チタン、タンタル、ジルコニウム、ホウ素、アルミニウム、マグネシウム、錫、亜鉛などの金属から成る金属アルコキシドに対してモル比が1未満であると、これら金属アルコキシドの安定性に効果が少なく、塗布液の貯蔵安定性が悪くなる。一方で、グリコール類又はそのモノエーテルを多量に用いることは何ら問題を生じない。例えば、金属酸化物被膜用塗布液に用いられる有機溶媒の全てが、上述のグリコール類又はそのモノエーテルであっても差支えない。 Examples of the alkylene glycols or monoethers thereof include ethylene glycol, diethylene glycol, propylene glycol, hexylene glycol, or monomethyl, monoethyl, monopropyl, monobutyl, and monophenyl ether thereof.
When these glycols or monoethers thereof have a molar ratio of less than 1 with respect to a metal alkoxide composed of a metal such as titanium, tantalum, zirconium, boron, aluminum, magnesium, tin, and zinc, the stability of these metal alkoxides And the storage stability of the coating solution is deteriorated. On the other hand, using a large amount of glycols or monoethers thereof causes no problem. For example, all of the organic solvents used in the coating solution for metal oxide coating may be the above-described glycols or monoethers thereof.
尚、他の金属アルコキシドを用いた場合にも、水の添加量については、同様の条件(モル比)を選択することが好ましい。
なお、本発明の塗布液を調製する際の加水分解過程において、共存する金属塩が含水塩の場合には、その含水分が反応に関与するため、加水分解に用いる水の量に対して金属塩の含水分を考慮する必要がある。 The amount of water used for hydrolysis of silicon alkoxide and / or titanium alkoxide is preferably 1 to 24 in terms of molar ratio with respect to the total number of moles of silicon alkoxide and / or titanium alkoxide. More preferably, it is 1-20. When the molar ratio (amount of water (mole) / (total number of moles of metal alkoxide)) is 1 or less, hydrolysis of the metal alkoxide becomes insufficient, resulting in reduced film formability or obtained metal. This is not preferable because the strength of the oxide film is lowered. On the other hand, when the molar ratio is more than 24, polycondensation continues to proceed, which is not preferable because storage stability is lowered.
In addition, also when using another metal alkoxide, it is preferable to select the same conditions (molar ratio) about the addition amount of water.
In addition, in the hydrolysis process when preparing the coating liquid of the present invention, when the coexisting metal salt is a hydrate salt, the moisture content is involved in the reaction, so the metal relative to the amount of water used for the hydrolysis. It is necessary to consider the moisture content of the salt.
[数1]
0.01≦M3/(M1+M2+M3)≦0.7
の関係を満たすことが好ましい。この値が0.01より小さいと、得られる被膜の機械的強度が充分でないため好ましくない。一方、0.7を越えると、ガラス基板や透明電極などの基材に対する金属酸化物膜の密着性が低下する。さらに、450℃以下の低温で焼成した場合、得られる金属酸化物膜の耐薬品性が低下する傾向にある。 The molar ratio of the sum of all metal atoms (M 1 + M 2 + M 3) contained in the coating liquid of the present invention, the metal atom of the metal salt (M 3) is
[Equation 1]
0.01 ≦ M 3 / (M 1 + M 2 + M 3 ) ≦ 0.7
It is preferable to satisfy the relationship. If this value is less than 0.01, the mechanical strength of the resulting coating is not sufficient, which is not preferable. On the other hand, when it exceeds 0.7, the adhesion of the metal oxide film to a substrate such as a glass substrate or a transparent electrode is lowered. Furthermore, when fired at a low temperature of 450 ° C. or lower, the chemical resistance of the resulting metal oxide film tends to be reduced.
無機微粒子としては、シリカ微粒子、アルミナ微粒子、チタニア微粒子、フッ化マグネシウム微粒子等の微粒子が好ましく、特にコロイド溶液の状態にあるものが好ましい。
コロイド溶液としては、無機微粒子を分散媒に分散したものでもよいし、市販品のコロイド溶液であってもよい。
本発明においては、無機微粒子を含有させることにより、形成される硬化被膜の表面形状及び屈折率の調整、その他の機能を付与することが可能となる。
無機微粒子としては、その平均粒子径が0.001~0.2μmであることが好ましく、更に好ましくは0.001~0.1μmである。無機微粒子の平均粒子径が0.2μmを超える場合には、調製される塗布液を用いて形成される硬化被膜の透明性が低下する場合がある。 In the present invention, other components such as inorganic fine particles, metalloxane oligomers, metalloxane polymers, leveling agents, and surfactants may be included as long as the effects of the present invention are not impaired. Good.
As the inorganic fine particles, fine particles such as silica fine particles, alumina fine particles, titania fine particles, and magnesium fluoride fine particles are preferable, and those in a colloidal solution state are particularly preferable.
The colloidal solution may be a dispersion of inorganic fine particles in a dispersion medium, or a commercially available colloidal solution.
In the present invention, by containing inorganic fine particles, it is possible to adjust the surface shape and refractive index of the formed cured film and to provide other functions.
The inorganic fine particles preferably have an average particle size of 0.001 to 0.2 μm, more preferably 0.001 to 0.1 μm. When the average particle diameter of the inorganic fine particles exceeds 0.2 μm, the transparency of the cured film formed using the prepared coating liquid may be lowered.
コロイド溶液の分散媒に用いる有機溶剤としては、メタノール、プロパノール、ブタノール、エチレングリコール、プロピレングリコール、ブタンジオール、ペンタンジオール、ヘキシレングリコール、ジエチレングリコール、ジプロピレングリコール、エチレングリコールモノプロピルエーテル等のアルコール類;メチルエチルケトン、メチルイソブチルケトン等のケトン類;トルエン、キシレン等の芳香族炭化水素類;ジメチルホルムアミド、ジメチルアセトアミド、N-メチルピロリドン等のアミド類;酢酸エチル、酢酸ブチル、γ-ブチロラクトン等のエステル類;テトラヒドロフラン、1,4-ジオキサン等のエ-テル類を挙げることができる。これらの中で、アルコール類、ケトン類が好ましい。これら有機溶剤は、単独で又は2種以上を混合して分散媒として使用することができる。 Examples of the dispersion medium for the inorganic fine particles include water and organic solvents. In the colloidal solution, the pH or pKa is preferably adjusted to 1 to 10, more preferably 2 to 7, from the viewpoint of the stability of the electrode protective film forming agent.
Examples of the organic solvent used for the dispersion medium of the colloidal solution include alcohols such as methanol, propanol, butanol, ethylene glycol, propylene glycol, butanediol, pentanediol, hexylene glycol, diethylene glycol, dipropylene glycol, and ethylene glycol monopropyl ether; Ketones such as methyl ethyl ketone and methyl isobutyl ketone; aromatic hydrocarbons such as toluene and xylene; amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone; esters such as ethyl acetate, butyl acetate and γ-butyrolactone; Examples include ethers such as tetrahydrofuran and 1,4-dioxane. Among these, alcohols and ketones are preferable. These organic solvents can be used alone or in admixture of two or more as a dispersion medium.
市販品のメタロキサンオリゴマー、又はメタロキサンポリマーの具体例としては、コルコート社製メチルシリケート51、メチルシリケート53A、エチルシリケート40、エチルシリケート48、EMS-485、SS-101等のシロキサンオリゴマー又はシロキサンポリマー、関東化学社製チタニウム-n-ブトキシドテトラマー等のチタノキサンオリゴマーが挙げられる。これらは単独又は2種以上混合して使用してもよい。
また、レベリング剤及び界面活性剤等は、公知のものを用いることができ、特に市販品は入手が容易なので好ましい。
また、ポリシロキサンに、上記したその他の成分を混合する方法は、ポリシロキサンと同時でも、後であってもよく、特に限定されない。 As the metalloxane oligomer or metalloxane polymer, single or composite oxide precursors such as silicon, titanium, aluminum, tantalum, antimony, bismuth, tin, indium, and zinc are used. The metalloxane oligomer or metalloxane polymer may be a commercially available product or may be obtained from a monomer such as a metal alkoxide, nitrate, hydrochloride, carboxylate or the like by a conventional method such as hydrolysis. .
Specific examples of commercially available metalloxane oligomers or metalloxane polymers include siloxane oligomers or siloxane polymers such as methyl silicate 51, methyl silicate 53A, ethyl silicate 40, ethyl silicate 48, EMS-485, and SS-101 manufactured by Colcoat. And titanoxane oligomers such as titanium-n-butoxide tetramer manufactured by Kanto Chemical Co., Inc. You may use these individually or in mixture of 2 or more types.
Moreover, a leveling agent, surfactant, etc. can use a well-known thing, and since a commercial item is easy to acquire especially, it is preferable.
Moreover, the method of mixing the above-mentioned other components with polysiloxane may be simultaneous with or after polysiloxane, and is not particularly limited.
本発明の金属酸化物被膜用の塗布液を、電極又は電極付き基材に塗布し、熱硬化することで所望の金属酸化物被膜を得ることができる。電極保護膜形成剤の塗布方法は、公知又は周知の方法を採用できる。例えば、スピンコート法、ディップ法、フローコート法、スプレー法、バーコート法、グラビアコート法、ロールコート法、ブレードコート法、エアーナイフコート法、フレキソ印刷法、インクジェット法、スリットコート法等を採用できる。これらの中でもスピンコート法、フレキソ印刷法、スリットコート法、インクジェット法、スプレーコート法、グラビアコート法等において良好な塗膜を形成することができる。 <Metal oxide coating>
A desired metal oxide film can be obtained by applying the coating liquid for a metal oxide film of the present invention to an electrode or a substrate with an electrode, followed by thermosetting. A well-known or well-known method can be employ | adopted for the coating method of an electrode protective film formation agent. For example, spin coating method, dip method, flow coating method, spray method, bar coating method, gravure coating method, roll coating method, blade coating method, air knife coating method, flexographic printing method, ink jet method, slit coating method, etc. it can. Among these, a good coating film can be formed by spin coating, flexographic printing, slit coating, ink jet, spray coating, gravure coating, and the like.
プラスチックとしては、ポリカーボネート、ポリ(メタ)アクリレート、ポリエーテルサルホン、ポリアリレート、ポリウレタン、ポリスルホン、ポリエーテル、ポリエーテルケトン、ポリオレフィン、ポリエチレンテレフタレート、ポリアクリロニトリル、トリアセチルセルロース、ジアセチルセルロース、アセテートブチレートセルロース等が挙げられる。その形状は、板、フィルム等が挙げられる。 In this case, the substrate used is plastic; glass; glass with transparent electrodes such as ATO (antimony-containing tin oxide), FTO (fluorine-doped tin oxide), ITO, IZO (indium / zinc composite oxide); Mo (molybdenum) ), Metal wiring such as Mo / Al / Mo (molybdenum / aluminum / molybdenum), Mo—Nb / Al—Nd / Mo—Nb (molybdenum-niobium / aluminum-neodymium / molybdenum-niobium), etc .; Can be mentioned.
Plastics include polycarbonate, poly (meth) acrylate, polyethersulfone, polyarylate, polyurethane, polysulfone, polyether, polyetherketone, polyolefin, polyethylene terephthalate, polyacrylonitrile, triacetylcellulose, diacetylcellulose, acetate butyratecellulose Etc. Examples of the shape include a plate and a film.
基材に形成された塗膜は、搬送中に塗膜の均一性が崩れない程度に乾燥しても良い。その際、乾燥方法としてはホットプレートを用いる方法が好ましい。乾燥温度は室温~120℃の範囲内であることが好ましい。乾燥に要する時間は、30秒間以上であればよいが、10分間以下で充分である。
また、基材に形成された塗膜は、焼成することにより熱硬化を行う。焼成温度は100~300℃の範囲であることが好ましく、150~250℃の範囲内であることがより好ましい。焼成による熱硬化方法としては、ホットプレート、熱循環式オーブン、赤外線オーブン等を用いる方法が好ましい。焼成による熱硬化に要する時間は、適宜選択することができるが、5分以上であればよく、さらに好ましくは30分以上である。
低い硬化温度を選択する場合は、硬化時間を長くすることで充分な硬さを有する金属酸化物被膜を得られやすい。
金属酸化物被膜の厚さは、1~3000nmが好ましく、より好ましくは10~2000nmである。
得られた金属酸化物被膜は、Moの腐食抑制能を有し、タッチパネル等の電気配線膜及び電極を保護する為の保護膜として有用である。 The coating solution for metal oxide coating is generally filtered using a filter or the like before coating.
The coating film formed on the substrate may be dried to such an extent that the uniformity of the coating film does not break during transportation. At this time, a method using a hot plate is preferable as a drying method. The drying temperature is preferably in the range of room temperature to 120 ° C. The time required for drying may be 30 seconds or more, but 10 minutes or less is sufficient.
Moreover, the coating film formed on the base material is thermally cured by firing. The firing temperature is preferably in the range of 100 to 300 ° C, and more preferably in the range of 150 to 250 ° C. As a thermosetting method by baking, a method using a hot plate, a thermal circulation oven, an infrared oven or the like is preferable. The time required for thermosetting by firing can be selected as appropriate, but it may be 5 minutes or longer, more preferably 30 minutes or longer.
When selecting a low curing temperature, it is easy to obtain a metal oxide film having sufficient hardness by increasing the curing time.
The thickness of the metal oxide film is preferably 1 to 3000 nm, more preferably 10 to 2000 nm.
The obtained metal oxide film has an ability to inhibit corrosion of Mo and is useful as a protective film for protecting electrical wiring films such as touch panels and electrodes.
実施例で用いた化合物における略語は以下のとおりである。
TEOS:テトラエトキシシラン
C18:オクタデシルトリエトキシシラン
ACPS:アクリロキシプロピルトリメトキシシラン
MPMS:メタクリロキシプロピルトリメトキシシラン
TIPT:テトライソプロポキシチタン
AN:硝酸アルミニウム九水和物
EG:エチレングリコール
HG:2-メチル-2,4-ペンタンジオール(別称:へキシレングリコール)
BCS:2-ブトキシエタノール(別称:ブチルセロソルブ) Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention should not be construed as being limited thereto.
Abbreviations in the compounds used in the examples are as follows.
TEOS: tetraethoxysilane C18: octadecyltriethoxysilane ACPS: acryloxypropyltrimethoxysilane MPMS: methacryloxypropyltrimethoxysilane TIPT: tetraisopropoxytitanium AN: aluminum nitrate nonahydrate EG: ethylene glycol HG: 2-methyl -2,4-pentanediol (also known as hexylene glycol)
BCS: 2-butoxyethanol (also known as butyl cellosolve)
<A1液>
200mLフラスコ中にAN12.7g、及び水3.0gを加えて攪拌し、ANを溶解した。そこに、EG13.1g、HG37.5g、BCS35.7g、及びMPMS37.0gを入れ、室温下で30分攪拌した。
<A2液>
300mLフラスコ中にTIPT4.7g、及びHG56.3gを入れ、室温下で30分攪拌した。
<A1液>と<A2液>を混合し、室温下で30分攪拌して溶液(K1)を得た。
[合成例2]
<B1液>
200mLフラスコ中にAN12.7g、及び水3.0gを加えて攪拌し、ANを溶解した。そこに、EG13.3g、HG37.9g、BCS36.0g、TEOS7.8g、及びMPMS27.8gを入れ、室温下で30分攪拌した。
<B2液>
300mLフラスコ中にTIPT4.7g、及びHG56.9gを入れ、室温下で30分攪拌した。
<B1液>と<B2液>を混合し、室温下で30分攪拌して溶液(K2)を得た。 [Synthesis Example 1]
<A1 liquid>
In a 200 mL flask, 12.7 g of AN and 3.0 g of water were added and stirred to dissolve AN. EG13.1g, HG37.5g, BCS35.7g, and MPMS37.0g were put there and it stirred under room temperature for 30 minutes.
<A2 liquid>
In a 300 mL flask, 4.7 g of TIPT and 56.3 g of HG were added and stirred at room temperature for 30 minutes.
<A1 liquid> and <A2 liquid> were mixed and stirred at room temperature for 30 minutes to obtain a solution (K1).
[Synthesis Example 2]
<B1 liquid>
In a 200 mL flask, 12.7 g of AN and 3.0 g of water were added and stirred to dissolve AN. EG13.3g, HG37.9g, BCS36.0g, TEOS7.8g and MPMS27.8g were put there, and it stirred under room temperature for 30 minutes.
<B2 liquid>
In a 300 mL flask, 4.7 g of TIPT and 56.9 g of HG were added and stirred at room temperature for 30 minutes.
<B1 liquid> and <B2 liquid> were mixed and stirred at room temperature for 30 minutes to obtain a solution (K2).
<C1液>
200mLフラスコ中にAN12.7g、及び水3.0gを加えて攪拌し、ANを溶解した。そこに、EG13.3g、HG38.2g、BCS36.3g、TEOS12.4g、及びMPMS22.2gを入れ、室温下で30分攪拌した。
<C2液>
300mLフラスコ中にTIPT4.7g、及びHG57.2gを入れ、室温下で30分攪拌した。
<C1液>と<C2液>を混合し、室温下で30分攪拌して溶液(K3)を得た。
[合成例4]
<D1液>
200mLフラスコ中にAN12.7g、及び水3.0gを加えて攪拌し、ANを溶解した。そこに、EG13.3g、HG38.1g、BCS36.2g、及びACPS34.9gを入れ、室温下で30分攪拌した。
<D2液>
300mLフラスコ中にTIPT4.7g、及びHG57.1gを入れ、室温下で30分攪拌した。
<D1液>と<D2液>を混合し、室温下で30分攪拌して溶液(K4)を得た。 [Synthesis Example 3]
<C1 liquid>
In a 200 mL flask, 12.7 g of AN and 3.0 g of water were added and stirred to dissolve AN. EG13.3g, HG38.2g, BCS36.3g, TEOS12.4g and MPMS22.2g were put there, and it stirred under room temperature for 30 minutes.
<C2 liquid>
In a 300 mL flask, 4.7 g of TIPT and 57.2 g of HG were put and stirred at room temperature for 30 minutes.
<C1 liquid> and <C2 liquid> were mixed and stirred at room temperature for 30 minutes to obtain a solution (K3).
[Synthesis Example 4]
<D1 liquid>
In a 200 mL flask, 12.7 g of AN and 3.0 g of water were added and stirred to dissolve AN. EG13.3g, HG38.1g, BCS36.2g, and ACPS34.9g were put there, and it stirred under room temperature for 30 minutes.
<D2 liquid>
In a 300 mL flask, 4.7 g of TIPT and 57.1 g of HG were put and stirred at room temperature for 30 minutes.
<D1 liquid> and <D2 liquid> were mixed and stirred at room temperature for 30 minutes to obtain a solution (K4).
<E1液>
200mLフラスコ中にAN12.7g、及び水3.0gを加えて攪拌し、ANを溶解した。そこに、EG13.2g、HG37.7g、BCS35.8g、TEOS7.5g、及びMPMS26.9gを入れ、室温下で30分攪拌した。
<E2液>
300mLフラスコ中にTIPT4.7g、及びHG56.5gを入れ、室温下で30分攪拌した。
<E1液>と<E2液>を混合し、室温下で30分攪拌して溶液(K5)を得た。
[合成例6]
<F1液>
200mLフラスコ中にAN12.7g、及び水3.0gを加えて攪拌し、ANを溶解した。そこに、EG12.5g、HG35.7g、BCS33.9g、MPMS26.9g、及びC18を15.0g入れ、室温下で30分攪拌した。
<F2液>
300mLフラスコ中にTIPT4.7g、及びHG53.5gを入れ、室温下で30分攪拌した。
<F1液>と<F2液>を混合し、室温下で30分攪拌して溶液(K6)を得た。 [Synthesis Example 5]
<E1 liquid>
In a 200 mL flask, 12.7 g of AN and 3.0 g of water were added and stirred to dissolve AN. EG13.2g, HG37.7g, BCS35.8g, TEOS7.5g, and MPMS26.9g were put there, and it stirred under room temperature for 30 minutes.
<E2 liquid>
In a 300 mL flask, 4.7 g of TIPT and 56.5 g of HG were put and stirred at room temperature for 30 minutes.
<E1 liquid> and <E2 liquid> were mixed and stirred at room temperature for 30 minutes to obtain a solution (K5).
[Synthesis Example 6]
<F1 liquid>
In a 200 mL flask, 12.7 g of AN and 3.0 g of water were added and stirred to dissolve AN. EG12.5g, HG35.7g, BCS33.9g, MPMS26.9g and 15.0g of C18 were put there, and it stirred under room temperature for 30 minutes.
<F2 liquid>
In a 300 mL flask, 4.7 g of TIPT and 53.5 g of HG were added and stirred at room temperature for 30 minutes.
<F1 liquid> and <F2 liquid> were mixed and stirred at room temperature for 30 minutes to obtain a solution (K6).
<G1液>
200mLフラスコ中にAN12.7g、及び水3.0gを加えて攪拌し、ANを溶解した。そこに、EG13.6g、HG39.1g、BCS37.1g、及びTEOS31.0gを入れ、室温下で30分攪拌した。
<G2液>
300mLフラスコ中にTIPT4.7g、及びHG58.7gを入れ、室温下で30分攪拌した。
<G1液>と<G2液>を混合し、室温下で30分攪拌して溶液(K7)を得た。
[合成例8]
<H1液>
200mLフラスコ中にAN12.7g、及び水3.0gを加えて攪拌し、ANを溶解した。そこに、EG13.4g、HG38.3g、BCS36.4g、TEOS15.5g、及びMPMS18.5gを入れ、室温下で30分攪拌した。
<H2液>
300mLフラスコ中にTIPT4.7g、及びHG57.5gを入れ、室温下で30分攪拌した。
<H1液>と<H2液>を混合し、室温下で30分攪拌して溶液(K8)を得た。
[合成例9]
<I1液>
200mLフラスコ中にAN12.7g、及び水3.0gを加えて攪拌し、ANを溶解した。そこに、EG13.5g、HG38.7g、BCS36.8g、TEOS23.3g、及びMPMS9.3gを入れ、室温下で30分攪拌した。
<I2液>
300mLフラスコ中にTIPT4.7g、及びHG58.1gを入れ、室温下で30分攪拌した。
<I1液>と<I2液>を混合し、室温下で30分攪拌して溶液(K9)を得た。 [Synthesis Example 7]
<G1 solution>
In a 200 mL flask, 12.7 g of AN and 3.0 g of water were added and stirred to dissolve AN. EG13.6g, HG39.1g, BCS37.1g and TEOS31.0g were put there, and it stirred under room temperature for 30 minutes.
<G2 liquid>
In a 300 mL flask, 4.7 g of TIPT and 58.7 g of HG were put and stirred at room temperature for 30 minutes.
<G1 liquid> and <G2 liquid> were mixed and stirred at room temperature for 30 minutes to obtain a solution (K7).
[Synthesis Example 8]
<H1 solution>
In a 200 mL flask, 12.7 g of AN and 3.0 g of water were added and stirred to dissolve AN. EG13.4g, HG38.3g, BCS36.4g, TEOS15.5g and MPMS18.5g were put there, and it stirred under room temperature for 30 minutes.
<H2 liquid>
In a 300 mL flask, 4.7 g of TIPT and 57.5 g of HG were added and stirred at room temperature for 30 minutes.
<H1 liquid> and <H2 liquid> were mixed and stirred at room temperature for 30 minutes to obtain a solution (K8).
[Synthesis Example 9]
<I1 liquid>
In a 200 mL flask, 12.7 g of AN and 3.0 g of water were added and stirred to dissolve AN. EG13.5g, HG38.7g, BCS36.8g, TEOS23.3g, and MPMS9.3g were put there and it stirred under room temperature for 30 minutes.
<I2 liquid>
In a 300 mL flask, 4.7 g of TIPT and 58.1 g of HG were put and stirred at room temperature for 30 minutes.
<I1 liquid> and <I2 liquid> were mixed and stirred at room temperature for 30 minutes to obtain a solution (K9).
[成膜法]
上記した各合成例の溶液を孔径0.5μmのメンブランフィルターで加圧濾過し、Moを蒸着させたガラス基板、あるいは2μmのアクリル膜を形成させたガラス基板にスピンコート法により成膜した。この基板を60℃のホットプレート上で3分間乾燥した後、紫外線照射装置(アイグラフィックス社製、UB 011-3A形)、及び高圧水銀ランプ(入力電源1000W)を用いて50mW/cm2(波長365nm換算)で2分間照射し(積算6000mJ/cm2)、次いで、230℃の熱風循環式オーブンで30分焼成して被膜を形成した。
合成例1~6の溶液(K1~K6)を上記成膜法にて成膜した金属酸化物被膜(KL1~KL6)を実施例1~6とした。
合成例7~9の溶液(K7~K9)を上記成膜法にて成膜した金属酸化物被膜(KM1~KM3)を比較例1~3とした。 A metal oxide film using the solution of the above synthesis example was produced as follows.
[Film formation method]
The solution of each synthesis example described above was pressure filtered through a membrane filter having a pore size of 0.5 μm, and a film was formed on a glass substrate on which Mo was deposited or a glass substrate on which a 2 μm acrylic film was formed by spin coating. The substrate was dried on a hot plate at 60 ° C. for 3 minutes and then 50 mW / cm 2 (using an ultraviolet ray irradiation device (UB Graphics, UB 011-3A type) and a high-pressure mercury lamp (input power supply 1000 W) ( The film was irradiated for 2 minutes at a wavelength of 365 nm (integrated 6000 mJ / cm 2 ) and then baked for 30 minutes in a hot air circulation oven at 230 ° C. to form a film.
Examples 1 to 6 are metal oxide films (KL1 to KL6) obtained by forming the solutions of Synthesis Examples 1 to 6 (K1 to K6) by the film forming method described above.
The metal oxide films (KM1 to KM3) obtained by forming the solutions of Synthesis Examples 7 to 9 (K7 to K9) by the above-described film formation method were used as Comparative Examples 1 to 3.
〔Mo腐食試験〕
ガラス基板上に膜厚30nmにてMoを蒸着させた。この基板を用い、その上に上記成膜法にて、膜厚100nmの金属酸化物被膜を形成した。この基板を温度60℃、相対湿度90%の恒温恒湿槽オーブンにてエージングした。Moの腐食は光学顕微鏡を用いて観察した。480時間エージングしてもMoの腐食が見られないものを◎、240時間エージングしてもMoの腐食が見られないものを○、240時間エージングしてMoの腐食が見られるものを×として評価した。 The coating evaluation method is shown below.
[Mo corrosion test]
Mo was vapor-deposited with a film thickness of 30 nm on a glass substrate. Using this substrate, a metal oxide film having a thickness of 100 nm was formed thereon by the film forming method. This substrate was aged in a constant temperature and humidity chamber oven at a temperature of 60 ° C. and a relative humidity of 90%. Mo corrosion was observed using an optical microscope. Evaluated as ◎ when Mo corrosion was not observed after 480 hours, ◯ when Mo corrosion was not observed after 240 hours, and x when Mo was observed after aging for 240 hours. did.
ガラス基板上に、膜厚2μmのアクリル膜を形成した。アクリル膜の形成は、次のようにして行った。まず、アクリル材料組成物を、孔径0.5μmのメンブランフィルターで加圧濾過し、ガラス基板全面にスピンコート法により塗膜を形成した。次いで、この基板をホットプレート上で2分間加熱乾燥した後、230℃の熱風循環式オーブン内に移し、30分間焼成した。これにより、ガラス基板上にアクリル膜が形成された。
上記のアクリル膜の上に、上記成膜法により溶液(K1~K9)を塗布し、膜厚100nmの厚さで金属酸化物被膜を形成した。次いで、アクリル膜の形成されたガラス基板上に、上記成膜法により成膜された実施例1~6の金属酸化物被膜及び比較例1~3の金属酸化物被膜を形成し、金属酸化物被膜のクラック評価を行った。
クラック評価の評価基準については、基板上の金属酸化物被膜において、クラックを生じないものを◎評価とし、面内は生じないがエッジのみクラックが生じるものを○評価とし、全面にクラックが生じるものを×評価とした。
得られた金属酸化物被膜のMo腐食試験の結果及びクラック評価の結果を表1に示す。 [Crack evaluation]
An acrylic film having a thickness of 2 μm was formed on the glass substrate. The acrylic film was formed as follows. First, the acrylic material composition was filtered under pressure with a membrane filter having a pore diameter of 0.5 μm, and a coating film was formed on the entire surface of the glass substrate by a spin coating method. Next, the substrate was heated and dried for 2 minutes on a hot plate, then transferred to a 230 ° C. hot air circulation oven and baked for 30 minutes. As a result, an acrylic film was formed on the glass substrate.
A solution (K1 to K9) was applied on the acrylic film by the above film forming method to form a metal oxide film with a thickness of 100 nm. Next, the metal oxide films of Examples 1 to 6 and the metal oxide films of Comparative Examples 1 to 3 formed by the above film formation method are formed on the glass substrate on which the acrylic film is formed, and the metal oxide is formed. The film was evaluated for cracks.
Regarding the evaluation criteria for crack evaluation, in the metal oxide film on the substrate, those that do not cause cracks are evaluated as ◎, and those that do not occur in the surface but crack only in the edges are evaluated as ○, and cracks occur on the entire surface. Was evaluated as x.
Table 1 shows the results of Mo corrosion test and crack evaluation of the obtained metal oxide coating.
実施例1~6の金属酸化物被膜はクラック及びMo腐食を同時に抑制することができる材料であることがわかった。 From the results shown in Table 1, it was found that the metal oxide films of Examples 1 to 6 were superior in Mo corrosion resistance to the metal oxide films of Comparative Examples 1 to 3. On the other hand, in Comparative Examples 1 to 3, the compatibility between Mo corrosivity and crack suppressing ability was not achieved.
It was found that the metal oxide films of Examples 1 to 6 are materials that can simultaneously suppress cracks and Mo corrosion.
なお、2012年2月1日に出願された日本特許出願2012-019718号の明細書、特許請求の範囲、及び要約書の全内容をここに引用し、本発明の明細書の開示として、取り入れるものである。 The metal oxide film obtained by using the coating solution for metal oxide film of the present invention has Mo corrosion inhibiting ability and crack inhibiting ability, and serves as a protective film for protecting electrical wiring films and electrodes such as touch panels. Useful.
The entire contents of the specification, claims, and abstract of Japanese Patent Application No. 2012-019718 filed on February 1, 2012 are hereby incorporated by reference as the disclosure of the specification of the present invention. Is.
Claims (14)
- 下記式(I)、
M1(OR1)n (I)
(式中、M1は珪素(Si)、チタン(Ti)、タンタル(Ta)、ジルコニウム(Zr)、ホウ素(B)、アルミニウム(Al)、マグネシウム(Mg)、錫(Sn)又は亜鉛(Zn)の金属を表し、R1は炭素数1~5のアルキル基を表し、nはM1の価数を表す。)で示される金属アルコキシド、
及び式(II)、
R2 lM2(OR3)4-l (II)
(式中、M2は珪素(Si)を表し、R2は、水素原子又はフッ素原子で置換されてもよく、且つ、ハロゲン原子、ビニル基、メタクリロキシ基、アクリロキシ基、スチリル基、フェニル基、又はシクロヘキシル基などで置換されていてもよく、且つ、ヘテロ原子を有していてもよい炭素数1~20の炭化水素基を表す。R3は、炭素数1~5のアルキル基を表す。lは1~3の整数を表す。)
で示される金属アルコキシドを、
下記式(III)、
M3(X)m (III)
(式中、M3は金属を表し、Xは塩素、硝酸、硫酸、酢酸、スファミン酸、スルホン酸、アセト酢酸、アセチルアセトナート又はこれらの塩基性塩を表し、mはM3の価数を表す。)
で示される金属塩又は式(III)で用いられる金属の蓚酸塩の存在下に、有機溶媒中で加水分解・重縮合し、さらに析出防止剤を添加して得られることを特徴とする金属酸化物被膜用塗布液。 The following formula (I),
M 1 (OR 1 ) n (I)
(Wherein M 1 is silicon (Si), titanium (Ti), tantalum (Ta), zirconium (Zr), boron (B), aluminum (Al), magnesium (Mg), tin (Sn) or zinc (Zn And R 1 represents an alkyl group having 1 to 5 carbon atoms, and n represents a valence of M 1 ).
And formula (II),
R 2 l M 2 (OR 3 ) 4-1 (II)
(Wherein M 2 represents silicon (Si), R 2 may be substituted with a hydrogen atom or a fluorine atom, and a halogen atom, a vinyl group, a methacryloxy group, an acryloxy group, a styryl group, a phenyl group, Alternatively, it represents a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a cyclohexyl group or the like and may have a hetero atom, and R 3 represents an alkyl group having 1 to 5 carbon atoms. l represents an integer of 1 to 3.)
A metal alkoxide represented by
The following formula (III),
M 3 (X) m (III)
(In the formula, M 3 represents a metal, X represents chlorine, nitric acid, sulfuric acid, acetic acid, sfamic acid, sulfonic acid, acetoacetic acid, acetylacetonate or a basic salt thereof, and m represents the valence of M 3. To express.)
A metal oxide obtained by hydrolysis / polycondensation in an organic solvent in the presence of a metal salt represented by formula (III) or a metal oxalate used in formula (III) and further adding a precipitation inhibitor Coating liquid for physical coating. - 式(I)で示される金属アルコキシド又は(II)で示される金属アルコキシドが、シリコンアルコキシド、シリコンアルコキシドの部分重縮合物、チタンアルコキシド及びチタンアルコキシドの部分重縮合物からなる群から選ばれる少なくとも1種である請求項1に記載の金属酸化物被膜用塗布液。 The metal alkoxide represented by the formula (I) or the metal alkoxide represented by (II) is at least one selected from the group consisting of silicon alkoxide, partial polycondensate of silicon alkoxide, titanium alkoxide and partial polycondensate of titanium alkoxide. The coating solution for metal oxide coating according to claim 1.
- 式(I)で表される金属アルコキシドが、使用する式(I)、式(II)及び式(III)の総モル数に対して、0.5~61.5モル%含有される請求項1又は2に記載の金属酸化物被膜用塗布液。 The metal alkoxide represented by the formula (I) is contained in an amount of 0.5 to 61.5 mol% based on the total number of moles of the formula (I), the formula (II) and the formula (III) used. 3. The coating solution for metal oxide coating according to 1 or 2.
- 式(II)で表される金属アルコキシドが、使用する式(I)、式(II)及び式(III)の総モル数に対して、38モル%以上含有される請求項1~3のいずれか1項に記載の金属酸化物被膜用塗布液。 The metal alkoxide represented by the formula (II) is contained in an amount of 38 mol% or more based on the total number of moles of the formula (I), the formula (II) and the formula (III) used. The coating solution for metal oxide coating according to claim 1.
- 式(III)で表される金属塩が、式(I)、式(II)及び式(III)の総モル数に対して、0.5~61.5モル%含有される請求項1~4のいずれか1項に記載の金属酸化物被膜用塗布液。 The metal salt represented by the formula (III) is contained in an amount of 0.5 to 61.5 mol% based on the total number of moles of the formula (I), the formula (II) and the formula (III). 5. The coating solution for metal oxide coating according to any one of 4 above.
- 式(II)中のR2が、メタクリロキシ基又はアクリロキシ基で置換された、炭素数1~20の炭化水素基である請求項1~5のいずれか1項に記載の金属酸化物被膜用塗布液。 6. The coating for metal oxide coating according to claim 1, wherein R 2 in the formula (II) is a hydrocarbon group having 1 to 20 carbon atoms substituted with a methacryloxy group or an acryloxy group. liquid.
- 析出防止剤が、N-メチル-ピロリドン、エチレングリコール、ジメチルホルムアミド、ジメチルアセトアミド、ジエチレングリコール、プロピレングリコール、ヘキシレングリコール及びこれらの誘導体よりなる群から選ばれる少なくとも1つである請求項1~6のいずれか1項に記載の金属酸化物被膜用塗布液。 The precipitation inhibitor is 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 coating solution for metal oxide coating according to claim 1.
- 析出防止剤の含有量が、式(III)の金属塩の金属の酸化物に換算で、
(析出防止剤/金属酸化物)≧1(質量比)である請求項1~7のいずれか1項に記載の金属酸化物被膜用塗布液。 The content of the precipitation inhibitor is converted into the metal oxide of the metal salt of the formula (III),
The coating solution for a metal oxide film according to any one of claims 1 to 7, wherein (precipitation inhibitor / metal oxide) ≥1 (mass ratio). - 金属酸化物被膜用塗布液に含まれる全金属原子の合計(M1+M2+M3)と、金属塩の金属原子(M3)とのモル比は、
[数1]
0.01≦M3/(M1+M2+M3)≦0.7
である請求項1~8のいずれか1項に記載の金属酸化物被膜用塗布液。 The molar ratio between the total of all metal atoms (M 1 + M 2 + M 3 ) contained in the coating solution for metal oxide coating and the metal atom (M 3 ) of the metal salt is:
[Equation 1]
0.01 ≦ M 3 / (M 1 + M 2 + M 3 ) ≦ 0.7
The coating solution for a metal oxide film according to any one of claims 1 to 8. - 有機溶媒は、アルキレングリコール類又はそのモノエーテル誘導体を含む請求項1~9のいずれか1項に記載の金属酸化物被膜用塗布液。 The coating solution for a metal oxide film according to any one of claims 1 to 9, wherein the organic solvent contains an alkylene glycol or a monoether derivative thereof.
- ポリシロキサンの濃度が、SiO2換算で、20質量%以下である請求項1~10のいずれか1項に記載の金属酸化物被膜用塗布液。 The coating solution for a metal oxide film according to any one of claims 1 to 10, wherein the concentration of polysiloxane is 20% by mass or less in terms of SiO 2 .
- 請求項1~11のいずれか1項に記載の金属酸化物被膜用塗布液から得られる金属酸化物被膜。 A metal oxide film obtained from the coating solution for a metal oxide film according to any one of claims 1 to 11.
- 厚さが、1~3000nmである請求項12に記載の金属酸化物被膜。 The metal oxide film according to claim 12, wherein the thickness is 1 to 3000 nm.
- 請求項13又は14に記載の金属酸化物被膜を具備する保護膜。 A protective film comprising the metal oxide film according to claim 13 or 14.
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WO2014203951A1 (en) * | 2013-06-19 | 2014-12-24 | 日産化学工業株式会社 | Composition for forming metal oxide film, and metal oxide film |
JPWO2015182657A1 (en) * | 2014-05-29 | 2017-04-20 | 日産化学工業株式会社 | Adhesive film forming agent for aluminum oxide or aluminum substrate |
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JPWO2014203951A1 (en) * | 2013-06-19 | 2017-02-23 | 日産化学工業株式会社 | Composition for forming metal oxide film and metal oxide film |
JPWO2015182657A1 (en) * | 2014-05-29 | 2017-04-20 | 日産化学工業株式会社 | Adhesive film forming agent for aluminum oxide or aluminum substrate |
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