CN104583350B - Metal oxide coating coating fluid and metal oxide coating - Google Patents
Metal oxide coating coating fluid and metal oxide coating Download PDFInfo
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- CN104583350B CN104583350B CN201380043117.1A CN201380043117A CN104583350B CN 104583350 B CN104583350 B CN 104583350B CN 201380043117 A CN201380043117 A CN 201380043117A CN 104583350 B CN104583350 B CN 104583350B
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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
- C09D183/14—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 in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
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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
- C09D185/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon; Coating compositions based on derivatives of such polymers
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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
- C08G77/48—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 in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
- C08G77/58—Metal-containing linkages
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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
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Abstract
The present invention provides a kind of formed with protecting the hardness of the transparency electrode such as ITO enough, can form with good film forming and by photoetching the metal oxide coating coating fluid of the envelope of pattern.The metal oxide coating of the present invention is in the presence of the metal salt shown in formula (III) with coating fluid, organo-tin compound shown in metal alkoxide shown in formula (I) and formula (IIA) or formula (IIB) is hydrolyzed in organic solvent, polycondensation, then add and separate out metal oxide coating coating fluid obtained by preventing agent.M1(OR1)n (I)(M1For Si, Mg, Zn, Ti, Ta, Zr, B, In, Bi or Nb.R1For the alkyl of carbon number 1~5.N is 2~5 integer).Sn(OOCR2)2 (IIA)(R2For that can be replaced by fluorine atoms or can have the alkyl of heteroatomic carbon number 1~20) Sn (R3COCHCOR4)2 (IIB)(R3、R4For that can be replaced by fluorine atoms or can have the alkyl of heteroatomic carbon number 1~20) M3(X)k (III)(M3For Al, In, Zn, Zr, Bi, La, Ta, Y or Ce.X is chlorine, nitric acid, sulfuric acid, acetic acid, oxalic acid, sulfamic acid, sulfonic acid, acetoacetate, acetylacetonate or their basic salt, k M3Valence mumber).
Description
Technical field
The present invention relates to photosensitive metal oxide coating coating fluid and metal oxide coating.
Background technology
In recent years, maximized along with the popularization of smart mobile phone, the display picture of mobile phone.With the above situation,
The exploitation that the touch-screen of input operation can be carried out using the display of display is just largely carried out.If using touch-screen, by
In the input method such as switch that need not be as the following formula, the maximization of display picture can be achieved.
Touch-screen detection finger or pen etc. touch the contact position of operating surface.Using the function, can using touch-screen as
Input unit uses.As the detection mode of contact position, for example, have resistive film mode or electrostatic capacitance mode etc., but electrostatic
Capacitive way realizes slimming due to substrate is set into 1 piece, therefore is adapted for the mode of portable equipment, in recent years just energetically
Developed.
Patent document 1 discloses the touch-screen of electrostatic capacitance mode.In the touch-screen, for detecting the coordinate of X-direction
The 1st transparency electrode and the 2nd transparency electrode of the coordinate for detecting Y-direction configured via as dielectric glass.Tool
For body, the multiple electrodes for being used to detect X-direction coordinate of interval configuration on a face of 1 piece of glass substrate, in another face
The upper multiple electrodes for being used to detect Y-direction coordinate of interval configuration.I.e., it is formed in the structure that each transparency electrode is set on 1 piece of substrate.
In addition, in patent document 2, the touch-screen of the electrostatic capacitance mode of another structure is disclosed.In the touch-screen,
On one face of transparency carrier, be configured to detect X-direction coordinate the 1st transparency electrode and for detecting Y-direction coordinate the 2nd
Transparency electrode, being situated between in their own portion of reporting to the leadship after accomplishing a task has insulating barrier and is not turned on it.If, need not be in base using the structure
Electrode is carried out on the two sides of plate to be formed.
Prior art literature
Patent document
Patent document 1：Japanese Patent Laid-Open 2003-173238 publications
Patent document 2：Japanese Patent Laid-Open 2010-28115 publications
The content of the invention
The technical problems to be solved by the invention
In conventional touch-screen, it is known that the acrylate layer being made up of acryhic material is set in the transparency electrodes such as ITO
Technology.The purpose of the acrylate layer is protection transparency electrode, but due to being organic material film, therefore as the hard of diaphragm
Degree deficiency.It is also weak with the adaptation of the transparency electrode such as ITO, turn into a reason of the reliability decrease for making touch-screen.
The present invention be in view of so the problem of and the invention completed.I.e., it is an object of the invention to provide have enough protections
The hardness of the transparency electrodes such as ITO, film forming are good and the inorganic oxide envelope of pattern can be formed by photo-mask process.
Technical scheme used by solution technical problem
The present inventor through conscientiously studying, as a result find by using containing by metal alkoxide, metal salt and tin compound with
Definite composition can solve above-mentioned technical problem than being condensed the polymeric metal oxide coating formation coating fluid that forms,
So as to complete the present invention.
That is, the present invention has following main points.
A kind of 1. metal oxide coating coating fluid, in the presence of the metal salt shown in lower formula (III), under containing
The mixture of the organo-tin compound shown in metal alkoxide and following formula (IIA) or (IIB) shown in formula (I) is in organic solvent
Hydrolysis, polycondensation, then add and separate out preventing agent and obtain.
M1(OR1)n (I)
In formula (I), M1Represent selected from silicon (Si), magnesium (Mg), zinc (Zn), titanium (Ti), tantalum (Ta), zirconium (Zr), boron (B), indium
(In), at least one or more metal of bismuth (Bi) and niobium (Nb).R1The alkyl of carbon number 1~5 is represented, n represents 2~5 integer.
Sn(OOCR2)2 (IIA)
In formula (IIA), R2Represent to be replaced by fluorine atoms and there can be the alkyl of heteroatomic carbon number 1~20.
Sn(R3COCHCOR4)2 (IIB)
In formula (IIB), R3And R4Represent to be replaced by fluorine atoms and there can be the alkyl of heteroatomic carbon number 1~20.
M2(X)k (III)
In formula (III), M2Represent selected from aluminium (Al), indium (In), zinc (Zn), zirconium (Zr), bismuth (Bi), lanthanum (La), tantalum (Ta),
At least one or more metal of yttrium (Y) and cerium (Ce), X represent chlorine, nitric acid, sulfuric acid, acetic acid, oxalic acid, sulfamic acid, sulfonic acid, second
Ethyl acetoacetic acid, acetylacetonate or their basic salt, k represent M2Valence mumber.
2. the metal oxide coating coating fluid as described in above-mentioned 1, wherein, the content of above-mentioned organo-tin compound is relative
In above-mentioned metal alkoxide molal quantity and above-mentioned organo-tin compound molal quantity 100 moles of % of total, be 30 moles of % with
On.
3. the metal oxide coating coating fluid as described in above-mentioned 1 or 2, wherein, above-mentioned precipitation preventing agent is selected from N-
Methyl-pyrrolidon, ethylene glycol, dimethylformamide, dimethyl acetamide, diethylene glycol, propane diols, hexylene glycol and they
At least one or more material of derivative.
4. the metal oxide coating coating fluid as any one of above-mentioned 1~3, wherein, relative to above-mentioned metal
Metallic atom (the M of alkoxide1) molal quantity (m1) and above-mentioned organo-tin compound metallic atom (Sn) molal quantity (mSn) and
Metallic atom (the M of above-mentioned metal salt2) molal quantity (m2) total, the metallic atom (M of above-mentioned metal salt2) molal quantity
(m2) mol ratio (m2/(m1+mSn+m2) it is 0.01~0.7.
5. the metal oxide coating coating fluid as any one of above-mentioned 1~4, wherein, above-mentioned metal alkoxide is
The hydrolytie polycondensation thing of silicon alkoxide or part thereof condensation polymer and Titanium alkoxides or part thereof condensation polymer.
6. the metal oxide coating coating fluid as any one of above-mentioned 1~4, wherein, above-mentioned metal alkoxide is
Silicon alkoxide.
7. the metal oxide coating coating fluid as any one of above-mentioned 1~6, wherein, above-mentioned organotin chemical combination
Thing is tin octoate (II), neodecanoic acid tin (II), oleic acid tin (II), tin oxalate (II), acetylacetone,2,4-pentanedione tin (II), hexafluoroacetylacetone
Tin (II) or trifluoroacetylacetone (TFA) tin (II).
8. the metal oxide coating coating fluid as any one of above-mentioned 1~7, wherein, above-mentioned metal salt is gold
Genus nitrobacter, metal sulfate, metal acetate, metal chloride, metal oxalate, metal aminosulfonate, metal sulfamate
Salt, metal acetyl acetate, metal acetylacetonates or their basic salt.
9. the metal oxide coating coating fluid as any one of above-mentioned 1~8, wherein, shown in upper formula (III)
Metal salt is the nitrate of aluminium, indium or cerium.
10. the metal oxide coating coating fluid as any one of above-mentioned 1~9, wherein, above-mentioned organic solvent bag
Include aklylene glycol class or its monoether derivative.
11. the metal of film forming aoxidizes using the metal oxide coating coating fluid any one of above-mentioned 1~10
Thing envelope.
The effect of invention
If using the present invention, it is possible to provide and energy good with the hardness of the transparency electrode such as protection ITO, film forming enough
Enough inorganic oxide envelopes that pattern is formed by photo-mask process, and for forming the painting of such inorganic oxide envelope
Cloth liquid.
Although still the effect above can be presented in uncertain why be made up of the present invention, speculate by containing appropriate metal
Salt, it can carry out the condensation reaction of the metal alkoxide and tin compound of the degree in composition state, it is anti-to thus be accordingly used in condensation
The light energy answered can be a small amount of, and the dissolubility difference of film as a result can be also produced under a small amount of light irradiation.
Embodiment
The metal oxide coating of the present invention is with the presence of the metal salt shown in formula (III), by formula with coating fluid
(I) organo-tin compound shown in metal alkoxide and formula (IIA) or formula (IIB) shown in hydrolyzes in organic solvent, polycondensation,
The metal oxide coating coating fluid that separates out preventing agent and must be characterized is added again.Hereinafter, each composition is described in detail respectively.
<Metal alkoxide>
Metal alkoxide is represented with following formula (I).
M1(OR1)n (I)
In formula (I), M1Represent selected from silicon (Si), magnesium (Mg), zinc (Zn), titanium (Ti), tantalum (Ta), zirconium (Zr), boron (B), indium
(In), at least one or more metal of bismuth (Bi) and niobium (Nb), wherein it is preferred that silicon (Si) or titanium (Ti), particularly preferred silicon
(Si)。R1The alkyl of carbon number 1~5 is represented, n represents 2~5 integer.
In addition, the metallic atom of formula (I) can be used alone, or it can be mixture of more than two kinds.
In the case where using silicon alkoxide or its part condensation polymer as the metal alkoxide shown in formula (I), it can use and contain
There are the one kind or two or more mixture or part condensation polymer of the compound shown in formula (V) (below 5 aggressiveness).
Si(OR’)4 (V)
In formula (V), R ' represents the alkyl of carbon number 1~5.
More specifically, as silicon alkoxide, for example, can be used tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane,
Tetraalkoxysilane class such as four butoxy silanes and four acetoxylsilanes etc..
In addition, in the case where using Titanium alkoxides or its part condensation polymer as the metal alkoxide shown in formula (I), can adopt
With the one kind or two or more mixture containing the compound shown in formula (VI) or part condensation polymer (below 4 aggressiveness).
Ti(OR”)4 (VI)
In formula (VI), R " represents the alkyl of carbon number 1~5.
More specifically, as Titanium alkoxides, the tetrol titanium compounds such as titanium tetraethoxide, four titanium propanolates and four butanol titaniums can be used
Deng.
Other, as the example of the metal alkoxide shown in formula (I), can enumerate tetraethoxide zirconium, four propyl alcohol zirconiums and four butanol zirconiums
Deng tetrol zirconium compounds, the triol aluminium compound such as three aluminium butoxides, aluminum isopropylate and three aluminium ethylates, or five propyl alcohol tantalums, with
And five pentol tantalum compound such as butanol tantalum etc..
<Organo-tin compound>
Organo-tin compound is divalence organo-tin compound, is represented with following formula (IIA) or formula (IIB).
Sn(OOCR2)2 (IIA)
R2Expression can be replaced by fluorine atoms and can have heteroatomic carbon number 1~20, preferably 1~10 alkyl.
Sn(R3COCHCOR4)2 (IIB)
R3And R4Expression can be replaced by fluorine atoms and can have heteroatomic carbon number 1~20, preferably 1~10 alkane
Base.
As above formula (IIA) concrete example, tin octoate (II), neodecanoic acid tin (II), oleic acid tin (II), tin oxalate can be enumerated
(II) etc..In addition, the concrete example as formula (IIB), can enumerate acetylacetone,2,4-pentanedione tin (II), hexafluoroacetylacetone tin (II), trifluoro
Acetylacetone,2,4-pentanedione tin (II) etc..
The content of the organo-tin compound of formula (IIA) or formula (IIB), it is mixed relative to formula (I) and formula (IIA) or formula (IIB)
Close total amount preferably 30 moles of more than the %, more preferably 25~70 moles of %, further preferred 30~70% of the mixture formed.Such as
Fruit is less than 25 moles of %, and the formation pattern of the metal oxide coating obtained sometimes can produce problem.If in addition, more than 70
Mole %, the then characteristic that hardness, storage stability, coating etc. are formed beyond pattern extremely decline sometimes.
<Metal salt>
The metal oxide coating of the present invention is organic in the presence of metal salt by above-mentioned mixture with coating fluid
In solvent hydrolysis, polycondensation and obtain.Herein, as metal salt, can be used in metal salt and the formula (III) shown in lower formula (III)
The oxalates of used metal.
M2(X)k (III)
(in formula (III), M2Represent selected from aluminium (Al), indium (In), zinc (Zn), zirconium (Zr), bismuth (Bi), lanthanum (La), tantalum
(Ta), at least one or more metal of yttrium (Y) and cerium (Ce), X represent chlorine, nitric acid, sulfuric acid, acetic acid, sulfamic acid, sulfonic acid, second
Ethyl acetoacetic acid, acetylacetonate or their basic salt, k represent M2Valence mumber.)
In the compound shown in formula (III), particularly preferred metal nitrate, metal chloride salt, metal oxalate or
Its basic salt of person.Wherein, in terms of the easiness and the storage stability of application composition obtained, more preferably aluminium, indium
Or the nitrate of cerium.
As the present invention metal oxide coating coating fluid used in organic solvent, can enumerate methanol, ethanol,
The glycols such as the esters such as the alcohols such as propyl alcohol, butanol, ethyl acetate, ethylene glycol or the ethers such as its ester derivant, diethyl ether, acetone,
The ketones such as methyl ethyl ketone, cyclohexanone, or aromatic hydrocarbons such as benzene, toluene etc., they can be used alone or in combination.
In the metal oxide coating coating fluid of the present invention, in the case of containing Titanium alkoxides composition, as organic molten
Contained aklylene glycol class or its monoether, can enumerate ethylene glycol, diethylene glycol, propane diols, hexylene glycol or their list in agent
Methyl, single ethyl, single propyl group, monobutyl or single phenyl ether.
If in the organic solvent for the metal oxide coating coating fluid of the present invention contained di-alcohols or its
Monoether is less than 1 relative to the mol ratio of Titanium alkoxides, then the stabilizing effect of Titanium alkoxides is tailed off, the storage of coating composition is steady
Qualitative variation.On the other hand, any problem will not be produced if largely glycols or its monoether is used.For example, even if coating
Even all above-mentioned glycols of organic solvent or its monoether used in composition.But in application composition not
In the case of containing Titanium alkoxides, it is not necessary to specially containing above-mentioned glycol and/or its monoether.
The metal oxide coating of the present invention is prevented with precipitation preventing agent contained in coating fluid when being formed and being coated with envelope
Metal salt separates out in film.As preventing agent is separated out, can enumerate selected from N- methyl-pyrrolidons, dimethylformamide, diformazan
Yl acetamide, ethylene glycol, diethylene glycol, propane diols, hexylene glycol and their derivative it is at least one kind of, these can be used extremely
It is few more than a kind.
For separating out preventing agent, the metal of metal salt is scaled metal oxide, with (precipitation preventing agent)/(metal oxygen
Compound) >=1 (weight ratio) ratio use.If weight than less than 1, formed be coated with envelope when metal salt precipitation prevent
Effect dies down.On the other hand, it is a large amount of that any influence will not be brought to application composition using precipitation preventing agent.
Separating out preventing agent can be in metal alkoxide, especially silicon alkoxide, Titanium alkoxides or silicon alkoxide or Titanium alkoxides in metal salt
In the presence of be hydrolyzed, polycondensation reaction when add, also can hydrolysis, polycondensation reaction terminate after add.
Relative to the metallic atom (M of above-mentioned metal alkoxide1) molal quantity (m1) and above-mentioned organo-tin compound metal raw
Molal quantity (the m of sub (Sn)Sn) and above-mentioned metal salt metallic atom (M2) molal quantity (m2) total, metal oxygen of the invention
Metallic atom (the M of contained above-mentioned metal salt in compound envelope coating fluid2) molal quantity (m2) mol ratio (m2/(m1+mSn
+m2) it is preferably 0.01~0.7.
If above-mentioned mol ratio is less than 0.01, because the obtained mechanical strength of envelope is not enough without preferred.The opposing party
Face, if it exceeds 0.7, then adaptation decline of the coat film to base materials such as glass substrate or transparency electrodes.Further, with 450
In the case that low temperature below DEG C is burnt till, the chemical-resistant of obtained coat film also has the tendency of decline.Wherein, it is above-mentioned
Mol ratio be particularly preferably more than 0.03, less than 0.6, in addition, the metal raw of metal alkoxide contained in application composition
In the case that son is a variety of, above-mentioned metallic atom (M1) refer to the total of various metals atom.
<Other compositions>
The metal oxide coating of present invention metal alkoxide used in coating fluid is not damaging the effect of the present invention
In the range of, the 2nd metal alkoxide represented by lower formula (IV) can be used as other compositions.
R2 lM3(OR3)m-1 (IV)
In formula (IV), M3Represent selected from silicon (Si), magnesium (Mg), zinc (Zn), titanium (Ti), tantalum (Ta), zirconium (Zr), boron (B), indium
(In), at least one or more metal of bismuth (Bi) and niobium (Nb).R2Represent hydrogen atom or can have heteroatomic carbon number 1~
20 1 valency alkyl, this can have heteroatomic carbon number 1~20 1 valency alkyl can be replaced by fluorine atoms, and can by halogen atom,
Vinyl, glycidoxy, sulfydryl, methacryloxy, acryloxy, NCO, amino or Carbamido substituted.
R3Represent the alkyl of carbon number 1~5.M represents 2~5 integer.L is 1 or 2 in the case where m is 3, is in the case where m is 4
Any value in 1~3, any value in being 1~4 in the case that m is 5.
In addition, metallic atom (the M of above-mentioned 2nd metal alkoxide3) consider from easness obtained etc., preferred silicon.
More specifically, MTMS, methyl tripropoxy silane, methyl triacetoxyl group silicon can be enumerated
Alkane, the butoxy silane of methyl three, the amoxy of methyl three (pentoxy) silane, the amoxy of methyl three (amyloxy) silane, methyl
Triple phenoxyl silane, the benzyloxy base silane of methyl three, methyl triphen Ethoxysilane, glycidyl oxy methyl trimethoxy silane,
Glycidyl oxy methyl triethoxysilane, α-glycidoxyethyl trimethoxy silane, the second of α-glycidoxyethyl three
TMOS, beta epoxide Among trimethoxy silane, beta epoxide Among triethoxysilane, the oxygen of α-epoxy third
Base propyl trimethoxy silicane, α-glycidoxypropyl group triethoxysilane, beta epoxide propoxypropyl trimethoxy silane,
Beta epoxide propoxypropyl triethoxysilane, γ-glycidoxypropyltrime,hoxysilane, γ-glycidoxypropyl group
Triethoxysilane, γ-glycidoxypropyl group tripropoxy silane, the butoxy silane of γ-glycidoxypropyl group three, γ-
Glycidoxypropyl group triple phenoxyl silane, α-glycidoxy butyl trimethoxy silane, α-second of glycidoxy butyl three
TMOS, beta epoxide propyloxybutyl triethoxysilane, γ-glycidoxy butyl trimethoxy silane, γ-epoxy third
Epoxide butyl triethoxysilane, δ-glycidoxy butyl trimethoxy silane, δ-glycidoxy butyl triethoxysilicane
Alkane, (3,4- epoxycyclohexyls) MTMS, (3,4- epoxycyclohexyls) MTES, β-(3,4-
Epoxycyclohexyl) ethyl trimethoxy silane, β-(3,4- epoxycyclohexyls) ethyl triethoxysilane, β-(3,4- epoxide rings
Hexyl) ethyl tripropoxy silane, the β-butoxy silane of (3,4- epoxycyclohexyls) ethyl three, β-(3,4- epoxycyclohexyls) second
Base triple phenoxyl silane, γ-(3,4- epoxycyclohexyls) propyl trimethoxy silicane, γ-(3,4- epoxycyclohexyls) propyl group three
Ethoxysilane, δ-(3,4- epoxycyclohexyls) butyl trimethoxy silane, δ-(3,4- epoxycyclohexyls) butyl triethoxy
Silane, glycidyl oxy methyl methyl dimethoxysilane, glycidyl oxy methyl methyldiethoxysilane, the oxygen of α-epoxy third
Base ethyl-methyl dimethoxysilane, α-glycidoxyethyl methyldiethoxysilane, beta epoxide Among methyl
Dimethoxysilane, beta epoxide Among ethyldimethoxysilane, α-glycidoxypropyl dimethoxy silicon
Alkane, α-glycidoxypropyl diethoxy silane, beta epoxide propoxypropyl methyl dimethoxysilane, beta epoxide third
Epoxide ethyl dimethoxysilane, γ-glycidoxypropyl dimethoxysilane, γ-glycidoxypropyl group
Methyldiethoxysilane, γ-glycidoxypropyl dipropoxy silane, the fourth of γ-glycidoxypropyl two
TMOS, γ-glycidoxypropyl hexichol TMOS, γ-glycidoxypropyl group ethyldimethoxysilane,
γ-glycidoxypropyl group ethyl diethoxy silane, γ-glycidoxypropyl group vinyl dimethoxysilane, γ-epoxy
Propoxypropylvinyl base diethoxy silane, ethyl trimethoxy silane, ethyl triethoxysilane, vinyl trimethoxy
Silane, VTES, vinyltriacetoxy silane, phenyltrimethoxysila,e, phenyltriethoxy silane
Alkane, phenyl triacetoxysilane, γ-r-chloropropyl trimethoxyl silane, γ-chloropropyl triethoxysilane, γ-chloropropyl three
Acetoxylsilane, 3,3,3- trifluoro propyls trimethoxy silane, beta-cyano ethyl triethoxysilane, chloromethyl trimethoxy
Silane, chloromethyl triethoxysilane, N- (beta-aminoethyl) gamma-aminos propyl trimethoxy silicane, N- (beta-aminoethyl)
Gamma-amino hydroxypropyl methyl dimethoxysilane, gamma-amino hydroxypropyl methyl dimethoxysilane, N- (beta-aminoethyl) gamma-amino
Propyl-triethoxysilicane, N- (beta-aminoethyl) gamma-amino hydroxypropyl methyl diethoxy silane, dimethylformamide dimethyl epoxide silicon
Alkane, phenyl methyl dimethoxysilane, dimethyldiethoxysilane, phenyl methyl diethoxy silane, γ-chloropropyl
Dimethoxysilane, γ-chloropropyl diethoxy silane, dimethyl 2 acetoxyl group silane, γ-methacryloxy
Hydroxypropyl methyl dimethoxysilane, γ-methacryloyloxypropyl methyl diethoxy silane, γ-mercaptopropyi methyl two
Methoxy silane, γ-mercapto methyl diethoxy silane, methylvinyldimethoxysilane, γ-ureido-propyl triethoxy
Silane, γ-ureido-propyl trimethoxy silane, γ-ureido-propyl tripropoxy silane, the second of (R)-N-1- phenylethyls-N'- three
TMOS base propyl group urea, (R)-N-1- phenylethyl-N'- trimethoxysilylpropyls urea, allyltriethoxysilane,
3- methacryloxypropyl trimethoxy silanes, 3- methacryloxypropyls, 3- acryloyl-oxies
Base propyl trimethoxy silicane, 3- acryloxypropyls triethoxysilane, 3- NCOs propyl-triethoxysilicane,
Trifluoro propyl trimethoxy silane, bromopropyl triethoxysilane, diethyldiethoxysilane, diethyl dimethoxy silicon
It is alkane, dimethoxydiphenylsilane, diphenyl diethoxy silane, trimethylethoxysilane, trimethylmethoxysilane, right
Styryl trimethoxy silane, to styryl triethoxysilane, to styryl tripropoxy silane or methyl second
Alkenyl diethoxy silane etc..They can be used alone or two or more is applied in combination.
In addition, in the case of containing above-mentioned 2nd metal alkoxide, relative to the metallic atom (M of above-mentioned metal alkoxide1)
Molal quantity (m1) and above-mentioned organo-tin compound metallic atom (Sn) molal quantity (mSn) and above-mentioned metal salt metallic atom
(M2) molal quantity (m2) and the 2nd metal alkoxide metallic atom (M3) molal quantity (m3) total, metal oxide coating use
Metallic atom (the M of contained above-mentioned metal salt in coating fluid2) molal quantity (m2) mol ratio (m2/(m1+mSn+m2+m3)) excellent
Elect 0.01~0.7, more preferably 0.03~0.6 as.
Moreover, in the present invention, on the premise of effect of the present invention is not damaged, such as inorganic particles, metal oxygen can be included
Alkane (メ タ ロ キ サ Application；Metalloxane) the composition such as oligomer, metal oxygen alkane polymer, levelling agent, surfactant.
As inorganic particles, preferably silicon dioxide microparticle, alumina particulate, titanium dioxide fine particles and magnesium fluoride particulate etc.
Particulate, the colloidal solution of these particularly preferred inorganic particles.The colloidal solution both can be to be scattered in inorganic particulate powder point
The colloidal solution or the colloidal solution of commercial goods that dispersion media forms.
In the present invention, by containing inorganic particles, formed solidification envelope can be assigned with surface configuration or other functions.
Preferably 0.001~0.2 μm, more preferably 0.001~0.1 μm of the average grain diameter of inorganic particles.The average grain diameter of inorganic particles exceedes
At 0.2 μm, the transparency reduction for the solidification envelope for sometimes using prepared coating fluid and being formed.
As the decentralized medium of inorganic particles, water, organic solvent can be enumerated.From the stability of envelope formation coating fluid
From the point of view of viewpoint, the pH or pKa of colloidal solution are preferably adjusted to 1~10.More preferably 2~7.
Organic solvent for the decentralized medium of colloidal solution can enumerate methanol, ethanol, propyl alcohol, butanol, ethylene glycol, the third two
The alcohols such as alcohol, butanediol, pentanediol, 2- methyl -2,4-PD, diethylene glycol, DPG, ethylene glycol monopropyl ether；First
The ketones such as base ethyl ketone, methyl iso-butyl ketone (MIBK)；The aromatic hydrocarbons such as toluene, dimethylbenzene；Dimethylformamide, dimethyl acetamide, N-
The amide-types such as methyl pyrrolidone；The esters such as ethyl acetate, butyl acetate, gamma-butyrolacton；Tetrahydrofuran, 1,4- bis-Alkane
Deng ethers.Wherein, preferably alcohols or ketone.These organic solvents can be used as decentralized medium individually or after two or more mixing.
<The polymerization of composition>
As the method for composition contained in the metal oxide coating coating fluid of the polycondensation present invention, use can be enumerated
Organo-tin compound shown in metal alkoxide, formula (IIA) or formula (IIB) shown in formula (I) and the formula used as needed
(IV) metal salt of the 2nd metal alkoxide and formula (III) shown in is hydrolyzed in alcohol or solvents such as glycols, the side of polycondensation
Method.Generally, for the purpose of promoting hydrolysis, condensation reaction, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, oxalic acid, maleic acid, richness are used
The catalyst such as the metal salt of the alkali such as the acid such as horse acid, ammonia, methylamine, ethamine, monoethanolamine, triethylamine, hydrochloric acid, sulfuric acid, nitric acid etc..This hair
In bright, the metal salt described in formula (III) is just in these.It is in addition, general also by the way that the solution of alkoxy silane will have been dissolved
Heated further to promote hydrolysis, condensation reaction.Now, heating-up temperature and heat time can suitably be selected as needed
Select.The scope that preferably 5 DEG C~100 DEG C of reaction temperature, more preferably 10 DEG C~80 DEG C of scope, further preferred 15 DEG C~60 DEG C
Scope.The scope in preferably 5 minutes~6 hours reaction time, the scope of more preferably 10 minutes~5 hours.
For the solid component concentration of the metal oxide coating coating fluid of the present invention, by metal alkoxide and organotin
In the case that compound and metal salt are scaled metal oxide, as solid constituent, preferably 0.5~20wt% scope.Such as
Fruit solid constituent is deteriorated more than 20wt%, the then storage stability of application composition, and unmanageable metal oxide layer
Thickness.On the other hand, if solid constituent is in below 0.5wt%, the thickness of obtained metal oxide layer is thinning, is terrible
Repeatedly coating is needed to defined thickness.
The metal oxide coating coating fluid of the present invention is by M (OR) in the presence of metal salt (such as aluminium salt)nInstitute
The metal alkoxide and organo-tin compound shown is hydrolyzed, is condensed and obtains in organic solvent.The hydrolysis of metal alkoxide is used
Water amount, relative to the total mole number of metal alkoxide, 2~24 are preferably set in terms of mol ratio conversion.More preferably 2~20.
In the case that mol ratio (amount (mole) of water/(total mole number of metal alkoxide)) is less than 2, the hydrolysis of metal alkoxide is not filled
Point, film forming reduces, and the intensity of obtained metal oxide coating also reduces, thus not preferred.In addition, it is more than in mol ratio
In the case of 24, because polycondensation continues, therefore storage stability reduces, thus not preferred.
Also it is identical in the case of using other metal alkoxides.
<Film>
The metal oxide coating of the present invention forms film with coating fluid using conventional rubbing method, can be used as this afterwards
The metal oxide coating of invention.As rubbing method, such as dip coating, spin-coating method, spraying process, flow coat method, bristle can be used to apply
Method, stick coating method, gravure coating process, roller transfer method, scraper for coating method, air knife coating method, slot coated method, silk screen print method, spray
The method of the use of ink and water or adagio print process etc..Wherein preferably use spin-coating method, slot coated method, scraper for coating method or spraying process.
<Dry>
By will be formed in the dried coating film on base material, burning till, the metal oxide coating of the present invention can obtain.Back tender
The scope of the temperature range, more preferably 40~120 DEG C of preferred room temperature~150 DEG C of sequence.In addition, preferably 30 seconds~10 minutes its time
Left and right, more preferably 1~8 minute or so.As drying means, preferably using heating plate or heated air circulation type stove etc..
<Form pattern process>
In the present invention, if being utilized to the film dried in the deliquescent scope kept to developer solution includes ultraviolet region
Light be exposed, then occur the oxidation of the tin compound in metal oxide coating, the desciccator diaphragm of exposure portion is optionally not
Dissolve.Light source as the light including ultraviolet region, including more than 180nm below 400nm wavelength is easily obtained due to commercially available
, thus preferably.As light source, such as irradiation energy line such as mercury lamp, metal halide lamp, xenon lamp, Excimer lamp etc. can be enumerated.
As exposure, can suitably it select as needed, preferably 100~10000mJ/cm in terms of wavelength 365nm conversions2,
More preferably 150~8000mJ/cm2。
Developer solution used in the present invention is the developer solution for the etching for carrying out metal oxide coating.Therefore, alkali can be used
Property compound solution or acid compound solution.As alkaline compound solution (alkaline-based developer), such as alkali metal can be used
Or the aqueous solution of the hydroxide of quaternary ammonium salt, silicate, phosphate, acetate, amine etc..As concrete example, hydrogen-oxygen can be enumerated
Change sodium, potassium hydroxide, ammonium hydroxide, trimethyl benzyl ammonium hydroxide, TMAH, sodium metasilicate, sodium phosphate, acetic acid
The aqueous solution of sodium, MEA, diethanol amine, triethanolamine etc..As acid compound solution (acid developer), preferably salt
The aqueous solution of the organic acid such as the inorganic acids such as acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, formic acid, acetic acid.Wherein, relative to the amount of water,
The amount of alkali compounds or acid compound is preferably capable of fully producing the amount of poor solubility between exposure portion and unexposed portion.
<Burn till>
In view of the heat resistance of other component parts of touch-screen, the scope that preferably 100 DEG C~300 DEG C of firing process, more
It is preferred that in the range of 150 DEG C~250 DEG C.In addition, preferably more than 5 minutes, more preferably more than 15 minutes its time.As burning till
Method, preferably using heating plate, heated air circulation type stove, infrared heating heating furnace etc..
Embodiment
Hereinafter, more specific description is carried out by embodiments of the invention, but is not read as pertaining only to these embodiments.
The abbreviation of compound used is as follows in the present embodiment.
TEOS：Tetraethoxysilane
OcSn：Tin octoate
TIPT：Titanium tetraisopropylate
InN：Indium nitrate trihydrate
AN：Aluminum nitrate nonahydrate
HG：2- methyl -2,4-PD (alias：Hexylene glycol)
BCS：Butoxy ethanol (alias：Butyl cellosolve)
PB：Propylene glycol monobutyl ether
EG：Ethylene glycol
<Synthesis example 1>(embodiment 1)
InN 11.2g and water 3.2g are added in 300mL flasks and are stirred, dissolve InN.HG is put into wherein
96.3g, PB 13.8g and TEOS 26.2g, it is stirred at room temperature 30 minutes.Afterwards, BCS 27.5g and OcSn are put into
21.8g, further it is stirred at room temperature 30 minutes, obtains solution<K1>.
<Synthesis example 2>(embodiment 2)
InN 9.2g and water 2.7g are added in 300mL flasks and are stirred, dissolve InN.HG is put into wherein
97.7g, PB 14.0g and TEOS 16.5g, it is stirred at room temperature 30 minutes.Afterwards, BCS 27.9g and OcSn are put into
32.1g, further it is stirred at room temperature 30 minutes, obtains solution<K2>.
<Synthesis example 3>(comparative example 1)
<A liquid>
AN 12.1g and water 2.8g are added in 200mL flasks and are stirred, dissolve AN.Be put into wherein EG 13.7g,
HG 39.2g, BCS 37.2g and TEOS 22.9g, it is stirred at room temperature 30 minutes.
<B liquid>
TIPT 13.4g and HG 58.8g are put into 300mL flasks, are stirred at room temperature 30 minutes.
Mixing<A liquid>With<B liquid>, it is stirred at room temperature and obtains within 30 minutes solution (K3).
<Synthesis example 4>(comparative example 2)
<C liquid>
AN 11.5g and water 2.7g are added in 200mL flasks and are stirred, dissolve AN.Be put into wherein EG 13.7g,
HG 39.3g, BCS 37.3g and TEOS 15.5g, it is stirred at room temperature 30 minutes.
<D liquid>
TIPT 21.2g and HG 58.9g are put into 300mL flasks, are stirred at room temperature 30 minutes.
Mixing<C liquid>With<D liquid>, it is stirred at room temperature and obtains within 30 minutes solution (K4).
<Film method>
The solution of embodiment is subjected to pressure filtration with the filter membrane in 0.5 μm of aperture, passes through spin-coating method film forming on substrate.Will
The substrate is dried 3 minutes in 60 DEG C of heating plate.
In above-mentioned film method, respectively will the envelope as obtained by solution K1 and K2, will be by solution K3 as KL1 and KL2
And envelope obtained by K4 is as KM1 and KM2.
<Film Thickness Ratio>
Envelope is made with above-mentioned film method in Si wafer substrates.Afterwards, using ultraviolet lamp (Ai Gela Ficks
This Co. Ltd. system (ア イ グ ラ Off ィ ッ Network ス societies), UB 011-3A types), high-pressure sodium lamp (input power 1000W) is with 50mW/
cm2(wavelength 365nm conversions) irradiates 10,20 and 60 seconds (accumulative 500,1000 and 3000mJ/cm respectively2), use optics
Formula film thickness gauge determines respective thickness, and (this Co., Ltd. (Off ィ Le メ ト リ ッ Network ス societies) of Fei Ermei Dorics makes, F20 films measure
System), obtain the ratio with the thickness of ultraviolet pre-irradiation using its result.
<Crackle is evaluated>
The acrylic film of 2 μm of thickness is formed on the glass substrate.The formation of acrylic film is carried out as follows.First, by propylene
Sour material compositions carry out pressure filtration with the filter membrane in 0.5 μm of aperture, and film is formed by spin-coating method in the whole face of glass substrate.Connect
, after the substrate on hot plate heat drying 2 minutes, move in heated air circulation type stove, burn till 30 minutes.Thereby, in glass
Acrylic film is formed on glass substrate.
Envelope is made with above-mentioned film method on aforesaid propylene sorrel.Then, using high-pressure sodium lamp (input power 1000W)
With 50mW/cm2The luminous intensity of (wavelength 365nm conversions) irradiates 2 minutes ultraviolets.Ultraviolet irradiation amount is set to 6000mJ/cm2。
After uv irradiation, move to and be set as in 230 DEG C of heated air circulation type stove, 30 minutes burn till.In this way, on substrate
Coat film is made.
For the metewand of crackle evaluation, on the coat film on substrate, what is do not cracked is evaluated as ◎, in face
What is do not produced but only cracked at edge is evaluated as zero, and what whole face cracked be evaluated as ×.
<Pattern forms experiment>
Envelope is made with above-mentioned film method on Cr evaporation glass substrates.Then, Cr is placed in the half of the substrate to steam
Glass plating, it can be made into ultraviolet exposure part and unexposed portion.Wherein, using ultraviolet lamp (Ai Gela Ficks this
Co. Ltd. system, UB 011-3A types), high-pressure sodium lamp (input power 1000W) is with 50mW/cm2(wavelength 365nm conversions) difference
Irradiation 10,20 and 60 seconds.(accumulative 500,1000 and 3000mJ/cm2)
Afterwards, impregnated in 2.38% tetramethylammonium hydroxide aqueous solution 30 seconds, it is winged unnecessary then to be blown by air blower
After water droplet, visual observations film surface.It is carried out as follows evaluation：To not there is no film completely in face as 0, only marginal portion remaining is some
The conduct 1 of film, if only in face remaining dry film conduct 2, the conduct 3 of a certain degree of film of remaining in face, only film surface has
Some rotten conducts 4, the completely conduct 5 without change.
Above-mentioned Film Thickness Ratio and crackle evaluation result is summarized in table 1, forms pattern result of the test and is summarized in table 2.
[table 1]
[table 2]
As shown in Table 1, compared with comparative example 1 and 2, the thickness reduction of embodiment 1 and 2 is less.In other words, volume
Shrink few.Therefore, when ultraviolet irradiates or when of burning till etc., the deformation with lower floor can diminish.Therefore, such as crackle evaluation result institute
Show, embodiment 1 and 2 does not also crack in the case that lower floor is protective organic.
In addition, as shown in Table 2, embodiment 1 and 2 can form pattern with 500mJ or so exposure.On the other hand,
Comparative example 1 and 2 irradiations without more than 3000mJ cannot form pattern.Think comparative example 2 and 3 in less photograph
Under the amount of penetrating, the consistency deficiency of film.
Understand that embodiment 1 and 2 is irradiated by ultraviolet, can be caused while the deformation efficiently and to other layers is small
Close film.
The possibility utilized in industry
, can be in the various electronics devices using touch-screen as representative by using the metal oxide coating coating fluid of the present invention
Obtain protecting the metal oxide coating of complicated electrode pattern in the manufacture of part.
Specification, the power for the Japanese patent application 2012-135055 filed an application on June 14th, 2012 are quoted herein
The announcement of sharp claim and the full content of specification digest as description of the invention.
Claims (9)
1. a kind of metal oxide coating coating fluid, it is characterised in that in following formula（III）In the presence of shown metal salt,
Following formula will be contained（I）Shown metal alkoxide and following formula（IIA）Or formula（IIB）The mixture of shown organo-tin compound exists
Water in Organic Solvents solution, polycondensation, then add and separate out preventing agent and obtain；
The content of the organo-tin compound is relative to the molal quantity of the metal alkoxide and mole of the organo-tin compound
Several 100 moles of % of total, it is 30 moles of more than %；
Relative to the metallic atom of the metal alkoxide（M1）Molal quantity（m1）With the metallic atom of the organo-tin compound
（Sn）Molal quantity（mSn）With the metallic atom of the metal salt（M2）Molal quantity（m2）Total, the metal of the metal salt
Atom（M2）Molal quantity（m2）Mol ratio（m2/（m1+mSn+m2）For 0.01~0.7；
M1（OR1）n（I）
Formula（I）In, M1Expression is selected from silicon（Si）, magnesium（Mg）, zinc（Zn）, titanium（Ti）, tantalum（Ta）, zirconium（Zr）, boron（B）, indium（In）、
Bismuth（Bi）And niobium（Nb）At least one or more metal, R1The alkyl of carbon number 1~5 is represented, n represents 2~5 integer；
Sn（OOCR2）2（IIA）
Formula（IIA）In, R2Represent to be replaced by fluorine atoms and there can be the alkyl of heteroatomic carbon number 1~20；
Sn（R3COCHCOR4）2（IIB）
Formula（IIB）In, R3And R4Represent to be replaced by fluorine atoms and there can be the alkyl of heteroatomic carbon number 1~20；
M2（X）k（III）
Formula（III）In, M2Expression is selected from aluminium（Al）, indium（In）, zinc（Zn）, zirconium（Zr）, bismuth（Bi）, lanthanum（La）, tantalum（Ta）, yttrium（Y）
And cerium（Ce）At least one or more metal, X represent chlorine, nitric acid, sulfuric acid, acetic acid, oxalic acid, sulfamic acid, sulfonic acid, acetyl second
Acid, acetylacetonate or their basic salt, k represent M2Valence mumber.
2. metal oxide coating coating fluid as claimed in claim 1, it is characterised in that it is described precipitation preventing agent be selected from
N- methyl-pyrrolidons, ethylene glycol, dimethylformamide, dimethyl acetamide, diethylene glycol, propane diols, hexylene glycol and they
Derivative at least one or more material.
3. metal oxide coating coating fluid as claimed in claim 1 or 2, it is characterised in that the metal alkoxide is silicon
The condensation polymer of alkoxide or part thereof condensation polymer and Titanium alkoxides or part thereof condensation polymer.
4. metal oxide coating coating fluid as claimed in claim 1 or 2, it is characterised in that the metal alkoxide is silicon
Alkoxide.
5. metal oxide coating coating fluid as claimed in claim 1 or 2, it is characterised in that the organo-tin compound
For tin octoate（II）, neodecanoic acid tin（II）, oleic acid tin（II）, tin oxalate（II）, acetylacetone,2,4-pentanedione tin（II）, hexafluoroacetylacetone tin
（II）Or trifluoroacetylacetone (TFA) tin（II）.
6. metal oxide coating coating fluid as claimed in claim 1 or 2, it is characterised in that the metal salt is metal
Nitrate, metal sulfate, metal acetate, metal chloride, metal oxalate, metal aminosulfonate, metal sulfonate,
Metal acetyl acetate, metal acetylacetonates or their basic salt.
7. metal oxide coating coating fluid as claimed in claim 1 or 2, it is characterised in that above formula（III）Shown gold
Category salt is the nitrate of aluminium, indium or cerium.
8. metal oxide coating coating fluid as claimed in claim 1 or 2, it is characterised in that the organic solvent includes
Aklylene glycol class or its monoether derivative.
9. usage right requires the metal oxide of the metal oxide coating coating fluid any one of 1~8 and film forming
Envelope.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012135055 | 2012-06-14 | ||
| JP2012-135055 | 2012-06-14 | ||
| PCT/JP2013/066269 WO2013187450A1 (en) | 2012-06-14 | 2013-06-12 | Coating fluid for metal oxide coating film and metal oxide coating film |
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| Publication Number | Publication Date |
|---|---|
| CN104583350A CN104583350A (en) | 2015-04-29 |
| CN104583350B true CN104583350B (en) | 2018-04-10 |
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| CN201380043117.1A Active CN104583350B (en) | 2012-06-14 | 2013-06-12 | Metal oxide coating coating fluid and metal oxide coating |
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| Country | Link |
|---|---|
| JP (1) | JP6156373B2 (en) |
| KR (1) | KR102190716B1 (en) |
| CN (1) | CN104583350B (en) |
| TW (1) | TWI613163B (en) |
| WO (1) | WO2013187450A1 (en) |
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| JPS549639B2 (en) * | 1973-04-12 | 1979-04-26 | ||
| JPS57140162A (en) * | 1981-02-24 | 1982-08-30 | Nippon Sheet Glass Co Ltd | Coating polycarbonate group resin shape article |
| JP2881847B2 (en) * | 1988-12-15 | 1999-04-12 | 日産化学工業株式会社 | Coating composition and method for producing the same |
| JP3825813B2 (en) * | 1992-07-17 | 2006-09-27 | 日産化学工業株式会社 | Coating liquid for forming high refractive index insulating coating for liquid crystal display |
| JPH06347605A (en) * | 1993-06-04 | 1994-12-22 | Asahi Optical Co Ltd | Production of coating composition |
| JP3360408B2 (en) * | 1994-04-15 | 2002-12-24 | 日産化学工業株式会社 | Coating solution for metal oxide film formation |
| JPH11209692A (en) * | 1998-01-23 | 1999-08-03 | Dainippon Ink & Chem Inc | Coated article |
| JP2003173238A (en) | 2001-12-05 | 2003-06-20 | Sharp Corp | Touch sensor and display device with touch sensor |
| JP4101632B2 (en) * | 2002-11-01 | 2008-06-18 | 株式会社カネカ | CURABLE COMPOSITION AND METHOD OF IMPROVING RESTORE AND CREEP |
| JP4542369B2 (en) * | 2004-05-21 | 2010-09-15 | 株式会社Ａｄｅｋａ | Coating liquid for forming transparent conductive film and method for forming transparent conductive film |
| JP4941302B2 (en) * | 2005-08-19 | 2012-05-30 | 日産化学工業株式会社 | Method for producing coating liquid for film formation |
| JP5432430B2 (en) * | 2006-11-07 | 2014-03-05 | 日揮触媒化成株式会社 | Coating liquid for forming transparent film and substrate with transparent film |
| US9556317B2 (en) * | 2007-07-03 | 2017-01-31 | Nippon Soda Co., Ltd. | Molding sheet for forming hard coat layer |
| JP5196993B2 (en) * | 2007-12-27 | 2013-05-15 | 伊藤光学工業株式会社 | Hard coat composition |
| US9342176B2 (en) | 2008-07-21 | 2016-05-17 | Samsung Display Co., Ltd. | Organic light emitting display device |
| JP5431055B2 (en) * | 2009-07-30 | 2014-03-05 | ナミックス株式会社 | Conductive composition, conductor and method for producing the same |
| CN103443750B (en) * | 2011-01-20 | 2017-02-15 | 日产化学工业株式会社 | Coating composition for touch panels, coating film, and touch panel |
| CN104011260B (en) * | 2011-10-31 | 2018-02-13 | 日产化学工业株式会社 | Manufacture method, metal oxide coating coating fluid and the metal oxide coating of metal oxide coating coating fluid |
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2013
- 2013-06-12 JP JP2014521379A patent/JP6156373B2/en active Active
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| KR102190716B1 (en) | 2020-12-14 |
| JPWO2013187450A1 (en) | 2016-02-08 |
| TWI613163B (en) | 2018-02-01 |
| JP6156373B2 (en) | 2017-07-05 |
| WO2013187450A1 (en) | 2013-12-19 |
| TW201412671A (en) | 2014-04-01 |
| CN104583350A (en) | 2015-04-29 |
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