CN102952423B - Organic conductive film - Google Patents
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- CN102952423B CN102952423B CN201210292322.9A CN201210292322A CN102952423B CN 102952423 B CN102952423 B CN 102952423B CN 201210292322 A CN201210292322 A CN 201210292322A CN 102952423 B CN102952423 B CN 102952423B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
- H01B1/124—Intrinsically conductive polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/38—Packaging materials of special type or form
- B65D65/40—Applications of laminates for particular packaging purposes
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- C09D181/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur, with or without nitrogen, oxygen, or carbon only; Coating compositions based on polysulfones; Coating compositions based on derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1343—Electrodes
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- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
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Abstract
The invention aims to provide an organic conductive film which having an excellent durability. The organic conductive film of the invention is an organic conductive film formed by using a conductive composition at least containing a conductive polymer. The organic conductive film is characterized in that the bosseyed largest height (RZ) is more than 35% relative to an average film thickness.
Description
【Technical field】
The present invention relates to the Organic Conductive Films of excellent in te pins of durability and the blooming with such Organic Conductive Films, packaging
Material, ELD and liquid crystal display cell.
【Background technology】
As the nesa coating (transparency electrode etc.) used in display applications etc., it is known to saturating by the inorganic system such as ITO
The conducting film that bright conductive material is formed.
But, in the formation using the nesa coating of ITO, large-scale vacuum equipment is typically used using sputtering
Carry out etc. method, have the tendency of manufacturing cost and increase.
In addition, ITO contains the indium as rare metal (so-called rare metal), the exhaustion of its resource that fears are entertained that.
Therefore, in recent years, just actively attempting using electric conductive polymer as the replacement material of ITO.
For as the electric conductive polymer of organic conductive material, can be by based on wet processings such as roll coater, printings
Short-cut method carrying out its film forming, and because electric conductive polymer is Organic substance, thus compared with inorganic system's conductive material, its
It is in the ascendance on this point aboundresources is present.
In this field is it known to electric conductive polymer can be used in almost various uses already；But using electric conductivity
In the case that polymer carries out film forming, its thickness is usually uniform.On the other hand, with leading for being formed by inorganic system's conductive material
Electrolemma is compared, and the Organic Conductive Films formed using electric conductive polymer have that thermostability, weatherability be low, class as poor durability
Topic.For example, as electric conductive polymer it is widely known be polythiophene system electric conductive polymer (such as PEDOT/PSS), but
Know that its electric conductivity is reduced over time, it is believed that the oxidation reaction that its degradation mechanism is the oxygen in air to be caused is (for example
Non-patent literature 1).
In addition, the present inventor using polythiophene system electric conductive polymer it will also be appreciated that in the case where uniform film is formed,
Its electric conductivity is lentamente lost, intolerant to life-time service.
【Prior art literature】
【Non-patent literature】
Non-patent literature 1：Kudo health husband writes, Electronic Journal Archives No.118, electronics monograph
(Electricity ジ ャ ー Na Le), 2011, page 133
【The content of the invention】
【Invent problem to be solved】
It is an object of the invention to solve above-mentioned problem, there is provided the Organic Conductive Films of excellent in te pins of durability and possess such
The blooming of Organic Conductive Films, packing timber, ELD and liquid crystal display cell.
【The means to solve the problem】
The present inventor has made intensive studies to solve above-mentioned problem, as a result finds, by the list for making Organic Conductive Films
The maximum height (Rz) in face is more than 35% relative to average film thickness, the durability of Organic Conductive Films is remarkably improved, so as to complete
The present invention.
That is, Organic Conductive Films of the invention are using having that the conductive composition at least containing electric conductive polymer is formed
Machine conducting film, the Organic Conductive Films are characterised by that the maximum height (Rz) of its one side is more than 35% relative to average film thickness.
In the Organic Conductive Films of the present invention, above-mentioned electric conductive polymer is preferably polythiophene system electric conductive polymer.
Also, poly- (the 3,4- bis- of the above-mentioned polythiophene system electric conductive polymer preferably repetitive structure with following formula (I)s
Alkoxy thiophene) or the complex (Complex of poly- (3,4- alklyenedioxy thiophenes) and dopant it is fit)：
【Change 1】
(in formula, R1And R2Hydrogen atom or C are represented independently of each other1-4Alkyl or represent together with or without replacement
The C of base1-4Alkylidene).
The blooming of the present invention is characterised by that it has the Organic Conductive Films of the present invention.
The packing timber of the present invention is characterised by that it has the Organic Conductive Films of the present invention.
The ELD of the present invention is characterised by that it has the Organic Conductive Films of the present invention.
The liquid crystal display cell of the present invention is characterised by that it has the Organic Conductive Films of the present invention.
【The effect of invention】
In the Organic Conductive Films of the present invention, because the maximum height (Rz) of its one side is more than 35% relative to average film thickness,
Thus durability is extremely excellent.
Also, possess blooming, packing timber, ELD and the liquid crystal display cell of such Organic Conductive Films also to distinguish
With excellent durability.
【Description of the drawings】
Fig. 1 (a) is the sectional view of of the Organic Conductive Films for schematically showing the present invention, and Fig. 1 (b)～Fig. 1 (d) is to show
The schematic diagram of the rheological parameters' change with time of the deterioration of Organic Conductive Films shown in Fig. 1 (a) is gone out.
Fig. 2 (a) is the sectional view of that diagrammatically illustrates existing Organic Conductive Films, and Fig. 2 (b)～Fig. 2 (d) is to show
The schematic diagram of the rheological parameters' change with time of the deterioration of Organic Conductive Films shown in Fig. 2 (a) is gone out.
【Symbol description】
11st, 21 base material
12a, 22a Organic Conductive Films
12b, 22b deteriorate part
【Specific embodiment】
The Organic Conductive Films of the present invention are illustrated first.
The Organic Conductive Films of the present invention are using the organic of the conductive composition formation at least containing electric conductive polymer
Conducting film, the Organic Conductive Films are characterised by that the maximum height (Rz) of its one side is more than 35% relative to average film thickness.
Herein, maximum height (Rz) is the value being measured on the basis of JIS B0601-2001.
In addition, so-called average film thickness is thickness average value when Organic Conductive Films to be approximately the smooth film in its surface, its
To be calculated the value tried to achieve by the thickness to even spread conductive composition and in the case of being dried.
For example, taking 9 μm of thickness applying solid composition as 1% conductive composition and in the case of being dried, having
The average film thickness of machine conducting film is 90nm.
Above-mentioned Organic Conductive Films are more than 35% relative to average film thickness due to the maximum height (Rz) of its one side, thus resistance to
Long property is extremely excellent.
Below, referring to the drawings for its reason is illustrated.
Fig. 1 (a) is the sectional view of of the Organic Conductive Films for schematically showing the present invention, and Fig. 1 (b)～Fig. 1 (d) is to show
The schematic diagram of the rheological parameters' change with time of the deterioration of Organic Conductive Films shown in Fig. 1 (a) is gone out.
Fig. 2 (a) is the sectional view of that diagrammatically illustrates existing Organic Conductive Films, and Fig. 2 (b)～Fig. 2 (d) is to show
The schematic diagram of the rheological parameters' change with time of the deterioration of Organic Conductive Films shown in Fig. 2 (a) is gone out.
For generally, for the Organic Conductive Films formed by the conductive composition containing electric conductive polymer, lead to
Cross and contacted with the oxygen in light or air, the chemical constitution of electric conductive polymer changes or occur dedoping, so as to electric conductivity
Reduce, this is well-known.
For example, the PEDOT/PSS typical example as electric conductive polymer being widely known by the people, it is believed that its deterioration
One of mechanism is the oxidation reaction (non-patent literature 1) that the oxygen in air is caused.
Thus, for the Organic Conductive Films formed by the conductive composition containing such electric conductive polymer,
It is contemplated that it starts deterioration from the surface of the film of air contact, the in-house development to film is deteriorated.
It is thought that the deterioration be by deteriorate triggering factors (trigger) --- oxygen to the infiltration in film, spread this mistake
Journey and carry out.But, because the deterioration reaction is the reaction in solid, thus (Expansion dissipates rule it is assumed that reaction is in diffusion rate controlling
Speed), as a result, it is contemplated that its film is more thick, the time deteriorating completely to film is longer.
In addition, as shown in Fig. 2 (a), the organic conductive formed using the conductive composition containing electric conductive polymer
Film is usually Organic Conductive Films 22a in uniform thickness (in addition, in Fig. 2,21 is base material).
Further, since the deterioration of Organic Conductive Films 22a is carried out by said process, thus deterioration part 22b is with uniform thick
Degree increases (deterioration is uniformly carried out in thickness direction) (with reference to Fig. 2 (b)～Fig. 2 (d)).Therefore, integrally deteriorating to film
Time shorten.
On the other hand, in Organic Conductive Films of the invention, the maximum height (Rz) of its one side is 35% relative to average film thickness
More than, such as shown in Fig. 1 (a), Organic Conductive Films 12a has concavo-convex on its surface.Therefore, in Organic Conductive Films 12a, although its film
In thinner part rapid degradation, but there is substantial amounts of thicker position in film, it is required deteriorating completely to the thick film part
The time Organic Conductive Films that are longer than the same amount of conductive composition of coating and formed.
That is, in Organic Conductive Films of the invention, the Organic Conductive Films formed with same amount of conductive composition is coated with
Compare, it is not easily deteriorated (remain the part for not occurring to deteriorate), thus, as a result the overall degradation speed of film is slack-off.In addition, figure
In 1,11 is base material, 12b is deterioration part.
In above-mentioned Organic Conductive Films, above-mentioned maximum height (Rz) is more than 35% relative to average film thickness.Its reason exists
In in the case where maximum height is less than 35%, the durability (film durability) of Organic Conductive Films is significantly deteriorated.
From film durability aspect, above-mentioned maximum height (Rz) is preferably more than 50% relative to average film thickness, more excellent
Elect more than 100%, more preferably more than 200%, most preferably more than 250% as.
In addition, above-mentioned maximum height (Rz) is preferably less than 600% relative to average film thickness.
Its reason is, if maximum height is more than 600%, significantly, optical characteristics are deteriorated for the irregular reference of the light on surface.
In addition, from optical characteristics aspect, maximum height (Rz) is more preferably less than 500%, is most preferably relative to average film thickness
Less than 450%.
In addition, for above-mentioned Organic Conductive Films, at 2 more than position above-mentioned maximum height (Rz) is measured
In the case of, the maximum height (Rz) of position is more than 250% at particularly preferably at least 1.This is excellent due to can positively guarantee
Durability.
The average film thickness of above-mentioned Organic Conductive Films is preferably more than 60nm, more preferably 60nm～400nm, further preferably
For 60nm～300nm, particularly preferably 80nm～200nm.
This is because, in the case that above-mentioned average film thickness is less than 60nm, the characteristic of Organic Conductive Films, such as film hardness or resistance to
Chemicals tend to be deteriorated；On the other hand, if more than 400nm, optical characteristics are tended to be deteriorated.
Due to having electric conductivity containing electric conductive polymer, its surface resistivity (SR) is preferably above-mentioned Organic Conductive Films
102～1011Ω/□.If this is because, the scope, then for example can as the characteristic required by antistatic layer or transparency electrode
Fully met.
Such Organic Conductive Films are formed using conductive composition.
Next, illustrating to each composition of above-mentioned conductive composition successively.
1. electric conductive polymer
Above-mentioned conductive composition contains electric conductive polymer as neccessary composition.
Above-mentioned electric conductive polymer is for giving electric conductivity (such as surface resistivity to the Organic Conductive Films for being formed；
Hereafter be designated as SR) complex.
As above-mentioned electric conductive polymer, polythiophene, polypyrrole, polyaniline, polyacetylene, polyphenylacetylene, poly- can be enumerated
Naphthalene, their derivant and their complex with dopant etc..
Among them, the polythiophene system electric conductive polymer formed by the coordination compound of polythiophene and dopant be it is appropriate,
As polythiophene system electric conductive polymer, poly- (3,4- dialkoxythiophene) or poly- (3,4- alklyenedioxy thiophene) and dopant
Complex be more appropriate.
As above-mentioned poly- (3,4- dialkoxythiophene) or poly- (3,4- alklyenedioxy thiophene), preferably contain following formula
(I) polythiophene of the cation form of the constitutional repeating unit shown in.
【Change 2】
Herein, R1And R2Hydrogen atom or C are represented independently of each other1-4Alkyl or represent together with or without replacement
The C of base1-4Alkylidene.
As above-mentioned C1-4Alkyl, can enumerate such as methyl, ethyl, propyl group, isopropyl, normal-butyl, isobutyl group, Zhong Ding
Base, tert-butyl group etc..
Also, as R1And R2The C with or without substituent group for being formed together1-4Alkylidene, can enumerate for example sub-
Methyl, 1,2- ethylidene, 1,3- propylidene, 1,4- butylidenes, 1- methyl isophthalic acids, 2- ethylidene, 1- ethyl -1,2- ethylidene, 1-
Methyl isophthalic acid, 3- propylidene, 2- methyl isophthalic acids, 3- propylidene etc..Preferably methylene, ethylene, trimethylene, especially excellent
Elect 1,2- ethylidene as.As the polythiophene with above-mentioned alkylidene, particularly preferably poly- (3,4- ethyldioxythiophene).
For the complex formed by poly- (3,4- ethyldioxythiophene) and dopant, in addition to electric conductivity and the transparency,
Chemical stability is also extremely excellent, and the Organic Conductive Films formed as electric conductive polymer using the complex are had and are independent of
In the extremely stable electric conductivity and the high transparency of humidity.Further, due to containing the complex as conductive poly
The conductive composition of compound can form overlay film with the short time at low temperature, thus also have extremely fitting required by a large amount of productions
In the productivity ratio of Organic Conductive Films manufacture.
By making the dopant of the above-mentioned polythiophene system electric conductive polymer of composition ion pair is formed come shape with above-mentioned polythiophene
Into complex, it is the polymer of the anionic form that polythiophene can be made to be stably dispersed in water.
As such dopant, can enumerate：Carboxylic acid polyalcohol class (for example, polyacrylic acid, poly, poly- methyl
Acrylic acid etc.), sulfonic acid polymer class (for example, polystyrolsulfon acid, polyvinylsulfonic acid, polyisoprene sulfonic acid etc.) etc..This
A little carboxylic acid polyalcohol classes and sulfonic acid polymer class can also be that vinyl carboxylic acid class and vinyl sulfonic acid class are polymerisable with other
The copolymer of monomer class (such as aromatic ethenyl compound such as esters of acrylic acid, styrene, vinyl naphthalene).It is wherein especially excellent
Select polystyrolsulfon acid.
Above-mentioned polystyrolsulfon acid preferable weight-average molecular weight is more than 20000, less than or equal to 500000.More preferably 40000
～200000.If the use of molecular weight being the polystyrolsulfon acid outside the scope, polythiophene system electric conductive polymer is relative to water
Dispersion stabilization may reduce.
In addition, the weight average molecular weight of above-mentioned polymer is the value being measured using gel permeation chromatography (GPC).Determine
Used in Waters societies manufacture the posts of ultrahydrogel 500.
Above-mentioned polythiophene system electric conductive polymer can carry out oxidation polymerization to obtain by using oxidant in water.Should
Two kinds of oxidants (the first oxidant and the second oxidant) used in oxidation polymerization.
As the first suitable oxidant, can enumerate for example, peroxy-disulfuric acid (sulphuric acid of ペ Le オ キ ソ bis-), peroxy-disulfuric acid
Sodium, potassium persulfate, ammonium peroxydisulfate, hydrogen peroxide, potassium permanganate, potassium dichromate, perboric acid alkali metal salt, mantoquita etc..This
In a little first oxidants, sodium persulfate, potassium persulfate, ammonium peroxydisulfate and peroxy-disulfuric acid are optimum.
The consumption of above-mentioned first oxidant is preferably 1.5mol equivalents～3.0mol relative to the thiophene-based monomer for being used
Equivalent, more preferably 2.0mol equivalents～2.6mol equivalents.
Above-mentioned second oxidant is preferably for example with catalytic amount addition metal ion (such as ferrum, cobalt, nickel, molybdenum, vanadium ion).
Wherein, iron ion is maximally effective.
The addition of above-mentioned metal ion relative to the thiophene-based monomer for being used be preferably 0.005mol equivalents～
0.1mol equivalents, more preferably 0.01mol equivalents～0.05mol equivalents.
Water is used as reaction dissolvent used in above-mentioned oxidation polymerization.In addition to water, it is also possible to add methanol, ethanol, 2-
The water-soluble solvent such as alcohol or acetone, acetonitrile such as propanol, 1- propanol.
The aqueous dispersion of electric conductive polymer is obtained by such oxidation polymerization.
The content of above-mentioned electric conductive polymer is simultaneously not limited, relative to the solid constituent of conductive composition, with solid into
Divide meter, preferably comprise 1 weight %～10 weight %.More preferably 3 weight %～6 weight %.If being less than 1 weight %, it is difficult to show
Electric conductivity；If being more than 10 weight %, by precipitating with the mixing of other compositions, the storage period of conductive composition can
Be able to can shorten.
In above-mentioned conductive composition, in addition to above-mentioned electric conductive polymer, it is also possible to as needed containing following
Composition.
2. Binder Composition
The conductive composition of the present invention can contain Binder Composition.
Above-mentioned Binder Composition contributes to that film is formed on base material using above-mentioned conductive composition.
As above-mentioned Binder Composition, can enumerate for example：It is 3- glycidoxypropyltrime,hoxysilanes, polyether-modified
The silane couplers such as polydimethylsiloxane, polyether modified siloxane；It is alkoxysilane oligomer, polyester, polyacrylate, poly-
The homopolymer such as methacrylate, polyurethane, polyvinyl acetate, polyvinylidene chloride, polyamide, polyimides；By benzene second
The monomers such as alkene, vinylidene chloride, ethlyene dichloride, alkyl acrylate, alkyl methacrylate are carried out obtained from copolymerization altogether
The resinoid bonds such as polymers.These compositions can be used alone one kind, it is also possible to share two or more.
In addition, by the present invention conductive composition coating on the glass substrate in the case of, as above-mentioned binding agent into
Point, preferably at least contain alkoxysilane oligomer.In the case of containing alkoxysilane oligomer, electric conductive polymer can
Enter into the inside of its compact texture favorable dispersibility, thus be obtained hardness and chemical proofing it is excellent, while having
The Organic Conductive Films of high conductivity.
As above-mentioned alkoxysilane oligomer, for example, can enumerate the material shown in following formula (II)s.
【Change 3】
In formula, R1And R2It is identical or different, represent the alkyl that carbon number is 1～4.R3And R4It is identical or different, represent H
(hydrogen atom), hydroxyl or carbon number are 1～4 alkoxyl.Wherein, the R of more than 23And R4In at least one be alkoxyl.
N represents 2～20 integer, more preferably represents 2～14 integer.
As the alkyl that carbon number is 1～4, can enumerate for example methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl,
Isobutyl group, tert-butyl group etc..
As the alkoxyl that carbon number is 1～4, such as methoxyl group, ethyoxyl, positive propoxy, isopropyl oxygen can be enumerated
Base, n-butoxy, isobutoxy, tert-butoxy etc..
Alkoxysilane oligomer used in the present invention can only containing the chemical combination represented by a kind of above-mentioned logical formula (II)
Thing, or two or more mixture.
Also, there is in advance the alkoxysilane oligomer of siloxanes key as above-mentioned binding agent by using in intramolecular
Composition, compares, it is easy to formed more in conductive film with not having alkoxy silane monomer or epoxy silane of siloxanes key etc.
For fine and close structure.
Film-forming temperature more low temperature, the effect is more notable.
In addition, using alkoxysilane polymer (polymer of the condensation number n more than alkoxysilane oligomer) as
In the case of Binder Composition, due to steric repulsion increase, thus reactivity is poor, it is difficult to forms fine and close structure, can speculate knot
Fruit makes film hardness die down.Molecular weight is bigger, and the tendency is more notable.
The alcoxyl of the molecular weight that above-mentioned alkoxysilane oligomer is formed for alkoxy silane monomer is condensed each other
Base silane, and it refers to the oligomer that has more than 1 siloxanes key (Si-O-Si) in 1 intramolecular.
The weight average molecular weight of above-mentioned oligomer is not particularly limited, and preferably greater than 152, less than or equal to 4000.More preferably
500～1500 or so.
In addition, the weight average molecular weight of above-mentioned oligomer is the value that determined by gel permeation chromatography (GPC).Determine
Used in Waters societies manufacture ultrahydrogel500 posts.
Relative to the whole Binder Compositions contained by above-mentioned conductive composition, the combined amount of alkoxysilane oligomer
Preferably 97 weight %～100 weight %.If more than 97 weight %, then film can be made by the cooperation of alkoxysilane oligomer
Compactness reaches sufficient degree, can form the conducting film for showing higher film hardness and excellent chemical proofing.
It is more than more preferably 98.5 weight %.
Relative to the weight portion of above-mentioned electric conductive polymer 100, total combined amount of above-mentioned Binder Composition is preferably 150 weight
Part～10000 weight portions.If more than 150 weight portions, then the use ratio of Binder Composition fully, can be organic to what is formed
Conducting film gives good hardness.If below 10000 weight portions, then the content of electric conductive polymer is abundant, it is thus possible to shape
Into the Organic Conductive Films with high conductivity.The combined amount is more preferably 300 weight portion～7000 weight portions.
3. electric conductivity dose
The conductive composition of the present invention can also contain conductive dose.
Above-mentioned electric conductivity dose can further increase the electric conductivity of formed Organic Conductive Films.
As above-mentioned electric conductivity dose, can enumerate for example：N-METHYLFORMAMIDE, N,N-dimethylformamide, γ-fourth
The amide compounds such as lactone, N-Methyl pyrrolidone；Ethylene glycol, diethylene glycol, Propylene Glycol, 1,3- Propylene Glycol, 1,4- butanediols, 1,
5- pentanediols, 1,6-HD, neopentyl glycol, catechol, cyclohexanediol, cyclohexanedimethanol, glycerol, diethylene glycol list second
The hydroxy-containing compounds such as base ether, propylene glycol monomethyl ether；Isophorone, propylene carbonate, Ketohexamethylene, acetylacetone,2,4-pentanedione, acetic acid second
The compounds containing carbonyl such as ester, ethyl acetoacetate, adjacent methyl acetate, adjacent Ethyl formate；Dimethyl sulfoxide etc. contains sulfo group
Compound etc..They can be used alone, it is also possible to which two or more is shared.
Among these, volatility under the storage period of coating fluid or low temperature, the electric conductivity of the Organic Conductive Films for being formed,
Set out with the aspect such as the adaptation of base material, preferred amide compound, particularly preferred N-Methyl pyrrolidone and N-METHYLFORMAMIDE.
In addition, the content of above-mentioned electric conductivity dose is not particularly limited, preferably with 0.1 in above-mentioned conductive composition
The amount of weight %～60 weight % contains.
4. solvent or disperse medium
As above-mentioned solvent or disperse medium, as long as each composition contained in dissolvable or dispersed electro-conductive compositionss is just
It is not particularly limited, such as water, organic solvent, their mixture etc. can be enumerated.
In addition, in the present invention, in each composition dissolving in addition to solvent or disperse medium contained by conductive composition
In the case of, referred to as solvent；In the case where at least one composition for constituting conductive composition is dispersed, referred to as divide
Dispersion media.
In above-mentioned conductive composition, in the case where the conductive composition contains above-mentioned alkoxysilane oligomer,
Because sometimes alkoxysilane oligomer is not dissolved in water, thus the mixture of water and organic solvent can be used as solvent or
Disperse medium.Further, in the case of the mixture using water and organic solvent, as organic solvent, preferably comprise to
Few a kind of organic solvent mixed with water, as long as containing the organic solvent mixed with water, it is also possible to further containing not mixing with water
(hydrophobic) organic solvent for closing.Sometimes, as solvent or disperse medium, by using low-boiling alcohol system organic solvent with
The mixture of water, can improve volatility, favourable when heat cure is dried.In addition, in the case of using resin base material, alcohol system
Organic solvent can also contribute to improve levelability.
4-1. organic solvent
As above-mentioned organic solvent, can enumerate that can to make to be difficult to the compositions such as the alkoxysilane oligomer that is dissolved in the water equal
Even dissolving or scattered solvent.
As the organic solvent mixed with water, can enumerate for example：The alcohols such as methanol, ethanol, 2- propanol, 1- propanol；Second
The glycols such as glycol, diethylene glycol, 2,2'-ethylenedioxybis(ethanol)., tetraethylene glycol (TEG)；Ethylene glycol single methyl ether, diethylene glycol monomethyl ether, ethylene glycol bisthioglycolate
The glycol ethers such as ethylether, diethylene glycol dimethyl ether；Ethylene glycol monomethyl ether acetate, TC acetic acid
The glycol ethers acetate esters such as ester, diethylene glycol monobutyl ether acetass；The propandiolses such as Propylene Glycol, dipropylene glycol, tripropylene glycol；
Propylene glycol monomethyl ether, propylene glycol monoethyl, DPGME, dihydroxypropane single-ethyl ether, Propylene Glycol Dimethyl Ether,
The Propylene Glycol ethers such as dipropylene glycol, Propylene Glycol diethyl ether, dipropylene glycol diethyl ether；Propylene glycol monomethyl ether
Acetass, propylene glycol monoethyl acetass, DPGME acetass, dihydroxypropane single-ethyl ether acetass etc. third
Glycol ethers acetate esters；Tetrahydrofuran, acetone, acetonitrile；And their mixture etc..
In addition, as hydrophobic organic solvent, can enumerate for example：The esters such as ethyl acetate, butyl acetate, ethyl lactate
Class；The ethers such as diisopropyl ether, diisobutyl ether；The ketones such as methyl ethyl ketone, methyl iso-butyl ketone (MIBK)；The fat such as hexane, octane, petroleum ether
Fat race hydro carbons；Toluene, dimethylbenzene etc. it is aromatic hydrocarbon；And their mixture etc..
These organic solvents can be used alone, it is also possible to two or more to share.
In the case that above-mentioned conductive composition is water system compositionss, relative to the weight portion of water 100, above-mentioned organic solvent
Content is preferably more than 20 weight portions.Will not be uniform if being less than the hydrophobic combinations such as 20 weight portions, alkoxysilane oligomer
Dissolving disperses, and may not show the performance such as overlay film outward appearance or the adaptation with base material, peeling force.In addition, above-mentioned lead
In the case that conductive composition is solvent system: compositions, the content of above-mentioned solvent is simultaneously unrestricted.
In addition, in the present invention, in the case where conductive composition contains water, said composition is referred to as into water system combination
Thing；In the case where conductive composition does not contain water, said composition is referred to as into solvent system: compositions.
4-2. water
As water used in above-mentioned water system conductive composition, can enumerate such as distilled water, ion exchange water and from
Son exchanges distilled water etc..In addition, also including contained in the aqueous dispersion and other compositions of electric conductive polymer in above-mentioned water
Moisture.
The content of above-mentioned water is preferably in conductive composition for more than 1 weight %.
In the case that above-mentioned conductive composition is water system compositionss, the pH of conductive composition is preferably 1～14 model
Enclose, if the electric conductivity of the curable or overlay film under consideration low temperature, it is more preferably 1～7, particularly preferably 1.5～4.It is conductive
Property compositionss pH can be adjusted using the pH adjusting agent such as alkali.
As above-mentioned pH adjusting agent, such as ethyl alcohol amine such as ammonia, ethanolamine, isopropanolamine etc. can be enumerated.
Herein, due to alkali and sour forming salt, thus it acts on curing catalysts, so as to reduce curing catalysts to alkane
The solidification facilitation effect of TMOS oligomer；The pH of conductive composition is higher, then the curable under low temperature is more reduced, and more may be used
Suppression alkoxysilane oligomer self-crosslinking in the solution, thus stability or the storage of conductive composition of possible solution
Phase improves；Consider the situation, can suitably determine the addition of pH adjusting agent.In addition, above-mentioned pH adjusting agent is the conduction of the present invention
Any condition in property compositionss.
5. other additives
Can also further contain other additives in the conductive composition of the present invention.
As other additives, such as levelling agent, microparticle dispersion, silane coupler, thickening agent etc. can be enumerated.
5-1. levelling agent
Above-mentioned levelling agent is the material for being uniformly coated on conductive composition on base material, and above-mentioned levelling agent can be improved
Wetting quality of the conductive composition on base material, is formed uniformly Organic Conductive Films.
As above-mentioned levelling agent, such as fluorochemical or silicone compounds, acrylic compounds etc. can be enumerated.
As fluorochemical levelling agent, such as perfluoroalkane hydrocarbon, perfluoro carboxylic acid, perfluoroalkyl epoxy can be enumerated
Ethane additive product etc..
As silicone compounds levelling agent, for example polyether-modified polydimethylsiloxane, polyethers can be enumerated ester modified poly-
Dimethyl siloxane, the polyether-modified polydimethylsiloxane of hydroxyl, the polyether-modified polydimethylsiloxanes containing acryloyl group
Alkane, the polyester modification dimethyl silicone polymer containing acryloyl group, perfluoropolyether-modified polydimethylsiloxane, perfluor polyester modification
Polydimethylsiloxane, silicone modified acrylic compounds etc..
In addition, as acrylic compounds levelling agent, its homopolymer or copolymer etc. can be enumerated.
These materials can be used alone, it is also possible to share two or more.
The content of above-mentioned levelling agent is not particularly limited, relative to the solid constituent of conductive composition, with solid constituent
Meter, its upper content limit is preferably 5 weight %～25 weight %, more preferably 7 weight %～15 weight %.
If above-mentioned content is reduced more than 25 weight %, the crosslink density of Organic Conductive Films, as a result, the adaptation with base material
Or peeling force may be reduced.Conversely, if the content of above-mentioned levelling agent is less than 5 weight %, overlay film outward appearance will not be improved.
Using the Organic Conductive Films that the present invention is formed containing the conductive composition for so constituting, as described above, of the invention
Organic Conductive Films above-mentioned maximum height (Rz) for average film thickness more than 35%；The apparent condition of above-mentioned Organic Conductive Films is (most
Big height (Rz)) it is controlled using various methods, can for example pass through the composition of conductive composition or described later organic lead
The forming method of electrolemma is controlled.
More specifically, for example, in the case of by spraying to form Organic Conductive Films, can be spued by control spraying
Amount, hydraulic pressure, the coating weight of unit area, translational speed of spraying etc. are (maximum come the apparent condition for controlling above-mentioned Organic Conductive Films
Highly (Rz)).
Next, illustrating to the manufacture method of Organic Conductive Films of the present invention.
Above-mentioned Organic Conductive Films are the overlay film that formed using above-mentioned conductive composition, and it is by by above-mentioned electric conductivity group
Compound coats base material, is dried heat cure to be formed.
It is not particularly limited as the coating process of above-mentioned conductive composition, it is possible to use known method, for example may be used
Using rotary coating, heliogravure coating, rod painting, Dipcoat method, heavy curtain coating, die coating (ダ イ コ ー テ ィ Application グ),
Spraying etc..And can also be using silk screen printing, spraying printing, ink jet printing, letterpress, intaglio printing, lithographic printing etc.
Print process.Now, as long as suitably setting application conditions so that the apparent condition (maximum height of the Organic Conductive Films for being formed
(Rz)) it is in above range.
As the coating process of above-mentioned conductive composition, preferred spraying.
Badger air-brush (badger air brush) or GSI that above-mentioned spraying for example can be manufactured using TAMIYA societies
The device such as PRO-SPRAY MK-2 of Creos societies manufacture is sprayed carrying out using said apparatus on the substrates such as glass plate
Mist is coated with.At this point it is possible to the technology general knowledge for being based on the field suitably sets the parameters such as uniform dispersion concentration, discharge-amount, hydraulic pressure
To be adjusted to coating weight, lead with desired apparent condition (maximum height (Rz)) and the organic of thickness so as to be formed
Electrolemma.
In addition, when above-mentioned conductive composition is coated with, can prepare and advance with alcohol etc. above-mentioned conductive composition is entered
The coating fluid of row dilution, carries out the coating of the coating fluid.
Above-mentioned conductive composition film be dried common throughcirculation dryer used in heat cure, air drier,
Drying machines such as infrared drier etc..Among these, if using drying machine (air drier, infrared ray with heater meanses
Drying machine etc.), then can simultaneously be dried and heat.As heater meanses, in addition to above-mentioned drying machine, it is also possible to added using possessing
Heating backer roll, forcing press of hot merit energy etc..
Herein, be dried the condition of heat cure temperature of (60 DEG C～130 DEG C) preferably below 150 DEG C carry out 30 minutes with
Under, the temperature of (80 DEG C～100 DEG C) carries out less than 15 minutes more preferably below 120 DEG C.Above-mentioned conductive composition can be upper
Organic Conductive Films are sufficiently formed under the conditions of stating, but above-mentioned condition is the condition of the relatively low temperature short time in the technical field.Therefore,
In the case where above-mentioned Organic Conductive Films are formed using above-mentioned conductive composition, productivity is also excellent.
It should be noted that in the case of solidifying insufficient grade under this condition, as needed, can be after roller coat in roll film
25 DEG C～60 DEG C of drying machine is utilized in the state of (the Le Off イ Le Si of mouth one) or storehouse (keeping Library) is preserved carries out 1 hour～several weeks
Solidify afterwards.
The preparation method of above-mentioned conductive composition is not particularly limited, using mechanical agitator or magnetic stirring apparatuss etc.
Blender is stirred while being mixed to prepare to each composition.Herein, above-mentioned stirring preferably lasts for about 1 minute～60
Minute.
The Organic Conductive Films of the present invention can be suitable as the structure of blooming, packing timber, ELD, liquid crystal display cell etc.
Use into part, possess the present invention the blooming of Organic Conductive Films, packing timber, ELD and liquid crystal display cell it is durable
Property is excellent.
As above-mentioned blooming, the optics that above-mentioned Organic Conductive Films are for example formed on transparent resin film can be enumerated
Film.In this case, using transparent resin film as the base material 11 shown in Fig. 1 (a), in its one side lamination Organic Conductive Films 12a.
As above-mentioned packing timber, can enumerate and for example form the packing timber of above-mentioned Organic Conductive Films in the one side of film.
As above-mentioned ELD, can enumerate and for example over the transparent substrate above-mentioned organic conductive be formed with arbitrary graphic pattern
The ELD of film.
As above-mentioned liquid crystal display cell, can enumerate for example the glass substrate for being sealed with liquid crystal single or double or
The single or double of glass substrate of the person before liquid crystal is enclosed defines the unit of above-mentioned Organic Conductive Films.
Above-mentioned each blooming, above-mentioned packing timber, above-mentioned ELD and above-mentioned liquid crystal display cell are also the present invention's
One.
【Embodiment】
Enumerate embodiment below to illustrate the present invention, but the present invention is not limited to these embodiments.
(embodiment 1)
Using the aqueous dispersions Clevios PH500 containing electric conductive polymer (manufacture of Heraeus societies) 100 weight portions
(wherein containing 1.1 weight portion electric conductive polymers), alkoxysilane oligomer MS-51 (manufacture of society of Mitsubishi Chemical) 24 weight
Part, N-METHYLFORMAMIDE (Nacalai Tesque societies manufacture, reagent) 19 weight portions, ethanol (manufacture of Nacalai Tesque societies,
Reagent) 514 weight portions, the weight portion of ion exchange water 48, prepare uniform dispersion.
Next, above-mentioned dispersion liquid is coated into glass plate using following methods, 30 points are heated at 130 DEG C using baking oven
Clock, film forming is the Organic Conductive Films of 100mm × 100mm, makes 13 Organic Conductive Films (embodiments 1-1～embodiment 1-
13), for evaluation.In addition, according to the relation adjustment coating weight of coating weight and uniform dispersion concentration, so that average film thickness is
80nm (embodiment 1-1,2,4,5,7～13), 120nm (embodiment 1-3) or 60nm (embodiment 1-6).
(coating process)
The Badger air-brush manufactured using YAMIYA societies, is adjusted to uniform dispersion concentration, discharge-amount and hydraulic pressure, with
It is 80nm, 120nm or 60nm that coating weight is adjusted to average film thickness.
(shape evaluations of Organic Conductive Films)
Using following methods, the maximum of maximum height (Rz) is carried out to position at respective the 10 of each Organic Conductive Films respectively
(MAX), the calculating of minima (MIN) and meansigma methodss (average), further calculate above-mentioned maximum and minima relative to
The ratio (%) of average film thickness (80nm, 120nm or 60nm).As a result it is listed in table 1.
For above-mentioned maximum height (Rz), using contact pin type surface shape measuring device DEKTAK 6M (manufacture of Veeco societies),
Mode determination be 3000 μm, 30 seconds, the condition of 10mg, surface is measured.
【Table 1】Unit (nm)
* average film thickness carries out calculating to calculate by using coating film thickness with solid constituent amount.
(comparative example 1)
The uniform dispersion made using method same as Example 1 is applied to into as follows glass plate, is utilized
Air drier carries out 30 minutes heating in 130 DEG C, film forming for 100mm × 100mm Organic Conductive Films, making 6, this is organic
Conducting film (comparative example 1-1～comparative example 1-6), for evaluating.In addition, according to coating weight and the relation of uniform dispersion concentration,
Adjustment coating weight, so that average film thickness is 80nm.
(coating process)
Using the wire rod (9 μm of wet coating thickness) of No.4, uniform force is coated with even speed.
(shape evaluations of Organic Conductive Films)
Using following methods, respectively to the maximum of position calculation maximum height (Rz) at the 10 of each Organic Conductive Films
(MAX), minima (MIN) and meansigma methodss (average), further calculate above-mentioned maximum and minima relative to average film
The ratio (%) of thick (80nm).As a result it is listed in table 2.
The assay method of above-mentioned maximum height (Rz) is same as Example 1.
【Table 2】Unit (nm)
* average film thickness carries out calculating to calculate by using coating film thickness with solid constituent amount.
(endurancing)
For in the Organic Conductive Films (embodiment 1-1～1-6,1-11～1-13) and comparative example 1 manufactured in embodiment 1
The Organic Conductive Films (comparative example 1-1～comparative example 1-6) of manufacture, carry out following endurancings (1) and (2) one of arbitrarily.
Endurancing (1)：Kept for 1100 hours at 85 DEG C
Endurancing (2)：Kept for 850 hours under 65 DEG C, 90% humidity
Specifically, for making respectively in embodiment 1-1～1-3,1-11 and 1-12 and comparative example 1-1～1-3
Organic Conductive Films carry out endurancing (1), before the test afterwards using following methods measure surface resistivity/SR (g/), meter
Calculate the rising multiple of endurancing front and rear surfaces resistivity/SR (Ω/).As a result it is listed in table 3.
In addition, for the organic conductive made respectively in embodiment 1-4～1-6 and 1-13 and comparative example 1-4～1-6
Film, carries out endurancing (2), is calculated resistance to using following methods measure surface resistivity/SR (Ω/) afterwards before the test
Long property tests the rising multiple of front and rear surfaces resistivity/SR (Ω/).As a result it is listed in table 4.
For upper table surface resistivity/SR (Ω/), based on JIS K 7194, the high resistance manufactured using society of Mitsubishi Chemical
The UA probes of rate instrument UP (MCP-HT450 types, trade name), apply 10V voltages, are measured.
【Table 3】
85 DEG C/heat-resistance test (unit：Ω/□)
【Table 4】
65 DEG C, 90% humidity/humidity resistance test (unit：Ω/□)
| Sample | Embodiment 1-4 | Embodiment 1-5 | Embodiment 1-6 | Embodiment 1-13 | Comparative example 1-4 | Comparative example 1-5 | Comparative example 1-6 |
| 0 hour | 2.2×104 | 1.7×104 | 3.3×104 | 3.9×104 | 1.1×104 | 1.2×104 | 1.1×104 |
| 850 hours | 5.1×104 | 5.0×104 | 4.8×105 | 8.4×105 | 6.1×106 | 4.7×106 | 7.7×106 |
| Rise multiple | 2 | 3 | 15 | 22 | 555 | 392 | 694 |
Can be clear and definite by the result of table 3 and 4, the excellent in te pins of durability of Organic Conductive Films of the present invention.
In addition, also having carried out endurancing (1) to embodiment 1-7～1-10, its excellent in te pins of durability can be equally specified.
【Industrial applicibility】
The Organic Conductive Films of the present invention are the conductive film covering of excellent in te pins of durability, and it is adapted as antistatic film or transparent electricity
Pole etc., suitably can be used in blooming or packing timber, ELD, liquid crystal display cell etc..
Claims (7)
1. a kind of Organic Conductive Films, it organic is led for what is formed using at least conductive composition containing electric conductive polymer
Electrolemma, the Organic Conductive Films are characterised by that maximum height Rz of its one side is more than 50% relative to average film thickness, average film
Thickness is 60nm～400nm, and the conductive composition includes water more than 1 weight %.
2. Organic Conductive Films as claimed in claim 1, wherein, the electric conductive polymer is the electric conductivity polymerization of polythiophene system
Thing.
3. Organic Conductive Films as claimed in claim 2, wherein, polythiophene system electric conductive polymer is dopant and have
The complex of poly- (the 3,4- dialkoxythiophenes) or poly- (3,4- alklyenedioxy thiophenes) of the repetitive structure of following formula (I)s；
【Change 1】
In formula, R1And R2Hydrogen atom or C are represented independently of each other1-4Alkyl or represent together with or without substituent group
C1-4Alkylidene.
4. a kind of blooming, the blooming is characterised by that it has the Organic Conductive Films described in any one of claims 1 to 3.
5. a kind of packing timber, the packing timber is characterised by that it has the Organic Conductive Films described in any one of claims 1 to 3.
6. a kind of ELD, the ELD is characterised by that it has having described in any one of claims 1 to 3
Machine conducting film.
7. a kind of liquid crystal display cell, the liquid crystal display cell is characterised by that it has having described in any one of claims 1 to 3
Machine conducting film.
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| JP6417621B2 (en) | 2014-02-12 | 2018-11-07 | ナガセケムテックス株式会社 | Ink composition and transparent electrode |
| JP2018514906A (en) * | 2015-03-30 | 2018-06-07 | ローム アンド ハース エレクトロニック マテリアルズ エルエルシーＲｏｈｍ ａｎｄ Ｈａａｓ Ｅｌｅｃｔｒｏｎｉｃ Ｍａｔｅｒｉａｌｓ ＬＬＣ | Transparent pressure-sensitive membrane composition |
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