JP2010167564A - Conductive multilayer body - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a conductive multilayer body which is excellent in transparency and electrical conductivity, having good adhesion between layers, and hardly deteriorates in conductive performance even it is used under severe conditions such as high temperature conditions. <P>SOLUTION: The conductive multilayer body comprises a transparent resin base 1, an anchor coat layer 2 formed on at least one side of the transparent resin base and a conductive resin composition layer formed on the surface of the anchor coat layer. The conductive resin composition layer 3 contains a composite body of a poly(3,4-dialkoxy thiophene) and a polyanion and at least one of polyurethane resins and polyester resins. The anchor coat layer 2 contains at least one of polyurethane resins and polyester resins. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a conductive laminate. More specifically, it has a transparent resin substrate, an anchor coat layer, and a conductive resin composition layer, and the conductive resin composition conducts a complex of poly (3,4-dialkoxythiophene) and a polyanion. The present invention relates to a conductive laminate that is contained as a property component and can be suitably used in various fields such as a resistive film switch such as a touch screen.

  Conventionally, a film having conductive performance is suitably used as a transparent electrode such as a liquid crystal display or a touch screen, an electron wave shielding material, or an antistatic film for a functional film such as a polarizing film. As such a film, a transparent film made of a polymer such as polyethylene terephthalate (PET) or triacetyl cellulose (TAC) is used as a base, and an inorganic metal oxide (for example, indium oxide and tin oxide) is formed on at least one surface thereof. A laminated film in which a conductive layer made of a mixed sintered body (ITO) is formed is widely used. A dry process or a wet process is used for forming the inorganic metal oxide layer.

  In the formation of a film having such an inorganic metal oxide layer, for example, an ITO film, various anchor coat layers are provided on the transparent resin substrate for the purpose of improving the adhesion between the substrate and the conductive layer, particularly in the wet process. There is a case. The anchor coat layer is also called an underlayer, an intermediate layer, a cushion layer, or the like. As such an anchor coat layer, an anchor coat layer formed of an alkoxysilane polycondensate is known. For example, Patent Document 1 describes a conductive laminate having an anchor coat layer made of a resin obtained by polycondensation of an alkoxysilane having an epoxy group, an alkoxysilane having an amino group or an imino group, or the like. Since the polycondensate formed from the alkoxysilanes has an organic part and an inorganic part in the molecule, both the base polymer and ITO have adhesion. Therefore, it is suitable as a material for the anchor coat layer.

  By the way, indium, which is a raw material of ITO, is a rare metal, and in recent years, the demand for the use of transparent electrodes has increased, so that the raw material price is currently rising. Accordingly, research on films having a conductive polymer layer as an alternative conductive layer has been conducted. Since a conductive film having such a conductive polymer film is more flexible than an ITO film, there is an advantage that it can be more suitably used for transparent electrodes such as a touch screen.

  For example, as a conductive coating agent for forming a conductive film, Patent Document 2 discloses an antistatic coating agent containing a complex of a polythiophene derivative and a polyanion, a water-soluble compound, and a self-emulsifying polyester resin. Is described. It is described that when this coating agent is applied (applied) to the surface of a plastic substrate, a coating film having excellent adhesion and durability, and good conductivity and transparency is formed. Further, Patent Document 3 describes a method for producing an aqueous dispersion of a complex of a polythiophene derivative and a polyanion with improved electrical conductivity. By using this, transparency and electrical conductivity are good. It is known that a smooth coating film is formed. However, when a conductive film obtained by applying such a conductive coating agent is used under severe conditions such as high temperature, high temperature and high humidity, the conductive thin film may peel off or the conductive performance will deteriorate. There is a case.

In order to improve the adhesion between the substrate and the conductive layer, an anchor coat layer may be provided between these layers. However, for example, even if an anchor coat layer made of a polycondensate formed from alkoxysilanes as described in Patent Document 1 is provided on the substrate surface, this layer is configured to be suitable for the ITO sputtering process. Therefore, when the conductive layer is not ITO but a conductive polymer, the adhesiveness becomes insufficient when used under such severe conditions.
Japanese Patent Laid-Open No. 10-180928 JP 2002-60736 A JP 2006-28214 A

  The present invention has been made to solve the above-described conventional problems, and an object of the present invention is to provide a conductive layer mainly composed of a conductive polymer such as a composite of a polythiophene derivative and a polyanion on a transparent resin substrate. A conductive laminate having excellent transparency and conductivity, good adhesion between a conductive layer and a substrate, and a conductive performance that is less likely to deteriorate even under high temperature conditions. There is. Another object of the present invention is to provide a conductive laminate having the above-mentioned excellent properties and suitable as a conductive film for resistance film type switches.

  The inventors applied a conductive laminate film including a conductive layer mainly composed of a conductive polymer, such as a composite of the above polythiophene derivative and a polyanion, to a high temperature condition, a high temperature / humidity condition, or a repeated force. The durability when used under harsh conditions, such as the conditions under which it is used, was examined. As a result, in the conductive laminate film known so far, in addition to the insufficient adhesion between the substrate and the conductive layer, the conductive performance when used under severe conditions such as high temperature conditions. It has been found that a major problem is a drop in

  After further examination of this, the following matters were found. That is, the raw material monomer can remain in the resin substrate, the resin substrate itself can be decomposed to form a low molecular decomposition product under high temperature conditions, and these low molecular decomposition products can be formed under high temperature conditions. It has been found that the raw material monomers migrate to the conductive layer, and as a result, the conductive performance of the conductive layer decreases. This tendency is particularly remarkable in the case of a polyethylene terephthalate (PET) substrate and a polyethylene terephthalate (PEN) substrate. In the resistance film type switch, it was also found that the part that repeatedly receives a load due to pressing becomes high temperature, and as a result, the above phenomenon occurs and the conductive performance deteriorates.

  As a result of further studies based on the above findings, the present inventors have completed the present invention.

  The conductive laminate of the present invention has a transparent resin substrate, an anchor coat layer provided on at least one surface of the transparent resin substrate, and a conductive resin composition layer provided on the surface of the anchor coat layer. The conductive resin composition layer includes a composite of poly (3,4-dialkoxythiophene) and a polyanion, and is formed of a conductive resin composition including at least one of a polyurethane resin and a polyester resin. The anchor coat layer contains at least one of a polyurethane resin and a polyester resin.

  According to an embodiment, the anchor coat layer is formed by applying an anchor coat agent containing at least one of the polyurethane resin and the polyester resin onto the transparent resin substrate, and drying. The conductive resin composition layer includes an aqueous dispersion of a complex of poly (3,4-dialkoxythiophene) and a polyanion, and includes at least one of a polyurethane resin and a polyester resin. An object paint is formed on the anchor coat layer and dried.

  According to an embodiment, the anchor coat layer includes at least a polyurethane resin.

  According to an embodiment, the conductive resin composition layer includes at least a polyurethane resin.

  According to an embodiment, the transparent resin substrate is mainly composed of polyethylene terephthalate or polyethylene naphthalate.

  According to one embodiment, the conductive laminate is a resistive film switch film.

  According to the present invention, in the conductive laminate in which the conductive resin composition layer mainly composed of a complex of poly (3,4-dialkoxythiophene) and polyanion is formed on the transparent resin substrate, An anchor coat layer is formed between the conductive layer and the substrate, and each of the anchor coat layer and the conductive layer contains a specific resin component. With such a configuration, the adhesion of the layer is excellent. Furthermore, even under high temperature conditions, it is possible to suppress degradation products that may be generated by thermal decomposition of the resin substrate itself, or low molecular components such as remaining monomers, to the conductive layer. As a result, even when used under harsh conditions such as high temperature conditions, layer peeling does not occur and the conductive performance is unlikely to deteriorate. Such a conductive laminate can be suitably used as a resistive film switch film or the like.

  Hereinafter, the material which comprises each layer which forms the electroconductive laminated body of this invention, and the electroconductive laminated body obtained using this are demonstrated one by one.

(1) Transparent resin substrate
The transparent resin substrate (hereinafter sometimes simply referred to as “substrate”) that can be used in the present invention is not particularly limited as long as it is a substrate composed of a transparent resin, and the type of resin and the shape of the substrate. The structure, size, thickness and the like can be appropriately selected according to the purpose. In the present specification, “transparent” includes colorless and transparent as well as colored and transparent, colorless and translucent, and colored and translucent.

  The material for the transparent resin substrate is not particularly limited as long as it is a resin having the necessary strength and transparency, and can be appropriately selected depending on the purpose. For example, the following resins can be used: polyethylene terephthalate resin, polybutylene terephthalate resin, polyethylene naphthalate resin, polyvinyl chloride resin, polyethersulfone resin, polycarbonate resin, polystyrene resin, polyimide resin, polyetherimide resin, Polyvinyl acetate resin, polyvinylidene chloride resin, polyvinylidene fluoride resin, polyvinyl alcohol resin, polyvinyl acetal resin, polyvinyl butyral resin, polyacrylonitrile resin, polyolefin resin, polystyrene resin, polyamide resin, polybutadiene resin, cellulose acetate, cellulose nitrate, acrylonitrile -Butadiene-styrene copolymer resin. These may be used individually by 1 type and may use 2 or more types together. Among these, polyethylene terephthalate resin (PET) and polyethylene naphthalate (PEN) are preferable in terms of excellent transparency and flexibility.

  As the shape of the transparent resin substrate, for example, a sheet shape, a film shape, a plate shape and the like are preferably exemplified.

  For example, the transparent resin substrate may be formed of a single member, or may be formed of two or more members. When formed with two or more members, a laminated structure or the like is preferable. For example, the laminated body which consists of two types of resin films, the laminated body of a metal film and a resin film, etc. are mentioned. One or more of the layers constituting such a laminate may be a layer having a predetermined function, such as a hard coat layer, an antireflection layer, or a glare prevention layer.

(2) Conductive resin composition layer The conductive resin composition layer (hereinafter sometimes referred to as a conductive layer) is a composite of poly (3,4-dialkoxythiophene), which is a conductive polymer, and a polyanion. And a conductive resin composition containing at least one of a polyurethane resin and a polyester resin and, if necessary, an organic compound, a conductivity improver, a crosslinking agent, a coating property improver, and other components. The Specifically, in addition to an aqueous dispersion of a complex of poly (3,4-dialkoxythiophene) and polyanion, at least one of a polyurethane resin and a polyester resin, and if necessary, an organic compound, a conductive material It is formed by applying (coating) a conductive resin composition paint containing a property improver, a crosslinking agent, a coatability improver, and other components onto an anchor coat layer described later and drying.

  Hereinafter, materials for forming the conductive resin composition layer will be sequentially described.

(2.1) Complex of poly (3,4-dialkoxythiophene) and polyanion The complex of poly (3,4-dialkoxythiophene) and polyanion is 3,4-dialkoxythiophene. Can be obtained by polymerizing with an oxidizing agent in the presence of a polyanion. The complex of poly (3,4-dialkoxythiophene) and polyanion is, for example, 3,4-dialkoxythiophene represented by the following formula (1):

(Wherein R ¹ and R ² are each independently hydrogen or an alkyl group having 1 to 4 carbon atoms, or together, they form an alkylene group having 1 to 4 carbon atoms, Optionally substituted) is obtained in the form of an aqueous dispersion by polymerization in an aqueous solvent using an oxidizing agent such as peroxodisulfuric acid in the presence of a polyanion.

In the 3,4-dialkoxythiophene, preferred examples of the alkyl group for R ¹ and R ² include a methyl group, an ethyl group, and an n-propyl group. Examples of the alkylene group formed by combining R ¹ and R ² include a 1,2-alkylene group, a 1,3-alkylene group, and the like, and preferably a methylene group, a 1,2-ethylene group, Examples include 1,3-propylene group. Of these, a 1,2-ethylene group is particularly preferred. Moreover, the C1-C4 alkylene group may be substituted, and a C1-C12 alkyl group, a phenyl group, etc. are mentioned as a substituent. Examples of the substituted alkylene group having 1 to 4 carbon atoms include 1,2-cyclohexylene group and 2,3-butylene group. A typical example of such an alkylene group is a 1,2-alkylene group substituted with an alkyl group having 1 to 12 carbon atoms formed by R ¹ and R ² together. It is derived from 1,2-dibromoalkanes obtained by brominating α-olefins such as ethene, propene, hexene, octene, decene, dodecene, styrene and the like.

  Examples of the polyanion used in the above method include polycarboxylic acids such as polyacrylic acid, polymethacrylic acid, and polymaleic acid; and polysulfonic acids such as polystyrene sulfonic acid and polyvinyl sulfonic acid. Of these, polystyrene sulfonic acid is particularly preferred. These carboxylic acids and sulfonic acids may also be copolymers of vinyl carboxylic acids or vinyl sulfonic acids and other polymerizable monomers (eg, acrylates, styrene, etc.). The number average molecular weight of the polyanion is preferably in the range of 1,000 to 2,000,000, more preferably in the range of 2,000 to 500,000, and most preferably from 10,000. It is in the range of 200,000. The amount of polyanion is preferably in the range of 50 to 3,000 parts by weight, more preferably in the range of 100 to 1,000 parts by weight, and most preferably 150 to 500 parts per 100 parts by weight of thiophene. It is the range of mass parts.

  The solvent used in the above method is an aqueous solvent, particularly preferably water. Alcohols such as methanol, ethanol, 2-propanol, and 1-propanol; water-soluble solvents such as acetone and acetonitrile may be added to water.

  Examples of the oxidizing agent for performing the polymerization reaction of 3,4-dialkoxythiophene include, but are not limited to, the following compounds: peroxodisulfuric acid, sodium peroxodisulfate, potassium peroxodisulfate, ammonium peroxodisulfate, Inorganic ferric oxide salt, organic ferric oxide salt, hydrogen peroxide, potassium permanganate, potassium dichromate, alkali perborate, copper salt, etc. Of these, peroxodisulfuric acid, sodium peroxodisulfate, potassium peroxodisulfate, and ammonium peroxodisulfate are most preferred. The amount of the oxidizing agent used is preferably in the range of 1 to 5 equivalents, more preferably in the range of 2 to 4 equivalents per mole of the thiophene.

  Poly (3,4-dialkoxythiophene) is generated by a polymerization reaction using the above materials. This poly (3,4-dialkoxythiophene) is considered to be in a state doped with a polyanion. In the present specification, this is referred to as “poly (3,4-dialkoxythiophene) and polyanion. “Composite” or simply “complex”.

  The complex of poly (3,4-dialkoxythiophene) and polyanion is described in detail in Patent Document 2, for example.

  The content of the composite in the conductive resin composition is not particularly limited, but is preferably 20 to 80% by mass, and more preferably 30 to 70% by mass in order to ensure sufficient conductivity. %. This content is an amount based on the mass of the entire composition constituting the conductive resin composition layer. However, the mass of the composition here does not include the mass of the conductivity improver and the solvent (water, organic solvent, etc.). The same applies to the contents of a polyester resin and a polyurethane resin, an organic compound, a cross-linking agent, and a coatability improver described later.

(2.2) Polyester resin and polyurethane resin The polyester resin contained in the conductive resin composition layer is not particularly limited, but is preferably a water-soluble polyester polymer or a water-dispersible polyester polymer. That is, the polyester is preferably soluble or dispersible in water or water containing some organic solvent.

  Such a polyester is formed from, for example, a polyester composed of the following polybasic acid and polyol, but is not particularly limited thereto.

  Polybasic acids that can form polyester resins include terephthalic acid, isophthalic acid, phthalic acid, phthalic anhydride, 2,6-naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, adipic acid, sebacic acid, trimellitic acid , Pyromellitic acid, dimer acid, 5-sodium sulfoisophthalic acid, and the like. Of these, a copolyester containing two or more of these acid components is preferred. In addition, if it is a slight amount, an unsaturated polybasic acid component such as maleic acid or itaconic acid or a hydroxycarboxylic acid such as p-hydroxybenzoic acid may be contained.

  Examples of polyols that can form a polyester resin include ethylene glycol, 1,4-butanediol, diethylene glycol, dipropylene glycol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, xylylene glycol, and dimethylolpropane. Can be mentioned. Poly (ethylene oxide) glycol, poly (tetramethylene oxide) glycol, and the like can also be used.

  Specific product names of such polyester resins include: Vylonal MD-1100, Vylonal MD-1500, Vylonal MD-1930 (above, manufactured by Toyobo), Nichigo Polyester WR-901, Nichigo Polyester W-0005 (above. , Manufactured by Nippon Synthetic Chemical Co., Ltd.), Gabsen ES-901A, Gabsen ES-210, Gabsen SR-150 (above, manufactured by Nagase ChemteX Corporation), Pestyrene A-100, Pestyrene A-510 (above, manufactured by Takamatsu Yushi) However, it is not limited to these.

  The polyurethane resin used in the present invention is not particularly limited, but is preferably a water-soluble polyurethane polymer or a water-dispersible polyurethane polymer. That is, the polyurethane is preferably soluble or dispersible in water or water containing some organic solvent.

  As such a polyurethane, for example, a polyurethane resin obtained by a reaction between a polyfunctional isocyanate and a hydroxyl group-containing compound can be used. Examples of the polyfunctional isocyanate include aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate and polymethylene polyphenylene polyisocyanate, and aliphatic polyisocyanates such as hexamethylene diisocyanate and xylylene diisocyanate. It is done. Examples of the hydroxyl group-containing compound include polyether polyol, polyester polyol, and polyacrylate polyol.

  Specific product names of such polyurethane resins include Superflex 150, Superflex 300, Superflex 420 (Daiichi Kogyo Seiyaku), Nikasol RX-7004 (Nippon Carbide Industries), Evaphanol HA -11, Evaphanol HA-15 (above, manufactured by Nikka Chemical), Hydran AP-20, Hydran WLS-201, Hydran WLS-221, Bondic 1230NE, Bondic 2210 (above, manufactured by Dainippon Ink and Chemicals, Inc.) For example, but not limited to.

  The polyester resin and / or polyurethane resin is usually contained in the conductive resin composition in a proportion of 1 to 80% by mass, preferably 5 to 60% by mass, more preferably 10 to 40% by mass. This amount is the amount of the resin when only one of the polyester resin and the polyurethane resin is contained, and is the total amount of those resins when both are contained.

  If the amount of these resins is too small, the resulting laminate may be peeled off or the conductivity may be lowered when used under severe conditions such as high temperature. On the other hand, if it is excessive, there is a risk of a decrease in conductivity due to a shortage of conductive components.

(2.3) Organic Compound The organic compound that can be contained in the conductive resin composition layer is an organic compound other than the polyester and polyurethane. The kind is not specifically limited, It selects suitably according to the objective. For example, the following compounds are preferably used: water-soluble acrylic monomers, water-soluble acrylic oligomers, water-soluble acrylic polymers, water-soluble acrylamide monomers, water-soluble acrylamide oligomers, water-soluble acrylamide polymers, water dispersibility. Acrylic monomers, water dispersible acrylic oligomers, water dispersible acrylic polymers, water dispersible acrylamide monomers, water dispersible acrylamide oligomers, water dispersible acrylamide polymers, and the like. These may be used individually by 1 type and may use 2 or more types together.

  When these organic compounds are contained, they are usually contained in the conductive resin composition in a proportion of 1 to 50% by mass, preferably 5 to 30% by mass.

(2.4) Conductivity improver The conductivity improver that can be contained in the conductive resin composition layer is not particularly limited and may be appropriately selected depending on the intended purpose. Use of a conductivity improver is advantageous in that the surface resistivity of the conductive film formed using the composition of the present invention can be further reduced.

  The type of the conductivity improver is not particularly limited and may be appropriately selected depending on the purpose. For example, ethylene glycol, diethylene glycol, propylene glycol, trimethylene glycol, 1,4-butanediol, 1,5- Pentanediol, 1,6-hexanediol, neopentyl glycol, catechol, cyclohexanediol, cyclohexanedimethanol, glycerin, dimethyl sulfoxide, N-methylformamide, N, N-dimethylformamide, isophorone, propylene carbonate, cyclohexanone, γ-butyrolactone And diethylene glycol monoethyl ether. Among these, ethylene glycol, dimethyl sulfoxide, N-methylformamide and the like are preferable. A conductivity improver may be used individually by 1 type, and may use 2 or more types together.

  There is no restriction | limiting in particular in content in the said conductive resin composition of an electroconductive improvement agent, According to the objective, it can select suitably. When a conductivity improver is contained, the amount of the complex of poly (3,4-dialkoxythiophene) and polyanion is usually 1 to 100 parts by mass, preferably 1 part by mass, preferably It is contained at a ratio of 20 to 60 parts by mass.

(2.5) Cross-linking agent The cross-linking agent has the effect of increasing the strength of the entire conductive resin composition layer by cross-linking the organic compound and the like in the conductive resin composition.

  There is no restriction | limiting in particular in the kind of such crosslinking agent, According to the objective, it can select suitably. For example, water-soluble acrylic monomers, water-soluble acrylic oligomers, water-soluble acrylic polymers, water-soluble melamine monomers, water-soluble melamine oligomers, water-soluble melamine polymers, water-soluble epoxy oligomers, water-soluble epoxy polymers, etc., among these, Water-soluble acrylic monomers and water-soluble melamine monomers are preferred. These may be used individually by 1 type and may use 2 or more types together.

  There is no restriction | limiting in particular in content in the said conductive resin composition of the said crosslinking agent, According to the objective, it can select suitably. When a crosslinking agent is contained, it is contained in the conductive resin composition in a proportion of 1% by mass to 60% by mass, preferably 3% by mass to 40% by mass.

(2.6) Applicability improver The applicability improver is applied to the surface of the substrate when each component of the composition is mixed with a solvent (described later) to form a conductive resin composition paint. It has a function to facilitate.

  There is no restriction | limiting in particular as a coating property improvement agent, According to the objective, it can select suitably. For example, water-soluble acrylic copolymer, silicon-modified water-soluble acrylic polymer, polyether-modified water-soluble dimethylsiloxane, fluorine-based modified polymer and the like can be mentioned, and among these, polyether-modified water-soluble dimethylsiloxane is preferable. A coatability improver may be used individually by 1 type, and may use 2 or more types together. When a coatability improver is contained, it is contained in the conductive resin composition layer in a proportion of 0.01% by mass to 10% by mass, and preferably 0.1% by mass to 1% by mass.

(2.7) Other components The other components that can be contained in the composition are not particularly limited, and can be appropriately selected from general additives used in this field. For example, ultraviolet absorbers, antioxidants, polymerization inhibitors, surface modifiers, defoaming agents, plasticizers, antibacterial agents, surfactants, metal fine particles, and the like can be mentioned. The said other component may be used individually by 1 type, and may use 2 or more types together.

(2.8) Conductive resin composition paint A conductive resin composition paint is obtained by mixing each material forming the conductive resin composition layer with a solvent. Using this paint, a conductive laminate is formed as described later.

  There is no restriction | limiting in particular in the kind of said solvent, According to the objective, it can select suitably. For example, water, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, acetone, methyl ethyl ketone, methyl butyl ketone, methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate, methyl propionate, acetonitrile, tetrahydrofuran, dioxane, etc. Among these, water and ethanol are preferable. A solvent may be used individually by 1 type and may use 2 or more types together.

  The amount of the solvent may be an amount that can be applied on the anchor coat layer described later by dissolving or uniformly dispersing the above-mentioned materials. Usually, the solvent is used in such an amount that the solid content concentration of the paint is 20% by mass or less. The solid content concentration is preferably 0.1 to 10% by mass. If the solid content concentration is less than 0.1% by mass, the wettability to the anchor coat layer may be insufficient. On the other hand, if the solid content concentration exceeds 20% by mass, it is difficult to apply uniformly, and the formed conductivity. The appearance of the resin composition layer may be inferior. Furthermore, the storage stability of the conductive resin composition paint may be inferior.

(3) Anchor coat layer The anchor coat layer contained in the laminate of the present invention contains at least one of a polyurethane resin and a polyester resin, and, if necessary, other resins, fillers, and other components. .

(3.1) Polyester resin and polyurethane resin The polyester resin is not particularly limited, but is preferably a water-soluble polyester polymer or a water-dispersible polyester polymer. That is, the polyester is preferably soluble or dispersible in water or water containing some organic solvent.

  As such a polyester resin, any of the polyester resins contained in the conductive resin composition layer can be used. The same type as the polyester resin contained in the conductive resin composition layer may be used, or a different type may be used. Preferably, a polyester resin having good adhesion is selected for both the transparent resin substrate and the conductive resin composition layer.

  The polyurethane resin is not particularly limited, but is preferably a water-soluble polyurethane polymer or a water-dispersible polyurethane polymer. That is, the polyurethane is preferably soluble or dispersible in water or water containing some organic solvent.

  As such a polyurethane resin, any polyurethane resin contained in the conductive resin composition layer can be used. The same type as the polyurethane resin contained in the conductive resin composition layer may be used, or a different type may be used. Preferably, a polyurethane resin having good adhesion is selected for both the transparent resin substrate and the conductive resin composition layer.

  The polyester resin and / or polyurethane resin is usually contained in the anchor coat layer in an amount of 5 to 100% by mass, preferably 50 to 90% by mass. This amount is the amount of the resin when only one of the polyester resin and the polyurethane resin is contained, and is the total amount of those resins when both are contained. The amount of these resins is a solid content conversion amount based on the mass of the entire material constituting the anchor coat layer. The same applies to other resins, fillers, and other components described below.

  If these resins are too small, delamination may occur or the conductivity may decrease when the resulting laminate is used under high temperature conditions.

(3.2) Other resins The resins that can be contained in addition to the polyester resin and polyurethane resin are not particularly limited, but acrylic resins and the like are preferably used. As the acrylic resin, acrylic homopolymers and copolymers are used. Monomers that can constitute these homopolymers and copolymers include the following compounds: alkyl acrylates, alkyl methacrylates (wherein the alkyl groups are methyl, ethyl, n-propyl, isopropyl, n- Butyl group, isobutyl group, t-butyl group, 2-ethylhexyl group, cyclohexyl group, etc.); hydroxy group-containing monomers such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate Epoxy group-containing monomers such as glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether; acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, styrene sulfonic acid and Monomers having a carboxyl group such as a salt (sodium salt, potassium salt, ammonium salt, tertiary amine salt, etc.) or salts thereof; acrylamide, methacrylamide, N-alkylacrylamide, N-alkylmethacrylamide, N, N-dialkyl Acrylamide, N, N-dialkylmethacrylamide (alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, 2-ethylhexyl, cyclohexyl, etc.) , Monomers having an amide group such as acryloylmorpholine, N-methylolacrylamide, N-methylolmethacrylamide, N-phenylacrylamide, N-phenylmethacrylamide; monomers of acid anhydrides such as maleic anhydride and itaconic anhydride Vinyl isocyanate, allyl isocyanate, styrene, vinyl methyl ether, vinyl ethyl ether, vinyl trialkoxysilane, alkyl maleic acid monoester, alkyl fumaric acid monoester, alkyl itaconic acid monoester, acrylonitrile, methacrylonitrile, vinylidene chloride, ethylene, Propylene, vinyl chloride, vinyl acetate, butadiene, etc.

  Specific examples of the acrylic resin include the following resins: polyethyl acrylate, polybutyl acrylate, polyethyl methacrylate, polybutyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, benzyl methacrylate, Aminoethyl acrylate, glycidyl acrylate, glycidyl methacrylate, etc.

  When the other resin is contained in the anchor coat layer, it is usually 80% by mass or less, preferably 0.1 to 80% by mass, particularly preferably 0% in the anchor coat layer. 0.1 to 20% by mass.

(3.3) Filler and other components Fillers that can be contained in the anchor coat layer include fine particles made of the following inorganic or organic materials: calcium carbonate, magnesium carbonate, calcium oxide, zinc oxide, magnesium oxide, oxidation Inorganic fine particles made of silicon, sodium silicate, aluminum hydroxide, iron oxide, zirconium oxide, barium sulfate, titanium oxide, tin oxide, antimony oxide, carbon black, molybdenum disulfide, acrylic cross-linked polymer, styrene cross-linked heavy Organic fine particles made of coalescence, silicone resin, fluorine resin, benzoguanamine resin, phenol resin, nylon resin, polyethylene wax, etc. Among these, it is preferable to use a water-insoluble solid substance whose specific gravity does not exceed 3 in order to prevent sedimentation in an aqueous dispersion.

  When the filler is contained, it is usually contained in the anchor coat layer at a ratio of 50% by mass or less.

  The anchor coat layer may further contain a surfactant, an ultraviolet absorber, a preservative, a pH adjuster and the like as necessary. These components may be used individually by 1 type, and may use 2 or more types together. When these components are contained in the anchor coat layer, they are usually contained in a proportion of 10% by mass or less.

(3.4) Anchor coat agent An anchor coat agent is obtained by mixing each material which forms the said anchor coat layer, and a solvent. Using this anchor coating agent, a conductive laminate is formed as described later.

  There is no restriction | limiting in particular in the kind of said solvent, According to the objective, it can select suitably. For example, water, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, acetone, methyl ethyl ketone, methyl butyl ketone, methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate, methyl propionate, acetonitrile, tetrahydrofuran, dioxane, etc. Is mentioned. In many cases, the polyester resin and polyurethane resin are commercially available in a state of being dispersed in water. In that case, water can be used as a solvent as it is. Of organic solvent can be added. As a solvent for diluting water, methanol, ethanol, and 2-propanol are preferable. A solvent may be used individually by 1 type and may use 2 or more types together.

  The amount of the solvent may be an amount that can be applied to the substrate surface by dissolving or uniformly dispersing the above-described materials. Usually, the solvent is used in such an amount that the solid content concentration of the paint in the anchor coating agent is 40% by mass or less. The solid content concentration is preferably 0.1 to 1% by mass. If the solid content concentration is less than 0.1% by mass, the wettability to the substrate surface may be insufficient. On the other hand, if the solid content concentration exceeds 40% by mass, it is difficult to apply uniformly. In some cases, the conductive resin composition layer is non-uniform. Furthermore, the storage stability of the anchor coat agent may be inferior.

(4) Conductive laminate The method for preparing the conductive laminate of the present invention is not particularly limited. Usually, as described below, the anchor coat layer is formed by applying the anchor coat agent to the surface of the transparent substrate (coating and coating) and drying. Next, the conductive resin composition paint is applied to the surface of the anchor coat layer and dried, whereby the conductive resin composition layer is formed and a conductive laminate is obtained.

(4.1) Formation of anchor coat layer When applying (coating) an anchor coat agent to a transparent resin substrate, as a pretreatment for improving the coating property, corona treatment, flame treatment, plasma treatment, etc. on the substrate surface The physical processing may be performed.

  The anchor coating agent is applied to the substrate surface by a method generally used in the field, such as a normal coating method or a printing method. Examples of methods for applying the anchor coating agent include gravure coating, small-diameter gravure coating, spin coating, die coating, roller coating, bar coating, dip coating, curtain coating, spray coating, and doctor coating. Method, kneader coat method, etc. are used. In particular, the gravure coating method and the small-diameter gravure coating method are preferable.

  Examples of the printing method include screen printing, spray printing, ink jet printing, letterpress printing, intaglio printing, and planographic printing.

  The anchor coat layer applied to the substrate surface by these methods is dried by a method generally used in the art. For example, drying is performed by a hot air drying method, an infrared drying method, a vacuum drying method, a hot plate drying method, or the like. In particular, it is preferable to employ a hot air drying method and an infrared drying method. Although there is no restriction | limiting in particular as drying temperature, It selects suitably according to the heat resistant grade of a base | substrate. Usually, a temperature of 80 ° C. to 150 ° C. is employed.

  The anchor coat layer may be formed on the entire surface of the substrate, or may be partially (partially) formed.

  The thickness of the anchor coat layer after drying is usually 0.003 to 0.10 μm, preferably 0.01 to 0.05 μm. If the thickness of the coating film is too thin, the adhesion to the substrate and the conductive resin composition layer is reduced. Conversely, if it is too thick, blocking may occur or the haze value may be increased.

(4.2) Formation of conductive resin composition layer A conductive resin composition layer is then formed on the surface of the anchor coat layer formed on the substrate.

  The conductive resin composition layer is usually formed by applying (coating) the conductive resin composition paint to the surface of the anchor coat layer. When forming a conductive resin composition layer by applying a conductive resin composition coating, as a pretreatment for improving the coating properties, the anchor coat layer surface is subjected to physical treatment such as corona treatment, flame treatment, plasma treatment, etc. It is also preferable to perform the treatment.

  As a method for applying the conductive resin composition paint, any of the same methods as those for applying the anchor coating agent, such as the coating method and the printing method described above, can be employed. Examples of the coating method and the printing method include the same methods as the coating method and the printing method that can be adopted in the formation of the anchor coat layer. In applying the conductive resin composition paint, two or more methods may be used in combination.

  The conductive resin composition layer may be formed on the entire surface of the anchor coat layer, or may be partially (partially) formed.

  The thickness of the conductive resin composition layer after drying is usually from 0.01 to 10 μm, preferably from 0.1 to 1 μm. If the thickness of the conductive resin composition layer is too thin, sufficient conductivity may not be obtained or the conductive performance may be uneven. On the other hand, if it is too thick, the adhesion with the anchor coat layer may be poor.

(4.3) Conductive Laminate In the conductive laminate of the present invention, the anchor coat layer is provided on at least one surface of the transparent resin substrate, and the conductive resin composition layer is formed on the surface of the anchor coat layer. Is provided.

  A schematic cross-sectional view of one example of the conductive laminate of the present invention is shown in FIG. This laminate has an anchor coat layer 2 on one surface of the transparent resin substrate 1, and a conductive resin composition layer 3 on the surface of the anchor coat layer 2. This conductive laminate can be prepared, for example, by sequentially forming an anchor coat layer and a conductive resin composition layer on the surface of the transparent resin substrate 1 as described above. The materials of the transparent resin substrate, the anchor coat layer, and the conductive resin composition layer are selected according to the purpose, and a conductive laminate having desired properties, shape, structure, and size is obtained.

  From an optical viewpoint, it is preferable to form an anchor coat layer and a conductive resin composition layer excellent in transparency on a transparent resin substrate to form a transparent conductive laminate. It is also possible to appropriately select a material of the substrate to be used to form a conductive laminate such as colored transparent, colorless translucent, colored translucent. Further, depending on the purpose, it is possible to make the whole opaque. Furthermore, depending on the purpose, a hard coat layer, an antireflection layer, an antiglare layer, etc. can be formed on the surface of the substrate of the conductive laminate. In such a laminate, a transparent resin substrate having a hard coat layer, an antireflection layer, an antiglare layer, etc. is formed on one surface in advance, and an anchor coat layer and a conductive resin composition layer are formed on the other surface. It can also be prepared.

The conductive laminate of the present invention obtained as described above has sufficient conductivity. Desired conductivity can be obtained by appropriately adjusting the components of the conductive resin composition used and adjusting the thickness of the conductive resin composition layer. Usually, the surface resistivity of the conductive laminate is 50Ω / □ to 5,000Ω / □, preferably 100Ω / □ to 2,000Ω / □. The surface resistivity is, for example, JIS
It can be measured according to K6911 or the like, and can also be easily measured using a commercially available surface resistivity meter.

  As described above, since this conductive laminate contains a polyester resin and / or a polyurethane resin in both the conductive resin composition layer and the anchor coat layer, the conductive laminate composition and the anchor coat layer Excellent adhesion, and excellent adhesion between the anchor coat layer and the resin substrate. Therefore, even if used under severe conditions, it does not peel easily.

  In the conductive laminate of the present invention, the anchor coat layer also plays a role of separating and blocking the substrate and the conductive resin composition layer. Therefore, for example, when the obtained conductive laminate is used under high temperature conditions, the monomer component remaining in the base resin or the decomposition product generated by decomposition of the base resin is transferred to the conductive resin composition. To be prevented. Therefore, these components prevent adverse effects on the conductivity in the conductive resin composition layer. For example, such an effect is remarkable when a substrate made of polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyvinyl alcohol, cellulose acetate or the like, particularly a substrate made of polyethylene terephthalate is used. Therefore, for example, in a later-described resistance film type switch using the conductive laminate, even when it is repeatedly used, the conductivity hardly decreases with time.

(4.4) Use of conductive laminate As described above, the conductive laminate of the present invention is excellent in transparency and conductivity, excellent in adhesion of each layer in the laminate, and high in high temperature. Even if it is a case where it hold | maintains for a long time on wet conditions, it can suppress effectively that surface resistivity becomes high. This conductive laminate can be mass-produced in a desired shape at low cost, and is excellent in flexibility. Therefore, it can be suitably used in various fields. For example, it can be suitably used in the fields of touch screens, capacitors, secondary batteries, conductive connection members, polymer semiconductor elements, antistatic films, displays, energy conversion elements, resists, and the like. Among these, the use of a resistive touch panel such as a touch screen is particularly preferable.

  The conductive resin composition itself used in the conductive laminate of the present invention can also be used as an antistatic material. This composition can be applied to the surface of a desired product to impart an antistatic function to the surface of the product without affecting the appearance.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated, this invention is not limited to a following example. In the following Examples and Comparative Examples, “parts” and “%” represent “parts by mass” and “mass%”, respectively, unless otherwise specified.

  In the following Examples and Comparative Examples, a 100 mm × 150 mm PET film (Toler mirror T60: thickness 188 μm, manufactured by Toray Industries, Inc.) was used as the transparent resin substrate.

  Various evaluations of the obtained conductive laminate were performed by the following methods.

(I) Layer adhesion The layer adhesion is evaluated as follows according to the cross-cut tape test method described in JIS K5400: the surface of the obtained conductive laminate is a base material, a polyethylene terephthalate resin Make a grid-like cut at 1.0 mm intervals with a cutter knife so as to penetrate to the film layer. A cellophane tape is bonded to the cut conductive laminate and peeled off. The result is evaluated based on the following evaluation criteria.

The conductive resin composition layer did not peel at all ○
The conductive resin composition layer was slightly peeled off (no peeling pieces were observed, but peeling was observed along the cuts)
Peeling of the conductive resin composition layer was conspicuous (number of peeled pieces: 1 or more) ×

(II) Surface resistivity The surface resistivity is measured using Loresta-GP (MCP-T600) manufactured by Mitsubishi Chemical Corporation according to the method of JIS K6911.

(III) Heat resistance (Increase rate of surface resistivity)
The increase in surface resistivity is calculated as follows. First, after measuring the initial surface resistivity of the conductive laminate, it is placed in an oven adjusted to 80 ° C. This is taken out after 240 hours and the surface resistivity is measured. The original surface resistivity was taken as 1, and the rate of increase (times) in surface resistivity was calculated.

Example 1
(1) Formation of Anchor Coat Layer Superflex 300 (polyurethane aqueous dispersion, polyurethane content 30% by mass: manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was diluted with ion exchange water to a solid content of 10%. Further, this aqueous dispersion was diluted to 0.1% using Solmix AP-7 (industrial modified alcohol: manufactured by Nippon Alcohol Sales) to obtain an anchor coating agent. This anchor coating agent is applied to a transparent resin base with a wire bar No. 4 (wet film thickness: 6 μm) was applied by a bar coating method and dried at 100 ° C. for 2 minutes to form an anchor coating layer on the substrate.

  The thickness of this anchor coat layer is shown by the thickness measured as follows. First, an anchor coating agent is placed on a glass substrate with a wire bar no. 4 (wet film thickness 6 μm) is applied by a bar coating method and dried at 100 ° C. for 2 minutes. The thickness of the obtained dry anchor coat layer is measured with a stylus type surface shape measuring instrument (DEKTAK8: manufactured by ULVAC), and this value is adopted. The same applies to the thickness of the anchor coat layer in Examples 2 to 4 described later and Comparative Examples 2 and 3.

(2) Preparation of electroconductive laminate Aqueous dispersion 10 of a composite of poly (3,4-ethylenedioxythiophene) and polystyrenesulfonic acid produced by a method according to Example 1.5 of Patent Document 3. 2.7 parts of Vylonal MD-1500 (polyester aqueous dispersion; polyester content: 30% by mass; manufactured by Toyobo Co., Ltd.), 4.2 parts of melamine crosslinking agent (Sumitomo Chemical) Product: Sumitex Resin M-3), 48 parts of N-methylformamide, a small amount of surfactant, a small amount of leveling agent, an appropriate amount of water, and denatured ethanol were added and stirred for 1 hour. This was filtered through a 400 mesh SUS sieve to obtain a conductive resin composition paint A.

  This conductive resin composition paint A was applied to the wire bar No. 1 on the anchor coat layer formed in the above item (1). 8 (wet film thickness 12 μm) was applied and dried by a bar coating method. Subsequently, this was heated for 15 minutes in 130 degreeC oven, and the laminated body film which has a conductive resin composition layer was obtained.

  About this laminated body film, evaluation about layer adhesiveness, surface resistivity, and heat resistance was performed by said method. Regarding the layer adhesion, first, an evaluation was performed immediately after preparation of the laminate film. Further, separately from this, the obtained laminated film was evaluated after being held in a constant temperature and humidity chamber having a temperature of 60 ° C. and a humidity of 93% for 240 hours (wet heat resistance test was performed). The results of the above tests are shown in Table 1.

  In each Example and Comparative Example described later, the obtained laminate film was subjected to the same evaluation, and the results are shown in Table 1.

(Example 2-1)
Nicazole RX-7004 (acrylic resin / polyurethane resin aqueous dispersion; solid content 35%; manufactured by Nippon Carbide) was diluted to 10% solid content using ion-exchanged water. Further, this aqueous dispersion was diluted to 0.1% using Solmix AP-7 to obtain an anchor coating agent. This anchor coating agent is applied to a transparent resin base with a wire bar No. 4 (wet film thickness: 6 μm) was applied by a bar coating method and dried at 100 ° C. for 2 minutes to form an anchor coating layer on the substrate.

  Next, a conductive resin composition coating A is applied onto this anchor coat layer in the same manner as in Example 1, dried, and heated in an oven at 130 ° C. to have a conductive resin composition layer. A body film was obtained.

(Example 2-2)
Nicazole RX-7004 is the same as Example 2-1 except that it is diluted with ion-exchanged water and then diluted to 0.5% with Solmix AP-7.

(Example 2-3)
Nicazole RX-7004 is the same as Example 2-1 except that it is diluted with ion-exchanged water and then diluted to 1.0% with Solmix AP-7.

(Example 3-1)
Evaphanol HA-15 (polyurethane aqueous dispersion; polyurethane content 30% by mass; manufactured by Nikka Chemical) was diluted to 10% solids using ion-exchanged water. Further, this aqueous dispersion was diluted to 0.5% using Solmix AP-7 to obtain an anchor coating agent. This anchor coating agent is applied to a transparent resin base with a wire bar No. 4 (wet film thickness: 6 μm) was applied by a bar coating method and dried at 100 ° C. for 2 minutes to form an anchor coating layer on the substrate.

  Next, the conductive resin composition paint A was applied onto the anchor coat layer in the same manner as in Example 1, dried, and heated in an oven at 130 ° C. to obtain a laminate film.

(Example 3-2)
In the same manner as in Example 3-1, an anchor coat layer was formed on the transparent resin substrate.

  Next, in the preparation process of the conductive resin composition paint A in Example 1, Evaphanol HA-15 (polyurethane aqueous dispersion; polyurethane content 30% by mass; manufactured by Nikka Chemical Co., Ltd.) was used instead of Vylonal MD-1500. Thus, a conductive resin composition paint B was obtained.

  On the anchor coat layer, this conductive resin composition paint B was applied to a wire bar No. 8 (wet film thickness 12 μm) was applied by a bar coating method. Subsequently, this was heated for 15 minutes in 130 degreeC oven, and the laminated body film was obtained.

(Example 4-1)
Byronal MD-1500 (polyester-based aqueous dispersion; polyester content 30% by mass; manufactured by Toyobo Co., Ltd.) was diluted to 10% solid content using ion-exchanged water. Furthermore, this aqueous dispersion was diluted to 0.5% using Solmix AP-7. This anchor coating agent is applied to a transparent resin base with a wire bar No. 4 (wet film thickness 6 μm) was applied by a bar coating method and dried at 120 ° C. for 2 minutes to form an anchor coating layer on the substrate.

  Next, a conductive resin composition coating A is applied onto this anchor coat layer in the same manner as in Example 1, dried, and heated in an oven at 130 ° C. to have a conductive resin composition layer. A body film was obtained.

(Example 4-2)
After diluting Bayronal MD-1500 using ion-exchanged water, it was diluted to 1.0% using Solmix AP-7, and Example 4-1 except that the drying temperature was 100 ° C. Similarly, an anchor coat layer was formed. Furthermore, the conductive resin composition layer was formed similarly to Example 4-1, and the laminated body film was obtained.

(Example 4-3)
An anchor coat layer was formed on the transparent resin substrate in the same manner as in Example 4-1, except that the drying temperature was 100 ° C.

  On the anchor coat layer, the same conductive resin composition paint B as that used in Example 3-2 was applied, dried, and heated in an oven at 130 ° C. A laminate film having a layer was obtained.

(Comparative Example 1)
A conductive resin composition layer was formed directly on the surface of the substrate without forming an anchor coat layer on the transparent resin substrate. Formation of the conductive resin composition layer was performed according to Example 1.

(Comparative Example 2)
Julimer SEK-301 (acrylic polymerization aqueous dispersion; acrylic resin content 40% by mass; manufactured by Nippon Pure Chemical) was diluted to 10% solids using ion-exchanged water. Further, this aqueous dispersion was diluted to 0.1% using Solmix AP-7 to obtain an anchor coating agent. This anchor coating agent is applied to a transparent resin base with a wire bar No. 4 (wet film thickness: 6 μm) was applied by a bar coating method and dried at 100 ° C. for 2 minutes to form an anchor coating layer on the substrate.

  Next, a conductive resin composition paint B was prepared in the same manner as in Example 3-2. This conductive resin composition paint B is coated on the anchor coat layer with a wire bar No. 8 (wet film thickness 12 μm) was applied by a bar coating method. Subsequently, this was heated for 15 minutes in 130 degreeC oven, and the laminated body film was obtained.

(Comparative Example 3)
As in Comparative Example 2, an anchor coat layer was formed on the transparent resin substrate.

  Next, in the preparation process of the conductive resin composition paint A in Example 1, instead of Vylonal MD-1500, Julimer SEK-301 (acrylic polymerization water dispersion; acrylic resin content 40% by mass; manufactured by Nippon Pure Chemical Co., Ltd.) ) To obtain a conductive resin composition paint C.

  On the anchor coat layer, this conductive resin composition paint C was applied to a wire bar No. 8 (wet film thickness 12 μm) was applied by a bar coating method. Subsequently, this was heated for 15 minutes in 130 degreeC oven, and the laminated body film was obtained.

  As is apparent from Table 1, in the conductive laminate (each example) of the present invention containing either a polyurethane resin or a polyester resin in both the anchor coat layer and the conductive resin composition layer, the adhesion of the layers Good properties. It is clear that sufficient adhesion is maintained even when this laminate is held at high temperature and high humidity. In comparison, the conductive laminate of Comparative Example 1 that does not have an anchor coat layer; the conductive laminate of Comparative Example 2 that does not include any of polyurethane resin and polyester resin in the anchor coat layer; and anchor coat In the conductive laminate of Comparative Example 3 in which neither the polyurethane resin nor the polyester resin is contained in both of the layer and the conductive resin composition layer, the adhesion of the layer is insufficient, and the high temperature / high humidity It can be seen that the adhesiveness is further reduced when stored in the container. About the layer adhesiveness of the electroconductive laminate of Comparative Example 1, although there is no problem as the adhesiveness in use under normal conditions, it is insufficient when used for a resistive film type touch panel film that repeatedly receives resistance. It is believed that there is.

  The laminates of the above examples have good heat resistance, and the rate of increase in surface resistivity is low even after heat treatment. In particular, in the conductive laminate of Example 3-2 containing a polyurethane resin in both the anchor coat layer and the conductive resin composition layer, the increase in surface resistivity after the heat treatment is suppressed to a low level. Compared with this, in each comparative example, the increase in the surface resistivity after the heat treatment is large.

  As described above, the conductive laminate of the present invention is excellent in transparency and conductivity, excellent in adhesion of each layer in the laminate, and maintained for a long time under high temperature and high humidity conditions. Also, it is possible to effectively suppress an increase in surface resistivity. Therefore, it can be widely used as a conductive laminate in various fields. For example, various types of resistive film switches such as touch screens, various conductive films, capacitors, secondary batteries, conductive connecting members, polymer semiconductor elements, antistatic films, displays, energy conversion elements, resists, etc. It can be preferably used. Especially, it can be used suitably as resistive film type switches, such as a touch screen.

It is a schematic cross section which shows the structure of the electroconductive laminated body of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Transparent resin base | substrate 2 Anchor coat layer 3 Conductive resin composition layer

Claims (6)

A conductive laminate having a transparent resin substrate, an anchor coat layer provided on at least one surface of the transparent resin substrate, and a conductive resin composition layer provided on the surface of the anchor coat layer,
The conductive resin composition layer comprises a conductive resin composition comprising a complex of poly (3,4-dialkoxythiophene) and a polyanion, and comprising at least one of a polyurethane resin and a polyester resin, And
The anchor coat layer includes at least one of a polyurethane resin and a polyester resin;
Conductive laminate.   The anchor coat layer is formed by applying an anchor coat agent containing at least one of the polyurethane resin and polyester resin onto the transparent resin substrate and drying, and the conductive resin composition layer A conductive resin composition paint comprising an aqueous dispersion of a composite of poly (3,4-dialkoxythiophene) and a polyanion, and containing at least one of a polyurethane resin and a polyester resin. The conductive laminate according to claim 1, which is formed by applying on a layer and drying.   The conductive laminate according to claim 1, wherein the anchor coat layer includes at least a polyurethane resin.   The conductive laminate according to claim 1, wherein the conductive resin composition layer contains at least a polyurethane resin.   The conductive laminate according to any one of claims 1 to 4, wherein the transparent resin substrate is mainly composed of polyethylene terephthalate or polyethylene naphthalate.   The electroconductive laminate according to any one of claims 1 to 5, which is a film for a resistance film type switch.

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