CN104916350A - Repairing and regeneration method for transparent conductive film and transparent conductive laminating body - Google Patents

Repairing and regeneration method for transparent conductive film and transparent conductive laminating body Download PDF

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Publication number
CN104916350A
CN104916350A CN201510109016.0A CN201510109016A CN104916350A CN 104916350 A CN104916350 A CN 104916350A CN 201510109016 A CN201510109016 A CN 201510109016A CN 104916350 A CN104916350 A CN 104916350A
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nesa coating
manufacture
society
recess
film
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CN104916350B (en
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大堀达也
久留岛康功
常田义真
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Nagase Chemtex Corp
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Nagase Chemtex Corp
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Abstract

The invention provides a repairing and regenerating method for a transparent conductive film and a transparent conductive laminating body. A method for repairing and regenerating a transparent conductive film by making the defect part of the film invisible when the defect part of the film exists in a full length scope and a transparent conductive laminating body having a transparent conductive film repaired and regenerated through the method are provided. The invention further relates to a repairing and regenerating method for a transparent conductive film. The method includes accumulating transparent resin layer on a recessed portion layer on the transparent conductive film, coating a composition for the transparent conductive film containing conductive material to form the transparent conductive film arranged on at least one surface of a substrate, and pressurizing the defect transparent film to form at least one of a recessed set with the total length of the recessed portion of 10-300 micrometers, wherein the recessed portion is selected from recessed portion due to substrate shape, damage or defect of the transparent conductive film and recessed portion formed due to removal of impurities from the transparent conductive film.

Description

The reparation of nesa coating and renovation process and electrically conducting transparent lamination body
Technical field
The present invention relates to the reparation of nesa coating and renovation process and electrically conducting transparent lamination body.
Background technology
Nesa coating is employed in the display unit of smart mobile phone etc., but, in the process forming nesa coating or in the process being assembled to display unit, produce various film defect sometimes.Particularly, in nesa coating, produce depression with certain above size or in the process of formation nesa coating, foreign matter or bubble are mixed into nesa coating, even if so direct formation display unit, these film defective part also can be clearly in sight.In general, use ITO sputtered film as nesa coating, but once the film defect produced is difficult to repair, have to discard as waste product.Therefore, existing problems in productivity ratio and cost.
Summary of the invention
The problem that invention will solve
The object of the present invention is to provide a kind of method of film defective part invisibleization being repaired nesa coating and being regenerated when there is the film defect of the total length of certain limit in nesa coating.In addition, object is also to provide a kind of electrically conducting transparent lamination body possessing nesa coating, and this nesa coating is repaired by the method and regenerated.
For solving the scheme of problem
Present inventor has performed further investigation, found that: when to there is total length in nesa coating be the film defect of 10 μm ~ 300 μm, by at film defective part lamination transparent resin layer, can by film defective part invisibleization, thus nesa coating is repaired and regenerates, this completes the present invention.
That is, the present invention relates to a kind of reparation and renovation process of nesa coating, the reparation of this nesa coating and the feature of renovation process are, are included in the operation of the recess lamination transparent resin layer on nesa coating,
Nesa coating is formed by the nesa coating formation composition of coating containing electric conducting material, and it is configured at least one face of base material,
Recess be selected from by result from the depression of substrate shapes, the damage being present in nesa coating and defect, the foreign matter being present in nesa coating removed the depression that formed and the defect being present in nesa coating pressurizeed at least one in group that the depression that formed forms
The total length of recess is 10 μm ~ 300 μm.
Reparation of the present invention and renovation process preferably, may further include the operation at recess coating remediation composition capable,
In this situation, the total light transmittance of remediation composition capable when making the desciccator diaphragm of thickness 300nm is more than 97%, and mist degree is less than 3%, is 1.40 ~ 1.70 in the refractive index of wavelength 633nm, and colourity is-1.5 ~ 1.5.
Reparation of the present invention and renovation process preferably, after the operation of recess coating remediation composition capable, comprise operation or the heating treatment step of the unwanted remediation composition capable removing by coating recess further.
In reparation of the present invention and renovation process, remediation composition capable is preferably containing electric conducting material and/or binding agent.
In reparation of the present invention and renovation process, nesa coating formation with composition preferably containing and the binder phase in remediation composition capable with binding agent.In addition, binding agent is preferably selected from least one in the group be made up of mylar, acrylic resin, polyurethane, epoxy resin, alkoxysilane oligomer and vistanex.
In reparation of the present invention and renovation process, nesa coating formation composition preferably containing at least one be selected from the group that is made up of inorganic conductive particulate, metal nanometer line and electric conductive polymer as electric conducting material.
In reparation of the present invention and renovation process, remediation composition capable preferably containing at least one be selected from the group that is made up of inorganic conductive particulate, metal nanometer line and electric conductive polymer as electric conducting material.
In addition, the present invention relates to a kind of electrically conducting transparent lamination body, it is characterized in that, it is the electrically conducting transparent lamination body possessing base material, nesa coating and transparent resin layer,
Nesa coating utilizes reparation of the present invention and renovation process repair and regenerate.
In electrically conducting transparent lamination body of the present invention, preferably, base material is glass baseplate, is laminated with glass baseplate, nesa coating and transparent resin layer successively in this electrically conducting transparent lamination body.
In electrically conducting transparent lamination body of the present invention, transparent resin layer is preferably adhesive layer or hard conating.
In electrically conducting transparent lamination body of the present invention, preferably, the thickness of nesa coating is 30nm ~ 500nm, and this electrically conducting transparent lamination body is used to electromagnetic shielding material, noise reduction, anti-static material or transparency electrode.
The effect of invention
According to reparation of the present invention and renovation process, when to there is total length in nesa coating be the film defect of 10 μm ~ 300 μm, by film defective part lamination transparent resin layer, thus film defective part is by invisibleization, and result can by nesa coating reparation and regeneration.Because the refractive index of nesa coating and the refractive index of transparent resin layer are same degree, therefore thinking can by film defective part invisibleization.
In addition, carry out by reparation of the present invention and renovation process the nesa coating repaired and regenerate because electrically conducting transparent lamination body of the present invention possesses, therefore, be present in the film defect of nesa coating by invisibleization, can not go out of use as waste product, be suitable for various uses.
Embodiment
[1] reparation of nesa coating and renovation process
Reparation of the present invention and renovation process are reparation and the renovation process of nesa coating, it is characterized in that, the reparation of this nesa coating and renovation process are included in the operation of the recess lamination transparent resin layer on nesa coating,
Nesa coating is formed by the nesa coating formation composition of coating containing electric conducting material, and it is configured at least one face of base material,
Recess be selected from by result from the depression of substrate shapes, the damage being present in nesa coating and defect, the foreign matter being present in nesa coating removed the depression that formed and the defect being present in nesa coating pressurizeed at least one in group that the depression that formed forms
The total length of recess is 10 μm ~ 300 μm.
Below, reparation of the present invention and renovation process are described in detail.
(1-1) nesa coating
Nesa coating in reparation of the present invention and renovation process is formed by the nesa coating formation composition of coating containing electric conducting material, is configured at least one face of base material.Nesa coating formation composition directly can be coated on base material and be formed by nesa coating, also can be arranged at by other layers such as priming coat in advance and on this layer, be coated with nesa coating formation composition again after on base material and formed.
As the base material of nesa coating, use transparent base.It should be noted that, in the present invention, " transparent base " refers to that total light transmittance is the base material of more than 60%.
As the material of transparent base, as long as transparent is just not particularly limited, such as glass can be enumerated, PETG (PET), PEN, the polyester based resins such as modified poly ester, polyethylene (PE) resin, polypropylene (PP) resin, polystyrene resin, the polyolefin resins such as annular ethylene series resin, polyvinyl chloride, the vinyl resins such as polyvinylidene chloride, polyether-ether-ketone (PEEK) resin, polysulfones (PSF) resin, polyether sulfone (PES) resin, Merlon (PC) resin, polyamide, polyimide resin, acrylic resin, triacetyl cellulose (TAC) resin etc.
The thickness of transparent base is not particularly limited, is preferably 10 μm ~ 10000 μm, is more preferably 25 μm ~ 5000 μm.In addition, as long as the total light transmittance of transparent base is more than 60% to be just not particularly limited, is preferably more than 70%, is more preferably more than 80%.
Nesa coating can by carrying out heat treated after at least one face of nesa coating formation composition being applied to transparent base and obtaining.
As method nesa coating formation composition is applied at least one face of transparent base, be not particularly limited, known method can be used, such as rolling method can be used, stick coating method, dip coating, spin-coating method, casting method, mould is coated with method, scraper plate rubbing method, stick coating method, woodburytype, curtain coating method, spraying process, knife coating, slot coated method, relief printing plate (typography) print process, hole version (silk screen) print process, lithographic plate (hectograph) print process, intaglio plate (heliogravure) print process, spraying print process, ink jet printing method, transfer printing etc.
Before at least one face nesa coating formation composition being applied to transparent base, surface treatment can be implemented to the surface of transparent base in advance as required.As surface treatment, such as corona treatment, plasma treatment, ITRO process, flame treatment etc. can be enumerated.
Heat treated when forming nesa coating is not particularly limited, utilizes known method to carry out, such as, use convection oven, infrared-ray oven, vacuum drying oven etc. to carry out.When nesa coating formation composition contains solvent, by heat treated except desolventizing.
The temperature conditions of heat treated when forming nesa coating is not particularly limited, is preferably less than 150 DEG C, be more preferably 50 DEG C ~ 140 DEG C, more preferably 60 DEG C ~ 130 DEG C.If the temperature of heat treated is more than 150 DEG C, then the material of used base material is limited, and such as, PET film, polycarbonate membrane, acrylic films etc. cannot be used to be generally used for the base material of ELD.The processing time of heat treated is not particularly limited, is preferably 0.1 minute ~ 60 minutes, is more preferably 0.5 minute ~ 30 minutes.
The surface resistivity of nesa coating is not particularly limited, when using in antistatic benefits, is preferably 10 4Ω/ ~ 10 11Ω/, is preferably 300 Ω/ ~ 10 when using in noise reduction purposes 4Ω/, is preferably 10 when using in transparency electrode purposes 3Ω/below, is preferably 1 Ω/ ~ 10 when using in electromagnetic wave shielding purposes 3Ω/.
The refractive index of nesa coating is not particularly limited, is generally 1.4 ~ 1.7, is preferably 1.5 ~ 1.6.
(1-2) nesa coating formation composition
Below, nesa coating formation composition is described.
Nesa coating formation composition contains electric conducting material.
As electric conducting material, be not particularly limited, conductivity during owing to making nesa coating and the transparency excellent, thus, such as inorganic conductive particulate, metal nanometer line, electric conductive polymer, material with carbon element etc. can be enumerated.These electric conducting materials can be used alone, and also can share two or more.
Electric conducting material is preferably selected from least one in the group be made up of inorganic conductive particulate, metal nanometer line and electric conductive polymer.
As inorganic conductive particulate, be not particularly limited, such as tin indium oxide (ITO) particulate, antimony tin (ATO) particulate, zinc oxide fine particles etc. can be enumerated.These inorganic conductive particulates can be used alone, and also can share two or more.
As the material of metal nanometer line, metal simple-substance or metallic compound can be enumerated.
As metal simple-substance, be not particularly limited, such as silver, copper, silver, iron, cobalt, nickel, zinc, ruthenium, rhodium, palladium, cadmium, osmium, iridium, platinum etc. can be enumerated, as metallic compound, be not particularly limited, the compound such as containing these metals can be enumerated.These metal nanometer lines can be used alone, and also can share two or more.
Metal nanometer line is preferably selected from least one in the group be made up of nano silver wire, copper nano-wire and nanowires of gold.Its reason be because: compared with other metal nanometer line, free electronic concentration is high, and conductivity is high.
The diameter of metal nanometer line is not particularly limited, is preferably 1nm ~ 1000nm, is more preferably 1nm ~ 100nm.If the diameter of metal nanometer line is less than 1nm, then line self is easily cut off sometimes; If more than 1000nm, then the haze value of coated film uprises sometimes.
The length of metal nanometer line is not particularly limited, is preferably 1 μm ~ 1000 μm, is more preferably 1 μm ~ 100 μm.If the length of metal nanometer line is less than 1 μm, then cause the reduction of the conductivity of coated film sometimes; If more than 1000 μm, then the stability of metal nanometer line dispersion is deteriorated sometimes.
The draw ratio of metal nanometer line is not particularly limited, is preferably 50 ~ 10000, is more preferably 70 ~ 7000.This is because, if the draw ratio of metal nanometer line is less than 50, the conductivity of coated film can be caused to reduce; If more than 10000, the bad stability of metal nanometer line dispersion can be caused.
It should be noted that, in the present invention, draw ratio represents the length-to-diameter of metal nanometer line.
As electric conductive polymer, be not particularly limited, existing known electric conductive polymer can be used, as concrete example, the compound etc. of such as polythiophene, polypyrrole, polyaniline, polyacetylene, polyphenylacetylene, poly-naphthalene, their derivative and they and dopant can be enumerated.These electric conductive polymers can be used alone, and also can share two or more.
As electric conductive polymer, in preferred molecule, comprise the electric conductive polymer of at least 1 thiphene ring.Its reason is because by comprising thiphene ring in molecule, thus easily form the high molecule of conductivity.
As electric conductive polymer, the more preferably compound of poly-(3,4-bis-substituted thiophene) or poly-(3,4-bis-substituted thiophene) and polyanion.This is because conductivity, chemical stability are extremely excellent.In addition, poly-(3 are contained at nesa coating formation composition, 4-bis-substituted thiophene) or poly-(3,4-bis-substituted thiophene) with the compound of polyanion when, by using this nesa coating formation composition, can form nesa coating in low-temperature short-time, productivity ratio is also excellent.
As poly-(3,4-bis-substituted thiophene), particularly preferably poly-(3,4-dialkoxythiophene) or poly-(3,4-alklyenedioxy thiophene).
As poly-(3,4-dialkoxythiophene) or poly-(3,4-alklyenedioxy thiophene), preferably by following formula (I):
The polythiophene of the cation form that the constitutional repeating unit represented is formed.Herein, R 1and R 2represent hydrogen atom or C independently of each other 1-4alkyl, or, at R 1and R 2c is represented when bonding 1-4alkylidene.
As C 1-4alkyl, be not particularly limited, such as methyl, ethyl, propyl group, isopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group etc. can be enumerated.In addition, at R 1and R 2when bonding, as C 1-4alkylidene, be not particularly limited, such as methylene, 1,2-ethylidene, 1,3-propylidene, Isosorbide-5-Nitrae-butylidene, 1-methyl isophthalic acid can be enumerated, 2-ethylidene, 1-ethyl-1,2-ethylidene, 1-methyl isophthalic acid, 3-propylidene, 2-methyl isophthalic acid, 3-propylidene etc.Among these, preferred methylene, 1,2-ethylidene, 1,3-propylidene, more preferably 1,2-ethylidene.C 1-4alkyl and C 1-4the part hydrogen of alkylidene can be substituted.As having C 1-4the polythiophene of alkylidene, particularly preferably poly-(3,4-ethyldioxythiophene).
Polyanion forms compound by forming ion pair with polythiophene (derivative), thus can make polythiophene (derivative) stable dispersion in water.
As polyanion, be not particularly limited, such as carboxylic acid polyalcohol class (such as polyacrylic acid, poly, polymethylacrylic acid etc.), sulfonic acid polymer class (such as polystyrolsulfon acid, polyvinylsulfonic acid, polyisoprene sulfonic acid etc.) etc. can be enumerated.For these carboxylic acid polyalcohol classes and sulfonic acid polymer class, it can also be the copolymer of vinyl carboxylic acid class and vinyl sulfonic acid class and other polymerisable monomer class (aromatic ethenyl compound such as such as esters of acrylic acid, styrene, vinyl naphthalene).Among these, particularly preferably polystyrolsulfon acid.
The weight average molecular weight of polystyrolsulfon acid be preferably greater than 20000 and be less than 500000, be more preferably 40000 ~ 200000.If use molecular weight at this extraneous polystyrolsulfon acid, then the dispersion stabilization of polythiophene system electric conductive polymer to water reduces sometimes.It should be noted that, the value that weight average molecular weight measures for utilizing gel permeation chromatography (GPC).The ultrahydrogel500 post that Waters society manufactures is employed in mensuration.
Electric conductive polymer due to the transparency and conductivity excellent especially, the thus compound of preferably poly-(3,4-ethyldioxythiophene) and polystyrolsulfon acid.
Electric conductive polymer is more preferably the compound of poly-(3,4-ethyldioxythiophene) and polystyrolsulfon acid, and has the conductivity of more than 0.01S/cm.Its reason be because, the transparency of the nesa coating formation composition containing this electric conductive polymer when making nesa coating and conductivity excellent especially.
As material with carbon element, be not particularly limited, such as carbon nano-tube, Graphene, fullerene etc. can be enumerated.These material with carbon elements can be used alone, and also can share two or more.
Be not particularly limited the content of the electric conducting material in nesa coating formation composition, such as, when using electric conductive polymer as electric conducting material, when making nesa coating, preferably this content is for reaching 0.01mg/m 2~ 50.0mg/m 2amount, be more preferably and reach 0.1mg/m 2~ 10.0mg/m 2amount.This is because, if be less than 0.01mg/m 2, then the ratio that exists of the electric conductive polymer in nesa coating tails off, and sometimes fully cannot guarantee the conductivity of nesa coating, on the other hand, if more than 50.0mg/m 2, then the ratio that exists of the electric conductive polymer in nesa coating becomes many, causes sometimes producing harmful effect to coating film strength, film forming.
Nesa coating formation composition, except electric conducting material, also optionally can contain other composition.
As other composition, binding agent, conductivity improving agent, solvent, crosslinking agent, catalyst, surfactant and/or levelling agent, water soluble antioxidant, defoamer, rheology control agent, nertralizer, thickener etc. can be enumerated.
Binding agent is not particularly limited, is preferably selected from least one in the group be made up of mylar, acrylic resin, polyurethane, epoxy resin, alkoxysilane oligomer and vistanex.Its reason be because: high with the compatibility of the composition such as electric conducting material, the nesa coating using the nesa coating formation composition containing these binding agents to be formed is good to the compatibility of base material, can effectively by film defective part invisibleization.In addition, the nesa coating using the nesa coating formation composition containing these binding agents to be formed has good hardness and chemical proofing.These binding agents can be used alone, and also can share two or more.
As mylar, as long as by there is in molecule the compound of more than 2 carboxyls and there is the compound polycondensation of more than 2 hydroxyls and the macromolecular compound that obtains just is not particularly limited, such as PETG, PTT, polybutylene terephthalate (PBT), PEN, PBN etc. can be enumerated.These can be used alone, and also can share two or more.
As acrylic resin, be not particularly limited, (methyl) acrylic resin, vinyl esters system resin etc. can be enumerated such as.As these acrylic resins, such as comprising the polymerizable monomer with acidic groups such as carboxyl, anhydride group, sulfonic group, phosphates as the polymer forming monomer, homopolymerization or the copolymer of the polymerizable monomer such as with acidic group can be enumerated, there is the polymerizable monomer of acidic group and the copolymer etc. of co-polymerized monomer.These can be used alone, and also can share two or more.
(methyl) is if acrylic resin contains (methyl) acrylic monomer as main formation monomer (such as more than 50 % by mole), then can with copolymerizable monomer polymerization, in this situation, at least one among (methyl) acrylic monomer and co-polymerized monomer has acidic group.
As (methyl) acrylic resin, (methyl) acrylic monomer [(methyl) acrylic acid, (methyl) sulfoethyl Arrcostab, containing sulfonic (methyl) acrylamide etc.] or its copolymer such as with acidic group can be enumerated; The copolymer of (methyl) acrylic monomer can with acidic group and other polymerizable monomer with acidic group [other polymerism carboxylic acid, polymerism polybasic carboxylic acid or acid anhydrides, vinyl aromatic sulfonic acid etc.] and/or co-polymerized monomer [such as (methyl) alkyl acrylate, (methyl) glycidyl acrylate, (methyl) acrylonitrile, aromatic vinyl monomer etc.]; There is other polymer monomer of acidic group and the copolymer of (methyl) acrylic copolymer monomer [such as (methyl) alkyl acrylate, (methyl) acrylic acid hydroxy alkyl ester, (methyl) glycidyl acrylate, (methyl) acrylonitrile etc.]; Abietyl modified urethane acrylate, special modified acrylic resin, urethane acrylate, epoxy acrylate, urethane acrylate emulsion etc.
In these (methyl) acrylic resins, preferably (methyl) acrylic acid-(methyl) acrylate polymer (acryl acid-methyl methacrylate copolymer etc.), (methyl) acrylic acid-(methyl) acrylic styrene copolymer (acrylic acid-methacrylic acid methyl esters-styrol copolymer etc.) etc.
As polyurethane, as long as the compound making to have NCO and the compound copolymerization with hydroxyl and the macromolecular compound that obtains just is not particularly limited, such as ester ether system polyurethane, ether system polyurethane, Polyester polyurethane, carbonic ester system polyurethane, acrylic acid series polyurethane etc. can be enumerated.These can be used alone, and also can share two or more.
As epoxy resin, be not particularly limited, can enumerate such as bisphenol A-type, bisphenol-f type, novolac type, as epoxy resin, the silicone epoxy etc. such as four (hydroxy phenyl) ethane type or three (hydroxy phenyl) methane type, biphenyl type, triphenol methane type, naphthalene type, adjacent phenolic varnish type, dicyclopentadiene type, aminobenzene phenolic, ester ring type of multifunctional type with multiple phenyl ring.These can be used alone, and also can share two or more.
As alkoxysilane oligomer, there is condensation between monomer such as the alkoxy silane by being represented by following formula (II) and alkoxy silane that the macromolecule that formed quantizes, the oligomer etc. in 1 molecule with more than 1 siloxane bond (Si-O-Si) can be enumerated.
SiR 4(II)
(alkoxyl that in formula, R is hydrogen, hydroxyl, carbon number are 1 ~ 4, have or not there is substituent alkyl, have or not there is substituent phenyl.Wherein, at least 1 among 4 R to be carbon number be 1 ~ 4 alkoxyl or hydroxyl.)
Being not particularly limited the structure of alkoxysilane oligomer, can be straight-chain, also can be branched.In addition, alkoxysilane oligomer can be used alone the compound represented by formula (II), also can share two or more.
The weight average molecular weight of alkoxysilane oligomer is not particularly limited, be preferably greater than 152 and be less than 4000, be more preferably 500 ~ 2500.
Herein, weight average molecular weight is the value utilizing gel permeation chromatography (GPC) to measure.
As vistanex, be not particularly limited, such as polyethylene, polypropylene, chlorinated polypropylene, maleic anhydride modified polypropylene, maleic anhydride modified chlorinated polypropylene etc. can be enumerated.These can be used alone, and also can share two or more.
When nesa coating formation composition contains binding agent, its content is not particularly limited, is preferably 0.1 weight portion ~ 1000 weight portion relative to content 100 weight portion of electric conducting material, is more preferably 5 weight portion ~ 500 weight portions.
If the content of binding agent is less than 0.1 weight portion, then electrically conducting transparent film strength dies down sometimes, and on the other hand, if more than 1000 weight portions, then the ratio of the electric conducting material in nesa coating tails off relatively, sometimes fully can not guarantee the conductivity of nesa coating.
When remediation composition capable described later contains binding agent, nesa coating formation composition is preferably containing the binding agent identical with remediation composition capable.This is because by containing identical binding agent, what can prevent thermal contraction from causing breaks, in addition, remediation composition capable has excellent wetability, adaptation to nesa coating.
Conductivity improving agent adds for the object of the conductivity improving nesa coating.By inference, conductivity improving agent evapotranspires by heating when forming nesa coating, and now it controls the orientation of electric conductive polymer, thus the conductivity of nesa coating is improved.
In addition, compared with not using the situation of conductivity improving agent, when using conductivity improving agent, the combined amount of electric conductive polymer can be reduced while maintaining surface resistivity, its result, there is the advantage can improving the transparency.
From the aspect positively guaranteeing conductivity required in the purposes of nesa coating, conductivity improving agent is preferably selected from least one compound in the group be made up of following (i) ~ (vii).
I () boiling point is more than 60 DEG C and has the compound of at least 1 ketone group in molecule
(ii) boiling point is more than 100 DEG C and has the compound of at least 1 ether in molecule
(iii) boiling point is more than 100 DEG C and has the compound of at least 1 sulfinyl in molecule
(iv) boiling point is more than 100 DEG C and has the compound of at least 1 amide groups in molecule
V () boiling point is more than 50 DEG C and has the compound of at least 1 carboxyl in molecule
(vi) boiling point is more than 100 DEG C and has the compound of more than 2 hydroxyls in molecule
(vii) boiling point is more than 100 DEG C and has the compound of at least 1 lactam group in molecule
Be more than 60 DEG C as boiling point and there is in molecule the compound (i) of at least 1 ketone group, such as isophorone, propylene carbonate, gamma-butyrolacton, beta-butyrolactone, DMI etc. can be enumerated.These can be used alone, and also can share two or more.
Be more than 100 DEG C as boiling point and there is in molecule the compound (ii) of at least 1 ether, such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, 2-phenoxetol, diox, morpholine, 4-acryloyl morpholine, N-methylmorpholine-N-oxide, 4-ethyl morpholine, 2-methoxyl group furans etc. can be enumerated.These can be used alone, and also can share two or more.
Be more than 100 DEG C as boiling point and there is in molecule the compound (iii) of at least 1 sulfinyl, such as dimethyl sulfoxide (DMSO) etc. can be enumerated.
Be more than 100 DEG C as boiling point and there is in molecule the compound (iv) of at least 1 amide groups, such as N can be enumerated, N-dimethylacetylamide, N-METHYLFORMAMIDE, DMF, acetamide, N-ethyl acetamide, N-phenyl-N-propyl acetamide, benzamide etc.These can be used alone, and also can share two or more.
Be more than 50 DEG C as boiling point and there is in molecule the compound (v) of at least 1 carboxyl, such as acrylic acid, methacrylic acid, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, sad, capric acid, dodecoic acid, benzoic acid, p-methylbenzoic acid, parachlorobenzoic-acid, paranitrobenzoic acid, 1-naphthoic acid, 2-naphthoic acid, phthalic acid, M-phthalic acid, oxalic acid, malonic acid, butanedioic acid, adipic acid, maleic acid, fumaric acid etc. can be enumerated.These can be used alone, and also can share two or more.
Be more than 100 DEG C as boiling point and there is in molecule the compound (vi) of more than 2 hydroxyls, such as ethylene glycol, diethylene glycol (DEG), propylene glycol, 1 can be enumerated, ammediol, β-Thiodiglycol, triethylene glycol, tripropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,3-butanediol, 1,6-hexylene glycol, neopentyl glycol, catechol, cyclohexanediol, cyclohexanedimethanol, glycerine, red moss alcohol, glycerine, hydroxyl isomaltulose (イ Application マ ト ー Le), lactitol, maltitol, sweet mellow wine, D-sorbite, xylitol, sucrose etc.These can be used alone, and also can share two or more.
Be more than 100 DEG C as boiling point and there is in molecule the compound (vii) of at least 1 lactam group, such as 1-METHYLPYRROLIDONE, beta-lactam, gamma-lactam, δ-lactams, epsilon-caprolactams, lauric lactam etc. can be enumerated.These can be used alone, and also can share two or more.
If the boiling point of conductivity improving agent is more than specified temp, heating when then being formed by nesa coating, conductivity improving agent can vapor away at leisure, can think, can be the orientation favourable to conductivity by the tropism control of electric conductive polymer in this process, its result conductivity improves.On the other hand, if the boiling point of conductivity improving agent does not meet specified temp, then conductivity improving agent can evaporate sharp, therefore, can think that the orientation of electric conductive polymer can not get fully controlling and haveing nothing to do with the raising of conductivity.
In addition, as conductivity improving agent, be not particularly limited, preferably there is δ D=12 ~ 30, δ H=3 ~ 30, δ P=5 ~ 30 and the SP value of δ D+ δ H+ δ P=35 ~ 70, more preferably there is δ D=15 ~ 25, δ H=10 ~ 25, δ P=10 ~ 25 and the SP value of δ D+ δ H+ δ P=35 ~ 70.
In this specification, SP value refers to the solubility parameter that the Chinese is gloomy, by the dissolubility of material to disperse item δ D, polarity item δ H, these 3 parameters of hydrogen bond item δ P show.Can thinking, by adding the conductivity improving agent of the SP value had in above-mentioned scope, by electric conductive polymer spurious solution, in evaporation process, promoting arrangement.On the other hand, the conductivity improving agent with above-mentioned extraneous SP value is difficult to produce the interaction with electric conductive polymer, therefore, sometimes can not obtain improving effect by controlling to arrange the sufficient conductivity brought.
In addition, the compatibility with the conductivity improving agent of the SP value in above-mentioned scope and electric conductive polymer is high, therefore can improve the stability of the dispersion liquid of electric conductive polymer.In addition, when nesa coating formation composition contains metal nanometer line and electric conductive polymer, can think, in dispersion liquid, electric conductive polymer, particularly polyanion can contribute to the dispersion stabilization of metal nanometer line by its polarity, by the interpolation of conductivity improving agent, not only can improve the dispersion stabilization of electric conductive polymer, the dispersion stabilization of metal nanometer line can also be improved.
Be δ D=12 ~ 30 as SP value, δ H=3 ~ 30, δ P=5 ~ 30, and the conductivity improving agent of δ D+ δ H+ δ P=35 ~ 70, be not particularly limited, can enumerate such as, isocyanates (δ D=15.8, δ H=10.5, δ P=13.6), methyl-isorhodanate (δ D=17.3, δ H=16.2, δ P=10.1), trimethyl phosphate (δ D=15.7, δ H=10.5, δ P=10.2), 2-methyl lactonitrile (δ D=16.6, δ H=12.2, δ P=15.5), ephedrine (δ D=18.0, δ H=10.7, δ P=24.1), thiocarbamide (δ D=20.0, δ H=19.4, δ P=14.8), carbamonitrile (δ D=15.5, δ H=27.6, δ P=16.8), 3-hydroxypropionitrile (δ D=17.2, δ H=18.8, δ P=17.6), pyrazoles (δ D=20.2, δ H=10.4, δ P=12.4) etc.These can be used alone, and also can share two or more.
In addition, as conductivity improving agent, can also use (i) ~ (vii) and there is the material of the SP value in above-mentioned scope.
When nesa coating formation composition is containing conductive improving agent, its content is not particularly limited, is preferably 5 mass parts ~ 2000 mass parts relative to electric conductive polymer 100 mass parts, be more preferably 10 mass parts ~ 1500 mass parts.If the content of conductivity improving agent is less than 5 mass parts, then sometimes fully can not enjoys the conductivity brought by interpolation conductivity improving agent and improve effect.On the other hand, if more than 2000 mass parts, then the combined amount of the electric conducting material in nesa coating formation composition tails off relatively, sometimes can not get sufficient conductivity when making nesa coating.
As solvent, be not particularly limited, such as water can be enumerated; The alcohols such as methyl alcohol, ethanol, 2-propyl alcohol, 1-propyl alcohol; The glycols such as ethylene glycol, diethylene glycol, triethylene glycol, TEG; The glycol ethers such as glycol monoethyl ether, diethylene glycol monomethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether; The glycol ethers acetate esters such as ethylene glycol monoethylether acetate, diethylene glycol monoethyl ether acetic acid esters, butyl carbitol acetate; The propandiolses such as propylene glycol, DPG, tripropylene glycol; The propylene glycol ethers such as propylene glycol monomethyl ether, dihydroxypropane single-ether, dipropylene glycol monomethyl ether, DPE, Propylene Glycol Dimethyl Ether, dimethyl ether, propylene glycol diethyl ether, dipropylene glycol diethyl ether; The propylene glycol ether acetate classes such as propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetic acid esters, DPE acetic acid esters; Oxolane; Acetone; Acetonitrile etc.These solvents can be used alone, and also can share two or more.
Solvent is preferably the mixture of water or water and organic solvent.When nesa coating formation composition contains water as solvent, the content of water is not particularly limited, is preferably 20 mass parts ~ 1000000 mass parts relative to electric conducting material 100 mass parts, be more preferably 200 mass parts ~ 500000 mass parts.This is because when the content of water is less than 20 mass parts, viscosity uprises sometimes, causes difficult treatment, during more than 1000000 mass parts, the concentration of solution is too low, and the adjustment of the thickness of nesa coating sometimes becomes difficult.
When the mixture that nesa coating formation composition contains water and organic solvent is as solvent, organic solvent is preferably methyl alcohol, ethanol or 2-propyl alcohol.In this situation, the content of organic solvent is not particularly limited, is preferably 20 mass parts ~ 700000 mass parts relative to electric conducting material 100 mass parts, be more preferably 200 mass parts ~ 350000 mass parts.In addition, the ratio of water and organic solvent is preferably 100:0 ~ 5:95, is more preferably 100:0 ~ 30:70.
Solvent is not preferably remained in the nesa coating formed by coating nesa coating formation composition.
It should be noted that, in this specification, about the consoluet material of whole compositions (i.e. " solvent ") making nesa coating formation composition and the material (i.e. " decentralized medium ") making insoluble composition disperse, do not distinguish especially, be all recited as " solvent ".
By mixture surfactant and/or levelling agent, wetability and the levelability of nesa coating formation composition can being improved, by using nesa coating formation composition to form nesa coating, uniform nesa coating can be obtained.It should be noted that, in the present invention, a compound is not only equivalent to surfactant but also be equivalent to levelling agent sometimes.
As surfactant, as long as there is levelability raising effect be just not particularly limited, as its concrete example, such as polyether-modified dimethyl silicone polymer, polyether modified siloxane, polyether ester modification hydroxyl dimethyl silicone polymer, polyether-modified acryloyl group dimethyl silicone polymer, the polyester modification of containing can be enumerated containing siloxane-based compounds such as acryloyl group dimethyl silicone polymer, perfluoro dimethyl silicone polymer, perfluoropolyether-modified dimethyl silicone polymer, perfluor polyester modification dimethyl silicone polymers; The fluorine based compounds such as perfluoro carboxylic acid, perfluoroalkyl polyoxy vinyl alcohol; The polyethers based compounds such as polyoxyethylene alkyl phenyl ether, propylene oxide polymer, ethylene oxide polymer; The carboxylic acids such as coconut oil fat amine acid salt, rosin; The ester based compounds such as castor oil class, phosphate, alkyl ether sulfate, sorbitan aliphatic ester, sulphonic acid ester, succinate; The sulfonate compounds such as alkyl aryl sulphonic acid amine salt, aerosol-OT salt; The phosphate compoundss such as lauryl sodium phosphate; The amide compounds such as coconut oil fat acid diethanolamide; Acrylic compounds etc.These surfactants can be used alone, and also can share two or more.Among these, from the aspect significantly obtaining levelability raising effect, preferred siloxane-based compound and fluorine based compound, more preferably polyether-modified dimethyl silicone polymer.
As surfactant, also can use commercially available product, as its concrete example, such as BYK-301 can be enumerated, BYK-302, BYK-307, BYK-331, BYK-333, BYK-337, BYK-341, BYK-375, BYK-378, BYK-380N, BYK-340, BYK-DYNWET800 (being Bi Ke chemistry Amada Co., Ltd. to manufacture), NIKKOL AM-101, NIKKOL AM-301, NIKKOL AM-3130N (being Nihon surfactantkogyo Co., Ltd. to manufacture), Asahi Guard AG-8025, Asahi Guard MA-91 (being Ming Cheng chemical industry Co., Ltd. to manufacture), AMIPOL AS-8 (Nicca Chemical Co., Ltd's manufacture), AMOGEN AOL, AMOGENCB-C, AMOGEN CB-H, AMOGEN LB-C, AMOGEN No.8, AMOGEN S, AMOGENS-H (being Di-ichi Kogyo Seiyaku Co., Ltd. to manufacture), AMPHITOL series (Kao Corp's manufacture), AMPHOREX 35N, AMPHOREX 50, AMPHOREX 50-SF (being Miyoshi Oil & Fat Co., Ltd. to manufacture), Plascoat RY-2 (Goo Chemical Co., Ltd.'s manufacture), ENAGICOL C-30B (manufacture of LION Co., Ltd.), Obazorin 662N, Catinal AOC (being Toho Chemical Industry Co., Ltd. (JP) Tokyo-To, Japan to manufacture), OfunonD (manufacture of Yushiro chemical industry Co., Ltd.), CLINK A-27 (Network リ Application Network A-27) (oil KCC of lucky village manufactures), Genagen B 1566 (manufacture of Clariant (Japan) Co., Ltd.), CAPSTONE FS-3100 (Dupont Kabushiki Kaisha's manufacture) etc.
As levelling agent, be not particularly limited, such as polyether-modified dimethyl silicone polymer, polyether modified siloxane, polyether ester modification hydroxyl dimethyl silicone polymer, polyether-modified acryloyl group dimethyl silicone polymer, the polyester modification of containing can be enumerated containing siloxane-based compounds such as acryloyl group dimethyl silicone polymer, perfluoro dimethyl silicone polymer, perfluoropolyether-modified dimethyl silicone polymer, perfluor polyester modification dimethyl silicone polymers; The fluorine based compounds such as perfluoro carboxylic acid, perfluoroalkyl polyoxy vinyl alcohol; The polyethers based compounds such as polyoxyethylene alkyl phenyl ether, propylene oxide polymer, ethylene oxide polymer; The carboxylic acids such as coconut oil fat amine acid salt, rosin; The ester based compounds such as castor oil class, phosphate, alkyl ether sulfate, sorbitan aliphatic ester, sulphonic acid ester, succinate; The sulfonate compounds such as alkyl aryl sulphonic acid amine salt, aerosol-OT salt; The phosphate compoundss such as lauryl sodium phosphate; The amide compounds such as coconut oil fat acid diethanolamide; Acrylic compounds etc.These levelling agents can be used alone, and also can share two or more.In these levelling agents, due to excellent with the compatibility of general silicone glue cloth, thus preferred siloxane-based compound, fluorine based compound, acrylic compounds.
As levelling agent, also commercially available product can be used, as its concrete example, such as BYK-325, BYK-345, BYK-346, BYK-347, BYK-348, BYK-349, BYK-UV3500, BYK-380N, BYK-381, BYKETOL-AQ, BYKETOL-WS (being Bi Ke chemistry Amada Co., Ltd. to manufacture), POLYFLOW WS, POLYFLOW WS-30, POLYFLOW WS-314 (being chemical industry Co., Ltd. of common prosperity society to manufacture) etc. can be enumerated.
By mixture water soluble antioxidant, can improve and use nesa coating formation composition and thermal endurance, the humidity resistance of nesa coating that are formed.
As water soluble antioxidant, be not particularly limited, the water soluble antioxidant of reproducibility, the water soluble antioxidant etc. of irreducibility can be enumerated.
As the water soluble antioxidant of reproducibility, such as L-AA, L-AA sodium, L-AA potassium, D (-)-arabo-ascorbic acid (arabo-ascorbic acid), sodium isoascorbate, arabo-ascorbic acid potassium etc. can be enumerated and have by the compound of the lactonic ring of 2 hydroxyls replacements; Monosaccharide or the disaccharides (wherein not comprising sucrose) such as maltose, lactose, cellobiose, wood sugar, arabinose, glucose, fructose, galactolipin, mannose; The flavonoids such as catechin, rutin, myricetin, Quercetin, Kaempferol, SANMELIN (registered trade mark) Y-AF; Curcumin, Rosmarinic acid, chlorogenic acid, hydroquinones, Gallic Acid, tannic acid etc. have the compound of more than 2 phenolic hydroxyl groups; Cysteine, glutathione, pentaerythrite four (3-mercaptobutylate) etc. have the compound etc. of thiol base.
As the water soluble antioxidant of irreducibility, can enumerate such as phenylimidazole sulfonic acid, Phenyltriazole sulfonic acid, 2-hydroxy pyrimidine, phenyl salicytate, BP-4 sodium etc. will cause the ultraviolet of oxidative degradation to carry out the compound absorbed.
These water soluble antioxidants can be used alone, and also can share two or more.
Among these, be preferably selected from least one compound in the group be made up of the compound with the lactonic ring replaced by 2 hydroxyls and the compound with more than 2 phenolic hydroxyl groups, more preferably L-AA, D (-)-arabo-ascorbic acid or SANMELIN (registered trade mark) Y-AF, tannic acid.
When nesa coating formation composition contains water soluble antioxidant, its content is not particularly limited, is preferably 0.001 weight portion ~ 1000 weight portion relative to solid constituent 100 weight portion of electric conducting material, is more preferably 0.1 weight portion ~ 500 weight portion, more preferably 0.05 weight portion ~ 300 weight portion.
When the content of water soluble antioxidant is less than 0.001 weight portion, sometimes fully can not improve and use nesa coating formation composition and the thermal endurance of nesa coating that formed and humidity resistance, on the other hand, during more than 1000 weight portion, use the ratio that exists of nesa coating formation composition and electric conducting material in the nesa coating that formed to tail off, sometimes fully can not guarantee the conductivity of nesa coating.
(1-3) recess
Recess on nesa coating in reparation of the present invention and renovation process be selected from by result from the depression of substrate shapes, the damage being present in nesa coating and defect, the foreign matter being present in nesa coating removed the depression that formed and the defect being present in nesa coating pressurizeed at least one in group that the depression that formed forms.
As resulting from the depression of substrate shapes, such as, can enumerate, the depression produced on nesa coating the base material that surface has the damage of scrobicula (dimple) and so on forms nesa coating.
As the damage and the defect that are present in nesa coating, can enumerate in the film at nesa coating in the process forming nesa coating or the process being assembled into display unit or the damage of concavity that film surface produces and defect.It should be noted that, in reparation of the present invention and renovation process, also can according to the shape of damage and defect at random with polishing paper etc. to the process damaged and defect surfaces is partly pruned.
As the foreign matter removing of nesa coating and the depression that formed will be present in, can enumerate when to be mixed into foreign matter in the process forming nesa coating and pass through foreign matter to remove the depression produced on nesa coating caused.
The depression formed as pressurizeing to the defect being present in nesa coating, can enumerate: in the film at nesa coating in the process forming nesa coating or film surface (comprising the interface of nesa coating and base material) has been mixed into bubble, by the depression produced on nesa coating caused of pressurizeing to this defect.
Forms the method for depression as the foreign matter removing that will be present in nesa coating, is not particularly limited, can enumerate such as with polishing paper prune foreign matter method, remove the method etc. of foreign matter with bond roll.
Form as to the defect pressurization being present in nesa coating the method caved in, be not particularly limited, can enumerate and utilize bond roll to carry out the method etc. of pressurizeing.
In reparation of the present invention and renovation process, the total length of recess be 10 μm ~ 300 μm very important, in the reparation of nesa coating of recess of total length with this scope and regeneration, effect of the present invention can be enjoyed significantly.It should be noted that, be not particularly limited the degree of depth of recess, is 20nm ~ 20 μm.
(1-4) transparent resin layer lamination operation
In reparation of the present invention and renovation process, the recess lamination transparent resin layer on nesa coating.
As the method for the recess lamination transparent resin layer on nesa coating, can enumerate: the method for carrying out heat treated after transparent resin layer formation composition described later being applied to the recess on nesa coating; The transparent resin layer formed as bonding film is in advance conformed to the method etc. of the recess on nesa coating.
Transparent resin layer formation composition is applied to the method for the recess on nesa coating and the condition of heat treated and adoptable method during above-mentioned formation nesa coating, condition is identical.
The refractive index of transparent resin layer is not particularly limited, is preferably 1.4 ~ 1.7, is more preferably 1.5 ~ 1.6.During when refractive index is less than 1.4 or more than 1.7, the refringence of nesa coating and transparent resin layer becomes greatly, sometimes effectively cannot carry out invisibleization of film defective part.
(1-5) transparent resin layer formation composition
Below, transparent resin layer formation composition is described.
As transparent resin layer formation composition, be not particularly limited, the composition containing binding agent, conductivity improving agent, solvent etc. can be used.
Can be used in binding agent that the binding agent of transparent resin layer formation composition, conductivity improving agent, solvent can be used in nesa coating formation composition with above-mentioned, conductivity improving agent, solvent are identical.
(1-6) remediation composition capable painting process
Reparation of the present invention and renovation process can also be included in the remediation composition capable painting process of recess coating remediation composition capable at the Optional of transparent resin layer lamination operation.
When recess on nesa coating is complicated shape, even if above-mentioned transparent resin layer formation composition is directly coated recess, transparent resin layer formation composition also cannot spread all over each corner of recess, produces the interstitial unfavorable condition in interface at nesa coating and transparent resin layer sometimes.But before transparent resin layer formation composition is coated recess, by being coated with remediation composition capable at recess in advance, remediation composition capable can spread all over each corner of recess, and the shape of recess becomes smooth, therefore, it is possible to prevent above-mentioned unfavorable condition.
As method remediation composition capable being applied to recess, be not particularly limited, can enumerate to utilize to infiltrate has the nonwoven fabrics of remediation composition capable, swab stick, bristle etc. to be applied to the method etc. of recess.
(1-7) remediation composition capable
Below, remediation composition capable is described.
Remediation composition capable is that the total light transmittance when making thickness and being the desciccator diaphragm of 300nm is more than 97%, mist degree is less than 3%, the refractive index of wavelength 633nm be 1.40 ~ 1.70, colourity is the composition of-1.5 ~ 1.5.
As long as the total light transmittance made when thickness is the desciccator diaphragm of 300nm is more than 97% to be just not particularly limited, be preferably more than 98%.
As long as mist degree is less than 3% to be just not particularly limited, be preferably less than 1%.
As long as be 1.40 ~ 1.70 to be just not particularly limited in the refractive index of wavelength 633nm, be preferably 1.50 ~ 1.60.
As long as colourity is-1.5 ~ 1.5 to be just not particularly limited, be preferably-0.5 ~ 0.5.
Remediation composition capable is preferably containing electric conducting material and/or binding agent.Its reason be because: by film defect invisibleization effectively under the state of conductivity keeping nesa coating, and can obtain good hardness and chemical proofing.
Can be used in the electric conducting material of remediation composition capable, binding agent and above-mentioned can be used in nesa coating formation composition electric conducting material, binder phase with.
When remediation composition capable contains electric conducting material, not only by film defective part invisibleization of nesa coating, but also the conductivity of recess can be repaired.When electrically conducting transparent lamination body is used for the purposes of noise reduction or anti-static material, only that film defective part invisibleization is just enough, but when the purposes for transparency electrode, due to the conducting of recess likely cannot be obtained, thus not only need film defective part invisibleization, but also need to repair conductivity.Therefore, when electrically conducting transparent lamination body is used for the purposes of transparency electrode, remediation composition capable is preferably containing electric conducting material.
Except electric conducting material and/or binding agent, remediation composition capable can also contain other composition.
As other composition, conductivity improving agent, solvent, crosslinking agent, catalyst, surfactant and/or levelling agent, water soluble antioxidant, defoamer, rheology control agent, nertralizer, thickener etc. can be enumerated.
Can be used in conductivity improving agent that the conductivity improving agent of remediation composition capable, solvent can be used in nesa coating formation composition with above-mentioned, solvent is identical.
As long as the viscosity of remediation composition capable is just not particularly limited lower than the viscosity of above-mentioned transparent resin layer formation composition, is preferably below 500mPas, is more preferably below 100mPas.When the viscosity of remediation composition capable is more than 500mPas, remediation composition capable likely cannot spread all over each corner of recess.
In addition, when reparation of the present invention and renovation process comprise remediation composition capable painting process, optionally can comprise the remediation composition capable removal step of the unwanted remediation composition capable removing by coating recess further.
As the method for the unwanted remediation composition capable removing by coating recess, being not particularly limited, the method etc. such as utilizing nonwoven fabrics to be wiped by unwanted remediation composition capable can be enumerated.
In addition, when reparation of the present invention and renovation process comprise remediation composition capable painting process, optionally can comprise further and make the heating treatment step that remediation composition capable is dry and solidify.
The condition of heat treated is not particularly limited, can enumerates and such as utilize convection oven in 50 DEG C ~ 120 DEG C heating method etc. of 1 minute ~ 15 minutes.
Reparation of the present invention and renovation process comprise operation described above, thus, even if when there is the film such as foreign matter or defect defect in the nesa coating formed when being contained the nesa coating formation composition of electric conducting material by coating, also can by film defective part invisibleization.
[2] electrically conducting transparent lamination body
Next, electrically conducting transparent lamination body of the present invention is described.
The feature of electrically conducting transparent lamination body of the present invention is, it is the electrically conducting transparent lamination body possessing base material, nesa coating and transparent resin layer, and nesa coating utilizes reparation of the present invention and renovation process repair and regenerate.
Preferably, in electrically conducting transparent lamination body of the present invention, base material is glass baseplate, is laminated with glass baseplate, nesa coating and transparent resin layer successively.In addition, between base material and nesa coating, can priming coat be set.
In electrically conducting transparent lamination body of the present invention, transparent resin layer is preferably adhesive layer or hard conating.
In electrically conducting transparent lamination body of the present invention, the thickness of nesa coating is not particularly limited, is preferably 10nm ~ 500nm, is more preferably 30nm ~ 500nm, more preferably 20nm ~ 400nm.Its reason be because: moderately can maintain the high transparency and conductivity, low haze value, these all character of good film-strength.
The total light transmittance of electrically conducting transparent lamination body of the present invention is not particularly limited, is preferably more than 50%, is more preferably more than 60%, more preferably more than 80%.
As long as the purposes of electrically conducting transparent lamination body of the present invention requires that the purposes of the transparency and conductivity is just not particularly limited, preferred electromagnetic shielding material, noise reduction, anti-static material or transparency electrode.Its reason be because: electrically conducting transparent lamination body of the present invention moderately can maintain the high transparency and conductivity, low haze value, these all character of good film-strength, thus, can be suitable for these purposes.
Embodiment
Enumerate embodiment below so that the present invention to be described, but the present invention is not limited in these embodiments.
1. use material
In following embodiment and comparative example, employ following material.
1-1. electric conducting material
Poly-(3,4-ethyldioxythiophene) polystyrolsulfon acid (PEDOT/PSS) (manufacture of Heraeus society, CleviosPH1000)
Nano silver wire (manufacture of starlight PMC society, T-YP808, draw ratio 230, solid constituent 1.0%)
Graphene (manufacture of XG Sciences society, H-5 aqueous dispersions, solid constituent 15%)
Carbon nano-tube (Meijo Nano Carbon manufacture, SWNT dispersion liquid, carbon nanotube concentration 0.1%)
1-2. binding agent
Alkoxysilane oligomer (manufacture of chemical industry society of Japan, N-POS)
Alkoxysilane oligomer (manufacture of Duo Mo chemical industry society, TEOS)
Alkoxysilane oligomer (manufacture of chemical industry society of SHIN-ETSU HANTOTAI, KBM-303)
Mylar (manufacture of Nagase chemteX society, Gabusen ES-210, solid constituent 25%)
Polyurethane (manufacture of the first industrial pharmaceutical society, Superflex 300, solid constituent 30%)
Acrylic resin (manufacture of East Asia synthesis society, Jurymer SEK301, solid constituent 40%)
Acrylic resin (Nagase chemteX manufacture, TEISAN RESIN SG-790, solid constituent 23%)
(Nagase chemteX society manufactures acrylic resin, TEISAN RESIN SG-600TEA (solid constituent 15%)
1-3. conductivity improving agent
3-hydroxypropionitrile (Tokyo changes into industry manufacture, δ D=17.2, δ H=18.8, δ P=17.6)
Pyrazoles (Tokyo changes into the manufacture of industrial society, δ D=20.2, δ H=10.4, δ P=12.4)
Ethylene glycol (Tokyo changes into the manufacture of industrial society, boiling point 196 DEG C)
1-4. solvent
Ethanol (manufacture of Nacalai Tesque society, boiling point 78.4 DEG C)
2-propyl alcohol (manufacture of Sagane Bussan society, boiling point 82.5 DEG C)
1-5 catalyst
1% nitric acid (manufacturing with Guang Chun medicine society)
1-6. crosslinking agent
Isocyanate compound (manufacture of Japanese polyurethane society, CORONET HL, solid constituent 75%)
1-7. surfactant/levelling agent
Polyether ester modification hydroxyl dimethyl silicone polymer (manufacture of Bi Ke chemistry Japanese society, BYK-375, nonvolatile component 25%)
1-8. water soluble antioxidant
Tannic acid (Wako Pure Chemical Industries, Ltd.'s manufacture)
2. the step of each operation
In following embodiment and comparative example, each operation is undertaken by following method.
2-1. nesa coating formation process
Utilize wire bar nesa coating formation composition to be applied to alkali-free glass plate (manufacture of Corning society, thickness 0.7mm, total light transmittance 92.1%), with baking oven 120 DEG C of heating 30 minutes, thus form nesa coating.
2-2. recess formation process
When nesa coating surface exists the recesses such as defect, directly use this recess.When the fragment of nesa coating does not peel off and remains on nesa coating, fragment is attached on bond roll and removes.
When nesa coating exists foreign matter, utilize polishing paper (manufacture of Sumitomo 3M society, 568XA) grind nesa coating and removed by foreign matter, nesa coating defines recess.When the fragment of nesa coating does not peel off and remains on nesa coating after grinding, fragment is attached on bond roll and removes.
In nesa coating or the interface of nesa coating and base material there is defect, on nesa coating, define recess by pressurizeing to defect.Herein, pressurization utilizes bond roll (enters the manufacture of industry society, clearer P-50) to carry out.
2-3. remediation composition capable painting process
Nonwoven fabrics (society of Asahi Chemical Industry manufacture, BEMCOT) is utilized remediation composition capable to be coated recess on nesa coating.
2-4. remediation composition capable removal step
Utilize nonwoven fabrics to be wiped by the unwanted remediation composition capable coating recess, thus be removed.
2-5. heating treatment step
Utilize baking oven 120 DEG C of heating 3 minutes, thus make remediation composition capable dry.
2-6. transparent resin layer lamination operation
Nesa coating is coated with transparent resin layer formation composition, utilizes baking oven within 3 minutes, to make it dry 120 DEG C of heating, thus lamination transparent resin layer.
3. evaluation method
In following embodiment and comparative example, the method below each evaluation ideas is carried out.
The mensuration of 3-1. thickness
Contact pin type surface-profile measuring instrument (manufacture of ULVAC society, Dektak6M) is utilized to measure.
The mensuration of 3-2. film defect part maximum length
Digital microscope (manufacture of KEYENCE society, VHX-500) is utilized to measure.
The mensuration of 3-3. surface resistivity (SR)
About the nesa coating of electrically conducting transparent lamination body, resistrivity meter (manufacture of society of Mitsubishi Chemical, LORESTAGP MCP-T600) is utilized to measure.Herein, preprosthetic surface resistivity refers to the value measured immediately after nesa coating formation process, and the surface resistivity after reparation refers to the value measured before being about to carry out transparent resin layer lamination operation.
The mensuration of 3-4. total light transmittance (Tt) and mist degree
According to JIS K7150, haze computer HGM-2B (manufacture of SUGA TEST INSTRUMENTS society) is utilized to measure.
The mensuration of 3-5. colourity
Spectral photometric colour measuring meter (manufacture of Konica Minolta society, CM3600d) is utilized to measure.
The mensuration of 3-6. refractive index
Ellipsometer (manufacture of society of groove buttocks optics industry institute, DHA-XA2/S6) is utilized to measure at wavelength 633nm.
3-7. outward appearance (visualization)
By the back side of visual examination illumination arrangement in electrically conducting transparent lamination body, whether there is concavo-convex or foreign matter by visual confirmation electrically conducting transparent lamination surface, unconfirmed is zero to average evaluation that is concavo-convex or foreign matter, confirm average evaluation that is concavo-convex or foreign matter to be ×.
3-8. outward appearance (amplifying observation)
Utilize Flied emission scanning electron microscope (FE-SEM) (manufacture of society of Hitachi, S-4500), confirm whether electrically conducting transparent lamination surface exists concavo-convex or foreign matter, unconfirmed is zero to average evaluation that is concavo-convex or foreign matter, confirm average evaluation that is concavo-convex or foreign matter to be ×.
3-9. thermal endurance
For nesa coating, measure the surface resistivity after just repairing and the surface resistivity after saving 1000 hours at 50 DEG C after repairing, calculate surface resistivity rising multiplying power (surface resistivity after the surface resistivity after preservation/just reparation), evaluate according to following 2 stages.
◎: surface resistivity rising multiplying power is less than 1.05
Zero: surface resistivity rising multiplying power is more than 1.05 and is less than 2
(embodiment 1)
To (3 be gathered; 4-ethyldioxythiophene) polystyrolsulfon acid (Heraeus society manufacture, Clevios PH1000) 100 parts, alkoxysilane oligomer (chemical industry society of Japan manufactures, N-POS) 14 parts, 3-hydroxypropionitrile (Tokyo changes into manufactures of industrial society, δ D=17.2, δ H=18.8, δ P=17.6) 37 parts, 19 parts, 1% nitric acid, ethanol (manufacture of Nacalai Tesque society, boiling point 78.4 DEG C) 255 parts, ion exchange water 45 parts mixing, thus obtain nesa coating formation composition.Utilize the nesa coating formation composition obtained, form nesa coating by the method recorded in 2-1..The thickness of the nesa coating obtained is 0.05 μm.
In nesa coating, as film defect, confirm the defect and foreign matter that are present in film surface.Film defect part maximum length is 20 μm.On this nesa coating, define recess by the method recorded in 2-2..
By alkoxysilane oligomer (manufacture of Duo Mo chemical industry society, TEOS) 90 parts, alkoxysilane oligomer (manufacture of chemical industry society of SHIN-ETSU HANTOTAI, KBM-303) 30 parts, ethanol (manufacture of Nacalai Tesque society, boiling point 78.4 DEG C) 4000 parts of mixing, obtain transparent resin layer formation composition.Utilize this transparent resin layer formation composition, by the method lamination transparent resin layer recorded in 2-6., obtain electrically conducting transparent lamination body.
(embodiment 2)
To (3 be gathered, 4-ethyldioxythiophene) (Heraeus society manufactures polystyrolsulfon acid, Clevios PH1000) 80 parts, (starlight PMC society manufactures nano silver wire, T-YP808, draw ratio 230, solid constituent 1.0%) 50 parts, (Nagase chemteX society manufactures mylar, Gabusen ES-210, solid constituent 25%) 42 parts, (Tokyo changes into industrial society and manufactures pyrazoles, δ D=20.2, δ H=10.4, δ P=12.4) 37 parts, (Nacalai Tesque society manufactures ethanol, boiling point 78.4 DEG C) 190 parts, (Sagane Bussan society manufactures 2-propyl alcohol, boiling point 82.5 DEG C) 10 parts, ion exchange water 100 parts mixing, thus obtain nesa coating formation composition.Utilize the nesa coating formation composition obtained, form nesa coating by the method recorded in 2-1..The thickness of nesa coating is 0.3 μm.
In nesa coating, as film defect, confirm the defect, the foreign matter that are present in film surface and be present in film or the defect at interface of film and base material.Film defect part maximum length is 500 μm.On this nesa coating, define recess by the method recorded in 2-2..
By acrylic resin (manufacture of Nagase chemteX society, TEISAN RESIN SG-790, solid constituent 23%) 200 parts, isocyanate compound (manufacture of Japanese polyurethane society, CORONET HL, solid constituent 75%) 10 parts, ethanol (manufacture of Nacalai Tesque society, boiling point 78.4 DEG C) 5 parts of mixing, obtain transparent resin layer formation composition.Utilize this transparent resin layer formation composition, by the method lamination transparent resin layer recorded in 2-6., obtain electrically conducting transparent lamination body.
(embodiment 3)
To (3 be gathered, 4-ethyldioxythiophene) polystyrolsulfon acid (Heraeus society manufacture, Clevios PH1000) 100 parts, 33 parts, mylar (manufactures of Nagase chemteX society, Gabusen ES-210, solid constituent 25%), ethanol (NacalaiTesque society manufactures, boiling point 78.4 DEG C) 255 parts, ion exchange water 45 parts, polyether ester modification hydroxyl dimethyl silicone polymer (manufacture of Bi Ke chemistry Japanese society, BYK-375, nonvolatile component 25%) 0.5 part mix, thus obtain nesa coating formation composition.Utilize the nesa coating formation composition obtained, form nesa coating by the method recorded in 2-1..The thickness of nesa coating is 0.5 μm.
In nesa coating, as film defect, confirm foreign matter and be present in film or the defect at interface of film and base material.Film defect part maximum length is 200 μm.On this nesa coating, define recess by the method recorded in 2-2..
By acrylic resin (manufacture of Nagase chemteX society, SG-790, solid constituent 23%) 200 parts, isocyanate compound (manufacture of Japanese polyurethane society, CORONET HL, solid constituent 75%) 10 parts, ethanol (manufacture of NacalaiTesque society, boiling point 78.4 DEG C) 5 parts of mixing, obtain transparent resin layer formation composition.Utilize this transparent resin layer formation composition, by the method lamination transparent resin layer recorded in 2-6., obtain electrically conducting transparent lamination body.
(embodiment 4)
To (3 be gathered; 4-ethyldioxythiophene) polystyrolsulfon acid (Heraeus society manufacture, Clevios PH1000) 100 parts, alkoxysilane oligomer (chemical industry society of Japan manufactures, N-POS) 14 parts, ethylene glycol (Tokyo change into industrial society manufactures, boiling point 196 DEG C) 5 parts, ethanol (Nacalai Tesque society manufactures, boiling point 78.4 DEG C) 255 parts, ion exchange water 45 parts mixing, thus obtain nesa coating formation composition.Utilize the nesa coating formation composition obtained, form nesa coating by the method recorded in 2-1..The thickness of nesa coating is 0.05 μm.
In nesa coating, as film defect, confirm the defect, the foreign matter that are present in film surface and be present in film or the defect at interface of film and base material.Film defect part maximum length is 20 μm.On this nesa coating, define recess by the method recorded in 2-2..
By alkoxysilane oligomer (manufacture of chemical industry society of Japan, N-POS) 100 parts, ethanol (manufacture of Nacalai Tesque society, boiling point 78.4 DEG C) 1395 parts of mixing, obtain remediation composition capable.For obtained remediation composition capable, utilize the method evaluation recorded in 3-4. ~ 3-6. total light transmittance, mist degree, refractive index and colourity, as a result, the total light transmittance made when thickness is the desciccator diaphragm of 300nm is 98.0%, mist degree is 0.3%, the refractive index of wavelength 633nm be 1.5, colourity is-0.01.
Be coated with remediation composition capable by the method recorded in 2-3. at recess, carry out heating treatment step by the method recorded in 2-5..
By acrylic resin (manufacture of Nagase chemteX society, TEISAN RESIN SG-600TEA, solid constituent 15%) 200 parts, isocyanate compound (manufacture of Japanese polyurethane society, CORONET HL, solid constituent 75%) 5 parts, ethanol (manufacture of Nacalai Tesque society, boiling point 78.4 DEG C) 5 parts of mixing, obtain transparent resin layer formation composition.Utilize this transparent resin layer formation composition, by the method lamination transparent resin layer recorded in 2-6., obtain electrically conducting transparent lamination body.
(embodiment 5)
By nano silver wire (manufacture of starlight PMC society, T-YP808, draw ratio 230, solid constituent 1.0%) 100 parts, 30 parts, mylar (manufacture of Nagase chemteX society, Gabusen ES-210, solid constituent 25%), pyrazoles (Tokyo changes into the manufacture of industrial society, δ D=20.2, δ H=10.4, δ P=12.4) 5 parts, ethanol (manufacture of Nacalai Tesque society, boiling point 78.4 DEG C) 255 parts, ion exchange water 45 parts mixing, thus obtain nesa coating formation composition.Utilize the nesa coating formation composition obtained, form nesa coating by the method recorded in 2-1..The thickness of nesa coating is 0.3 μm.
In nesa coating, as film defect, confirm the defect that is present in film surface and be present in film or the defect at interface of film and base material.Film defect part maximum length is 200 μm.On this nesa coating, define recess by the method recorded in 2-2..
By 100 parts, mylar (manufacture of Nagase chemteX society, Gabusen ES-210, solid constituent 25%), ethanol (manufacture of Nacalai Tesque society, boiling point 78.4 DEG C) 1500 parts of mixing, obtain remediation composition capable.For obtained remediation composition capable, utilize the method evaluation recorded in 3-4. ~ 3-6. total light transmittance, mist degree, refractive index and colourity, as a result, the total light transmittance made when thickness is the desciccator diaphragm of 300nm is 99.0%, mist degree is 0.3%, the refractive index of wavelength 633nm be 1.5, colourity is-0.01.Be coated with remediation composition capable by the method recorded in 2-3. at recess, carry out heating treatment step by the method recorded in 2-5..
By alkoxysilane oligomer (manufacture of chemical industry society of Japan, N-POS) 110 parts, alkoxysilane oligomer (manufacture of Duo Mo chemical industry society, TEOS) 20 parts, ethanol (manufacture of Nacalai Tesque society, boiling point 78.4 DEG C) 3000 parts of mixing, obtain transparent resin layer formation composition.Utilize this transparent resin layer formation composition, by the method lamination transparent resin layer recorded in 2-6., obtain electrically conducting transparent lamination body.
(embodiment 6)
To (3 be gathered, 4-ethyldioxythiophene) polystyrolsulfon acid (Heraeus society manufacture, Clevios PH1000) 100 parts, polyurethane (manufactures of the first industrial pharmaceutical society, Superflex 300, solid constituent 30%) 28 parts, 3-hydroxypropionitrile (Tokyo changes into the manufacture of industrial society, δ D=17.2, δ H=18.8, δ P=17.6) 37 parts, ethanol (manufacture of Nacalai Tesque society, boiling point 78.4 DEG C) 255 parts, ion exchange water 45 parts mixing, thus obtain nesa coating formation composition.Utilize the nesa coating formation composition obtained, form nesa coating by the method recorded in 2-1..The thickness of nesa coating is 0.5 μm.
In nesa coating, as film defect, confirm the defect, the foreign matter that are present in film surface and be present in film or the defect at interface of film and base material.Film defect part maximum length is 500 μm.On this nesa coating, define recess by the method recorded in 2-2..
To (3 be gathered, 4-ethyldioxythiophene) polystyrolsulfon acid (Heraeus society manufacture, Clevios PH1000) 30 parts, polyurethane (manufactures of the first industrial pharmaceutical society, Superflex 300, solid constituent 30%) 100 parts, ethanol (NacalaiTesque society manufactures, boiling point 78.4 DEG C) 1500 parts mixes, and obtains remediation composition capable.For obtained remediation composition capable, utilize the method evaluation recorded in 3-4. ~ 3-6. total light transmittance, mist degree, refractive index and colourity, as a result, the total light transmittance made when thickness is the desciccator diaphragm of 300nm is 97.3%, mist degree is 0.4%, the refractive index of wavelength 633nm be 1.5, colourity is-1.3.Be coated with remediation composition capable by the method recorded in 2-3. at recess, carry out heating treatment step by the method recorded in 2-5..
By acrylic resin (manufacture of East Asia synthesis society, Jurymer SEK301, solid constituent 40%) 100 parts, ethanol (manufacture of Nacalai Tesque society, boiling point 78.4 DEG C) 75 parts of mixing, obtain transparent resin layer formation composition.Utilize this transparent resin layer formation composition, by the method lamination transparent resin layer recorded in 2-6., obtain electrically conducting transparent lamination body.
(embodiment 7)
To (3 be gathered, 4-ethyldioxythiophene) polystyrolsulfon acid (Heraeus society manufacture, Clevios PH1000) 100 parts, acrylic resin (manufactures of East Asia synthesis society, Jurymer SEK301, solid constituent 40%) 21 parts, 3-hydroxypropionitrile (Tokyo changes into the manufacture of industrial society, δ D=17.2, δ H=18.8, δ P=17.6) 35 parts, ethanol (manufacture of Nacalai Tesque society, boiling point 78.4 DEG C) 255 parts, ion exchange water 45 parts mixing, thus obtain nesa coating formation composition.Utilize the nesa coating formation composition obtained, form nesa coating by the method recorded in 2-1..The thickness of nesa coating is 0.05 μm.
In nesa coating, as film defect, confirm the defect, the foreign matter that are present in film surface and be present in film or the defect at interface of film and base material.Film defect part maximum length is 20 μm.On this nesa coating, define recess by the method recorded in 2-2..
To (3 be gathered, 4-ethyldioxythiophene) polystyrolsulfon acid (Heraeus society manufacture, Clevios PH1000) 30 parts, acrylic resin (manufactures of East Asia synthesis society, Jurymer SEK301, solid constituent 40%) 100 parts, ethanol (NacalaiTesque society manufactures, boiling point 78.4 DEG C) 2000 parts mixes, and obtains remediation composition capable.For obtained remediation composition capable, utilize the method evaluation recorded in 3-4. ~ 3-6. total light transmittance, mist degree, refractive index and colourity, as a result, the total light transmittance made when thickness is the desciccator diaphragm of 300nm is 97.8%, mist degree is 0.4%, the refractive index of wavelength 633nm be 1.5, colourity is-1.5.Be coated with remediation composition capable by the method recorded in 2-3. at recess, will the unwanted remediation composition capable removing of recess be coated by the method recorded in 2-4., and carry out heating treatment step by the method recorded in 2-5..
By acrylic resin (manufacture of Nagase chemteX society, TEISAN RESIN SG-600TEA (solid constituent 15%)) 200 parts, isocyanate compound (manufacture of Japanese polyurethane society, CORONET HL, solid constituent 75%) 5 parts, ethanol (manufacture of Nacalai Tesque society, boiling point 78.4 DEG C) 5 parts of mixing, obtain transparent resin layer formation composition.Utilize this transparent resin layer formation composition, by the method lamination transparent resin layer recorded in 2-6., obtain electrically conducting transparent lamination body.
(embodiment 8)
By Graphene (manufacture of XG Sciences society, H-5 aqueous dispersions, solid constituent 15%) 10 parts, acrylic resin (manufacture of East Asia synthesis society, Jurymer SEK301, solid constituent 40%) 28.5 parts, ethanol (manufacture of Nacalai Tesque society, boiling point 78.4 DEG C) 350 parts, ion exchange water 50 parts mixing, thus obtain nesa coating formation composition.Utilize the nesa coating formation composition obtained, form nesa coating by the method recorded in 2-1..The thickness of nesa coating is 0.3 μm.
In nesa coating, as film defect, confirm foreign matter and be present in film or the defect at interface of film and base material.Film defect part maximum length is 500 μm.On this nesa coating, define recess by the method recorded in 2-2..
By acrylic resin (manufacture of East Asia synthesis society, Jurymer SEK301, solid constituent 40%) 100 parts, ethanol (manufacture of Nacalai Tesque society, boiling point 78.4 DEG C) 2000 parts of mixing, obtain remediation composition capable.For obtained remediation composition capable, utilize the method evaluation recorded in 3-4. ~ 3-6. total light transmittance, mist degree, refractive index and colourity, as a result, the total light transmittance made when thickness is the desciccator diaphragm of 300nm is 99.0%, mist degree is 0.2%, be-0.01 in the refractive index 1.5 of wavelength 633nm, colourity.Be coated with remediation composition capable by the method recorded in 2-3. at recess, will the unwanted remediation composition capable removing of recess be coated by the method recorded in 2-4., and carry out heating treatment step by the method recorded in 2-5..
By acrylic resin (manufacture of Nagase chemteX society, TEISAN RESIN SG-600TEA, solid constituent 15%) 200 parts, isocyanate compound (manufacture of Japanese polyurethane society, CORONET HL, solid constituent 75%) 5 parts, ethanol (manufacture of Nacalai Tesque society, boiling point 78.4 DEG C) 5 parts of mixing, obtain transparent resin layer formation composition.Utilize this transparent resin layer formation composition, by the method lamination transparent resin layer recorded in 2-6., obtain electrically conducting transparent lamination body.
(embodiment 9)
By carbon nano-tube (manufacture of Meijo Nano Carbon society, SWNT dispersion liquid, carbon nanotube concentration 0.1%) 100 parts, alkoxysilane oligomer (manufacture of chemical industry society of Japan, N-POS) 1.3 parts, ethanol (manufacture of Nacalai Tesque society, boiling point 78.4 DEG C) 10 parts, the mixing of 1 part, 1% nitric acid, thus obtain nesa coating formation composition.Utilize the nesa coating formation composition obtained, form nesa coating by the method recorded in 2-1..The thickness of nesa coating is 0.5 μm.
In nesa coating, as film defect, confirm the defect, the foreign matter that are present in film surface and be present in film or the defect at interface of film and base material.Film defect part maximum length is 200 μm.On this nesa coating, define recess by the method recorded in 2-2..
By alkoxysilane oligomer (manufacture of chemical industry society of Japan, N-POS) 100 parts, ethanol (manufacture of Nacalai Tesque society, boiling point 78.4 DEG C) 3000 parts of mixing, obtain remediation composition capable.For obtained remediation composition capable, utilize the method evaluation recorded in 3-4. ~ 3-6. total light transmittance, mist degree, refractive index and colourity, as a result, the total light transmittance made when thickness is the desciccator diaphragm of 300nm is 98.0%, mist degree is 0.3%, the refractive index of wavelength 633nm be 1.5, colourity is-0.01.Be coated with remediation composition capable by the method recorded in 2-3. at recess, will the unwanted remediation composition capable removing of recess be coated by the method recorded in 2-4., and carry out heating treatment step by the method recorded in 2-5..
By alkoxysilane oligomer (manufacture of chemical industry society of Japan, N-POS) 100 parts, ethanol (manufacture of Nacalai Tesque society, boiling point 78.4 DEG C) 950 parts of mixing, obtain transparent resin layer formation composition.Utilize this transparent resin layer formation composition, by the method lamination transparent resin layer recorded in 2-6., obtain electrically conducting transparent lamination body.
(embodiment 10)
Have on the glass plate that diameter is the damage of 150 μm on surface, utilize the nesa coating formation composition made in embodiment 1, form nesa coating by the method recorded in 2-1..The thickness of nesa coating is 0.2 μm.In nesa coating, as film defect, confirm the defect being present in film surface, film defect part maximum length is 150 μm.
By acrylic resin (manufacture of Nagase chemteX society, SG-790, solid constituent 23%) 200 parts, isocyanate compound (manufacture of Japanese polyurethane society, CORONET HL, solid constituent 75%) 10 parts, ethanol (manufacture of NacalaiTesque society, boiling point 78.4 DEG C) 5 parts of mixing, obtain transparent resin layer formation composition.Utilize this transparent resin layer formation composition, by the method lamination transparent resin layer recorded in 2-6., obtain electrically conducting transparent lamination body.
(embodiment 11)
Have on the glass plate that diameter is the damage of 150 μm on surface, utilize the nesa coating formation composition made in embodiment 1, form nesa coating by the method recorded in 2-1..The thickness of nesa coating is 0.2 μm.In nesa coating, as film defect, confirm the defect being present in film surface, film defect part maximum length is 150 μm.
By alkoxysilane oligomer (manufacture of chemical industry society of Japan, N-POS) 100 parts, ethanol (manufacture of Nacalai Tesque society, boiling point 78.4 DEG C) 3000 parts of mixing, obtain remediation composition capable.For obtained remediation composition capable, utilize the method evaluation recorded in 3-4. ~ 3-6. total light transmittance, mist degree, refractive index and colourity, as a result, the total light transmittance made when thickness is the desciccator diaphragm of 300nm is 98.0%, mist degree is 0.3%, the refractive index of wavelength 633nm be 1.5, colourity is-0.01.Be coated with remediation composition capable by the method recorded in 2-3. at recess, will the unwanted remediation composition capable removing of recess be coated by the method recorded in 2-4., and carry out heating treatment step by the method recorded in 2-5..
By acrylic resin (manufacture of Nagase chemteX society, SG-790, solid constituent 23%) 200 parts, isocyanate compound (manufacture of Japanese polyurethane society, CORONET HL, solid constituent 75%) 10 parts, ethanol (manufacture of NacalaiTesque society, boiling point 78.4 DEG C) 5 parts of mixing, obtain transparent resin layer formation composition.Utilize this transparent resin layer formation composition, by the method lamination transparent resin layer recorded in 2-6., obtain electrically conducting transparent lamination body.
(embodiment 12)
Add tannic acid (Wako Pure Chemical Industries, Ltd.'s manufacture) 1.1 parts in the nesa coating formation composition made in embodiment 5, obtain nesa coating formation composition.Utilize the nesa coating formation composition obtained, form nesa coating by the method recorded in 2-1..The thickness of nesa coating is 0.3 μm.
In nesa coating, as film defect, confirm the defect that is present in film surface and be present in film or the defect at interface of film and base material.Film defect part maximum length is 200 μm.On this nesa coating, define recess by the method recorded in 2-2..
Then, add tannic acid (Wako Pure Chemical Industries, Ltd.'s manufacture) 5 parts in the remediation composition capable made in embodiment 5, obtain remediation composition capable.For obtained remediation composition capable, utilize the method evaluation recorded in 3-4. ~ 3-6. total light transmittance, mist degree, refractive index and colourity, as a result, the total light transmittance made when thickness is the desciccator diaphragm of 300nm is 99.0%, mist degree is 0.3%, the refractive index of wavelength 633nm be 1.5, colourity is-0.01.Be coated with remediation composition capable by the method recorded in 2-3. at recess, carry out heating treatment step by the method recorded in 2-5..
And then, utilize the transparent resin layer formation composition made in embodiment 5, by the method lamination transparent resin layer recorded in 2-6., obtain electrically conducting transparent lamination body.
(embodiment 13)
Add tannic acid (Wako Pure Chemical Industries, Ltd.'s manufacture) 1.1 parts in the nesa coating formation composition made in embodiment 5, obtain nesa coating formation composition.Utilize the nesa coating formation composition obtained, form nesa coating by the method recorded in 2-1..The thickness of nesa coating is 0.3 μm.
In nesa coating, as film defect, confirm the defect that is present in film surface and be present in film or the defect at interface of film and base material.Film defect part maximum length is 200 μm.On this nesa coating, define recess by the method recorded in 2-2..
Then, utilize the remediation composition capable made in embodiment 5, be coated with remediation composition capable by the method recorded in 2-3. at recess, carried out heating treatment step by the method recorded in 2-5..
And then, utilize the transparent resin layer formation composition made in embodiment 5, by the method lamination transparent resin layer recorded in 2-6., obtain electrically conducting transparent lamination body.
(embodiment 14)
Add tannic acid (Wako Pure Chemical Industries, Ltd.'s manufacture) 1.2 parts in the nesa coating formation composition made in embodiment 1, obtain nesa coating formation composition.Utilize the nesa coating formation composition obtained, form nesa coating by the method recorded in 2-1..The thickness of nesa coating is 0.2 μm.In nesa coating, as film defect, confirm the defect being present in film surface.Film defect part maximum length is 150 μm.
Utilize the transparent resin layer formation composition made in embodiment 10, by the method lamination transparent resin layer recorded in 2-6., obtain electrically conducting transparent lamination body.
(comparative example 1)
To (3 be gathered, 4-ethyldioxythiophene) polystyrolsulfon acid (Heraeus society manufacture, Clevios PH1000) 100 parts, 34 parts, mylar (manufactures of Nagase chemteX society, Gabusen ES-210, solid constituent 25%), 3-hydroxypropionitrile (Tokyo changes into the manufacture of industrial society, δ D=17.2, δ H=18.8, δ P=17.6) 37 parts, ethanol (manufacture of Nacalai Tesque society, boiling point 78.4 DEG C) 255 parts, ion exchange water 45 parts mixing, thus obtain nesa coating formation composition.Utilize the nesa coating formation composition obtained, form nesa coating by the method recorded in 2-1..The thickness of nesa coating is 0.3 μm.
In nesa coating, as film defect, confirm the defect, the foreign matter that are present in film surface and be present in film or the defect at interface of film and base material.Film defect part maximum length is 20 μm.
(comparative example 2)
According to the method recorded in Japanese Unexamined Patent Publication 2013-142194 publication, define the ITO sputtered film that thickness is 0.02 μm on the glass substrate.
In nesa coating, as film defect, confirm foreign matter.Film defect part maximum length is 20 μm.On this nesa coating, define recess by the method recorded in 2-2..
By alkoxysilane oligomer (manufacture of chemical industry society of Japan, N-POS) 100 parts, ethanol (manufacture of Nacalai Tesque society, boiling point 78.4 DEG C) 1395 parts of mixing, obtain remediation composition capable.For obtained remediation composition capable, utilize the method evaluation recorded in 3-4. ~ 3-6. total light transmittance, mist degree, refractive index and colourity, as a result, the total light transmittance made when thickness is the desciccator diaphragm of 300nm is 98.0%, mist degree is 0.3%, the refractive index of wavelength 633nm be 1.5, colourity is-0.01.Be coated with remediation composition capable by the method recorded in 2-3. at recess, will the unwanted remediation composition capable removing of recess be coated by the method recorded in 2-4., and carry out heating treatment step by the method recorded in 2-5..
By acrylic resin (manufacture of East Asia synthesis society, Jurymer SEK301, solid constituent 40%) 40 parts, ethanol (manufacture of Nacalai Tesque society, boiling point 78.4 DEG C) 100 parts of mixing, obtain transparent resin layer formation composition.Utilize this transparent resin layer formation composition, by the method lamination transparent resin layer recorded in 2-6., obtain electrically conducting transparent lamination body.
In above embodiment and comparative example, after following nesa coating formation process closely by the method evaluation recorded in 3-3. ~ 3-8., after (before reparation) and transparent resin layer lamination operation, surface resistivity (SR), total light transmittance (Tt), mist degree, colourity, refractive index and the outward appearance (visualization, amplifying observation) of (repairs afterwards) be (wherein, as mentioned above, be only repair after surface resistivity evaluate before being about to carry out transparent resin layer lamination operation).In addition, the thermal endurance of (after repairing) after transparent resin layer lamination operation by the method evaluation recorded in 3-9..Show the result in table 2.

Claims (12)

1. the reparation of nesa coating and a renovation process, the method is characterized in that, the method is included in the operation of the recess lamination transparent resin layer on nesa coating,
Nesa coating is formed by the nesa coating formation composition of coating containing electric conducting material, and this nesa coating is configured at least one face of base material,
Recess be selected from by result from the depression of substrate shapes, the damage being present in nesa coating and defect, the foreign matter being present in nesa coating removed the depression that formed and the defect being present in nesa coating pressurizeed at least one in group that the depression that formed forms
The total length of recess is 10 μm ~ 300 μm.
2. reparation as claimed in claim 1 and renovation process, wherein, the method is included in the operation of recess coating remediation composition capable further,
The total light transmittance of remediation composition capable when making the desciccator diaphragm of thickness 300nm is more than 97%, and mist degree is less than 3%, is 1.40 ~ 1.70 in the refractive index of wavelength 633nm, and colourity is-1.5 ~ 1.5.
3. reparation as claimed in claim 1 or 2 and renovation process, wherein, after the operation of recess coating remediation composition capable, comprises operation or the heating treatment step of the unwanted remediation composition capable removing by coating recess further.
4. the reparation according to any one of claims 1 to 3 and renovation process, wherein, remediation composition capable contains electric conducting material and/or binding agent.
5. reparation as claimed in claim 4 and renovation process, wherein, nesa coating formation composition contains the binding agent same with the binder phase in remediation composition capable.
6. as claimed in claim 5 repair and renovation process, wherein, binding agent is be selected from least one in the group that is made up of mylar, acrylic resin, polyurethane, epoxy resin, alkoxysilane oligomer and vistanex.
7. the reparation according to any one of claim 1 ~ 6 and renovation process, wherein, nesa coating formation composition contains at least one in the group being selected from and being made up of inorganic conductive particulate, metal nanometer line and electric conductive polymer as electric conducting material.
8. the reparation according to any one of claim 4 ~ 7 and renovation process, wherein, remediation composition capable contains at least one in the group being selected from and being made up of inorganic conductive particulate, metal nanometer line and electric conductive polymer as electric conducting material.
9. an electrically conducting transparent lamination body, it is the electrically conducting transparent lamination body possessing base material, nesa coating and transparent resin layer, it is characterized in that,
Nesa coating utilizes the reparation according to any one of claim 1 ~ 8 and renovation process repair and regenerate.
10. electrically conducting transparent lamination body as claimed in claim 9, wherein, base material is glass baseplate, in this electrically conducting transparent lamination body, be laminated with glass baseplate, nesa coating and transparent resin layer successively.
11. electrically conducting transparent lamination bodies as described in claim 9 or 10, wherein, transparent resin layer is adhesive layer or hard conating.
12. electrically conducting transparent lamination bodies according to any one of claim 9 ~ 11, wherein, the thickness of nesa coating is 30nm ~ 500nm, and this electrically conducting transparent lamination body is used to electromagnetic shielding material, noise reduction, anti-static material or transparency electrode.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH032378A (en) * 1989-05-26 1991-01-08 Matsushita Electric Ind Co Ltd Method for repairing defect part of transparent conductive film
EP0990178A1 (en) * 1997-06-16 2000-04-05 Minnesota Mining And Manufacturing Company Self light-emitting retroreflective sheet and method for producing the same
CN101081951A (en) * 2006-05-30 2007-12-05 奇美实业股份有限公司 Ink component for micro color-patch pattern defect correction of colorful filter
CN102559043A (en) * 2010-11-15 2012-07-11 长濑化成株式会社 Conductive coating composition and laminate
TWI388530B (en) * 2006-01-26 2013-03-11 Au Optronics Corp Method of repairing a transparent conductive film

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007220789A (en) * 2006-02-15 2007-08-30 Fujimori Kogyo Co Ltd Optical filter for display and its manufacturing method
JP4978072B2 (en) * 2006-06-16 2012-07-18 大日本印刷株式会社 Method for correcting protrusion defect of alignment control protrusion
JP5286960B2 (en) * 2008-06-17 2013-09-11 日油株式会社 Transparent conductive film and touch panel provided with the same
JP2010015072A (en) * 2008-07-07 2010-01-21 Hitachi High-Technologies Corp Correcting method of color filter substrate, and its device
JP2010080693A (en) * 2008-09-26 2010-04-08 Dainippon Printing Co Ltd Electromagnetic wave shield filter, and image display device using the same
JP5679565B2 (en) * 2011-03-10 2015-03-04 パナソニックＩｐマネジメント株式会社 Transparent conductive film, substrate with transparent conductive film, and organic electroluminescence device using the same
JP5908287B2 (en) * 2012-01-24 2016-04-26 日立マクセル株式会社 Composition for forming transparent conductive film and transparent conductive film
JP2013222590A (en) * 2012-04-16 2013-10-28 Shin Etsu Polymer Co Ltd Conductive pattern formation substrate and manufacturing method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH032378A (en) * 1989-05-26 1991-01-08 Matsushita Electric Ind Co Ltd Method for repairing defect part of transparent conductive film
EP0990178A1 (en) * 1997-06-16 2000-04-05 Minnesota Mining And Manufacturing Company Self light-emitting retroreflective sheet and method for producing the same
CN1264473A (en) * 1997-06-16 2000-08-23 美国3M公司 Self light-emitting retroreflective sheet and method for producing the same
TWI388530B (en) * 2006-01-26 2013-03-11 Au Optronics Corp Method of repairing a transparent conductive film
CN101081951A (en) * 2006-05-30 2007-12-05 奇美实业股份有限公司 Ink component for micro color-patch pattern defect correction of colorful filter
CN102559043A (en) * 2010-11-15 2012-07-11 长濑化成株式会社 Conductive coating composition and laminate

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
周令治: "《稀散金属手册》", 31 March 1993 *
姜辛等: "《透明导电氧化物薄膜》", 31 October 2008 *
曲喜新等: "《电子薄膜材料》", 31 October 1996 *

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107305928A (en) * 2016-04-22 2017-10-31 三星显示有限公司 Nesa coating and the electronic equipment including the nesa coating
CN107545949A (en) * 2016-06-29 2018-01-05 日立麦克赛尔株式会社 Transparent conductivity piece and its manufacture method
CN109476864A (en) * 2016-06-30 2019-03-15 可隆工业株式会社 Polyester multilayer film
CN109476864B (en) * 2016-06-30 2021-08-06 可隆工业株式会社 Polyester multilayer film
CN106205863A (en) * 2016-07-19 2016-12-07 中山大学 A kind of volume to volume manufacturing method thereof for preparing high-performance nano silver wire transparent conductive film
CN106409152A (en) * 2016-09-26 2017-02-15 昆山工研院新型平板显示技术中心有限公司 A metal wire, a metal wire self-repairing method and a flexible display screen
CN106409152B (en) * 2016-09-26 2019-03-08 昆山工研院新型平板显示技术中心有限公司 A kind of metal wire, metal wire selfreparing method and flexible display screen
CN114395293A (en) * 2016-10-14 2022-04-26 C3内诺公司 Stabilized sparse metal conducting membranes and solutions for stable compound delivery
CN109575760A (en) * 2017-09-29 2019-04-05 麦克赛尔控股株式会社 The manufacturing method of transparent and electrically conductive film, the coating composition for being used to form transparent and electrically conductive film and transparent and electrically conductive film
TWI799440B (en) * 2017-09-29 2023-04-21 日商麥克賽爾股份有限公司 Transparent conductive film, coating composition for forming transparent conductive film, and method for producing transparent conductive film
CN108728817A (en) * 2018-05-21 2018-11-02 中山大学 A kind of infrared transparent window and preparation method thereof with electro-magnetic screen function
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CN108642473A (en) * 2018-05-21 2018-10-12 中山大学 A kind of infrared transparent window and preparation method thereof with electro-magnetic screen function
CN110721881A (en) * 2019-11-04 2020-01-24 中国人民解放军国防科技大学 On-site repairing method for high-temperature radar and infrared compatible stealth coating
CN110721881B (en) * 2019-11-04 2021-10-15 中国人民解放军国防科技大学 On-site repairing method for high-temperature radar and infrared compatible stealth coating

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