JP2012064498A - Transparent electrode substrate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a transparent electrode substrate excellent in conductivity, capable of maintaining high levels of adhesion, storage stability and conductivity, and also excellent in heat resistance and moist heat resistance, while a pattern with high resolution can be formed in an electrode obtained by performing patterning and a pattern shape is also excellent.SOLUTION: In a transparent electrode substrate including a conductive layer formed on a transparent substrate, the conductive layer is formed of a conductive resin composition containing (A) a heterocyclic ring-containing aromatic polymer represented by the following general formula (1) and comprising a heterocyclic ring-containing aromatic compound as a monomer: M-N...(1) (In the formula, M represents a substituted or unsubstituted thiophene ring group, and N represents a substituted or unsubstituted pyrrole ring group. The ring represented by M is directly bonded with the ring represented by N.).

Description

The present invention relates to an electrode substrate excellent in transparency.

In recent years, touch panels have been rapidly spread as human-friendly interfaces, and are used in many devices such as portable small electronic devices, bank ATMs, ticket vending machines, and POS. There are many types of touch panels such as optical, ultrasonic, capacitive, and resistive film types. Among them, capacitive and resistive touch panels that have a simple structure and low manufacturing costs are often used. Yes. These touch panels require the formation of a conductive layer to be a transparent electrode, and generally require patterning.

Conventionally, a film obtained by sputtering ITO (tin oxide doped indium oxide) is used as the transparent electrode substrate, and a pattern is formed by a technique such as dry etching. However, the ITO sputtered film has poor flexibility and high manufacturing cost. Therefore, the conductive layer is formed by wet coating using a conductive polymer such as a polymer of 3,4-ethylenedioxythiophene and polystyrenesulfonic acid. There are many attempts to form it (see, for example, Patent Document 1).

JP 2008-115362 A JP 2010-161013 A JP 2004-14215 A

However, the conductive polymer described in Patent Document 1 has a problem that patterning is difficult because it is difficult to dissolve in an organic solvent or water.

That is, as a patterning method using a conductive polymer, patterning methods such as wet etching (for example, see Patent Document 2) and a lift-off method (for example, see Patent Document 3) are known. Because it is difficult to dissolve in organic solvents and water, it is difficult to meet the demand for high-resolution pattern formation, and there are similar issues in the formation of transparent electrodes such as liquid crystal displays and electronic paper. There was a problem.

An object of the present invention is to provide a transparent electrode substrate which can form a high resolution pattern and has a good pattern shape. Furthermore, electronic paper, solar cells, electromechanical elements, resistive switches, capacitive switches, touch screens, keyboards, liquid crystal displays, plasmas using the resistive switches or capacitive switches. An object is to provide a display and an organic EL display.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have achieved high transparency by using a conductive resin composition containing a specific heterocyclic ring-containing aromatic polymer in a conductive layer formed on a transparent substrate. In addition, it has excellent conductivity, maintains adhesion, storage stability, and conductivity at a high level, and also has good heat resistance and moist heat resistance, and is obtained by patterning. As a result, the inventors have found that a transparent electrode substrate having a high resolution and a good pattern shape can be obtained, and the present invention has been completed.

That is, the present invention
A transparent electrode substrate in which a conductive layer is formed on a transparent substrate, wherein the conductive layer contains a heterocycle-containing aromatic compound represented by the following general formula (1) as a monomer (A) containing a heterocycle Aromatic polymer MN (1)
(In the formula, M represents a substituted or unsubstituted thiophene ring group, and N represents a substituted or unsubstituted pyrrole ring group. The ring represented by M and the ring represented by N are directly bonded to each other. ),
The present invention relates to a transparent electrode substrate formed of a conductive resin composition containing

In the transparent electrode substrate of the present invention, the heterocycle-containing aromatic compound is preferably a heterocycle-containing aromatic compound represented by the following general formula (2 ′),

(In the formula, R ³ and R ⁴ each independently represent a hydrogen atom or an organic group, but at least one represents an organic group. When both R ³ and R ⁴ represent an organic group, these May be bonded to each other to form a ring structure.)
More preferably, it is at least one of the heterocyclic ring-containing aromatic compounds represented by the following structural formulas (2-1) to (2-17).

In the transparent electrode substrate of the present invention, the transparent substrate is preferably a resin film.

In the transparent electrode substrate of the present invention, the conductive layer preferably has a pattern.

In the transparent electrode substrate of the present invention, the pattern is preferably formed by wet etching.

In the transparent electrode substrate of the present invention, the pattern is preferably formed by a lift-off method.

The electronic paper of the present invention relates to an electronic paper having the transparent electrode substrate.

The resistive membrane switch of the present invention is a resistive membrane switch having a first conductive member having a first conductive layer on a transparent substrate, a second conductive member having a second conductive layer on the substrate, and an insulating spacer. The first conductive member and / or the second conductive member is the transparent electrode substrate, the insulating spacer is provided on a part of the second conductive layer, and the first conductive layer and the second conductive member The present invention relates to a resistance film type switch arranged so that two conductive layers face each other.

The capacitance switch of the present invention is a capacitance switch composed of a first conductive member having a first conductive layer on a transparent substrate and a second conductive member having a second conductive layer on the substrate, or A capacitance switch composed of a third conductive member having a first conductive layer and a second conductive layer on both sides of a transparent substrate, the first conductive member, the second conductive member, and the third conductive member The present invention relates to a capacitance switch in which any of the conductive members is the transparent electrode substrate.

The touch screen of this invention is related with the touch screen which has the said resistive film type switch or an electrostatic capacitance switch.

The keyboard of this invention is related with the keyboard which has the said resistive film type switch or an electrostatic capacitance switch.

The transparent electrode substrate of the present invention contains a specific heterocyclic ring containing a coupling body in which a thiophene ring group and a pyrrole ring group are directly bonded as a conductive polymer to a conductive layer formed on a transparent substrate. By using a conductive resin composition containing an aromatic polymer, while maintaining high transparency, it is excellent in conductivity, and can maintain adhesion, storage stability, conductivity at a high level, The heat resistance and heat-and-moisture resistance are also good, and the electrode obtained by patterning can form a pattern with high resolution and the pattern shape is also good.
Further, the transparent electrode substrate of the present invention is an electronic paper, a solar cell, an electronic device, a resistive switch, a capacitive switch, or a touch screen using the resistive switch or the capacitive switch. It can be suitably used for the manufacture of keyboards, liquid crystal displays, plasma displays and organic EL displays.

First, the transparent electrode substrate of the present invention will be described.
The transparent electrode substrate of the present invention is a transparent electrode substrate in which a conductive layer is formed on a transparent substrate, and the conductive layer is a monomer containing the heterocyclic ring-containing aromatic compound represented by the general formula (1). (A) A transparent electrode substrate formed of a conductive resin composition containing a heterocyclic ring-containing aromatic polymer.
Hereinafter, each component which comprises the conductive layer used for this invention is demonstrated in order.
First, the (A) heterocycle-containing aromatic polymer, which is an essential component of the conductive resin composition forming the conductive layer used in the present invention, will be described.

(A) Heterocycle-containing aromatic polymer The heterocycle-containing aromatic polymer contains a heterocycle-containing aromatic compound represented by the following general formula (1) as a monomer.
MN ... (1)
(In the formula, M represents a substituted or unsubstituted thiophene ring group, and N represents a substituted or unsubstituted pyrrole ring group. The ring represented by M and the ring represented by N are directly bonded to each other. Yes.)

Here, the thiophene ring group means a 2-thienyl group, and may have a substituent on a carbon atom.
The pyrrole ring group means a 2-pyrrolyl group, and may have a substituent on a carbon atom or a nitrogen atom.

Examples of the substituted thiophene ring group represented by M in the general formula (1) include the following structures.

(In each formula, n represents an integer of 1 to 10.)

Examples of the substituted pyrrole ring group represented by N in the general formula (1) include the following structures.

(In each formula, n represents an integer of 1 to 10.)

(In each formula, n represents an integer of 1 to 10, and R represents an aromatic group which may have a substituent or an alkyl group having 1 to 10 carbon atoms.)

Examples of the substituent of the thiophene ring group include an organic group described later, and an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 5 carbon atoms is preferable.
Examples of the substituent of the pyrrole ring group include an organic group described later, and the substituent on the carbon atom is preferably an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 5 carbon atoms. As the substituent on the nitrogen atom, an alkyl group having 1 to 10 carbon atoms or an optionally substituted phenyl group is preferable.
Here, a functional group such as a halogen element, a carboxylic acid group, or a sulfonic acid group may be bonded to the alkyl group or alkoxy group that is a substituent of the thiophene ring group or the pyrrole ring group.

In the heterocyclic ring-containing aromatic compound represented by the general formula (1) (hereinafter also referred to as the heterocyclic ring-containing aromatic compound (1)), the thiophene ring and the pyrrole ring are connected via an atom not included in the ring structure. Are not directly bonded, but are directly bonded by a bond between atoms contained in both rings.
As the heterocyclic ring-containing aromatic compound (1), the total number of substituents bonded to the 3-position or 4-position of the thiophene ring group or the pyrrole ring group is from the viewpoint of solvent solubility, heat resistance, and weather resistance. Two or more compounds are preferred. In addition, in order to avoid steric hindrance when the total number of substituents bonded to the 3-position or 4-position is 4 (that is, when the substituents are bonded to all the 3-position and 4-position). In addition, in at least one of M and N, the 3-position substituent and 4-position substituent are preferably bonded to form a ring structure.

In the heterocycle-containing aromatic compound (1), at least one carbon atom on the thiophene ring represented by M is unsubstituted and at least one carbon atom on the pyrrole ring represented by N Is unsubstituted. When such a heterocyclic ring-containing aromatic compound (1) is oxidatively polymerized as a monomer, a coupling reaction proceeds between unsubstituted carbon atoms, so that the repeating unit is -M as a heterocyclic ring-containing aromatic polymer. A linear polymer represented by -N- is obtained.
It is preferable that the thiophene ring and the pyrrole ring represented by M and N are bonded to each other between one of the 2-position carbon atoms and the other 2-position carbon atom is unsubstituted.

As said heterocyclic ring-containing aromatic compound, the heterocyclic ring-containing aromatic compound represented by either the following general formula (2) or (3) is preferable.
When oxidative polymerization is performed using these heterocyclic ring-containing aromatic compounds as monomers, the oxidative polymerization is performed at the 2-position unsubstituted carbon atom on the thiophene ring or the 2-position unsubstituted carbon atom on the pyrrole ring. proceed.

In the heterocyclic ring-containing aromatic compound represented by the following general formula (2), M in the general formula (1) is a thiophene ring group that may have a substituent at the 3-position and / or 4-position, and N is It is a pyrrole ring group that may have a substituent at the 3-position and / or 4-position.

In general formula (2), R ¹ and R ² each independently represent a hydrogen atom or an organic group, but at least one of them represents an organic group, and R ³ and R ⁴ each independently represent It represents a hydrogen atom or an organic group (case i), or R ¹ and R ² both represent a hydrogen atom, and R ³ and R ⁴ each independently represent an organic group (case ii).
Here, when both R ¹ and R ² represent an organic group, they may be bonded to each other to form a ring structure, and when both R ³ and R ⁴ represent an organic group, They may combine with each other to form a ring structure. Examples of such a ring structure include a ring structure formed by an ethylenedioxy group.

The heterocyclic ring-containing aromatic compound represented by the general formula (2) is a compound in which, in case i, R ¹ and R ² each independently represent an organic group, and these are bonded to each other to form a ring structure, In case ii, a compound in which R ³ and R ⁴ each independently represents an organic group and these are bonded to each other to form a ring structure is preferable. In case i, R ¹ and R ² are each independently an organic group. And a compound in which they are bonded to each other to form a ring structure is more preferable.

More preferably, in case i, a heterocyclic ring-containing aromatic compound represented by the following general formula (2 ′) in which R ¹ and R ² are bonded to each other to represent an ethylenedioxy group.

Particularly preferably, in order to achieve both high conductivity and stability, the compound has a small band gap and a high oxidation potential, and is a compound represented by the following structural formulas (2-1) to (2-17). is there.

In the heterocyclic ring-containing aromatic compound represented by the following general formula (3), M in the general formula (1) is a thiophene ring group that may have a substituent at the 3-position and / or 4-position, and N is It is an N-substituted pyrrole ring group which may have a substituent at the 3-position and / or the 4-position.

In general formula (3), R ⁵ and R ⁶ each independently represent a hydrogen atom or an organic group, but at least one of them represents an organic group, and R ⁷ and R ⁸ are each independently It represents a hydrogen atom or an organic group (case i), or R ⁵ and R ⁶ both represent a hydrogen atom, and R ⁷ and R ⁸ each independently represent an organic group (case ii).
Here, when both R ⁵ and R ⁶ represent an organic group, they may combine with each other to form a ring structure, and when both R ⁷ and R ⁸ represent an organic group, They may combine with each other to form a ring structure. Examples of such a ring structure include a ring structure formed by an ethylenedioxy group. Further, in the general formula (3), Rn ¹ represents an organic group.

In the case i, the heterocyclic ring-containing aromatic compound represented by the general formula (3) is a compound in which R ⁵ and R ⁶ each independently represent an organic group, and these are bonded to each other to form a ring structure, In case ii, a compound in which R ⁷ and R ⁸ each independently represents an organic group and these are bonded to each other to form a ring structure is preferred. In case i, R ⁵ and R ⁶ are each independently an organic group. And a compound in which they are bonded to each other to form a ring structure is more preferable.

More preferably, in case i, a heterocyclic ring-containing aromatic compound represented by the following general formula (3 ′) in which R ⁵ and R ⁶ are bonded to each other to represent an ethylenedioxy group.

In particular, in the general formula (3 ′), a compound represented by the following formula (3 ″) in which R ⁷ and R ⁸ represent a hydrogen atom and Rn ¹ represents a phenyl group which may have a substituent is preferable.

In the general formulas (2), (3), and (3 ″), examples of the organic group represented by each of R ^{1 to} R ⁸ , Rn ¹ , and Rx include, for example, linear or branched having 1 to 10 carbon atoms Or a cyclic alkyl group (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a s-butyl group, a t-butyl group, a hexyl group, a cyclohexyl group, etc.), a straight chain having 1 to 10 carbon atoms Branched or cyclic alkenyl groups (for example, ethylene group, propylene group, butane-1,2-diyl group, cyclohexenyl group, etc.), alkoxy groups having 1 to 5 carbon atoms (for example, methoxy group, ethoxy group, iso Propoxy group etc.), optionally substituted phenyl group (eg phenyl group, tolyl group, dimethylphenyl group, biphenyl group, cyclohexylphenyl group etc.), aralkyl group For example, a benzyl group, phenethyl group, etc.), an alkoxycarbonyl group (for example, methoxycarbonyl group) and the like.
Furthermore, for example, functional groups such as carboxyl group, amino group, nitro group, cyano group, sulfonic acid group and hydroxyl group, and halogen elements such as fluorine, chlorine, bromine and iodine are bonded to these organic machines. Also good.
R ^{1 to} R ⁸ may be a carboxyl group, an amino group, a nitro group, a cyano group, a sulfonic acid group, a hydroxyl group, a halogen element, or the like.
The above organic groups are independently selected.

The organic group represented by R ^{1 to} R ⁸ is preferably an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 5 carbon atoms, and the organic group represented by Rn ¹ is an alkyl group having 1 to 10 carbon atoms, Alternatively, a phenyl group is preferable, and a phenyl group is particularly preferable.

Adjacent R ^{1 to} R ⁸ (R ¹ and R ² , R ³ and R ⁴ , R ⁵ and R ⁶ , R ⁷ and R ⁸ ) are both organic groups, and they are bonded to each other to form a ring structure In this case, the ring structure is not particularly limited, but an alicyclic structure having 2 to 10 carbon atoms is preferable.
The alicyclic structure may contain an oxygen atom, a silicon atom, a sulfur atom, a nitrogen atom and the like, and among them, a ring structure having an alkylenedioxy group containing an oxygen atom is particularly preferable.
Furthermore, the alicyclic structure may have aromaticity. In this case, M and N of the heterocyclic ring-containing aromatic compound (1) have a condensed ring structure (for example, isothianaphthene). Means.

A method for producing the heterocyclic ring-containing aromatic compound (1) will be described.
The heterocycle-containing aromatic compound (1) can be produced by coupling two types of heteroaromatic compounds in the presence of a hypervalent iodine reactant. Such a coupling reaction proceeds efficiently at a ratio of 1: 1 in the presence of a hypervalent iodine reactant. As the hypervalent iodine reactant, the same ones as described below can be used.

In the above coupling reaction, the amount of the hypervalent iodine reactant used is not particularly limited, and is preferably 0.1 to 4 mol, more preferably 0.2 to 3 mol, per 1 mol of one raw material. Used in a proportion, more preferably in a proportion of 0.3 to 2 mol.

In the above coupling reaction, a substituted or unsubstituted thiophene compound MH and a substituted or unsubstituted pyrrole compound NH are used as raw materials. Here, M and N are the same as described above. These compounds may be appropriately selected in order to obtain a desired product.

The above coupling reaction is usually carried out in the presence of a solvent.
The solvent may be any solvent that dissolves or disperses the raw material, the heterocycle-containing aromatic compound (1), and the hypervalent iodine reactant. Examples of such a solvent include water, methanol, and ethanol. Alcohols such as 2-propanol, 1-propanol and n-butanol; ethylene glycols such as ethylene glycol, diethylene glycol, triethylene glycol and tetraethylene glycol; ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol Glycol ethers such as diethyl ether and diethylene glycol dimethyl ether; ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether Glycol ether acetates such as acetate and diethylene glycol monobutyl ether acetate; Propylene glycols such as propylene glycol, dipropylene glycol and tripropylene glycol; Propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol mono Propylene glycol ethers such as ethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, propylene glycol diethyl ether, dipropylene glycol diethyl ether; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene Propylene glycol ether acetates such as glycol monomethyl ether acetate and dipropylene glycol monoethyl ether acetate; N-methylformamide, N, N-dimethylformamide, N-methylpyrrolidone, dimethylacetamide, dimethylsulfoxide, acetone, acetonitrile, toluene, xylene (O-, m-, or p-xylene), benzene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, diethyl ether, diisopropyl ether, methyl-t-butyl ether, hexane, heptane, chloromethane (methyl chloride), Organic solvents such as dichloromethane (methylene chloride), trichloromethane (chloroform), tetrachloromethane (carbon tetrachloride), water and their organic Examples thereof include a mixed solvent (hydrous organic solvent) with a solvent. These may be used alone or in combination of two or more.

Additives may be appropriately added to the coupling reaction system. By using the hypervalent iodine reactant and the additive in combination, the yield of the heterocyclic ring-containing aromatic compound can be improved, and the amount of the hypervalent iodine reactant can be reduced.
Examples of the additive include bromotrimethylsilane, chlorotrimethylsilane, trimethylsilyl triflate, boron trifluoride, trifluoroacetic acid, hydrochloric acid, sulfuric acid, and the like. Among these, bromotrimethylsilane is preferable. These may be used alone or in combination.
The amount of the additive used is preferably 0.1 to 4 mol, more preferably 0.2 to 3 mol, and still more preferably 0.5 to 1 mol per 1 mol of the heterocyclic ring-containing aromatic compound. The ratio is 2 moles.

Further, a fluorinated alcohol may be added to the coupling reaction system. By using a hypervalent iodine reactant and a fluoroalcohol in combination, the yield of the heterocyclic ring-containing aromatic compound can be improved, and the amount of the hypervalent iodine reactant can be reduced.
Examples of the fluorinated alcohol include 1,1,1,3,3,3-hexafluoro-2-propanol, trifluoroethanol, hexafluoroethanol, and the like. Among these, 1,1,1 3,3,3-hexafluoro-2-propanol is preferred.
Although the usage-amount of the said fluorine-type alcohol is not specified in particular, 1-80 weight part is preferable with respect to 100 weight part of solvents to be used, and 10-40 weight part is especially preferable.

The above coupling reaction is usually performed by mixing each raw material, a hypervalent iodine reactant, a solvent, other reagents and the like at a temperature range of −50 ° C. to 100 ° C. for 10 minutes to 48 hours, The heterocycle-containing aromatic compound can be produced.
The coupling reaction is preferably performed at a temperature range of 0 to 50 ° C for 30 minutes to 8 hours, and more preferably at a temperature range of 10 to 40 ° C for 1 to 4 hours. At this time, the order of the reagents to be added does not matter.

Next, a method for producing a heterocyclic ring-containing aromatic polymer using the heterocyclic ring-containing aromatic compound (1) as a monomer will be described.
In the production of the heterocyclic ring-containing aromatic polymer, the monomer (heterocyclic ring-containing aromatic compound (1)) is oxidatively polymerized by a chemical polymerization method using various oxidizing agents.
Since the chemical polymerization method is simple and capable of mass production, it is a method suitable for an industrial production method as compared with the conventional electrolytic polymerization method.

Although it does not specifically limit as an oxidizing agent used for the said chemical polymerization method, For example, the oxidizing agent which uses a sulfonic acid compound as an anion and uses an expensive number of transition metals as a cation is mentioned. Examples of the expensive transition metal ions constituting this oxidant include Cu ²⁺ , Fe ³⁺ , Al ³⁺ , Ce ⁴⁺ , W ⁶⁺ , Mo ⁶⁺ , Cr ⁶⁺ , Mn ⁷⁺ and Sn ⁴⁺ . Of these, Fe ³⁺ and Cu ²⁺ are preferred.
Specific examples of the oxidizing agent having a transition metal as a cation include FeCl ₃ , Fe (ClO ₄ ) ₃ , K ₂ CrO ₇ , alkali perborate, potassium permanganate, copper tetrafluoroborate and the like. It is done.
Examples of the oxidizing agent other than the oxidizing agent having a transition metal as a cation include alkali persulfate, ammonium persulfate, and H ₂ O ₂ . Furthermore, hypervalent compounds represented by hypervalent iodine reactants can be mentioned.

In a particularly preferred embodiment, the oxidizing agent is a hypervalent iodine reactant.
A hypervalent iodine reactant refers to a reactant containing an iodine atom in a trivalent or pentavalent hypervalent state. Since the hypervalent iodine reactant has the property of returning to a more stable octet state (monovalent iodine), a heavy metal oxidizing agent such as lead (IV), thallium (III), mercury (II), etc. And similar reactivity. Furthermore, the hypervalent iodine reactant is less toxic than such a heavy metal oxidant, has excellent safety, and is suitable for an industrial production method.

The hypervalent iodine reactant is not particularly limited, and examples of the trivalent hypervalent iodine reactant include phenyliodine bis (trifluoroacetate) or (bis (trifluoroacetoxy) iodobenzene (hereinafter referred to as “bivalent trivalent iodine”). , PIFA)), phenyliodine diacetate (iodosobenzene diacetate (hereinafter sometimes referred to as PIDA)), hydroxy (tosyloxy) iodobenzene, iodosylbenzene, and the like. The structural formulas of these reactants are shown below.

Examples of pentavalent hypervalent iodine reactants include Dess-Martin periodinane (DMP), o-iodoxybenzoic acid (o-iodoxybenzoic acid).
acid (IBX)) and the like. The structural formulas of these reactants are shown below.

Among these, a trivalent hypervalent iodine reactant is preferable, and PIFA is more preferable because it is stable and easy to handle and has a sufficiently high oxidizing ability.

In addition, among the hypervalent iodine reactants, it is preferable to select a hypervalent iodine reactant having an adamantane structure and a hypervalent iodine reactant having a tetraphenylmethane structure because they can be recovered and reused. More specifically, 1,3,5,7-tetrakis- (4- (diacetoxyiodo) phenyl) adamantane, 1,3,5,7-tetrakis-((4- (hydroxy) tosyloxyiodo) phenyl ) A hypervalent iodine reactant having a trivalent adamantane structure such as adamantane, 1,3,5,7-tetrakis- (4-bis (trifluoroacetoxyiodo) phenyl) adamantane, or tetrakis-4- (di Hypervalent iodine reactants having a trivalent tetraphenylmethane structure such as acetoxyiodo) phenylmethane and tetrakis-4-bis (trifluoroacetoxyiodo) phenylmethane are stable and easy to handle and have a sufficiently high oxidizing ability Furthermore, it is more preferable because it has high fat solubility and can be recovered and reused.
When a pentavalent hypervalent iodine reactant is used, desmartin periodinane (DMP) is preferred.

As such a hypervalent iodine reactant, one obtained by synthesis may be used, or a commercially available product may be used. For example, PIFA can be obtained by adding trifluoroacetic acid to PIDA and reacting, so that PIFA is precipitated as a reaction product (see J. Chem. Soc. Perkin Trans. 1, 1985, 757). ). PIDA is obtained by oxidizing iodobenzene with sodium peroxoborate (tetrahydrate) (NaBO ₃ .4H ₂ O) in acetic acid (Tetrahedron, 1989, 45, 3299 and Chem. Rev.,
1996, 96, 1123). In addition, PIDA is obtained from iodobenzene using m-chloroperbenzoic acid (mCPBA) as an oxidizing agent (see Angew. Chem. Int. Ed., 2004, 43, 3595). 1,3,5,7-tetrakis- (4- (diacetoxyiodo) phenyl) adamantane, 1,3,5,7-tetrakis-((4- (hydroxy) tosyloxyiodo) phenyl) adamantane, 1,3 , 5,7-tetrakis- (4-bis (trifluoroacetoxyiodo) phenyl) adamantane, tetrakis-4- (diacetoxyiodo) phenylmethane, tetrakis-4-bis (trifluoroacetoxyiodo) phenylmethane, for example It can be synthesized by the method described in Kaikai 2005-220122.

Although the usage-amount of the said oxidizing agent is not specifically limited, The range of 1-5 mol per 1 mol of said monomers is preferable, More preferably, it is the range of 2-4 mol. In particular, when a hypervalent iodine reactant is used as the oxidizing agent, it is preferably used in a proportion of 1 to 4 mol, more preferably 1.5 to 4 mol, more preferably 1 mol of the monomer. Used in a proportion of 2 to 2.5 mol.
When the amount of the hypervalent iodine reactant is small, the oxidative polymerization reaction may be difficult to proceed. On the other hand, if the amount of the hypervalent iodine reactant is too large, excessive oxidation may occur and a product that is completely insoluble in the solvent may be obtained, and the yield of the desired polymer may be reduced.

In the method for producing a heterocyclic ring-containing aromatic polymer, a hypervalent iodine reactant and a metal-free oxidizing agent may be used in combination. The combined use of a hypervalent iodine reactant and an oxidizing agent that does not contain a metal can reduce the amount of hypervalent iodine reactant used. Examples of the metal-free oxidizing agent include peroxodisulfuric acid, ammonium peroxodisulfate, hydrogen peroxide, metachloroperbenzoic acid, and the like.

As described above, when the hypervalent iodine reactant and the metal-free oxidizing agent are used in combination, the hypervalent iodine reactant acts as an oxidation catalyst, and preferably with respect to 1 mol of the monomer. It is used in a proportion of 0.001 to 0.3 mol, more preferably 0.01 to 0.1 mol. On the other hand, the metal-free oxidizing agent is preferably used in a proportion of 1 to 4 molar equivalents, more preferably 1.5 to 2.5 molar equivalents, relative to 1 mol of the monomer.

Moreover, when using together the oxidizing agent which does not contain a metal, and a hypervalent iodine reactant, when there is too little quantity of a hypervalent iodine reactant, a polymerization reaction may not fully advance. On the other hand, even if the amount of the hypervalent iodine reactant is too large, the degree of polymerization does not exceed a certain degree of polymerization, and the hypervalent iodine reactant may be wasted.

In the case where a hypervalent iodine reactant and an oxidizing agent not containing a metal are used in combination, a precursor of the hypervalent iodine reactant may be used when starting the polymerization reaction. Specifically, for example, 1,3,5,7-tetrakis- (4-iodophenyl) adamantane, which is a precursor of 1,3,5,7-tetrakis- (4- (diacetoxyiodo) phenyl) adamantane A hypervalent iodine reagent may be generated in the reaction system by adding a catalytic amount and a stoichiometric amount of metachloroperbenzoic acid.

In the method for producing a heterocyclic ring-containing aromatic polymer, the heterocyclic ring-containing aromatic polymer may be doped with a dopant. By doping with a dopant, higher conductivity can be imparted to the resulting heterocyclic ring-containing aromatic polymer. The dopant may be charged as a raw material before the polymerization reaction, may be added during the polymerization reaction, or may be added to the heterocyclic ring-containing aromatic polymer obtained after the polymerization reaction.

Is not particularly restricted but includes dopants _{such, Cl 2, Br 2, I} 2, halogen such as _ICl; PF 5, BF _3, Lewis acids such as trimethylsilyl _{trifluoromethanesulfonate; HF, HCl, HNO 3,} H 2 SO Protic acids such as ₄ ; organic acids such as p-toluenesulfonic acid and polystyrenesulfonic acid.

The dopant used for the purpose of imparting conductivity is preferably used in a proportion of 0.05 to 6 mol, more preferably in a proportion of 0.2 to 4 mol, relative to 1 mol of the monomer.
When the amount of the dopant is less than 0.05 mol, sufficient conductivity may not be imparted to the heterocyclic ring-containing aromatic polymer. On the other hand, when the amount of the dopant is more than 6 moles, all the dopant added to the heterocyclic ring-containing aromatic polymer is not doped, and an effect proportional to the added amount cannot be expected. Also, excess dopant is wasted.

The Lewis acid not only functions as a dopant but also has an effect of promoting an oxidative polymerization reaction. When a Lewis acid is used for the purpose of promoting the oxidative polymerization reaction, trimethylsilyl trifluoromethanesulfonate is particularly preferably used.

The oxidative polymerization reaction is usually carried out in the presence of a solvent.
The solvent may be any solvent that dissolves or disperses the monomer, oxidizing agent, and dopant. Examples of such a solvent include water, methanol, ethanol, 2-propanol, 1-propanol, alcohols such as n-butanol; ethylene glycols such as ethylene glycol, diethylene glycol, triethylene glycol and tetraethylene glycol; glycol ethers such as ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether and diethylene glycol dimethyl ether Class: Ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol Glycol ether acetates such as coal monobutyl ether acetate; propylene glycols such as propylene glycol, dipropylene glycol and tripropylene glycol; propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether , Propylene glycol ethers such as propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, propylene glycol diethyl ether, dipropylene glycol diethyl ether; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether Propylene glycol ether acetates such as diacetate and dipropylene glycol monoethyl ether acetate; N-methylformamide, N, N-dimethylformamide, N-methylpyrrolidone, dimethylacetamide, dimethylsulfoxide, acetone, acetonitrile, toluene, xylene (o -, M-, or p-xylene), benzene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, diethyl ether, diisopropyl ether, methyl-t-butyl ether, hexane, heptane, chloromethane (methyl chloride), dichloromethane ( Organic solvents such as methylene chloride), trichloromethane (chloroform), tetrachloromethane (carbon tetrachloride), mixed solvents of water and these organic solvents (hydrous organic solutions) Medium) and the like. These may be used alone or in combination of two or more.

The temperature of the oxidative polymerization reaction is preferably -100 ° C to 100 ° C. In either case of using an organic solvent as the solvent and water, the temperature is more preferably 0 ° C to 40 ° C. When the reaction temperature is lower than −100 ° C., the reaction rate becomes slow, or depending on the solvent, the yield of the heterocyclic ring-containing aromatic polymer may be lowered. On the other hand, when the reaction temperature is higher than 100 ° C., side reaction or excessive oxidation occurs, and the yield of the heterocyclic ring-containing aromatic polymer may be reduced.

The reaction time of the oxidative polymerization reaction is not particularly limited. When a Lewis acid is used to promote the oxidative polymerization reaction, about 12 hours are preferable, and when a Lewis acid is not used, about 20 hours are preferable.

The thus obtained heterocyclic ring-containing aromatic polymer may be subjected to a purification treatment.
Although it does not specifically limit as a purification method (purification process), For example, after reaction, a solvent is filtered with a glass filter and methanol, ethanol, 2-propanol, n-hexane, diethyl ether, acetonitrile, acetic acid is obtained. Examples include a method of washing with ethyl, toluene, and the like. Other purification methods include purification by Soxhlet extraction and the like.

In such a method for producing a heterocyclic ring-containing aromatic polymer, after washing, the obtained heterocyclic ring-containing aromatic polymer is dried by a usual means as necessary (drying step).
Here, the drying method can be appropriately determined depending on the degree of polymerization, the substituent, and the dopant contained. For example, drying under reduced pressure (about 0.5 mmHg) at room temperature (about 25 ° C.), heating air blowing under normal pressure ( About 60 ° C.) and the like. The drying temperature is preferably 100 ° C. or lower, and if it exceeds 200 ° C., the risk of decomposition of the heterocyclic ring-containing aromatic polymer increases.

In the above oxidative polymerization, when a hypervalent iodine reactant having an adamantane structure and a tetraphenylmethane structure is used, it is desirable to recover by the following method. For example, the solution after the reaction is concentrated under reduced pressure and methanol is added to the residue (polymer, adamantane or tetraphenylmethane structure hypervalent iodine reactant, metal-free oxidant, unreacted monomer). By mixing and filtering using a glass filter, the metal-free oxidizing agent and unreacted monomer can be removed as a methanol solution. The polymer remaining as a residue and a hypervalent iodine reactant having an adamantane structure or a tetraphenylmethane structure are mixed with diethyl ether and filtered using a glass filter, whereby the polymer in the residue and the adamantane structure of the diethyl ether solution and It can be separated into a hypervalent iodine reactant having a tetraphenylmethane structure. By concentrating the diethyl ether, the hypervalent iodine reactant having an adamantane structure and a tetraphenylmethane structure can be recovered. The recovery method of the hypervalent iodine reactant having an adamantane structure and a tetraphenylmethane structure is not limited to the above example, but the polymer, the hypervalent iodine reactant having the adamantane structure or the tetraphenylmethane structure, and the oxidizing agent not containing a metal. Each component can be separated by selecting an appropriate solvent using the difference in solubility between the unreacted monomer and the solvent species.

The conductive resin composition used in the present invention comprises (B) a binder resin, (C) a cross-linking agent, (D) a curing agent, (E), if necessary, in addition to (A) the heterocyclic ring-containing aromatic polymer. An additive and (F) a solvent may be contained.
Hereinafter, the components (B) to (F) will be described.

(B) Binder resin Examples of the binder resin include polyester, poly (meth) acrylate, polyurethane, polyvinyl acetate, polyvinylidene chloride, polyamide, polyimide, epoxy resin, styrene, vinylidene chloride, vinyl chloride, and alkyl ( Examples thereof include a copolymer composed of two or more monomers selected from the group consisting of (meth) acrylates.
When mix | blending the said binder resin, it is preferable that the compounding quantity is 10-5000 weight part with respect to 100 weight part of solid content of the said heterocyclic-containing aromatic polymer (A). More preferably, it is 30 to 2000 parts by weight. If the blending amount exceeds 5000 parts by weight, transparency and conductivity may be deteriorated. On the other hand, when the amount is less than 10 parts by weight, the curability is lowered, and sufficient water resistance and solvent resistance may not be imparted to the conductive layer.

(C) Crosslinking agent Although it does not specifically limit as said crosslinking agent, For example, a low molecular acrylate, a low molecular epoxy resin, isocyanate etc. can be used. Specifically, bifunctional low-molecular acrylates such as ethylene oxide-modified bisphenol diacrylate, ethylene oxide-modified isocyanuric acid diacrylate, tripropylene glycol diacrylate, pentaerythritol diacrylate monostearate, pentaerythritol triacrylate, trimethylolpropane triacrylate , Trifunctional low molecular acrylates such as propylene oxide modified trimethylolpropane triacrylate, ethylene oxide modified isocyanuric acid triacrylate, propylene oxide modified trimethylolpropane triacrylate, ethylene oxide modified trimethylolpropane triacrylate, dipentaerythritol pentaacrylate, dipenta Erythritol hexaacrylate, Tetramethylolpropane tetraacrylate, pentaerythritol tetraacrylate and other low molecular acrylates having a functionality of 4 or more, 3,4-epoxycyclohexenylmethyl-3′-4′-epoxycyclohexenecarboxylate, vinylcyclohexene monooxide-1,2- Alicyclic epoxy such as epoxy-4-vinylcyclohexane, acrylate having an epoxy group such as 3,4-epoxycyclohexylmethyl methacrylate, 1,6-hexanediol diglycidyl ether, 1,4-butanediol diglycidyl ether, Polyfunctional aliphatic epoxy compounds such as cyclohexanedimethanol diglycidyl ether, trimethylolpropane polyglycidyl ether, diethylene glycol diglycidyl ether, 4,4′-di Phenylmethane diisocyanate, tolylene diisocyanate, 1,3-phenylene bismethylene diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, isophorone diisocyanate, 1,6-diisocyanate hexane, polymethylene polyphenyl isocyanate, trimethylolpropane modified tri Examples of the isocyanate include range isocyanate, trimethylolpropane-modified hexamethylene diisocyanate, and trimethylolpropane-modified isophorone diisocyanate.
When mix | blending the said crosslinking agent, it is preferable that the compounding quantity is 1-100 weight part with respect to 100 weight part of solid content of the said heterocyclic containing aromatic polymer (A). More preferably, it is 10 to 70 parts by weight. If the amount exceeds 100 parts by weight, the conductive layer may become brittle. Conversely, when the amount is less than 1 part by weight, the strength of the conductive layer may be insufficient.

(D) When using an epoxy resin for a hardener binder, a hardener can be added. Examples of the curing agent include epoxy resin curing agents such as acid anhydrides, phenol compounds, and amines. When mix | blending the said hardening | curing agent, it is preferable that the compounding quantity is 1-100 weight part with respect to 100 weight part of resin parts of an epoxy resin. More preferably, it is 4 to 60 parts by weight. If the amount exceeds 100 parts by weight, the conductive layer may become brittle. Conversely, when the amount is less than 1 part by weight, the strength of the conductive layer may be insufficient.

(E) Additive As the additive, for example, a conductivity improver, a surfactant for improving coatability, an ultraviolet absorber for improving light resistance, an infrared absorber for absorbing heat rays, When forming a coating film using an antioxidant for suppressing the decomposition of the polymer, inorganic fine particles for increasing the film strength of the conductive layer, a polymerization initiator, and the conductive resin composition, adhesion to the substrate And silane coupling agents for improving the durability of the coating film.

Examples of the conductivity improver include amide compounds such as N-methylformamide, N, N-dimethylformamide, fumaramide and benzamide, imide compounds such as phthalimide and 1,8-naphthylimide, o-cresol, Phenolic compounds such as m-cresol, p-cresol, catechol, resorcinol, chlorophenol, hydroxynaphthalene, tetracyanoethylene, 7,7,8,8, -tetracyanoquinodimethane, 2,3,6,7- Examples include cyano compounds such as tetracyano-1,4,5,8-tetraazanaphthalene, and aliphatic polyhydric alcohols such as ethylene glycol, glycerin, and sorbitol.
When mix | blending the said electroconductivity improver, it is preferable that the compounding quantity is 1-5000 weight part with respect to 100 weight part of solid content of the said heterocyclic containing aromatic polymer (A). More preferably, it is 10 to 1000 parts by weight.

Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkylphenyl ether, polyoxyethylene alkyl ether, sorbitan fatty acid ester, and fatty acid alkylolamide; fluoroalkylcarboxylic acid, perfluoroalkylbenzenesulfonic acid, Fluorosurfactants such as perfluoroalkyl quaternary ammonium and perfluoroalkyl polyoxyethylene ethanol are listed.
When mix | blending the said surfactant, it is preferable that the compounding quantity is 0.1-60 weight part with respect to 100 weight part of solid content of the said heterocyclic-containing aromatic polymer (A). More preferably, it is 0.2 to 20 parts by weight.

Examples of the ultraviolet absorber include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-5′-tert-butylphenyl) benzotriazole, and 2- (2 ′ -Hydroxy-3 ', 5'-ditert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2 '-Hydroxy-3', 5'-ditert-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-ditert-amylphenyl) benzotriazole, 2-{( 2'-hydroxy-3 ', 3 ", 4", 5 ", 6" -tetrahydrophthalimidomethyl) -5'-methylphenyl} ben Benzotriazole ultraviolet absorbers such as triazole, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2 ' Benzophenone-based UV absorbers such as benzophenone such as dihydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, phenyl salicylate, p Salicylate ultraviolet absorbers such as t-butylphenyl salicylate and p-octylphenyl salicylate, ethyl-α-cyano-β, β-diphenylacrylate, methyl-2-cyano-3-methyl-3- (p- Cyanoacrylate ultraviolet absorbers such as toxiphenyl) acrylate, oxanilide ultraviolet absorbers such as 2-ethyl-2′-ethoxyoxanilide, 2-ethoxy-4′-dodecyloxanilide, TINUVIN (registered trademark) 770 , TINUVIN (registered trademark) 622LD (all manufactured by Ciba Specialty Chemicals), Adekastab (registered trademark) LA-57 (manufactured by Asahi Denka Kogyo Co., Ltd.), etc., hindered amine-based ultraviolet absorbers, phenyl salicylate, resorcinol monobenzoate, 2 , 4-Ditert-butylphenyl-3,5-ditert-butyl-4-hydroxybenzoate, 2,4-ditert-amylphenyl-3,5-ditert-butyl-4-hydroxybenzoate, hexadecyl-3 , 5-Ditert-butyl-4-hydroxybenzoate What benzoate-based ultraviolet absorbers, and the like. When mix | blending the said ultraviolet absorber, it is preferable that the compounding quantity is 0.1-20 weight part with respect to 100 weight part of solid content of the said heterocyclic-containing aromatic polymer (A). More preferably, it is 0.3 to 10 parts by weight.

Examples of the infrared absorber include organic infrared absorbers such as cyanine compounds, phthalocyanine compounds, and chlorinated phenylenedianium salts, transparent conductive materials such as ITO (tin-doped indium oxide) and ATO (antimony-doped tin oxide). Inorganic near-infrared absorbers such as conductive oxide, zinc oxide, indium oxide, and tin oxide.
When mix | blending the said infrared absorber, it is preferable that the compounding quantity is 0.1-20 weight part with respect to 100 weight part of solid content of the said heterocyclic containing aromatic polymer (A). More preferably, it is 0.3 to 10 parts by weight.

Examples of the antioxidant include IRGANOX (registered trademark) 1010 (manufactured by Ciba Special Te Chemicals), NOCRACK NS-30 (trade name) (manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.), Tominox TT (trade name) ( Phenolic antioxidants such as Yoshitoyo Fine Chemical), amine antioxidants such as hydroxylamine and N-phenyl-1,1,3,3-tetramethylbutylnaphthalene-1-amine, and trisnonylphenylphos Phyto, Tris (2,4-ditert-butylphenyl) phosphite, Tris [2-tert-butyl-4- (3-tert-butyl-4-hydroxy-5-methylphenylthio) -5-methylphenyl] Phosphite, tridecyl phosphite, octyl diphenyl phosphite, di (decyl) monophenyl phosphite, di (tridec ) Pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, bis (2,4-ditert-butylphenyl) pentaerythritol diphosphite, bis (2,6-ditert-butyl-4-methyl) Phenyl) pentaerythritol diphosphite, bis (2,4,6-tritert-butylphenyl) pentaerythritol diphosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite, tetra (tridecyl) isopropyl Dendiphenol diphosphite, tetra (tridecyl) -4,4′-n-butylidenebis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl) -1,1,3-tris (2-methyl- 4-hydroxy-5-tert-butylphenyl) butane Rephosphite, tetrakis (2,4-ditert-butylphenyl) biphenylenediphosphonite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2,2′-methylenebis (4 6-tert-butylphenyl) -2-ethylhexyl phosphite, 2,2′-methylenebis (4,6-tert-butylphenyl) -octadecyl phosphite, 2,2′-ethylidenebis (4,6-ditertiary Butylphenyl) fluorophosphite, tris (2-[(2,4,8,10-tetrakis tert-butyldibenzo [d, f] [1,3,2] dioxaphosphin-6-yl) oxy] Phosphorous antioxidants such as phosphites of ethyl) amine, 2-ethyl-2-butylpropylene glycol and 2,4,6-tritert-butylphenol , Dialkylthiodipropionates such as dilauryl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate, and β-alkylmercaptopropion of polyols such as pentaerythritol tetra (β-dodecyl mercaptopropionate) Examples thereof include sulfur-based antioxidants such as acid esters and vitamins such as ascorbic acid (vitamin C).
When mix | blending the said antioxidant, it is preferable that the compounding quantity is 0.1-20 weight part with respect to 100 weight part of solid content of the said heterocyclic containing aromatic polymer (A). More preferably, it is 0.3 to 10 parts by weight.

Examples of the inorganic fine particles include fine particles composed of metal oxides such as titanium oxide, niobium oxide, antimony oxide, indium tin mixed oxide and antimony tin mixed oxide, zirconia, silica, and the like. From the viewpoint of transparency and hardness, the primary particle diameter is preferably less than 100 nm, and more preferably less than 50 nm.
When mix | blending the said inorganic fine particle, it is preferable that the compounding quantity is 0.5-200 weight part with respect to 100 weight part of solid content of the said heterocyclic-containing aromatic polymer (A). More preferably, it is 1 to 50 parts by weight.

Examples of the polymerization initiator include acetophenones such as acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone and p-tert-butylacetophenone; benzophenone Benzophenones such as 2-chlorobenzophenone, p, p′-bisdimethylaminobenzophenone, 1,3 α-aminoalkylphenone; benzoin ethers such as benzyl, benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether; Benzyl dimethyl ketal, thioxanthene, 2-chlorothioxanthene, 2,4-diethylthioxanthene, 2-methylthioxanthene, 2-isopropyl Sulfur compounds such as pyrthioxanthene; anthraquinones such as 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone; azobisisobutyronitrile, benzoyl peroxide, cumene peroxide, etc. Organic peroxides; thermal cation catalysts such as aromatic sulfonium salts; and thiol compounds such as 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, and the like. These compounds may be used individually by 1 type, and may be used in combination of 2 or more type.
When mix | blending the said polymerization initiator, it is preferable that the compounding quantity is 0.1-50 weight part with respect to 100 weight part of solid content of the said binder resin (A). More preferably, it is 0.1 to 10 parts by weight.

Furthermore, a compound which does not act as a photopolymerization initiator itself but can increase the ability of the photopolymerization initiator by using it in combination with the above compound can also be added. Examples of such compounds include tertiary amines such as triethanolamine which are effective when used in combination with benzophenone.

Examples of the silane coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) methyltrimethoxysilane, 2- (3, 4-epoxycyclohexyl) methyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3-methacryloxypropyltriethoxysilane, 3 -(Meth) acryloxytrialkoxysilane such as methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, p- Tyryltrimethoxysilane, vinyl-tris (βmethoxyethoxy) silane, γ-aminopropyltriethoxysilane, vinyltriethoxysilane, β-3,4epoxycyclohexylethyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, etc. It is done. These may be used alone or in combination of two or more.
When mix | blending the said silane coupling agent, it is preferable that the compounding quantity is 0.2-10 weight part with respect to 100 weight part of solid content of the said heterocyclic-containing aromatic polymer (A). More preferably, it is 0.5 to 5 parts by weight.

(F) Solvent solvent may be omitted. Examples of the solvent include water and alcohols such as methanol, ethanol, 2-propanol, 1-propanol, and n-butanol; ethylene glycol, diethylene glycol, and triethylene glycol. Ethylene glycols such as tetraethylene glycol; glycol ethers such as ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether; ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol Glycol ether acetate such as monobutyl ether acetate Propylene glycols such as propylene glycol, dipropylene glycol, tripropylene glycol; propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, propylene glycol dimethyl ether, dipropylene glycol Propylene glycol ethers such as dimethyl ether, propylene glycol diethyl ether, dipropylene glycol diethyl ether; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate Any propylene glycol ether acetates; N-methylformamide, N, N-dimethylformamide, N-methylpyrrolidone, dimethylacetamide, dimethylsulfoxide, acetone, acetonitrile, toluene, xylene (o-, m-, or p-xylene), Benzene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, diethyl ether, diisopropyl ether, methyl-t-butyl ether, hexane, heptane, chloromethane (methyl chloride), dichloromethane (methylene chloride), trichloromethane (chloroform), tetra Examples thereof include organic solvents such as chloromethane (carbon tetrachloride), mixed solvents of water and these organic solvents (hydrous organic solvents), and the like. These may be used alone or in combination of two or more.
The conductive resin composition used in the present invention preferably contains an organic solvent. The reason is that it has high hardness, high adhesion to the base material, and is suitable for forming a uniform conductive layer.

When mix | blending the said solvent, it is preferable that the compounding quantity is 100-5000 weight part with respect to 100 weight part of solid content of the said heterocyclic-containing aromatic polymer (A). More preferably, it is 500 to 3000 parts by weight.

The conductive layer formed of the conductive resin composition used in the present invention having such a configuration is disposed on the transparent substrate.

The transparent substrate used in the present invention is an organic polymer film such as polyethylene terephthalate, polyethylene naphthalate, polycarbonate, acrylic, triacetyl cellulose, polyimide, a composite film of an inorganic filler (including glass cloth) and an organic resin, and a glass substrate. Etc.

The transparent electrode substrate of this invention can be manufactured by apply | coating the said conductive resin composition on the said transparent base | substrate, hardening by drying and exposure, and forming a conductive layer.

Furthermore, the patterning method to the transparent electrode substrate of this invention is demonstrated.
Examples of the patterning method include wet etching and a lift-off method.

First, a case where a positive resist is used as an example of a conductive layer patterning method by wet etching will be described as an example. However, the present invention is not limited to this, and a negative resist may be used. it can.
A conductive resin composition is coated on a transparent substrate, a resist is coated on the transparent substrate, and exposed through a photomask having a desired pattern. Next, the exposed resist is removed with a developing solution to expose the conductive layer. The developed substrate is etched using an etchant, and the conductive layer is removed and patterned. Thereafter, the remaining resist portion is removed using a release agent, and a substrate on which the conductive layer is patterned can be obtained.

A general-purpose photoresist or dry film resist can be used as the resist used in the conductive layer patterning method by wet etching.
There are two types of photoresists: a positive type in which the UV-irradiated part dissolves in the developer, and a negative type in which the UV-irradiated part becomes insoluble in the developer. The width (line) is used for etching in the order of several μm to several tens of μm. The positive type liquid resist preferably contains a naphthoquinone diazide compound and a novolac resin. More preferably, the novolac resin is a cresol novolac resin.
The negative type includes a dry film resist in addition to a liquid resist, and the display is used for etching of a PDP (plasma display panel) or the like whose line width is on the order of several tens of micrometers.
Both positive type and negative type resists can be used, and it is only necessary to select the desired pattern definition and usability.

Examples of the developer used for the conductive layer patterning method by wet etching include organic developers such as tetramethylammonium hydroxide aqueous solution, and inorganic developers such as sodium carbonate aqueous solution and potassium carbonate aqueous solution.

As an etching solution used in the conductive layer patterning method by wet etching, an etching solution containing cerium ammonium nitrate, an etching solution containing cerium ammonium sulfate, an etching solution that is an aqueous hypochlorite solution, or the like can be used. .

The release agent used in the conductive layer patterning method by wet etching has a resist pattern peeling ability, and (a) an aprotic organic solvent (aprotic organic solvent (a) containing no nitrogen atom) And (b) a group having a nitrogen atom in the chemical structure and an organic solvent (organic solvent (b)) other than the primary amine compound, secondary amine compound and quaternary ammonium salt. It is necessary to contain at least one organic solvent selected from the group consisting of the aprotic organic solvent (a) and / or the organic solvent (b). More preferably, the organic solvent (a) or the organic solvent (b) is a main component.

In the present invention, an aprotic organic solvent means an organic solvent having a remarkably low ability to donate protons. In contrast, a protic organic solvent is a solvent that dissociates itself and generates protons, such as water, alcohols such as methanol and ethanol, carboxylic acids such as acetic acid, phenol, and liquid ammonia. is there.

(A) Aprotic organic solvent In the present invention, the aprotic organic solvent (a) is a dialkyl sulfone such as dimethyl sulfone, a dialkyl sulfoxide such as dimethyl sulfoxide or diethyl sulfoxide, or a carbonic acid such as ethylene carbonate or propylene carbonate. Selected from the group consisting of alkylenes and alkylolactones such as γ-butyrolactone, δ-valerolactone, ε-caprolactone, etc., containing an oxygen atom and / or a sulfur atom in the chemical structure, and a nitrogen atom An aprotic organic solvent not contained is preferable. These aprotic organic solvents (a) may be used alone or in admixture of two or more.

The dialkyl sulfoxides and the dialkyl sulfones may form a ring by bonding two alkyl groups. For example, the dialkyl sulfones includes sulfolanes such as sulfolane and tetramethylsulfolane. is there.

In the present invention, another aprotic organic solvent containing an oxygen atom and / or a sulfur atom in the chemical structure and not containing a nitrogen atom can be used in combination.

(B) a chemical compound having a nitrogen atom and an organic solvent other than a primary amine compound, a secondary amine compound and an organic quaternary ammonium salt, wherein the primary amine compound is ammonia (NH ₃ ) is a compound in which one of the hydrogen atoms is substituted with a hydrocarbon residue, and the secondary amine compound is a compound in which two hydrogen atoms of ammonia (NH ₃ ) are substituted with a hydrocarbon residue. The quaternary ammonium salt is an ionic compound in which all four hydrogen atoms attached to the nitrogen atom of the ammonium salt (NH ₄ X) are substituted with hydrocarbon residues.
In the present invention, the organic solvent (b) is preferably a tertiary amine compound or an amide compound. In the present invention, the amide compound only needs to have a partial structure of —C═O—NR ^a — and includes a urea compound. Here, R ^a represents a hydrogen atom or a monovalent substituent.
Among these, the organic solvent (b) is preferably an amide compound.

Examples of the organic solvent (b) include N-alkylpyrrolidones such as N-methyl-2-pyrrolidone and N-vinyl-2-pyrrolidone, N-alkenylpyrrolidones, N, N-dimethylformamide, N, N-dimethyl. Examples thereof include dialkylcarboxamides such as acetamide and N, N-diethylacetamide, 1,3-dimethyl-2-imidazolidinone, tetramethylurea, hexamethylphosphoric triamide, triethanolamine and the like.

These organic solvents (b) may be used alone or in admixture of two or more.

The primary amine compound, secondary amine compound and organic quaternary ammonium salt are preferably not contained as a whole release agent, and the primary amine compound, secondary amine compound and organic quaternary ammonium salt The content is preferably 5% by weight or less of the entire release agent, more preferably 3% by weight or less, and still more preferably not contained.

In the present invention, the aprotic organic solvent (a) or the organic solvent (b) can be used alone, or the aprotic organic solvent (a) and the organic solvent (b) can be used in combination.
The mixture of the aprotic organic solvent (a) and the organic solvent (b) has good releasability of the resist film from the conductive polymer and does not increase the surface resistance of the conductive polymer, that is, deteriorates the conductivity. And the adhesion between the substrate and the conductive polymer is not deteriorated.
The ratio of the aprotic organic solvent (a) to the organic solvent (b) is preferably (a) / (b) = 99/1 to 10/90 (weight ratio), and (a) / (b) = 70. / 30-20 / 80 (weight ratio) is more preferable.

In the present invention, in addition to the aprotic organic solvent (a) and the organic solvent (b), other compounds can be added to the release agent as long as the release characteristics are not deteriorated. Examples of such compounds include alcohols such as methanol, ethanol, ethylene glycol, and glycerin, alkylene glycols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol monobutyl ether. Examples thereof include glycol ethers having a flash point of 21 ° C. or higher, water and the like.
The components other than the aprotic organic solvent (a) and / or the organic solvent (b) are preferably 0 to 50% by weight based on the total weight of the release agent. More preferably, it is 0-30 weight%, More preferably, it is 0-10 weight%, Especially preferably, it is 0-5 weight%, Most preferably, it is 0-3 weight%.

Next, an example of a method for patterning a conductive layer by a lift-off method will be described.
The method for forming a current electrode substrate having a desired pattern according to the present invention by the lift-off method is as follows: (1) a step of forming a reverse pattern of the target transparent electrode pattern on the substrate with a radiation sensitive resin composition; A step of applying and drying a conductive resin composition on the surface of the substrate having the reverse pattern to form a transparent conductive film that covers the entire surface of the pattern and the substrate, and (3) the transparent conductive film By treating the formed substrate with a release agent, the reverse pattern is removed together with the transparent conductive film on the pattern to obtain a target transparent electrode pattern.

As the radiation sensitive resin composition, any of a positive radiation sensitive resin composition and a negative radiation sensitive resin composition can be used. A typical positive radiation sensitive resin composition is a mixture of a phenol novolac resin and naphthoquinone diazide (for example, a mixture of about 80% phenol novolac resin and about 20% naphthoquinone diazide). Examples of the negative radiation sensitive resin composition include a mixture of a cyclized rubber and an aromatic bisazide, and a mixture of a phenol resin and an aromatic azide.

In order to form a reverse pattern on the substrate, for example, first, the radiation-sensitive resin composition containing a solvent or a dispersion medium is applied onto the substrate, and then heated and dried to form a radiation-sensitive resin composition. A physical layer is formed. Examples of the application method include spin coating, roll coating, dip coating, slit coating, blade coating, and spray coating.

Although the film thickness of the radiation sensitive resin composition layer formed in this way is not specifically limited, 0.5-50 micrometers is preferable, More preferably, it is the range of 1-10 micrometers. If the film thickness is too thin, the resolution of the pattern of the conductive layer is lowered. Conversely, if the film thickness is too thick, the resolution is not improved.

Next, a pattern opposite to the intended conductive layer pattern is formed by patterning the obtained radiation-sensitive resin composition layer as follows. When using a positive-type radiation-sensitive resin composition as the radiation-sensitive resin composition, first, on the surface of the radiation-sensitive resin composition layer on the substrate, a reverse pattern of the desired conductive layer pattern (radiation sensitivity to be formed). A photomask having a light-shielding layer having the same pattern as that of the resin composition thin film is placed and irradiated with radiation. The irradiated part becomes soluble in a predetermined solvent. Next, the irradiated portion is dissolved and removed with the solvent, and a reverse pattern of the intended conductive layer pattern is obtained.

On the other hand, in the case of a negative radiation-sensitive resin composition, first, a laminate having a radiation-sensitive resin composition layer on a substrate is prepared as in the case of a positive type. On the surface of the resin composition layer, a photomask having a light shielding layer having a pattern opposite to that of the target conductive layer is placed, and radiation is irradiated through the photomask. The pattern of the radiation-sensitive resin composition thin film before irradiation is soluble in a predetermined solvent, but the irradiated portion is cured and becomes insoluble in the solvent. Therefore, the light-shielding portion can be dissolved and removed with the solvent to form a reverse pattern of the target conductive layer pattern.

Next, the conductive resin composition is applied so as to cover the reverse pattern. The conductive layer is formed by applying onto a substrate having a reverse pattern by spin coating, roll coating, dip coating, slit coating, blade coating, spray coating, or the like, followed by heating and drying. Since the liquid composition is applied, the conductive layer is applied to the entire surface (including side surfaces) of the substrate surface and the thin film having the reverse pattern.

Although the film thickness of a conductive layer is not specifically limited, 0.01-0.8 micrometer is preferable, More preferably, it is the range of 0.04-0.3 micrometer. If the film thickness is too thin, sufficient functions cannot be imparted to the thin film. Conversely, if the film thickness is too thick, the resolution of the pattern is lowered.

Next, the reverse pattern formed on the substrate is removed together with the conductive layer on the pattern. This is achieved, for example, by immersing the substrate on which the conductive layer is formed in a release agent that can dissolve a radiation-sensitive resin composition or a thin film made of a solubilized radiation-sensitive resin composition.

The release agent varies depending on the type of the radiation-sensitive resin composition. For example, in the case of a mixture of a cresol novolak resin that is a positive-type radiation-sensitive resin and naphthoquinone diazide, an aqueous solution containing an alkali such as an amine as the release agent. However, in the case of a mixture of cyclized rubber and aromatic bisazide, which is a negative radiation sensitive resin, alkylbenzene sulfonic acid or the like is used as a release agent, and in the case of a mixture of phenol resin and aromatic azide, a release agent. For example, an aqueous solution containing an alkali such as an amine is used. The release agent penetrates through the pores of the conductive layer or dissolves the binder contained in the conductive layer, contacts the pattern, and dissolves it. As a result, a desired pattern of the conductive layer can be obtained.

Next, electronic paper using the transparent electrode substrate of the present invention will be described.
The electronic paper of the present invention is a reflective electronic display, can achieve high definition and a high contrast ratio, and has a display medium and a thin film transistor (TFT) for driving the display medium on a substrate. Any conventionally known display medium can be used as the display medium. Any display medium such as an electrophoretic method, an electronic powder particle flying method, a charged toner method, and an electrochromic method is preferably used, but an electrophoretic display medium is more preferable, and in particular, a microcapsule type electrophoresis. A display medium of the type is particularly preferred. An electrophoretic display medium is a display medium that includes a plurality of capsules, each of the plurality of capsules including at least one particle that is movable within the suspending fluid. The at least one particle referred to here is preferably an electrophoretic particle or a rotating ball. In addition, the electrophoretic display medium has a first surface and a second surface facing the first surface, and is observed through one of the first and second surfaces. Display an image. Further, the TFT provided on the substrate has at least a gate electrode, a gate insulating film, an active layer, a source electrode, and a drain electrode, and at least one between the active layer and the source electrode or between the active layer and the drain electrode. It further has a resistance layer to be electrically connected. Electronic paper produces light shading when a voltage is applied.

Next, a resistance film type switch using the transparent electrode substrate of the present invention will be described.
The resistive membrane switch of the present invention is a resistive membrane switch having a first conductive member having a first conductive layer on a transparent substrate, a second conductive member having a second conductive layer on the substrate, and an insulating spacer. The first conductive member and / or the second conductive member is the transparent electrode substrate, the insulating spacer is provided on a part of the second conductive layer, and the first conductive layer and the second conductive member In this structure, the two conductive layers are arranged to face each other.

When this resistive film type switch is a touch screen, the surface of the transparent substrate (the surface not in contact with the first conductive layer) becomes the touch surface. When the touch surface is pressed with a finger or the tip of a pen, the first conductive member is deformed, and the pressed portion of the first conductive layer comes into contact with the second conductive layer. As a result, electricity is conducted at the contact portion, an electric signal can be output, and the resistive film switch is activated or driven. By using this electrical signal, the resistive film switch functions as an input device.

The first conductive member constituting the resistance film type switch of the present invention is formed by forming a conductive thin film (first conductive layer) on a transparent substrate. The transparent electrode substrate is used as the first conductive member. The conductive layer of this transparent electrode substrate is a first conductive layer. For example, when the resistive film type switch is a touch screen or the like, the size of the transparent substrate is preferably the same or almost the same size as the touch screen surface. For example, when the resistive film type switch is a touch screen or the like, the thickness of the transparent substrate is sufficient as long as the mechanical strength is sufficient and moderate flexibility is exhibited. The first conductive member is obtained by applying the conductive resin composition on the transparent substrate, drying it, and forming a thin film.

The first conductive layer may be formed on the entire surface of the transparent substrate or may be formed in part. In the latter case, when the resistive film type switch is a touch screen or the like, it is advantageous in that a space for forming an electrode, a wiring pattern or the like can be secured. That is, in a touch screen or the like, if a substrate having an ITO conductive layer formed on the entire surface is used, it is necessary to perform complicated and expensive processing such as etching removal or covering with an insulating film or the like. On the other hand, when the conductive layer is partially formed, it is advantageous in that such treatment is not necessary.

The first conductive member is preferably optically excellent in transparency and flexible. By being flexible, the first conductive member can be deformed by pressing, and when pressed, the first conductive member can partially contact the second conductive member. There is no restriction | limiting in particular about the grade of electroconductivity, ie, a resistivity, It can determine suitably so that it may become a required grade according to the objective. For example, it can be in the same range as the resistivity of the transparent conductive layer in a commonly used touch screen. For example, when the first conductive member is used in a touch screen, it is preferable that the first conductive member has the same or almost the same size as the touch screen surface.

The second conductive member constituting the resistance film type switch of the present invention is formed by forming a conductive thin film (second conductive layer) on a base. There are no particular restrictions on the material, color, shape, structure, size, etc. of this substrate, and it can be appropriately selected according to the purpose. Specific examples of the material for the substrate include, for example, glass and resin in view of excellent hardness and easy formation of a conductive layer on the surface. Examples of the resin that can be used for the substrate include a hard resin.

Examples of the hard resin include acrylic resin, methacrylic resin, hard polyvinyl chloride resin, polysulfone resin, polyether sulfone resin, polyether ether ketone resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polyethylene naphthalate resin, and polyacetal resin. , Polyamide resin, polyimide resin, polyamideimide resin, polymaleimide resin and the like.

The substrate may be optically opaque, but a transparent or translucent material, particularly a transparent material, is preferably used depending on the purpose. The shape of the substrate is not particularly limited and can be appropriately selected according to the purpose. For example, a plate-like shape is preferable from the viewpoint of being disposed in a liquid crystal display or the like. The substrate may be formed of, for example, a single member or may be formed of two or more members. In this case, it is preferably a laminated structure. For example, the laminated body which consists of 2 types of resin films is mentioned. There is no restriction | limiting in particular in the magnitude | size of a base | substrate, According to the objective, it can select suitably. For example, a size approximately equal to the size of the first conductive member is employed.

There is no restriction | limiting in particular as a material which can form said 2nd conductive layer, It can select suitably from the electroconductive materials generally used in the said field | area. Examples of such a conductive material include ITO, and the conductive resin composition of the present invention can be used. The conductive layer made of ITO can be formed by a known thin film forming method such as a vapor deposition method or a sputtering method. When the conductive resin composition of the present invention is used, a conductive layer is formed on the substrate by a process such as coating similar to the first conductive layer.

The second conductive member can be a film having the same configuration as the first conductive member. In this case, since both the first conductive member and the second conductive member are flexible, the resistive switch can be designed and arranged in a curved shape, and the installation location and the design can be freely selected. The degree can be improved. Further, when a hard material such as glass is not used, it is possible to reduce the size and weight, which is advantageous in that a resistance film type switch excellent in portability can be obtained.

The shape, structure, material, size and the like of the insulating spacer used in the present invention are not particularly limited, and can be appropriately selected from those generally used in the field. Examples of the insulating spacer material include acrylic resins. Examples of the shape of the insulating spacer include a columnar shape, a hemispherical shape, and a rectangular parallelepiped shape. This insulating spacer is formed on the surface of the second conductive layer formed on the substrate. Specifically, a known method such as photolithography can be employed.

The resistance film type switch of the present invention may have other members appropriately selected as necessary in addition to the above-described components. There is no restriction | limiting in particular as another member, According to the objective, it can select suitably. For example, an electrode, a land pattern, a wiring pattern, a dot spacer, etc. are mentioned.

The material constituting the electrode, the land pattern, the wiring pattern, etc., its shape, structure, size, etc. are not particularly limited as long as it is a conductive material, and can be appropriately selected from known materials. . Examples of the material include polyester silver paste. A method for forming the electrode, the land pattern, the wiring pattern and the like is not particularly limited and can be appropriately selected from methods generally used in the field. For example, a method such as a coating method or a printing method can be used. Can be mentioned.

There is no restriction | limiting in particular about the material of the said dot spacer, a shape, a structure, a magnitude | size, It can select suitably from well-known things. Examples of the material used for the dot spacer include an acrylic resin, and examples of the shape include a columnar shape, a hemispherical shape, and a rectangular parallelepiped shape. There is no restriction | limiting in particular as a formation method of the said dot spacer, It can select suitably from the methods generally used in the said field | area, For example, photolithography etc. are mentioned.

Among the other members, the electrodes are formed on the second conductive layer so that the electrodes are in contact with the first conductive layer of the first conductive member and the second conductive layer of the second conductive member. The

The resistance film type switch of the present invention thus obtained is excellent in transparency and conductivity of the conductive layer, excellent in conductivity when a predetermined portion is pressed, and excellent in flexibility. Furthermore, even if it is a case where it preserve | saves for a long time on the conditions of high temperature and high humidity, the raise of the surface resistivity of a conductive layer is suppressed effectively. Furthermore, it can be mass-produced into a desired shape at a low cost. Therefore, it can be suitably used in various fields. For example, it can be particularly suitably used for touch screens, membrane switches and the like.

Next, a capacitance switch using the transparent electrode substrate of the present invention will be described.
The capacitance switch of the present invention is a function of a switch unit for switching the switch ON and OFF by utilizing the phenomenon that the capacitance of the electrode changes when an object to be detected such as a finger approaches the electrode provided inside. It is one of switches used for display panels and key buttons for home appliances, audio equipment, automobile indicators, and the like. This capacitance switch is connected to a detection circuit for detecting a change in capacitance of the electrode, and the detection circuit is connected to a control means for controlling the operation of various devices. For example, there is a capacitance switch in which the conductive resin composition is applied on a transparent substrate, dried, and a thin film is formed as an electrode. For example, it is particularly preferably used for a touch screen, a membrane switch, and the like. it can.

Next, a keyboard having a resistance film type switch or a capacitance switch using the transparent electrode substrate of the present invention will be described.
The keyboard of the present invention is one of membrane switches that switches the switch on and off by pressing the key against the conductive layer. Specifically, it is used in household appliances such as PC keyboards, mobile phone switches, and rice cookers. The membrane switch etc. which are made are mentioned.

The transparent electrode substrate of the present invention can also be used for an electrode of a solar cell, an electronic device, a liquid crystal display, a plasma display, an organic EL display, and the like.

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

(Production Example 1)
In a 200 mL beaker, 120 g of methyl ethyl ketone (MEK), 8.0 g of methanol, 13.91 g of iron (III) p-toluenesulfonate (40% butanol solution), 1.3 g (3.3 mmol) of the above structural formula A heterocyclic ring-containing aromatic compound represented by (2-3) (hereinafter also referred to as a heterocyclic ring-containing aromatic compound (2-3)) was added.
Thereafter, the mixture was stirred for 2 hours in an ice bath (internal temperature of 5 to 7 ° C.), and disappearance of the heterocyclic ring-containing aromatic compound (2-3) was confirmed by HPLC. As a result, 110 g (solid content: 1.5%) of a p-toluenesulfonic acid-doped heterocyclic ring-containing aromatic compound (2-3) polymer MEK dispersion was obtained.

The heterocyclic ring-containing aromatic compound (2-3) polymer MEK dispersion does not dissolve in the GPC eluent, and the GPC measurement shows that the heterocyclic ring-containing aromatic compound (2-3) polymer MEK dispersion itself It was difficult to measure the molecular weight. However, in the polymerization reaction, the heterocycle-containing aromatic compound (2-3) has completely disappeared and the test results of the conductive resin composition shown below show that the heterocycle-containing aromatic compound (2- 3) From the result that the polymer MEK dispersion shows conductivity, it is clear that the heterocyclic ring-containing aromatic compound (2-3) polymer MEK dispersion is produced.

(Comparative Production Example 1)
In a 2000 mL three-necked flask, 1.53 g (10.9 mmol) of 3,4-ethylenedioxythiophene (EDOT), 410 g of ion-exchanged water, 253 g of 12.8 mass% polystyrene sulfonic acid aqueous solution, 16.5 g (0 .41 mmol) of 1% aqueous iron (III) sulfate solution was added. Next, 11.8 g (6.6 mmol) of 10.9 mass% peroxodisulfuric acid aqueous solution was added. Thereafter, the mixture was stirred at room temperature (about 25 ° C.) for 24 hours, disappearance of EDOT was confirmed by HPLC, and 650 g of a polystyrenesulfonic acid-doped poly (3,4-ethylenedioxythiophene) (PEDOT) aqueous dispersion ( Solid content 1.3%).

About this PEDOT aqueous dispersion, since polystyrene sulfonic acid is used as a dopant, it was difficult to measure the molecular weight of PEDOT itself by GPC measurement. However, in the above polymerization reaction, EDOT has completely disappeared, and the following results of the conductive resin composition of the present invention show that the water dispersion exhibits conductivity. It is clear that PEDOT is generated.

Table 1 below shows the formulation of Production Example 1 and Comparative Production Example 1.

Next, the conductive resin composition was manufactured by the following method (Example 1 and Comparative Example 1). Table 2 shows the composition of the conductive resin compositions produced in Examples and Comparative Examples.

Example 1
1.4 g of the heterocyclic ring-containing aromatic compound (2-3) polymer MEK dispersion obtained in Production Example 1, polyester binder (Aronix M6100, manufactured by Toagosei Co., Ltd.), dipentaerythritol hexaacrylate (Nippon Kayaku) KAYARAD DPHA), 0.02 g, alkylphenone photopolymerization initiator (Ciba Specialty Chemicals, Irgacure 184) 0.002 g, and methyl ethyl ketone 4.0 g were mixed to produce a conductive resin composition.

(Comparative Example 1)
Polystyrenesulfonic acid-doped poly (3,4-ethylenedioxythiophene) (PEDOT) aqueous dispersion 1.4 g obtained in Comparative Production Example 1, polyester binder (Aronix M6100, manufactured by Toagosei Co., Ltd.) 0.05 g, melamine series A conductive resin composition was produced by mixing 0.02 g of a crosslinking agent (Sumitomo Chemical Co., SumtexResin M-3), 1.0 g of ethanol, and 1.0 g of water.

The conductive resin compositions produced in Example 1 and Comparative Example 1 were evaluated as follows.
That is, the conductive resin composition was applied onto a blue glass substrate with a wire bar, dried, and cured by exposure to a high-pressure mercury lamp to form a transparent electrode substrate having a 0.8 μm thick conductive layer. And about this electroconductive layer, surface resistivity (SR), total light transmittance (Tt), haze value, adhesion (cross cut test), storage stability (SR increase rate, film appearance), Heat resistance, moist heat resistance, and conductivity were measured. The results are shown in Table 3.

Surface resistance (SR)
According to JIS K6911, it measured using Mitsubishi Chemical Corporation make Hirestar UP (MCP-HT450).

Total light transmittance (Tt) / haze value Measured according to JIS K 7150 using a haze computer HGM-2B manufactured by Suga Test Instruments Co., Ltd.

Adhesion (cross cut test)
It was carried out in accordance with a grid peel test of JIS K 5400.

Storage stability Storage stability was evaluated using the rate of increase in surface resistivity (SR) before and after a certain time and the appearance of the liquid as indicators.
That is, using the conductive resin composition immediately after preparation, a conductive layer was formed by the above method, the surface resistivity (SR) measured at that time was used as the initial surface resistivity, and the conductive resin composition was further heated to 40 ° C. After storing in a dark place for 1 week, a coating film was formed in the same manner, and the measured surface resistivity (SR) was taken as the post-test surface resistivity, and the post-test surface resistivity was divided by the initial surface resistivity. As a result, the rate of increase in surface resistivity (SR) was calculated.

Moreover, after leaving the conductive resin composition used for the measurement of the surface resistivity after the test for 1 hour, the liquid was visually observed and evaluated in three stages of 1 to 3 according to the following criteria.
1: No precipitate is observed.
2: A slight precipitate is observed.
3: A large amount of precipitate is observed.

Heat resistance test The conductive layer formed by the above method was placed in an oven adjusted to 95 ° C., and the rate of increase in surface resistivity after 100 hours was observed.

The conductive layer formed by the above method was placed in a thermo-hygrostat adjusted to 60 ° C. and a relative humidity of 93%, and the rate of increase in surface resistivity after 100 hours was observed.

Conductivity test Using the conductive layer formed by the above method and using a touch panel evaluation device (manufactured by Touch Panel Laboratories), the number of conductions when 100 points were touched with a load of 100 g was defined as the conductivity.

(Examples 2-3, Comparative Example 2)
The conductive resin compositions produced in Example 1 and Comparative Example 1 were evaluated as follows.
That is, the conductive resin composition was applied to a polyethylene terephthalate film Lumirror T60 (thickness: 188 μm) manufactured by Toray Industries, Inc. with a wire bar, dried, and cured by exposure to a high-pressure mercury lamp to form a conductive layer having a thickness of 0.8 μm. A transparent electrode substrate was prepared. And about this conductive layer, surface resistivity (SR), total light transmittance (Tt), and haze value were measured by said method, and the resistance between terminals (kohm) after patterning was measured by the following method. . The results are shown in Table 4.

Terminal resistance (kΩ) measurement test after patterning On the surface of the conductive layer of the transparent electrode substrate, a silver paste ECM-100 made by Taiyo Ink Co., Ltd. was applied in parallel near the both ends of the substrate. A metal terminal having a thickness of 50 μm was disposed. A conductive adhesive tape CU7636R manufactured by Sony Chemical Co., Ltd. was attached to only one end of each metal terminal in the same direction so as to protrude 5 cm toward the outer side of the substrate, and an extraction electrode was prepared for each. The tip of each test electrode of Sanwa Digital Multimeter PC5000 manufactured by Sanwa Electric Meter Co., Ltd. was strongly bonded to the end of each extraction electrode, and the resistance between terminals (kΩ) was measured.

The resolution was measured by the following method, and the pattern shape was observed. The results are shown in Table 4.

Resolution test A screen having a lattice shape or a line-and-space (LS) pattern having various line widths was placed on a blue plate glass, and a conductive resin composition was applied thereon with a wire bar. Thereafter, a film was formed by the wet etching or lift-off method to form a conductive layer.
The drawn pattern was observed with a microscope, and the smallest line width drawn without defects was taken as the resolution.

Pattern shape test Visually check the linearity and visibility of the transparent electrode substrate (blue plate glass substrate) used in the above resolution test. did.

From the above results, the transparent electrode substrates of Examples 2 to 3 are more transparent than the transparent electrode substrate of Comparative Example 2 containing another conductive polymer (poly (3,4-polyethylenedioxythiophene)). In addition, it has excellent conductivity, maintains adhesion, storage stability, and conductivity at a high level, and also has good heat resistance and moist heat resistance, and is obtained by patterning. It was revealed that the electrode can form a high-resolution pattern and has a good pattern shape.

The transparent electrode substrate of the present invention is an electronic paper, a solar cell, an electronic device, a resistive switch, a capacitive switch, and a touch screen, keyboard, liquid crystal display using the resistive switch or capacitive switch, It can be suitably used for the production of plasma displays and organic EL displays.

Claims (11)

A transparent electrode substrate in which a conductive layer is formed on a transparent substrate, wherein the conductive layer contains a heterocycle-containing aromatic compound represented by the following general formula (1) as a monomer (A) containing a heterocycle Aromatic polymer MN (1)
(In the formula, M represents a substituted or unsubstituted thiophene ring group, and N represents a substituted or unsubstituted pyrrole ring group. The ring represented by M and the ring represented by N are directly bonded to each other. ),
A transparent electrode substrate formed of a conductive resin composition containing The transparent electrode substrate according to claim 1, wherein the heterocyclic ring-containing aromatic compound is a heterocyclic ring-containing aromatic compound represented by the following general formula (2 ′).

(In the formula, R ³ and R ⁴ each independently represent a hydrogen atom or an organic group, but at least one represents an organic group. When both R ³ and R ⁴ represent an organic group, these May be bonded to each other to form a ring structure.) The transparent according to claim 1 or 2, wherein the heterocycle-containing aromatic compound is at least one of heterocycle-containing aromatic compounds represented by the following structural formulas (2-1) to (2-17). Electrode substrate.

The transparent electrode substrate according to claim 1, wherein the transparent substrate is a resin film. The transparent electrode substrate according to claim 1, wherein the conductive layer has a pattern. The transparent electrode substrate according to claim 5, wherein the pattern is formed by wet etching or a lift-off method. An electronic paper comprising the transparent electrode substrate according to claim 1. A first conductive member having a first conductive layer on a transparent substrate, a second conductive member having a second conductive layer on the substrate, and a resistive film switch having an insulating spacer, the first conductive member And / or the second conductive member is the transparent electrode substrate according to any one of claims 1 to 6, wherein the insulating spacer is provided on a part of the second conductive layer, and the first conductive layer and A resistive film type switch disposed so as to face the second conductive layer. Capacitance switch comprising a first conductive member having a first conductive layer on a transparent substrate and a second conductive member having a second conductive layer on the substrate, or a first conductive layer on both sides of the transparent substrate And a third conductive member having a second conductive layer, wherein the first conductive member, the second conductive member, or the third conductive member is claimed. The electrostatic capacity switch which is a transparent electrode substrate in any one of 1-6. A touch screen comprising the switch according to claim 8. A keyboard comprising the switch according to claim 8.