JP2011014443A - Substrate with conductive thin film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a substrate with a conductive thin film in which conductivity of a conductive polymer thin film is improved while ensuring airtightness to the substrate.SOLUTION: The substrate with the conductive thin film has a base film B and a conductive film A on a surface of the substrate C in this order. The conductive film A contains polythiophene-based polymer as the main component, the base film B is airtightly in close contact by physically or chemically acting on the substrate C, and furthermore a controlling function of molecular orientation against the conductive film A is equipped.

Description

  The present invention relates to a substrate with a conductive thin film.

  A thiophene polymer represented by Poly (3,4-ethylenedioxythiophene) (PEDOT) is known as a conductive polymer having excellent conductivity. Although the conductivity of the conductive polymer is lower than that of the metal conductor, it has flexibility and transparency, which are characteristics not found in metal conductors. Therefore, it is mainly used for transparent wiring members for display devices such as liquid crystal and touch panels, and electromagnetic shielding. It is used as a membrane. And since it utilizes in a wider range, the further electroconductivity improvement is desired. For example, in the transparent wiring member application, since the improvement in conductivity is directly linked to the improvement in transmittance, a new technique for improving conductivity has been eagerly desired.

  As a technique for improving the conductivity of a polythiophene-based conductive polymer, for example, Patent Document 1 describes improvement in conductivity by adding a highly polar solvent, alcohol, ether, DMSO (dimethylsulfoside), DMF (dimethylformamide), or the like. ing.

JP 2000-153229 A

However, since this highly polar solvent is volatile and flammable, when it is used as an electric / electronic material, there is a possibility that the conductive characteristics become unstable. Moreover, in the conventional method as described in Patent Document 1 exemplified here, in order to improve the conductivity of a thin film made of a polythiophene-based conductive polymer formed on a substrate, the molecular design of the conductive polymer itself is designed. However, we have tried to improve the conductivity by controlling the molecular orientation and doping by controlling the composition, but there is a limit to improving the conductivity with the conductive polymer itself in order to improve the conductivity stably over time. Therefore, it has been desired to develop a new method for improving conductivity by a simple method.
For example, since the solvent is added to the conductive polymer, there is a problem in the stability of the conductivity due to the composition change of the conductive composition due to the volatilization of the solvent over time or the solvent deterioration.
Further, when the conductivity of a conventional conductive polymer is improved other than the conductivity, there is a problem that the adhesion of the thin film made of the conductive polymer to the substrate is lowered.
That is, conventionally, there is a trade-off relationship between improvement in conductivity and improvement in adhesion to the substrate, and it has been difficult to achieve both.

An object of the present invention is to solve the above problems.
That is, the subject of this invention is providing the board | substrate with an electroconductive thin film which improves the electroconductivity of an electroconductive polymer thin film, ensuring the adhesiveness to a board | substrate.

  The inventor has intensively studied, and a substrate with a conductive thin film having a base film containing a compound having a specific structure as a main component on a substrate and a conductive thin film containing polythiophene as a main component on the substrate has the above-mentioned problems. The inventors have found that this can be solved and completed the present invention.

The present invention includes the following (i) to (xiii).
(i) A substrate with a conductive thin film having a base film B and a conductive film A in this order on the surface of the substrate C, wherein the conductive film A contains a polythiophene-based polymer as a main component, and the base film B A substrate with a conductive thin film, which is in close contact with the substrate C by physical or chemical action, and further has a molecular orientation control ability with respect to the conductive film A.
(ii) the underlayer B comprises alternating adsorption film B _1, a conductive thin film-attached substrate according to the above (i).
(iii) the underlayer B is the alternate adsorption film B _1, the (i) or a conductive thin film-attached substrate according to (ii).
(iv) The alternating adsorption film B ₁ and the conductive film A are in close contact, and the surface of the alternating adsorption film B ₁ that is in close contact with the conductive film A is made of a polymer electrolyte. The board | substrate with an electroconductive thin film as described in).
(V) the underlayer B contains a modified film B ₂ having a highly polar substituents, the conductive thin film-attached substrate according to the above (i).
(vi) The base film B includes a modified film B ₂ formed using the compound α, and the compound α is a compound having a highly polar substituent and an adhesive substituent, as described in (v) above Substrate with conductive thin film.
(vii) the underlayer B is the modifying film B _2, (v) above or a conductive thin film-attached substrate according to (vi).
(viii) the highly polar substituent is a cyclic substituent having a hetero atom and a cationic group and / or —N (R ^Y ) (R ^Z ) [R ^Y and R ^Z are each a hydrogen atom, a carbon number of 1; It is a C1-C20 alkyl group which may have -20 alkoxy groups or an ether bond. ] The board | substrate with an electroconductive thin film in any one of said (v)-(vii) which is N containing functional group which is cationic represented by these.
(ix) The substrate with a conductive thin film according to any one of (v) to (viii) above, wherein the compound α is an imidazolium derivative, a pyridinium derivative, or a pyrrolidinium derivative.
(x) the modified membrane B ₂ is, the surface is obtained by ion exchange treatment, (v) above conductive thin film-attached substrate according to any one of ~ (ix).
(xi) The base film B includes the alternate adsorption layer B ₁ and the modification film B ₂ , and the modification film B ₂ , the alternate adsorption layer B _1, and the conductive film A are formed on the surface of the substrate C. The substrate with a conductive thin film according to the above (i), (ii), (iv), (v), (viii), (ix) or (x) in this order.
(xii) The substrate with a conductive thin film according to any one of (i) to (xi) above, wherein the polythiophene polymer is 3,4-ethylenedioxythiophene and / or a derivative thereof.
(xiii) Any one of the above (i) to (xii) obtained by forming the base film B on the surface of the substrate C and then forming the conductive film A on the surface of the base film B The board | substrate with an electroconductive thin film of description.

  According to the present invention, it is possible to provide a substrate with a conductive thin film even when the thin film has high conductivity, high adhesion to the substrate, the conductive polymer is stable, and the thin film contains a solvent. .

It is a schematic sectional drawing which shows the board | substrate with a thin film of this invention. It is a schematic diagram for demonstrating the compound (alpha) which forms the base film B of this invention. 10 is a graph showing the results of Example 3. It is a graph which shows the result of Example 4. 10 is a graph showing the results of Example 8. 10 is a graph showing the results of Example 9. It is a graph which shows the result of Example 10. 10 is a graph showing the results of Example 11.

The present invention will be described in detail.
The present invention is a substrate with a conductive thin film having a base film B and a conductive film A in this order on the surface of a substrate C, wherein the conductive film A contains a polythiophene polymer as a main component, and the base film B However, it is a substrate with a conductive thin film that is physically and chemically bonded to the substrate C and has a molecular orientation control ability with respect to the conductive film A.
Hereinafter, such a substrate with a conductive thin film is also referred to as a “substrate with a thin film of the present invention”.

  An example of the substrate with a thin film of the present invention is shown in FIG. FIG. 1 is a schematic sectional view of a substrate with a thin film according to the present invention. In FIG. 1, the substrate with a thin film of the present invention has a base film B and a conductive film A in this order on the surface of the substrate C.

First, the base film B will be described.
In the substrate with a thin film of the present invention, the base film B is particularly limited as long as it is in close contact with the substrate C by physical or chemical action and further has a molecular orientation control ability with respect to the conductive film A. Not. Several modes are conceivable as the base film B. Specifically, the mode 1 in which the base film B is the alternate adsorption film B ₁ , the mode 2 in which the base film B is the modification film B ₂ , and the base film B are alternately arranged. An embodiment 3 comprising the adsorption film B ₁ and the modification film B ₂ can be mentioned.

  Examples of the physical or chemical action of the base film B on the substrate C include a hydrophobic interaction, a charge transfer interaction, and an electrostatic interaction. Further, the base film B and the substrate C may be chemically bonded. Examples of the chemical bond include coordinate bond, hydrogen bond, bond by antigen-antibody reaction, covalent bond, and bond by van der Waals force.

  Next, Embodiments 1 to 3 will be specifically described.

<Embodiment 1: alternate adsorption film B _1>
Base film B will be described embodiments 1 is alternately adsorbed film B _1.
The alternately adsorbed film B ₁ is formed by alternately laminating a thin film having a cationic property and a thin film having an anionic property, and a physical or chemical action (mainly an electrostatic interaction) between each thin film and between the thin film and the substrate C. ). The alternating adsorption film B ₁ acts physically or chemically on the substrate C, but its degree (the degree of electrostatic interaction) is high, so that the adhesion is high. For example, the alternating adsorption film B ₁ on the substrate Even if the adhesive tape is attached to the surface and then peeled off, the alternating adsorption film B ₁ is not peeled off from the substrate C.

  The thin film having a cationic property or an anionic property can be formed from a polymer material, protein, colloidal particles (metal colloid, oxide colloid, latex colloid), clay mineral, semiconductor fine particles, heteropolyacid, dye, and the like. Among these, a thin film formed using a polymer material having water solubility or water dispersibility (for example, a polymer electrolyte) is preferable. This is because the resulting thin film has excellent flexibility, better molecular orientation control with respect to the conductive film A, and tends to increase the effect as a dopant.

  Examples of the anionic polymer electrolyte include those having a negatively charged functional group such as sulfonic acid and carboxylic acid, specifically polystyrene sulfonic acid (PSS), polyvinyl sulfonic acid, dextran sulfate, chondroitin sulfate, Pearuronic acid, polyacrylic acid, poly (meth) acrylic acid and its ionized product, polymaleic acid, polyfumaric acid, Poly (1- (4- (3-carboxy-4-hydroxyphenylazo) benzenesulfonamido) -1,2-ethanediyl), Poly (anilinepropanesulfonic acid), Sulfonated polyaniline, Poly (thiophene-3-acetic acid), Poly (2-acrylamido-2-methy1-1-propanesulfonic acid), Poly (2-acrylamido-2-methyl-1-propanesulfonic acid) ), Polyamic acid, and monomers constituting the polymer and (meth) acrylamide, 2-hydroxyethyl (meth) acrylate, N-isopropyl (meth) acrylamide Copolymers of any nonionic aqueous monomer, conductive polymers such as polythiophene, polyaniline, a polymer having a chromophore, a liquid crystal polymer include biopolymers, such as DNA.

  Examples of the cationic polymer electrolyte include those having a positively charged functional group such as a quaternary ammonium group and an amino group, specifically, polyethyleneimine and its quaternized product, polydiallyldimethylammonium chloride, poly (N , N′-dimethyl-3,5-dimethylene-piperidinium chloride), polyallylamine and its quaternized product, polydimethylaminoethyl (meth) acrylate and its quaternized product, polydimethylaminopropyl (meth) acrylamide and its Quaternized products, polydimethyl (meth) acrylamide and its quaternized products, polyethyleneimine, polydiallyldimethylammonium chloride, polyvinylpyridine, polylysine, polystyrenemethylenediethylmethylamine, polymethylpyridylvinyl can be mentioned.

  The molecular weight of the anionic or cationic polymer electrolyte is preferably 1,000 to 5,000,000 g / mol, more preferably 10,000 to 1,000,000 g / mol.

The alternating adsorption film B ₁ includes at least one thin film having a cationic property and at least one thin film having an anionic property. Although the total thickness of the alternating adsorption film B ₁ is not particularly limited, It is preferably 5 to 50 nm, and more preferably 1 to 10 nm.
The thickness of such a film can be controlled by the type of polymer electrolyte, etc. used when forming the alternately adsorbing film B ₁ , molecular weight, aqueous solution concentration, pH, viscosity, temperature, and the like.

In the substrate with a conductive thin film of the present invention, the alternately adsorbing film B ₁ and the conductive film A are in contact and in close contact with each other, and the surface of the alternating adsorbing film B ₁ in close contact with the conductive film A is made of an anionic polymer electrolyte. It is preferable to become. This is because the molecular orientation control for the conductive film A becomes better and the effect as a dopant tends to be higher.

When forming the alternate adsorption film B ₁ represents, in a cationic or anionic polyelectrolyte salt as described above, sodium chloride, potassium chloride, it may be used by adding an electrolytic salt such as lithium perchlorate.

<Embodiment 2: modifying film B _2>
Next, Embodiment ₂ in which the base film B is the modification film B2 will be described.
The modified film B ₂ is a thin film having a highly polar substituent. The modification film B ₂ is a thin film containing the compound α as a main component.

The compound α is a compound having a highly polar substituent and an adhesive substituent.
The highly polar substituent is a cyclic substituent having a hetero atom and being cationic, or —N (R ^Y ) (R ^Z ) [R ^Y and R ^Z are each a hydrogen atom, an alkoxyl group having 1 to 20 carbon atoms, Or it is a C1-C20 alkyl group which may have an ether bond. It is preferable that it is an N containing functional group which is cationic represented by these.
That is, the compound α is a compound having the cyclic substituent and the adhesive substituent, a compound having the N-containing functional group and the adhesive substituent, or the cyclic substituent and the N-containing functional group and the adhesive. It is preferable that the compound has an ionic substituent.

  The cyclic substituent is preferably an imidazolium derivative or a pyridium derivative represented by the formula (1).

In Formula (1), R ^{1 to} R ¹² are each independently a hydrogen atom, an alkoxyl group having 1 to 20 carbon atoms, or an alkyl group having 1 to 20 carbon atoms that may have an ether bond. . R ^{1 to} R ¹² may be the same or different, and may form a heterocyclic ring.
Here, as a C1-C20 alkoxy group, a methoxy group, an ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, various pentoxy groups , Various heptoxy groups, various octoxy groups and the like.
The alkyl group of R ¹ to R ¹² of the ether bond carbon atoms, which may have 1 to 20, a methyl group, an ethyl group, n- propyl group, an isopropyl group, n- butyl group, an isobutyl group, Examples thereof include a sec-butyl group, a tert-butyl group, various pentyl groups, various hexyl groups, various heptyl groups, various octyl groups, and 2-methoxyethyl groups.

Next, the N-containing functional group in the compound α will be described.
The N-containing functional group is -N (R ^Y ) (R ^Z ) [R ^Y and R ^Z are each a hydrogen atom, an alkoxyl group having 1 to 20 carbon atoms, or an optionally bonded ether bond. ˜20 alkyl groups. ] Which is a functional group that is cationic.

Next, the adhesive substituent in the compound α will be described.
The adhesive substituent is not particularly limited as long as it is a substituent that chemically reacts with and bonds to the surface of the substrate C. Chemical bonds include covalent bonds, coordination bonds, ionic bonds, and hydrogen bonds. Examples of the substituent that reacts with the surface of the substrate C to form a covalent bond include Si-X (X is halogen such as methoxy, ethoxy, Cl, Br, etc., H, etc.), phosphoric acid group, acid chloride, carboxylic acid, Isocyanates, thiols, epoxies and the like. In addition, examples of the substituent bonded by a covalent bond, a coordinate bond, an ionic bond, or a hydrogen bond include an alkoxy group, an ether group, an ester group, a carbonyl group, and a carboxy group.

The compound α is a compound having a cyclic substituent having a hetero atom having such a cationic property and / or the N-containing functional group and the adhesive substituent. For example, as shown in FIG. In this embodiment, the group (or N-containing functional group) 10 and the adhesive substituent 20 are connected by a connecting portion 30.
Such a connecting portion 30 is not particularly limited as long as both substituents can be connected, but preferably has a structure that promotes the self-arrangement of the cyclic substituent or the N-containing functional group. This is because the self-alignment increases the doping effect and the alignment control effect.

In such a compound α, the adhesive substituent is chemically bonded to the surface of the substrate C. Specifically, they are bonded by a covalent bond, a coordination bond, an ionic bond, a hydrogen bond, or the like. Therefore, the modification film B ₂ and the substrate C can be firmly bonded.

  Preferred examples of the compound α having the cyclic substituent and the adhesive substituent include compounds represented by the following formulas (2), (3) and (4).

In the formula (2), R ¹³ and R ¹⁴ each independently represents hydrogen, a methyl group, an ethyl group, a propyl group or a phenyl group.
Moreover, in Formula (3), R < ¹⁵ > is respectively independently hydrogen, a C1-C20 alkyl group, or an alkoxy group, and a 1-8 oxygen atom and / or a sulfur atom may be inserted. For example, it may be a C 1-20 dioxyalkylene group or a C 1-20 dioxyarylene group.

  Examples of the compound α having the N-containing functional group and the adhesive substituent include trimethoxysilane, specifically 3-aminopropyltrimethoxysilane, N-trimethoxylsilylpropyl-N, N, N-trimethylammonium chloride, N- (2-aminoethyl ) -3-amionopropyltrimethoxysilane, (3-Trimethoxysilylpropyl) diethiylentriamino are preferred examples.

<Aspect 3>
Next, Embodiment 3 in which the base film B is composed of the alternating adsorption film B ₁ and the modification film B ₂ will be described.
In aspect 3, the substrate with a conductive thin film of the present invention has the modification film B ₂ , the alternating adsorption layer B _1, and the conductive film A in this order on the surface of the substrate C.
For example, when the modified film B ₂ is formed on the surface of the substrate C using the compound represented by the above formula (2), formula (3), or formula (4), the surface of the obtained modified film B ₂ is positive. It has a charge or a negative charge or both. Therefore, a thin film is formed on the surface using the cationic polymer electrolyte, another thin film is formed on the top surface using the anionic polymer electrolyte, and then the alternating adsorption layer B ₁ is repeatedly modified. it can be formed on the layer B _2.
With such an embodiment 3 in close contact substrate C is modifying film B ₂ and chemically coupled to form further a modified film B ₂ and alternate adsorption film B ₁ is strongly bonded by the Coulomb force.

It is preferable that the modified film B ₂ is further subjected to an ion exchange treatment to be described later.

The base film B is preferably in the first to third embodiments as described above, but is in close contact with the substrate C by physical or chemical action, and further controls molecular orientation with respect to the conductive film A. Other aspects may be used as long as they have the ability. For example, the base film B may be composed of the alternating adsorption film B ₁ and other films. Further, for example, the base film B may be composed of the modification film B ₂ and other films.

  In addition, since each of the thin film of the present invention having the base film B of aspects 1 to 3 corresponds to a case where the technical significance of the invention is common or closely related to the prior art, the invention Meets the requirements of unity.

<Conductive film A>
Next, the conductive film A included in the substrate with a conductive thin film of the present invention will be described.
The conductive film A contains a polythiophene polymer as a main component.

The thiophene polymer is not particularly limited, and for example, a known thiophene polymer can be used.
As preferred examples of the repeating unit constituting the thiophene polymer, the embodiments shown in the formula (5), the formula (6), and the formula (7) can be given.

In the formula (5), R ¹⁵ and R ¹⁶ are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms or an alkoxy group, and 1 to 8 oxygen atoms and / or sulfur atoms may be inserted. Good. For example, it may be a C 1-20 dioxyalkylene group or a C 1-20 dioxyarylene group.

In Formula (6), A is an optionally substituted alkylene residue having 1 to 5 carbon atoms or an arylene residue having 1 to 12 carbon atoms, and among these, A is an alkylene residue having 2 or 3 carbon atoms. Preferably there is.
Here, the alkylene residue A having 1 to 5 carbon atoms is, for example, methylene, ethylene, n-propylene, n-butylene or n-pentylene.
Moreover, the C1-C12 arylene residue A is, for example, phenylene, naphthylene, benzylidene, or anthracenylidene.

In the formula (6), R ¹⁷ is a linear or branched alkyl residue having 1 to 18 carbon atoms which may be substituted, and is linear or branched substituted. C1-C14 alkyl residue, C5-C12 cycloalkyl residue which may be substituted, C6-C14 aryl residue which may be substituted, C7 which may be substituted It is preferably an aralkyl residue of -18, or an optionally substituted hydroxyalkyl residue having 1 to 4 carbon atoms, and is an optionally substituted hydroxyalkyl residue or hydroxyl residue having 1 or 2 carbon atoms. It is more preferable.

Here, the alkyl group having 1 to 18 carbon atoms is linear or branched, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n- Pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylpropyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, n-hexyl, n-heptyl, n- Octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.
Moreover, a C1-C20 alkyl group is n-nonadecyl and n-eicosyl, for example.
C5-C12 cycloalkyl is, for example, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl or cyclodecyl.
Moreover, C5-C14 aryl is a phenyl or a naphthyl, for example.
Aralkyl having 7 to 18 carbon atoms is, for example, benzyl, o-tolyl, m-tolyl, p-tolyl, 2,3-xylyl, 2,4-xylyl, 2,5-xylyl, 2,6-xylyl, 3,4-xylyl, 3,5-xylyl or mesityl.
The oxyalkyl having 1 to 20 carbon atoms is, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentyloxy, 1-methylbutyloxy, 2 -Methylbutyloxy, 3-methylbutyloxy, 1-ethylpropyloxy, 1,1-dimethylpropyloxy, 1,2-dimethylpropyloxy, 2,2-dimethylpropyloxy, n-hexyloxy, n-heptyloxy N-octyloxy, 2-ethylhexyloxy, n-nonyloxy, n-decyloxy, n-undecyloxy, n-dodecyloxy, n-tridecyloxy, n-tetradecyloxy, n-hexadecyloxy, n- Nonadecyloxy or n-eicosyloxy.

In the formula (6), X represents the number of functional groups represented by R ^17. Specifically, X is an integer of 0 to 8, preferably an integer of 0 to 6, preferably 0 or 1. More preferably.
Here, when X is 2 or more, the functional groups represented by R ¹⁷ may be the same or different.
When a plurality of R ¹⁷ is bonded to A, these may be the same or may be different.
R ¹⁷ may be bonded to the alkylene residue or arylene residue A by X.
Here, the alkylene residue or arylene residue A is, for example, an alkyl group, cycloalkyl group, aryl group, halogen group, ether group, thioether group, disulfide group, sulfoxide group, sulfone group, sulfonate group, amino group, aldehyde group. , Keto group, carboxylic acid ester group, carboxylic acid group, carbonate group, carboxylate group, cyano group, alkylsilane group, alkoxysilane group and carboxylamide group.

In the formula (7), R ¹⁸ and X may be the same as R ¹⁷ and X in the formula (6).

The thiophene polymer may contain one or more repeating units represented by the formulas (5) to (7), and may be a copolymer.
Thiophene-based polymers may have one or more optical isomers, and thiophene derivatives can be racemic, enantiomerically pure or diastereomeric pure compounds, or optical isomers in any proportion. You may adjust the body ratio. A mixture thereof may also be used.

  The molecular weight of the thiophene polymer is preferably 100 to 10,000,000 g / mol.

  The thiophene polymer is preferably 3,4-ethylenedioxythiophene and / or a derivative thereof. This is because the film forming process is easy and proven.

  The conductive film A has the above polythiophene polymer as a main component, but in addition, a dopant, a catalyst, a polymer electrolyte, an ion exchange resin, water, an alcohol, a glycol, a solvent such as an amine solvent, a salt, a surfactant. Further, it may contain a wax or the like. Further, it may contain a curing agent, an antiwear agent, a binder and the like.

  The thickness of the conductive film A is not particularly limited, but is preferably 0.001 to 1000 μm, more preferably 0.001 to 10 μm, and still more preferably 0.05 to 1 μm.

<Substrate C>
Next, the board | substrate C in the board | substrate with an electroconductive thin film of this invention is demonstrated.
The substrate C is not particularly limited. For example, a substrate such as glass or quartz, (meth) acrylic resin, polystyrene, polyvinyl acetate, polyolefin such as polyethylene or polypropylene, polyvinyl chloride, polyvinylidene chloride, polyimide, polyamide, polysulfone. , Polycarbonate, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyester such as liquid crystal polymer, resin partially modified with functional groups such as amino group, epoxy group, hydroxyl group, carbonyl group, triacetyl cellulose, etc. The film which becomes is mentioned.

  The size and thickness of the substrate C are not particularly limited.

  An example of the substrate C is a glass plate having a thickness of about 1 mm.

  The substrate C may be washed or dried. Moreover, it is preferable that easy-adhesion treatments such as corona treatment, plasma treatment, and flame treatment have been performed.

Next, the manufacturing method of the board | substrate with a thin film of this invention is demonstrated.
The manufacturing method of the board | substrate with a thin film of this invention is not specifically limited, For example, it can manufacture by a conventionally well-known method. Below, the manufacturing method of the board | substrate with a thin film of this invention which has the base film B of aspect 1 or aspect 2 demonstrated above is demonstrated.

<Production Method 1: If the underlying film B is alternately adsorbed film B _1>
Base film B will be described conductive manufacturing method of a thin film-attached substrate of the present invention when it is alternately adsorbed film B _1.
The alternately adsorbing film B ₁ is alternately adsorbed by alternately immersing the substrate C to which surface charge is applied in the cationic (+) polymer electrolyte aqueous solution and the anionic (−) polymer electrolyte aqueous solution as described above. A membrane can be obtained. Specifically, for example, when a glass substrate is used as the substrate C, when the surface of the glass substrate is subjected to a hydrophilic treatment to introduce an OH ^- group and immersed in an aqueous cationic polymer electrolyte, the Coulomb force (electrostatic property) The cationic polymer electrolyte is adsorbed on the surface of the glass substrate until the surface charge (OH ⁻ ) is neutralized by the interaction. After washing and drying, when the substrate is immersed in an aqueous anionic polymer electrolyte solution, the anionic polymer electrolyte is adsorbed by Coulomb force. The alternating adsorption film B ₁ can be formed by repeating such an operation.

Other methods for manufacturing the alternate adsorption film B _1, for example, the method published by G. Decker et al in 1992 (Decher.G, Hong.JDand J.Schmit, Thin Solid Films, 210 / 211,831 (1992)) is Can be mentioned.

After the alternate adsorption film B ₁ is formed on the surface of the substrate C, the conductive film A is formed.
The formation method is not particularly limited, and for example, a conventionally known method can be applied. However, the conductive film A can be formed by applying a liquid constituting the conductive film A on the surface of the alternating adsorption film B _1. preferable. This is because the alternating adsorption layer and the polythiophene polymer interact with each other in the formation process of the conductive film A, the orientation of the polythiophene polymer is promoted, and the conductivity of the conductive film A is increased.
For example, a mixed solution such as PEDOT / PSS may be used as it is, or a thiophene polymer may be polymerized on the surface of the substrate C.
The coating method is not particularly limited. For example, screen printing method, ink jet printing method, lip direct method, comma coater method, slit reverse method, die coater method, gravure roll coater method, blade coater method, spray coater method, air knife coating method. Examples thereof include a dip coating method and a bar coater method. Two or more of these methods may be used in combination.

<Method 2: If the underlying film B is a modified film B _2>
A method for producing a substrate with a conductive thin film of the present invention when the base film B is the modification film B ₂ will be described.
Preferred production methods include the following (Production Method 1) to (Production Method 3).
(Production Method 1): A compound α having a cyclic substituent having a hetero atom and an adhesive substituent is directly applied to the substrate C.
(Production Method 2): A substance having a cyclic substituent having a hetero atom is applied to the substrate C. Here, the substance having a cyclic substituent having a hetero atom may have a cyclic substituent having a hetero atom, and may contain a resin exemplified by polyester, phenol, epoxy, polyimide, and silicon. Good. For example, it may be a mixture of a substance having a cyclic substituent having a hetero atom and a resin, or a molecule having a cyclic substituent having a hetero atom may be bonded to the resin.
(Preparation method 3): to form after the formation of the modified layer B ₂ on the substrate C, the other film between the modified membrane B ₂ and the conductive film A (gap adjustment, easy adhesion, the adhesive layer, mutual adsorption film layer) of .

A method of forming a surface modifying film B ₂ of substrate C is not particularly limited, it can be applied, for example a conventionally known method. For example, screen printing method, inkjet printing method, lip direct method, comma coater method, slit reverse method, die coater method, gravure roll coater method, blade coater method, spray coater method, air knife coating method, dip coating method, bar coater method Etc. can be illustrated. Two or more of these methods may be used in combination.

After the modification film B ₂ is formed, the surface is preferably subjected to ion exchange treatment. For example, in the case where the surface of the modified film B ₂ is cationic, an ion is used so that the aqueous solution containing anion ions and the modified film B ₂ come into contact (for example, the substrate C on which the modified film B ₂ is formed is immersed in the aqueous solution). Can be exchanged. Examples of the anion ions include I ⁻ , Br ⁻ , Cl ⁻ , ClO ₄ ⁻ , BF ₄ ⁻ , SbF ₆ ⁻ , PF ₆ ⁻ , (CF ₃ SO ₂ ) ₂ N ⁻ (that is, bis (trifluoromethylsulfonyl) imide). Anion (TFSI)), (C ₂ F ₅ SO ₂ ) ₂ N ⁻ , RSO ₃ ⁻ (where R is an aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, ether group, ester group) And an acyl group, and a hydrogen atom may be substituted with a fluorine atom). An anion ion having a large ionic radius is preferable because the doping effect is high.

After the modification film B ₂ is formed on the surface of the substrate C, the conductive film A is formed.
The forming method is not particularly limited, and for example, a conventionally known method can be applied. The conductive film A can be formed in the same manner as in the case where the base film B is the alternating adsorption film B ₁ .

  The substrate with a thin film of the present invention having the base film B of the aspect 3 described above can be manufactured by combining the manufacturing method 1 and the manufacturing method 2 described here.

  Examples of the present invention are shown below.

<Example 1 (alternate adsorption film B _1)>
(Substrate cleaning method)
First, a glass slide (25 mm × 38 mm) was prepared as the substrate C. The substrate C was washed with acid, rinsed 4 times with pure water, further washed with pure water ultrasonic waves for 10 minutes, and then dried overnight in an oven with the atmospheric temperature adjusted to 60 ° C. The dried substrate C obtained here is also referred to as “post-dried substrate C ₁ ”.

(Substrate processing)
After drying, the substrate C ₁ was immersed in 0.01M aminopropyltetraethoxysilane (APS) (toluene solution) overnight, and after drying, the surface of the substrate C ₁ was modified with APS. Furthermore, it was immersed in 0.01M hydrochloric acid aqueous solution for 3 hours, and the surface was made cationic.
It was then washed 3 times with distilled water to remove excess salt or acid and eliminate the effects of the residue.
What was obtained here is also referred to as “APS-modified substrate C ₁ ”.

(Creation of alternating adsorption film B ₁ )
As a polymer electrolyte having a cation (+), a 1 mg / ml aqueous solution of poly (diallyldimethylammonium chloride) (PDADMAC) manufactured by Aldrich was prepared. The obtained aqueous solution is also called "PDADMAC aqueous solution".
Moreover, a 1 mg / ml aqueous solution of poly (sodium 4-styrenesulfonate) (PSS) manufactured by Aldrich was prepared as a polymer electrolyte having an anion (-). The obtained aqueous solution is also referred to as “PSS aqueous solution”.

Next, the APS-modified substrate C ₁ was immersed in an aqueous PSS solution for 15 minutes, and PSS was adsorbed on the surface of the APS-modified substrate C ₁ . After the APS-modified substrate C ₁ is taken out from the PSS aqueous solution, it is washed with distilled water three times or more to remove excess PSS, and the APS-modified substrate C ₁ with the PSS film (“PSS-coated substrate C ₁ ”).
Next, the substrate C ₁ with a PSS film was immersed in a PDADMAC aqueous solution, and the PDADMAC was adsorbed on the surface of the PSS film of the substrate C _{1 with} the PSS film. After removing from the PDADMAC aqueous solution, the substrate is washed with distilled water three or more times to remove excess PDADMAC, and the PSS film-coated substrate C ₁ (also referred to as “PDADMAC film-coated substrate C ₁ ”) with a film made of PDADMAC is removed. Obtained.

(Conductive film A)
Ultrasonic waves were applied to an aqueous solution of PEDOT / PSS (CLEVIOS P) (PEDOT: PSS = 1: 2.5 (mass ratio)) (manufactured by HCStarck), which is a conductive polymer solution, for 10 minutes for dispersion.
Next, a PEDOT / PSS aqueous solution was spin-coated at 3000 rpm on the surface of the PDADMAC film of the substrate C _{1 with} a PDADMAC film. Thereafter, the film was kept in an air atmosphere at 120 ° C. for 30 minutes and dried to form a conductive film A made of PEDOT / PSS having a thickness of 100 nm.

By performing such an operation, a PSS film and a PDADMAC film are formed in this order on the surface of the APS-modified substrate C ₁ , and a conductive film A is formed thereon, which is referred to as “1BL”. Further, after forming the PSS film and the PDADMAC film in this order on the surface of the APS-modified substrate C ₁ , the same operation is repeated, and after further forming the PSS film and the PDADMAC film in this order, the conductive film A is formed thereon. The formed one is referred to as “2BL”.
In this example, 1BL to 10BL and 15BL were prepared, and each surface resistivity was measured by a direct current four-terminal method.
The measurement results are shown in Table 1.
Table ₁ also shows the results of measuring the surface resistivity of the dried substrate C ₁ and the APS-modified substrate C ₁ by the direct current four-terminal method.

As shown in Table ₁ , it has been found that the surface resistivity decreases as the number of alternately adsorbed films B ₁ stacked increases.

<Example 2 (alternate adsorption film B _1)>
In the same manner as described in Example 1, a PSS film and a PDADMAC film were formed in this order on the surface of the APS-modified substrate C ₁ . Then, a PSS film was formed on the surface of the PDADMAC film by the same method as described in Example 1, and a conductive film A was further formed thereon.

Such operation, PSS film on the surface of the APS-modified pre substrate C _1, to form a PDADMAC film and PSS film in this order, a material obtained by forming a conductive film A on it is referred to as "1BL + PSS". Further, PSS film on the surface of the APS-modified pre substrate C _1, after forming a PDADMAC film and PSS film in this order, by repeating the same operation, further PDADMAC film and PSS film after forming in this order, a conductive thereon The film A formed is referred to as “2BL + PSS”.
In this example, 1BL + PSS to 10BL + PSS and 15BL + PSS were prepared, and each surface resistivity was measured by a direct current four-terminal method.
The measurement results are shown in Table 2.
Table 2 also shows the results of measuring the surface resistivity of the dried substrate C ₁ and the APS-modified substrate C ₁ by the direct current four-terminal method.

As shown in Table 2, it was found that the surface resistivity decreased as the number of alternately adsorbed films B ₁ stacked increased.
Further, it was found that the surface resistivity of Example 2 was lower than that of Example 1. This is considered to mean that the surface resistivity of the surface of the alternating adsorption layer B ₁ in contact with the conductive film A is lower than that of the PDADMAC film (cation) when the surface is a PSS film (anion). .

<Example 3 (modifying film B _2)>
(Substrate cleaning method)
First, ten glass slides (25 mm × 38 mm) were prepared as the substrate C. These substrates C were washed with Piranha (concentrated sulfuric acid: hydrogen peroxide solution (30 mass%) = 3: 1 (volume ratio)) for 1 hour, rinsed 4 times with pure water, and further subjected to 10 ultrasonic waves with pure water. After minute washing, the film was dried overnight in an oven with the atmospheric temperature adjusted to 60 ° C. The substrate C after drying obtained here is also referred to as “substrate C ₃ after drying”.

(Preparation of modified film B ₂ )
Six types of compounds α shown in the formula (2) were prepared.
Each of the six types of compounds α is different in R ¹³ and R ^{14 in} the formula (2).
Abbreviations of compounds with specific contents and their R ¹³ and R ¹⁴ of R ¹³ and R ¹⁴ alpha, shown in Table 3.

  Each type of compound α was prepared by boiling reflux in toluene for 1 day or longer in an equimolar amount of imidazole represented by the following formula (8) and (3-chloropropyl) trimethoxysilane. After purification, identification using a nuclear magnetic resonance method confirmed that the product was the desired product.

Next, three types of compounds α shown in Formula (3) were prepared.
Each of the three types of compounds α is different in R ^{15 of} formula (3).
Abbreviations of compounds with specific contents and R ¹⁵ of R ¹⁵ alpha, shown in Table 3.

  Each type of compound α was prepared by boiling reflux in toluene for 1 day or longer in an equimolar amount of imidazole represented by the following formula (9) and (3-chloropropyl) trimethoxysilane. After purification, identification using a nuclear magnetic resonance method confirmed that the product was the desired product.

Next, one type of compound α shown in Formula (4) was prepared.
This compound α was prepared by boiling reflux of pyrrolidine and (3-chloropropyl) trimethoxysilane in toluene in equimolar amounts for 1 day or longer in toluene. After purification, identification using a nuclear magnetic resonance method confirmed that the product was the desired product.
The compound α represented by the formula (4) obtained here is also referred to as “Me-Pyz-TMS”.

Ten compounds α (Me-Im-TMS, Et-Im-TMS, Bu-Im-TMS, Di-Me-Im-TMS, Bz-Me-Im-TMS, 2-Me obtained as described above. -Im-TMS, Py-TMS, Me-Py-TMS, Et-Py-TMS, Me-Pyz-TMS) were dissolved in toluene to a concentration of 0.05% by mass to obtain various toluene solutions. .
Next, after drying one by one in each of the various toluene solutions, the substrate C ₃ was dipped for one night or longer, then washed twice with toluene, twice with ethanol, twice with pure water, and from compound α. A substrate C having 10 types of modified films B ₂ was obtained. Substrates C having a modification film B ₂ made of each kind of compound α are referred to as “Substrate C with Me-Im-TMS film”, “Substrate C with Et-Im-TMS film”, “Bu-Im-TMS”, respectively. Substrate with film C, Substrate C with Di-Me-Im-TMS film, Substrate C with Bz-Me-Im-TMS film, Substrate C with 2-Me-Im-TMS film, Py Also referred to as “-TMS film-coated substrate C”, “Me-Py-TMS film-coated substrate C”, “Et-Py-TMS film-coated substrate C”, and “Me-Pyz-TMS film-coated substrate C”.

A conductive film A was formed in the same manner as in Example 1 on each of the substrates C having 10 types of modification films B ₂ and on the substrate C ₃ after drying. The same applies to the type and thickness of the conductive film A.
For each of the 10 substrates with conductive thin films thus obtained, and the substrate C ₃ after drying having only the conductive film A (also referred to as “comparative substrate C ₃ ”), DC 4 terminals as in Example 1. The surface resistivity was measured by the method. Then it was determined the relative values of the case where the surface resistivity in Comparative board C ₃ as 100 (percent). The surface resistivity of the comparative substrate C ₃ was 16.7 Ω · cm.
The results are shown in FIG. 3 and Table 4.

From FIG. 3 and Table 4, it can be seen that the conductivity of all the modification films B ₂ is improved as compared with the comparative substrate C ₃ . Also, the surface resistivity of the substrate C with Me-Im-TMS film, the substrate C with Et-Im-TMS film, the substrate C with Bu-Im-TMS film, and the substrate C with Di-Me-Im-TMS film are compared. Then, it can be seen that the shorter the alkyl chain, the lower the surface resistivity and the better the conductivity.

<Example 4 (modified film B _2)>
After obtaining 15 Me-Im-TMS film-coated substrates C by the method shown in Example 3, each of the surfaces thereof was subjected to ion exchange treatment.
Prepare 11 types of salt as ion source, adjust each to 0.01M, and immerse the substrate C with Me-Im-TMS film in each of the obtained aqueous solutions for 3 hours or more. went.
Eleven types of ion source salts are LiCl, NaCl, KCl, CaCl ₂ , LiClO ₄ , NaClO ₄ , KClO ₄ , NH ₄ ClO ₄ , [(C ₂ H ₅ ) ₄ N] ClO ₄ , LiBETI (lithium hiss). (Hentafluoroethanesulfone) imido), LiTFSI (Lithium hiss (trifluoromethanesulfone) imido).

Next, four kinds of hydrochloric acid solutions of 0.1 mM, 1.0 mM, 10 mM, and 100 mM were prepared, and ion exchange treatment was performed by immersing the substrate C with Me-Im-TMS film in each for 3 hours or more. . These are experimental results when the surface treatment agent is acid-treated.
A conductive film A was formed in the same manner as in Example 1 on the 15 substrates with Me-Im-TMS film after the ion exchange treatment thus obtained.
Then, the surface resistivity was measured by the direct current four-terminal method in the same manner as in Example 1.
The results are shown in FIG. 4 and Table 5. The volume resistivity (Ω · m) of the comparative substrate C ₃ is also shown.

  From FIG. 4 and Table 5, it can be confirmed that the conductivity is improved by the ion exchange treatment.

<Example 5 (modifying film B _2)>
A 100 μm thick PET film was prepared, and the surface was plasma treated.
Then, using the obtained plasma-treated PET film as a substrate C, a modification film B _{2 made of} Me-Im-TMS and a conductive film A are formed in the same manner as in Example 3, and a substrate with a conductive thin film is formed. to obtain a C _5.
And when the surface resistivity of the plasma film-treated PET film and the substrate C ₅ with a conductive thin film was measured by the direct current four-terminal method, the substrate C ₅ with a conductive thin film was compared to the PET film after the plasma treatment. It was found that the conductivity was improved by 25%.

<Example 6 (modified film B ₂ + alternative adsorption film B ₁ )>
A substrate C with a Me-Im-TMS film was obtained in the same manner as in Example 3.
Next, the PDADMAC aqueous solution and the PSS aqueous solution used in Example 1 were prepared.
And the board | substrate C with a Me-Im-TMS film | membrane was immersed in PSS aqueous solution for 15 minutes, and PSS was made to adsorb | suck to the surface of the board | substrate C with a Me-Im-TMS film | membrane. After removing the substrate C with Me-Im-TMS film from the PSS aqueous solution, it was washed with distilled water three times or more to remove excess PSS, and the substrate C with Me-Im-TMS film with the PSS film ( (Also referred to as “PSS film-coated substrate C ₆ ”).
Next, the substrate C ₆ with a PSS film was immersed in a PDADMAC aqueous solution, and PDADMAC was adsorbed on the surface of the PSS film of the substrate C _{6 with} the PSS film. The obtained after removal from PDADMAC solution and washed three times or more with distilled water to remove excess PDADMAC, PSS film coated substrate C marked with film made of PDADMAC (also referred to as a "PDADMAC film coated substrate C _6") It was.
Then, by forming a conductive film A in the same manner as in Example 1 on the surface of PDADMAC film coated substrate C ₆ obtained, to obtain a conductive thin film-substrate C _6.

Next, when the surface resistivity of the substrate C ₆ with a conductive thin film was measured by the direct current four-terminal method, the conductivity of the substrate C ₆ with a conductive thin film was improved by 24% with respect to the comparative substrate C ₃ . all right.

<Example 7 (modifying film B _2)>
In the same manner as in Example 3, four dried substrates C (also referred to as “dried substrate C ₇ ”) were obtained.

(Creation of modified film B ₂ (in the case of compound α having an N-containing functional group))
Four types of trimethoxysilane were prepared as corresponding to the compound α. In particular
3-Aminopropyltrimethoxysilane, N-Trimethoxylsilylpropyl-N, N, N-trimethylammonium chloride, N- (2-aminoethyl) -3-amionopropyltrimethoxysilane, (3-Trimethoxysilylpropyl) diethiylentriamino. These are also referred to as MASi, TMASi, DASi, and TASi, respectively.
Then, these four kinds of compounds α (MASi, TMASi, DASi, TASi) were each dissolved in toluene so as to be 0.05% by mass to obtain various toluene solutions. Next, after drying the substrate after C ₇ to various toluene solution was immersed overnight or more, washed twice with toluene, ethanol twice with wash, and washed twice with deionized water, 4 kinds of modified membrane of Compound α A substrate C having B ₂ was obtained. Substrates C having a modification film B ₂ made of each type of compound α are respectively referred to as “substrate C with MASi film”, “substrate C with TMASi film”, “substrate C with DASi film”, and “substrate C with TASi film”. "

Next, a conductive film A was formed in the same manner as in Example 1 on each of the substrates C having the four types of modification films B ₂ and on the dried substrate C ₃ by the same method as in Example 1. The same applies to the type and thickness of the conductive film A.
For each of the four substrates with conductive thin films thus obtained and the dried substrate C ₃ having only the conductive film A (“comparison substrate C ₃ ”), the direct current four-terminal method was applied in the same manner as in Example 1. The surface resistivity was measured.
The results are shown in Table 6.

<Example 8 (modifying film B _2)>
Five substrates C with MASi films were prepared by the method shown in Example 7. Thereafter, their respective surfaces were subjected to ion exchange treatment.
Five types of salts, which are ion sources, were prepared, each adjusted to 0.01 M, and the ion exchange treatment was performed by immersing the substrate C with MASi film in each of the obtained aqueous solutions for 3 hours or more. The salts which are five kinds of ion sources are LiClO ₄ , NaClO ₄ , KClO ₄ , NH ₄ ClO ₄ , [(C ₂ H ₅ ) ₄ N] ClO ₄ .
A conductive film A was formed in the same manner as in Example 1 on the five substrates C with the MASi film after the ion exchange treatment thus obtained.
Then, the surface resistivity was measured by the direct current four-terminal method in the same manner as in Example 1.
The results are shown in FIG. 5 and Table 7. The surface resistivity of the comparative substrate C ₃ is also shown.

Figures 5 and Table 7, both the surface resistivity was improved compared to Comparative board C _3. Moreover, it turned out that electroconductivity is so high that the cation with a large ionic radius.

<Example 9 (modifying film B _2)>
Five substrates C with MASi films were prepared by the method shown in Example 7. Thereafter, their respective surfaces were subjected to ion exchange treatment.
The ion exchange treatment was performed by preparing five types of salts as ion sources, adjusting each to 0.01 M, and immersing the substrate C with MASi film in each of the obtained aqueous solutions for 3 hours or more. The salts which are five types of ion sources are LiCl, NaClO ₄ , LiPF ₆ , LiTFSI, and LiBETI.
A conductive film A was formed in the same manner as in Example 1 on the five substrates C with MASi film after the ion exchange treatment thus obtained.
Then, the surface resistivity was measured by the direct current four-terminal method in the same manner as in Example 1.
The results are shown in FIG. The surface resistivity of the comparative substrate C ₃ is also shown.

<Example 10 (modifying film B _2)>
Four substrates C with MASi film were prepared by the method shown in Example 7. Thereafter, their respective surfaces were subjected to ion exchange treatment.
The ion exchange treatment was performed by preparing four types of salts as ion sources, adjusting each to 0.01 M, and immersing the substrate C with MASi film in each of the obtained aqueous solutions for 3 hours or more. Five salt is an ion source, LiCl, NaCl, KCl, a CaCl _2.
The conductive film A was formed in the same manner as in Example 1 on the four substrates C with the MASi film after the ion exchange treatment thus obtained.
Then, the surface resistivity was measured by the direct current four-terminal method in the same manner as in Example 1.
The results are shown in FIG. 7 and Table 8. The surface resistivity of the comparative substrate C ₃ is also shown.

7 and Table 8, both the surface resistivity was improved compared to Comparative board C _3. Moreover, it turned out that electroconductivity is so high that a cation with a small ionic radius.

<Example 11 (modifying film B _2)>
Five substrates C with MASi films were prepared by the method shown in Example 7. Thereafter, their respective surfaces were subjected to ion exchange treatment.
As the ion exchange treatment, a 0.01 M hydrochloric acid solution was first prepared, and five substrates C with MASi films were immersed in the solution for 3 hours or more. Next, five types of salts as ion sources are prepared, each adjusted to 0.01M, and the MASi film-coated substrate C after being immersed in the hydrochloric acid solution is immersed in each of the obtained aqueous solutions for 3 hours or more. I went there. The salts which are five kinds of ion sources are LiClO ₄ , NaClO ₄ , KClO ₄ , NH ₄ ClO ₄ , [(C ₂ H ₅ ) ₄ N] ClO ₄ .
A conductive film A was formed in the same manner as in Example 1 on the five substrates C with the MASi film after the ion exchange treatment thus obtained.
Then, the surface resistivity was measured by the direct current four-terminal method in the same manner as in Example 1.
The results are shown in FIG. 8 and Table 9. The surface resistivity of the comparative substrate C ₃ is also shown.

Figures 8 and Table 9, both the surface resistivity was improved compared to Comparative board C _3. It was also found that perchlorate has low conductivity dependency due to cations.

<Example 12 (modifying film B _2)>
A 100 μm thick PET film was prepared, and the surface was plasma treated.
Then, the obtained plasma-treated PET film is used as the substrate C, and the modified film B ₂ and the conductive film A subjected to the ion exchange treatment are formed by the same method as in Example 11, and the substrate C ₁₂ with the conductive thin film is formed. Obtained. However, the one used in the ion exchange treatment is LiCl (hydrochloric acid is the same as in Example 11).
Then, the surface resistivity was measured by the direct current four-terminal method in the same manner as in Example 1.
Also, except for changing the substrate to the PET film substrate C after the plasma treatment as compared substrate, the comparative substrate prepared in the same manner as in Example 1 was C _8. This surface resistivity was measured in the same manner.
The results are shown in Table 10.

  From Table 10, it was confirmed that the surface resistivity was improved even when the PET film was used.

  All samples showed good adhesion as a result of the adhesion test.

DESCRIPTION OF SYMBOLS 1 Cyclic substituent 2 Adhesive substituent 3 Connection part 10 Conductive film A
20 Base film B
30 Substrate C

Claims (13)

A substrate with a conductive thin film having a base film B and a conductive film A in this order on the surface of the substrate C,
The conductive film A contains a polythiophene polymer as a main component,
A substrate with a conductive thin film, wherein the base film B is in close contact with the substrate C by physical or chemical action, and further has a molecular orientation control ability with respect to the conductive film A. The substrate with a conductive thin film according to claim 1, wherein the base film B includes an alternating adsorption film B ₁ . The underlayer B is the alternate adsorption film B _1, a conductive thin film-attached substrate according to claim 1 or 2. The alternate adsorption film B ₁ and is in close contact with the conductive film A is the surface in close contact with the conductive film A is formed of a polymer electrolyte in the alternate adsorption film B _1, conductive according to claim 2 or 3 Substrate with thin film. The substrate with a conductive thin film according to claim 1, wherein the base film B includes a modification film B ₂ having a highly polar substituent. The base film B includes a modification film B ₂ formed using the compound α,
The board | substrate with an electroconductive thin film of Claim 5 whose said compound (alpha) is a compound which has a highly polar substituent and an adhesive substituent. The underlayer B is the modifying film B _2, a conductive thin film-attached substrate according to claim 5 or 6. The highly polar substituent is a cyclic substituent having a hetero atom and being cationic and / or —N (R ^Y ) (R ^Z ) [R ^Y and R ^Z are each a hydrogen atom, a carbon number of 1 to 20 An alkoxyl group or an alkyl group having 1 to 20 carbon atoms which may have an ether bond. ] The board | substrate with an electroconductive thin film in any one of Claims 5-7 which is N containing functional group which is cationic represented by these.   The board | substrate with an electroconductive thin film in any one of Claims 5-8 whose said compound (alpha) is an imidazolium derivative, a pyridinium derivative, or a pyrrolidinium derivative. It said modified layer B ₂ is one in which the surface was ion-exchange treatment, the conductive thin film-attached substrate according to any one of claims 5-9. The base film B includes the alternate adsorption layer B ₁ and the modification film B ₂ , and has the modification film B ₂ , the alternate adsorption layer B _1, and the conductive film A in this order on the surface of the substrate C. A substrate with a conductive thin film according to claim 1, 2, 4, 5, 8, 9, or 10.   The substrate with a conductive thin film according to claim 1, wherein the polythiophene polymer is 3,4-ethylenedioxythiophene and / or a derivative thereof.   The conductive film with conductive thin film according to claim 1, obtained by forming the base film B on the surface of the substrate C and then forming the conductive film A on the surface of the base film B. substrate.

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