JP2009158410A - Conductive laminated body - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a conductive laminated body which is excellent in transparency and conductivity and is suitable for an adhesive property of layers and has high scratch-resistance and hardly deteriorate its conductivity in use under a condition that repetitive force is applied. <P>SOLUTION: The conductive laminated body has a transparent resin base A, an anchor coat layer B arranged on at least one face of the transparent resin base A, and a conductive layer C arranged on the surface of the anchor coat layer B. The anchor coat layer B is made of an anchor coat agent composition including a binder resin and a material having a cationic functional group, and the conductive layer C is made of a conductive resin composition including a π-conjugated conductive polymer and a complex of an acceptor as a dopant. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a conductive laminate. More specifically, the present invention relates to a conductive laminate that is excellent in scratch resistance and can be suitably used in fields such as a resistive film switch to which a repeated force is applied.

  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. As such an anchor coat layer, for example, Patent Document 1 discloses a conductive material 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. A laminate is described. 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 suitably used 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 conditions where a repeated force is applied, the conductive layer may be peeled off and the conductivity may be lowered. In order to improve the durability under a condition where a repetitive force is applied, it is necessary to improve not only the adhesion of the conductive layer but also the scratch resistance of the conductive layer.

  In order to improve the adhesion between the substrate and the conductive layer and the scratch resistance of the conductive layer, an anchor coat layer may be provided between these layers. However, for example, an anchor coat layer made of a polycondensate formed from alkoxysilanes as described in Patent Document 1 is configured so as to be suitable for the ITO sputtering process. When a conductive polymer is used, if it is used under the above severe conditions, the adhesion and scratch resistance become insufficient.

Further, it is conceivable to improve the durability of the coating film by utilizing the interaction between the coating film and the anchor coat layer. For example, Patent Document 4 proposes that an amphoteric compound is blended in the anchor coat layer to improve the scratch resistance when wet with a cationic resin as a coating film. However, sufficient scratch resistance has not been obtained for applications that require mechanical properties that are subject to repeated forces. Furthermore, the technology using the interaction between the anchor coat layer and the coating film is limited to the use of the coating film and the like, and at present, application to a conductive film such as a conductive polymer has been achieved. Not.
Japanese Patent Laid-Open No. 10-180928 JP 2002-60736 A JP 2006-28214 A JP 2004-181935 A

  The present invention has been made in order to solve the above-described conventional problems, and an object thereof is a laminate having a conductive layer containing a conductive polymer as a main component on a transparent resin substrate, and is excellent in transparency and conductivity. In addition, the present invention provides a conductive laminate having good adhesion between a conductive layer and a substrate, high scratch resistance, and low resistance to electrical conductivity even when used under conditions where repeated force is applied. 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 examined the durability of the conductive laminate film in which a conductive layer mainly composed of a conductive polymer is provided on a transparent resin substrate under a condition where a repeated force is applied. As a result, in the conductive laminate film known so far, the adhesion between the substrate and the conductive layer is sufficient, but the conductive performance deteriorates when used under a condition where a repeated force is applied. It turns out that this is a big problem.

  After further examination of this, the following matters were found. That is, by providing an anchor coat layer between the conductive layer and the transparent resin substrate, a good evaluation can be obtained in a test for evaluating temporary adhesion such as a tape peeling test. And / or the adhesion between the anchor coat layer and the transparent resin substrate was found to dramatically improve. However, under conditions where repeated force is applied, peeling between the conductive layer and the anchor coat layer and / or between the anchor coat layer and the transparent resin substrate may gradually occur, resulting in a decrease in conductive performance. It was found that the durability of the adhesion between each layer was not sufficient. It has also been found that, in the resistive film type switch, there is a portion that is repeatedly subjected to a load of force due to pressing, so that 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 comprises a transparent resin substrate (A), an anchor coat layer (B) provided on at least one surface of the transparent resin substrate (A), and a surface of the anchor coat layer (B). The conductive layer (C) is provided, the anchor coat layer (B) is an anchor coating agent composition containing a binder resin and a substance having a cationic functional group, and the conductive layer (C) And a conductive resin composition containing a complex of a π-conjugated conductive polymer and an acceptor as a dopant.

  In one embodiment, the π-conjugated conductive polymer is polyalkyldioxythiophene, and the acceptor is polystyrene sulfonic acid.

  According to an embodiment, the binder resin is a polyester resin or a polyurethane resin.

  In one embodiment, the substance having a cationic functional group is a compound having an amino group, a compound having a hydrazino group, or a derivative thereof.

  According to an embodiment, the compound having an amino group, the compound having a hydrazino group, or a derivative thereof has a weight average molecular weight of 100 to 50,000.

  According to one embodiment, the compound having an amino group, the compound having a hydrazino group, or a derivative thereof is carbohydrazide, succinic dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, dodecanedioic acid dihydrazide, isophthalic acid dihydrazide, It is at least one selected from the group consisting of hydrazino isocyanurate, polyallylamine, diallylamine acetate / sulfur dioxide copolymer, and acrylamide / diallyldimethylammonium chloride copolymer.

  The present invention also provides a method for producing a conductive laminate, which comprises applying an anchor coating agent composition paint containing a binder resin and a substance having a cationic functional group onto the transparent resin substrate (A). And drying to form an anchor coat layer (B), a conductive resin composition paint containing a complex of a π-conjugated conductive polymer and an acceptor as a dopant is applied on the anchor coat layer (B). And a step of forming the conductive layer (C) by drying.

  The resistance film type switch film of the present invention comprises a conductive laminate obtained by the above method.

  In the conductive laminate of the present invention, an anchor coat layer is formed between a transparent resin substrate and a conductive layer mainly composed of a complex of a π-conjugated conductive polymer and an acceptor as a dopant. Since this anchor coat layer contains a substance having a cationic functional group that attracts the acceptor in the composite by electrostatic attraction, and a binder resin, it is static between the conductive layer and the anchor coat layer. Electrical interaction (attraction) occurs, and the adhesion between the conductive layer and the anchor coat layer is excellent. Such a strong adhesion between the conductive layer and the anchor coat layer provides not only good results in tests for evaluating temporary adhesion such as a tape peeling test, but also a condition under which repeated force is applied. Even under the condition (for example, under the condition of an abrasion resistance test), peeling does not occur between the conductive layer and the anchor coat layer, 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.

(Material of conductive laminate)
(1) Transparent resin substrate (A)
The transparent resin substrate (A) that can be used in the present invention (hereinafter sometimes simply referred to as “substrate”) is not particularly limited as long as it is a substrate composed of a transparent resin. The shape, structure, size, thickness, etc. of the substrate 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 (A) is not particularly limited as long as it is a resin having a necessary strength and transparency, and can be appropriately selected according to 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.

  Suitable examples of the shape of the transparent resin substrate (A) include a sheet shape, a film shape, and a plate shape.

  The transparent resin substrate (A) may be formed of, for example, a single member or may be formed of two or more types of members. When formed with two or more kinds of 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) Anchor coat layer (B)
The anchor coat layer (B) contained in the laminate of the present invention is an anchor coat agent composition containing a binder resin and a substance having a cationic functional group, and may contain a filler, other components, etc., if necessary. Become. In the present specification, the anchor coat layer (B) is obtained by applying an anchor coat agent composition paint obtained by adding a solvent to the anchor coat agent composition to the transparent resin substrate (A) and drying it.

(2.1) Binder resin The binder resin is not particularly limited and can be appropriately selected depending on the purpose. The binder resin contributes to improving the adhesion between the transparent resin substrate (A) and the anchor coat layer (B) and the film formability.

  The binder resin is preferably a water-soluble polymer or a water-dispersible polymer. That is, the polymer is preferably soluble or dispersible in water or water containing some organic solvent. Examples of such binder resins include acrylic resins, polyurethane resins, epoxy resins, polyester resins, phenol resins, melamine resins, fluorocarbon resins, polypropylene resins, and mixtures or copolymers thereof. Of these, polyester resins (water-soluble polyester resins, water-dispersible polyester resins) and polyurethane resins (water-soluble polyurethane resins, water-dispersible polyurethane resins) are preferably used. In the case of using a water-dispersible polymer, it is preferable to use a polymer having a particle size that is smaller than the desired thickness of the anchor coat layer and that does not easily aggregate in the bath. Usually, the particle size is preferably about 50 to 300 nm.

  Examples of the water-soluble or water-dispersible polyurethane resin include, but are not limited to, a reaction between a polyfunctional isocyanate and a hydroxyl group-containing compound. 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. Naruto. Examples of the hydroxyl group-containing compound include polyether polyol, polyester polyol, and polyacrylate polyol.

  Specific trade names of water-soluble or water-dispersible polyurethane resins include Superflex (registered trademark) 150, Superflex (registered trademark) 300, Superflex (registered trademark) 420 (above, Daiichi Kogyo Seiyaku Co., Ltd.) Nicazole (registered trademark) RX-7004 (manufactured by Nippon Carbide Industries Co., Ltd.), Evaphanol (registered trademark) HA-11, Evaphanol (registered trademark) HA-15 (manufactured by Nikka Chemical Co., Ltd.), Hydran (registered trademark) AP-20, Hydran (registered trademark) WLS-201, Hydran (registered trademark) WLS-221, Bondic 1230NE, Bondick 2210 (above, manufactured by Dainippon Ink and Chemicals, Inc.) and the like can be mentioned. However, it is not limited to these.

  The water-soluble or water-dispersible polyester resin can be obtained from, for example, the following polybasic acid and polyol, but is not limited thereto.

  Polybasic acids 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, copolymer polyesters using two or more of these polybasic acids are preferred. In addition, if it is a slight amount, unsaturated polybasic acids such as maleic acid and itaconic acid, and hydroxycarboxylic acids such as p-hydroxybenzoic acid may be contained.

  Examples of the polyol include ethylene glycol, 1,4-butanediol, diethylene glycol, dipropylene glycol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, xylylene glycol, and dimethylolpropane. Examples include poly (ethylene oxide) glycol, poly (tetramethylene oxide) glycol, and the like.

  Specific trade names of water-soluble or water-dispersible polyester resins include Vylonal (registered trademark) MD-1100, Vylonal (registered trademark) MD-1500, Vylonal (registered trademark) MD-1930 (above, Toyobo Co., Ltd.) Nichigo Polyester WR-901, Nichigo Polyester W-0005 (Nippon Synthetic Chemical Industry Co., Ltd.), Gabsen (registered trademark) ES-901A, Gabsen (registered trademark) ES-210, Gabsen (registered) (Trademark) SR-150 (manufactured by Nagase ChemteX Corporation), Pestyrene A-100, Pestyrene A-510 (manufactured by Takamatsu Yushi Co., Ltd.), and the like, are not limited thereto.

  The binder resin is usually contained in the anchor coating composition (anchor coat layer) in an amount of 30 to 99% by mass, preferably 50 to 90% by mass. When binder resin is less than 30 mass%, there exists a possibility that the adhesiveness of the laminated body obtained may fall, or electroconductivity may fall in the use in the conditions on which repeated force is loaded. The content of the binder resin is the amount of the resin when the binder resin is used alone, and the total amount of the resins when a plurality of binder resins are contained. The amount of the binder resin is a solid content conversion amount based on the mass of the entire material (anchor coat agent composition) constituting the anchor coat layer (B). The same applies to substances having a cationic functional group described later, other resins, fillers, and other components.

(2.2) Substance having a cationic functional group The substance having a cationic functional group is contained in the anchor coat layer (B) and contained in the conductive layer (C) as described above. It attracts by an electrostatic attractive force with the acceptor as a dopant present in the substrate. Therefore, strong adhesion between the anchor coat layer (B) and the conductive layer (C) is possible. Examples of such a substance having a cationic functional group include compounds having an amino group, an amide group, an imino group, an imide group, an amidino group, a hydrazino group (amine, amide, imine, imide, amidine, hydrazide, Piperidine, pyridine and the like) and derivatives thereof, pyrazine, pyrimidine, pyridazine and the like. These compounds and their derivatives may be polymers. Substances having a cationic functional group may be used alone or in combination of two or more.

  Among substances having a cationic functional group, compounds having an amino group, compounds having a hydrazino group (hydrazide), and derivatives thereof are preferably used.

  The compound having an amino group and its derivative are not particularly limited, and for example, any of primary amine, secondary amine, tertiary amine, and quaternary amine can be used. A compound having a water-soluble amino group is preferred, and specifically, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, propylamine, isopropylamine, dipropylamine, butylamine, isobutylamine, sec-butylamine, monoethanolamine , Diethanolamine, triethanolamine, triisopropanolamine, isopropanolamine, dimethylethanolamine, diethylethanolamine, N-butyldiethanolamine and the like.

  Compounds having an amide group and derivatives thereof include hexaneamide, octanediamide, cyclohexanecarboxamide, succinamide, benzenesulfonamide, methanesulfinamide, ethanesulfenamide, benzeneselenamide, oxamide, ethanediamide, N-methylacetamide, benzanilide Hexane anilide, cyclohexane carboxanilide, benzenesulfonanilide, 2,4′-dichloroacetanilide, oxanilide and the like.

  Examples of the compound having an imino group and derivatives thereof include hexane-1-imine, propan-2-imine, ethane-1,2-diimine, N-methylethaneimine, and methanediimine.

  Examples of the compound having an imide group and derivatives thereof include N-phenylphthalimide, cyclohex-3-ene-1,2-dicarboximide, and cyclohexane-1,2-dicarboximide.

  Examples of the compound having an amidino group and derivatives thereof include acetamidine and benzamidine.

  A compound having a hydrazino group (hydrazide) and a derivative thereof are water-soluble compounds. Specifically, acetohydrazide (acetic hydrazide), benzohydrazide (benzoic hydrazide), pentanohydrazide (pentanoic hydrazide), cyclohexane Carbohydrazide (cyclohexanecarboxylic acid hydrazide), benzenesulfonohydrazide (benzenesulfonic acid hydrazide), thiobenzohydrazide (benzenecarbothiohydrazide, benzenecarbothioic hydrazide), pentaneimide hydrazide (pentaneimide hydrazide, pentanohydrazide = imide) ), Carbohydrazide, succinic acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, dodecanedioic acid dihydrazide, isophthalic acid dihydrazide, hydrazinoy Cyanurate and the like. Carbohydrazide, succinic acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, dodecanedioic acid dihydrazide, isophthalic acid dihydrazide, or hydrazino isocyanurate is non-volatile at 100 ° C. and has a primary amino group, Preferably used.

  Examples of piperidine and its derivatives include methylpiperidine, dimethylpiperidine, 2-propylpiperidine, piperidinone, piperidin-2-one, piperidine-2,6-dione, (2-piperidyl) acetone and the like.

  Pyridine and its derivatives include pyridinyl, pyridinylidene, pyridinediyl, 1,2-dihydropyridin-2-one, 1,4-dihydropyridin-4-one, methylpyridine, dimethylpyridine, 4-ethyl-2-methylpyridine, 3 -Ethyl-4-methylpyridine, 2,4,6-trimethylpyridine, 3- (1-methylpyrrolidin-2-yl) pyridine, 1-methyl-5- (3-pyridyl) -2-pyrrolidone, 1,2 , 3,6-tetrahydro-2,3′-bipyridine, 3- (2-piperidyl) pyridine, 1-methyl-5- (3-pyridyl) -2-pyrrolidone, 3- (1-methylpyrrolidin-2-yl) ) Pyridine and the like.

  The substance having a cationic functional group may be a polymer as described above. For example, polyallylamine, diallylamine acetate / sulfur dioxide copolymer, and acrylamide / diallyldimethylammonium chloride copolymer are preferably used as the polymer having an amino group. From the viewpoint of compatibility with the binder resin, the molecular weight of the polymer having such a cationic functional group is preferably 100 to 50000, more preferably 100 to 20000 in terms of weight average molecular weight. The weight average molecular weight is a value measured by GPC method (molecular weight marker: polystyrene standard).

  In the present invention, for example, the anchor coat agent composition paint containing a binder resin and a substance having a cationic functional group is applied to the transparent resin substrate (A), and then dried to form the anchor coat layer (B). In the case of using a substance having a cationic functional group that is volatile at 100 ° C., it may volatilize depending on the drying temperature. Therefore, a substance having a non-volatile cationic functional group at 100 ° C. is preferably used. The purpose of the substance having a cationic functional group is to attract the acceptor existing in the composite in the upper conductive layer (C) by electrostatic attraction, and further to the upper part of the anchor coat layer (B). When a conductive resin composition coating is applied to the conductive layer, a drying process for forming the conductive layer (C) is performed, and the conductive layer is subjected to a morphological change advantageous for scratch resistance. For this reason, it is preferable to have a cationic property necessary for causing an electrostatic interaction with an acceptor (dopant), and in this respect, a primary amine is particularly preferable.

  The substance having a cationic functional group is usually contained in the anchor coating agent composition (anchor coating layer) in an amount of 1 to 70% by mass, preferably 5 to 60% by mass. When these substances are less than 1% by mass, the adhesion between the obtained anchor coat layer (B) and the conductive layer (C) is lowered and sufficient scratch resistance cannot be obtained. When it exceeds 70% by mass, the compatibility with the binder resin in the anchor coating composition paint is deteriorated.

(2.3) 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 composed 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 coating agent composition (anchor coat layer) at a ratio of 50% by mass or less.

  The anchor coat agent composition (anchor coat layer) may further contain other components such as a surfactant, an ultraviolet absorber, a preservative, and a pH adjuster, if 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 coating agent composition (anchor coat layer), they are usually contained at a ratio of 10% by mass or less.

(2.4) Anchor coat agent composition paint An anchor coat agent composition paint is obtained by mixing each material (anchor coat agent composition) forming the anchor coat layer (B) with a solvent. The anchor coat layer (B) of the conductive laminate of the present invention is formed using this anchor coat agent composition paint.

  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 material in the anchor coating composition paint is 40% by mass or less. The solid content concentration is preferably 0.1 to 40% 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 it exceeds 40% by mass, it is difficult to apply uniformly. The formed conductive resin composition layer may be non-uniform. Furthermore, the storage stability of the anchor coating composition paint may be inferior.

(3) Conductive layer (C)
The conductive layer (C) includes a composite of a π-conjugated conductive polymer that is a conductive polymer and an acceptor as a dopant, and if necessary, a binder resin, a conductivity improver, a crosslinking agent, and an improved coating property. It is formed with the conductive resin composition which may contain an agent, another component, etc. Specifically, a conductive material containing a binder resin, a conductivity improver, a crosslinking agent, a coating property improver, and other components, if necessary, in a complex of a π-conjugated conductive polymer and an acceptor as a dopant. It is formed by applying (applying) a conductive resin composition paint on the anchor coat layer and drying. In this specification, the conductive layer (C) is obtained by applying a conductive resin composition paint obtained by adding a solvent to the conductive resin composition to the anchor coat layer (B) and drying it.

(3.1) Composite The composite of the π-conjugated conductive polymer that is the conductive polymer and the acceptor as the dopant is a state in which the acceptor as the dopant is doped into the π-conjugated conductive polymer. Say.

  Examples of the π-conjugated conductive polymer include polythiazyl, polyacetylene, polydiacetylene, poly (p-phenylene), poly (p-phenylene sulfide), poly (p-phenylene vinylene), polyazulene, polypyrrole, polythiophene, polyalkylthiophene, poly Examples thereof include alkyldioxythiophene, polyisothianaphthene, polyaniline, derivatives thereof, and copolymers obtained by combining two or more thereof. In particular, from the viewpoint of excellent electrical conductivity, polypyrrole, polythiophene, polyalkylthiophene, polyalkyldioxythiophene, polyaniline, and derivatives thereof are more preferable, and polythiophene, polyalkylthiophene, and polyalkyldioxy are more preferable. Thiophene.

  The π-conjugated conductive polymer is classified into an organic solvent-soluble polymer (such as a water-soluble polymer) and an organic solvent-dispersible polymer (such as a water-dispersible polymer) depending on the compatibility with the organic solvent. A dispersible polymer, more preferably a water dispersible polymer.

Examples of the acceptor include halides such as Cl ₂ , Br ₂ , I ₂ , ICl, ICl ₃ , IBr ₃ and IF, PF ₅ , AsF ₅ , SbF ₅ , BF ₅ , BCl ₃ , BBr ₃ , SO _{3 and the} like. Lewis acids, HF, HCl, HNO ₃ , H ₂ SO ₄ , HClO ₄ , FSO ₃ H, CFSO ₃ H and other protonic acids, FeCl ₃ , FeOCl, TiCl ₄ , ZrCl ₄ , HfCl ₄ , NbF ₅ , NbF ₅ , Transition metal compounds such as NbCl ₅ , TaCl ₅ , MoF ₅ , MoCl ₅ , WF ₆ , UF ₆ , LnCl ₃ , Cl ⁻ , Br ⁻ , I ⁻ , ClO ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , BF ₄ ^- electrolyte anions such as, and polycarboxylic acids (polyacrylic acid, polymethacrylic acid, polymaleic acid Etc.), polysulfone acids (polystyrene sulfonic acid and polyvinyl sulfonic acid), but polyanion include such as but not limited to. Polycarboxylic acids and polysulfonic acids may be copolymers obtained from other polymerizable monomers (for example, acrylates, styrene, etc.).

  Among the acceptors, poly anions are particularly preferably used. The number average molecular weight of this 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 even more preferably 10,000 to 200,000. 000 range.

  A composite is obtained by appropriately combining the π-conjugated conductive polymer and the acceptor. Preferably, a combination of polythiophene, polyalkylthiophene, or polyalkyldioxythiophene as a π-conjugated conductive polymer and a polyanion as an acceptor, more preferably a polyalkyldioxythiophene as a π-conjugated conductive polymer And a combination of polystyrene sulfonic acid as an acceptor.

  The complex of the π-conjugated conductive polymer and the acceptor is, for example, 50 to 3,000 parts by weight, preferably 100 to 1,000 parts by weight with respect to 100 parts by weight of the π-conjugated conductive polymer. More preferably, it is obtained by combining at a ratio of 150 to 500 parts by mass. Specifically, it can be obtained by dispersing a π-conjugated conductive polymer in a solvent and dispersing the acceptor in the above ratio. As the solvent used, a solvent used in the conductive resin composition paint can be used. For example, the solvent used in the above-described anchor coat agent composition paint can be appropriately selected.

  The content of the composite in the conductive resin composition is not particularly limited. From the viewpoint of ensuring sufficient conductivity, the content is preferably 20 to 80% by mass, and more preferably 30 to 70% by mass. This content is based on the mass obtained by removing the mass of the conductivity improver and the solvent (water, organic solvent, etc.) from the mass of the entire conductive resin composition. The same applies to the contents of the binder resin, the crosslinking agent, and the coatability improver described later.

(3.2) Binder resin The binder resin can be contained in the conductive resin composition for the purpose of improving the film formability and thermal durability of the conductive layer. The binder resin is not particularly limited, and the same resin as the binder resin used for the anchor coating agent composition is used.

  The binder resin is usually contained in the conductive resin composition in an amount of 1 to 80% by mass, preferably 5 to 60% by mass, and more preferably 10 to 40% by mass. When content of binder resin exceeds 80 mass%, there exists a possibility of the electroconductivity fall by the shortage of a composite_body | complex (conductive component).

(3.4) Conductivity improver The conductivity improver is contained for the purpose of lowering the surface resistivity of the conductive layer (conductive film) formed using the conductive resin composition.

  The conductivity improver is not particularly limited and can be appropriately selected according to 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, diethylene glycol monoethyl Examples include ether. Among these, ethylene glycol, dimethyl sulfoxide, and N-methylformamide are preferably used. A conductivity improver may be used individually by 1 type, and may use 2 or more types together.

  The content of the conductivity improver in the conductive resin composition is not particularly limited and is appropriately set depending on the purpose. Preferably, the conductivity improver is usually contained in a proportion of 0.1 to 50 parts by mass, preferably 1 to 40 parts by mass with respect to 1 part by mass of the composite.

(3.5) Crosslinking agent The crosslinking agent is contained for the purpose of increasing the strength of the entire conductive layer (C) obtained by crosslinking the binder resin and the like contained in the conductive resin composition.

  A crosslinking agent in particular is not restrict | limited, According to the objective, it can select suitably. Examples include 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, and the like. Among these, a water-soluble acrylic monomer and a water-soluble melamine monomer are preferable. A crosslinking agent may be used individually by 1 type, and may use 2 or more types together.

  The content of the crosslinking agent in the conductive resin composition is not particularly limited and is appropriately set depending on the purpose. Preferably, the conductivity improver is usually contained in an amount of 1 to 60 parts by mass, preferably 3 to 40 parts by mass with respect to 1 part by mass of the composite.

(3.6) Coating property improver The coating property improving agent is used as an anchor coat layer when a conductive resin composition paint is formed by mixing each component of the conductive resin composition and a solvent (described later). (B) It has a function of facilitating application to the surface.

  The coatability improver is not particularly limited and can be appropriately selected depending on the purpose. 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 given. 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.

  The content of the coatability improver in the conductive resin composition is not particularly limited, and is appropriately set depending on the purpose. Preferably, the coating property improver is contained in the conductive resin composition in a proportion of 0.01% by mass to 10% by mass, preferably 0.1% by mass to 1% by mass.

(3.7) Filler and other components As the filler that can be contained in the conductive resin composition, for example, fillers used in the anchor coating agent composition can be used in addition to indium oxide, antimony oxide, and the like. When a filler is contained, it is usually contained in the conductive resin composition at a ratio of 50% by mass or less.

  Other components that can be contained in the conductive resin composition are not particularly limited, and general additives used in the field can be appropriately selected. 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.

(3.8) Conductive Resin Composition Paint A conductive resin composition paint is obtained by mixing each material forming the conductive resin composition and a solvent. Using this paint, the conductive layer (C) of the conductive laminate of the present invention is formed. A solvent in particular is not restrict | limited, The solvent used for the anchor coat agent composition coating material can be selected suitably. Water and ethanol are preferably used. 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 (B) 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 conductive resin composition paint is 20% by mass or less, preferably 0.1 to 10% by mass. When the solid content concentration is less than 0.1% by mass, the wettability to the anchor coat layer (B) may be insufficient. When it exceeds 20 mass%, it becomes difficult to apply uniformly and the external appearance of the conductive layer (C) formed may be inferior. Furthermore, the storage stability of the conductive resin composition paint may be inferior.

(Method for producing conductive laminate)
The method for producing a conductive laminate of the present invention includes, for example, applying (coating or coating) the above-mentioned anchor coating composition composition paint to at least one surface (surface) of the transparent resin substrate (A), and drying the anchor. A step of forming a coat layer (B), a step of applying the conductive resin composition (paint) on the surface of the anchor coat layer (B) and drying to form a conductive layer (C).

  In applying the anchor coating composition paint to the transparent resin substrate (A), physical treatment such as corona treatment, flame treatment, and plasma treatment is applied to the surface of the substrate (A) as a preliminary treatment for improving the coating property. May be.

  The method for applying the anchor coating composition paint is not particularly limited. For example, a coating method, a printing method, or a coating method usually used by those skilled in the art is used.

  Examples of the coating method or the coating method include a gravure coating method, a small diameter gravure coating method, a spin coating method, a die coating method, a roller coating method, a bar coating method, a dip coating method, a curtain coating method, a spray coating method, a doctor coating method, A kneader coat method is 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 agent composition paint applied to the surface of the transparent resin substrate (A) is then dried. The drying method is not particularly limited, and is performed by a method commonly used by those skilled in the art. For example, a hot air drying method, an infrared drying method, a vacuum drying method, a hot plate drying method, or the like is used. In particular, it is preferable to employ a hot air drying method and an infrared drying method. The drying temperature is not particularly limited, but is appropriately selected according to the heat resistance of the substrate (A). Usually, it is performed at a temperature of 80 ° C to 150 ° C. In this way, the anchor coat layer (B) is formed. The anchor coat layer (B) may be formed on the entire surface of the substrate (A) or may be partially (partially) formed.

  The thickness (after drying) of the anchor coat layer (B) is usually 0.003 to 0.10 μm, preferably 0.01 to 0.05 μm. When the thickness of the anchor coat layer (B) is less than 0.003 μm, the adhesion to the substrate (A) and the conductive layer (C) may be reduced. When it exceeds 0.10 μm, blocking may occur or the haze value may increase.

  Next, a conductive resin composition paint is applied on the surface of the anchor coat layer (B) formed on the transparent resin substrate (A) and dried.

  In applying the conductive resin composition (paint) to the anchor coat layer (B), the surface of the anchor coat layer (B) is subjected to corona treatment, flame treatment, plasma treatment, etc. as a preliminary treatment for improving coatability. Physical processing may be performed.

  The application method and the drying method of the conductive resin composition coating are not particularly limited. Any of the application methods (coating method, printing method, coating method) and drying method used in the anchor coating composition paint can be employed. In applying the conductive resin composition (paint), a combination of two or more methods may be used. In this way, the conductive layer (C) is formed. The conductive layer (C) may be formed on the entire surface of the anchor coat layer or may be partially (partially) formed.

  The thickness (after drying) of the conductive layer (C) is usually 0.01 to 10 μm, preferably 0.1 to 1 μm. When the thickness of the conductive layer (C) is less than 0.01 μm, sufficient conductivity may not be obtained, or the conductive performance may be uneven. When exceeding 10 micrometers, it may be inferior to adhesiveness with an anchor coat layer (B).

(Conductive laminate)
The conductive laminate of the present invention includes the transparent resin substrate (A), the anchor coat layer (B) provided on at least one surface of the transparent resin gas (A), and the anchor coat layer (B). The conductive layer (C) provided on the surface is included.

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

  From an optical viewpoint, it is preferable to form an anchor coat layer (B) and a conductive layer (C) excellent in transparency on the transparent resin substrate (A) to obtain a transparent conductive laminate. Therefore, it is possible to make a conductive laminate such as colored transparent, colorless translucent, colored translucent by appropriately selecting from the above materials. Further, depending on the purpose, it is possible to make the whole opaque. Alternatively, depending on the purpose, a hard coat layer, an antireflection layer, an antiglare layer, or the like can be formed on the surface of the substrate of the conductive laminate. In such a laminate, a transparent resin substrate (A) having a hard coat layer, an antireflection layer, an antiglare layer, etc. on one surface is used in advance, and an anchor coat layer (B) and a conductive layer ( C) and 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 can be measured based on, for example, JIS K6911, and can be easily measured using a commercially available surface resistivity meter.

  As described above, this conductive laminate includes a dopant (acceptor) present in the composite contained in the conductive layer (C) and a substance having a cationic functional group contained in the anchor coat layer (B). Since it attracts by electrostatic attraction, it is particularly excellent in adhesion between the conductive layer (C) and the anchor coat layer (B). Furthermore, it is excellent also in the adhesiveness between an anchor coat layer (B) and a transparent resin base | substrate (A). Therefore, the conductive layer and the anchor coat layer are not easily peeled even when used under conditions where a repeated force is applied.

  In the conductive laminate of the present invention, the anchor coat layer (B) also serves to separate and block the transparent resin substrate (A) and the conductive layer (C). Therefore, for example, when the obtained conductive laminate is used under high-temperature conditions, the monomer component remaining in the transparent resin substrate (A) or a decomposition product generated by decomposition of the transparent resin substrate (A) From being transferred to the conductive layer (C). Therefore, the monomer component or decomposition product of the substrate (A) is prevented from adversely affecting the conductivity in the conductive layer (C). For example, such an effect is remarkable when a substrate (A) made of polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyvinyl alcohol, cellulose acetate or the like, particularly a substrate (A) 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.

(Use of conductive laminate)
As described above, the conductive laminate of the present invention is excellent in transparency and conductivity, is excellent in adhesion of each layer in the laminate, and has conductivity even under conditions where a repeated force is applied. It decreases very little over time. Moreover, even if it is a case where it hold | maintains for a long time on the conditions of high temperature and high humidity, it is suppressed 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 is suitable for use in fields such as touch screens, capacitors, secondary batteries, conductive connection members, polymer semiconductor elements, antistatic films, displays, energy conversion elements, resists, e-paper, solar cells, etc. Can do. Among these, it is particularly preferably used for applications of resistive touch panels such as touch screens.

  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 polyethylene terephthalate resin film (Toler mirror T60: thickness 188 μm, manufactured by Toray Industries, Inc.) was used as the transparent resin substrate (A).

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

(1) Layer adhesion The layer adhesion was evaluated as follows according to the cross cut tape test method described in JIS K5400: the surface of the obtained conductive laminate was a polyethylene terephthalate resin as a substrate. 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. Δ: The conductive resin composition layer peeled slightly.
(Peeling piece was not recognized, but peeling was recognized along the cut)
X: Peeling of the conductive resin composition layer was conspicuous (number of peeled pieces: 1 or more)

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

(3) Scratch resistance (Increase rate of surface resistivity after scratch test)
The scratch resistance was evaluated as follows. A test piece having a length of 10 cm and a width of 5 cm was prepared, the initial surface resistivity of the test piece was measured at five points, and the average value was calculated (initial surface resistivity average value). Then, it set to the test piece stand of the Gakushin type dyeing friction fastness tester (made by Yasuda Seiki Seisakusyo Co., Ltd.). A horizontal test piece was used, the weight of the friction element was 200 g, and a white cotton cloth for friction was a Hakujuji gauze (manufactured by White Cross Co., Ltd.) cut to 8 cm in length and 8 cm in width. After 100 round-trip tests, the surface resistivity at 5 points in the test area was measured and the average value was calculated (post-test surface resistivity average value). The surface resistivity increase rate (scratch resistance increase rate) R (times) after the scratch test was calculated according to the following formula (1).

  A small increase rate R indicates that the scratch resistance is high, and a high increase rate R indicates that the scratch resistance is low.

(Example 1-1)
(1) Formation of anchor coat layer Evaphanol (registered trademark) HA-15 (polyurethane-based aqueous dispersion, polyurethane resin content 30%: manufactured by Nikka Chemical Co., Ltd.) is made to have a solid content of 10% with ion-exchanged water. Diluted. This aqueous dispersion was diluted to 1.0% using Solmix AP-7 (industrial modified alcohol: manufactured by Nippon Alcohol Sales Co., Ltd.). To this diluted solution, HCIC (hydrazinocarbonylethyl isocyanurate: manufactured by Nippon Finechem Co., Ltd.) was added at a ratio of 100 parts with respect to 100 parts in terms of the solid content of HA-15, and an anchor coating agent composition paint (a ') Was obtained. This anchor coat agent composition paint (a ′) is applied on the transparent resin substrate (A) 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 coat layer (a) on the substrate (A).

(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 (registered trademark) MD-1500 (polyester aqueous dispersion; polyester content 30% by mass; manufactured by Toyobo Co., Ltd.), 4.2 parts of melamine A system cross-linking agent (Sumitomo Chemical Co., Ltd .: 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 with a 400 mesh SUS sieve to obtain a conductive resin composition paint 1-1.

  This conductive resin composition paint is 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 electroconductive laminated body film which has the electroconductive layer which consists of an electroconductive resin composition was obtained.

  About this laminated body film, evaluation about layer adhesiveness, surface resistivity, and abrasion resistance was performed by said method. 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 1-2)
An anchor coat agent composition paint (b ′) was obtained in the same manner as in Example 1-1 except that 10 parts of HCIC was used instead of 100 parts of HCIC, and an anchor coat layer ( b) was formed. Furthermore, using the conductive resin composition paint 1-1 prepared in Example 1-1, a conductive laminate film was obtained in the same manner as in Example 1-1.

(Example 1-3)
An anchor coating agent composition paint (c ′) was prepared in the same manner as in Example 1-1 except that 100 parts of ADH (adipic acid dihydrazide: manufactured by Nippon Finechem Co., Ltd.) was used instead of 100 parts of HCIC. As a result, an anchor coat layer (c) was formed on the substrate (A). Furthermore, using the conductive resin composition paint 1-1 prepared in Example 1-1, a conductive laminate film was obtained in the same manner as in Example 1-1.

(Example 1-4)
An anchor coat agent composition paint (d ′) was obtained in the same manner as in Example 1-1 except that 10 parts of ADH was used instead of 100 parts of HCIC, and an anchor coat layer ( d) was formed. Furthermore, using the conductive resin composition paint 1-1 prepared in Example 1-1, a conductive laminate film was obtained in the same manner as in Example 1-1.

(Example 2-1)
Example 1-1 was used except that Bayronal (registered trademark) MD-1500 (polyester aqueous dispersion, polyester resin content 30%: manufactured by Toyobo Co., Ltd.) was used instead of Evaphanol (registered trademark) HA-15. In the same manner as described above, an anchor coat composition paint (e ′) was obtained, and an anchor coat layer (e) was formed on the substrate (A). Furthermore, using the conductive resin composition paint 1-1 prepared in Example 1-1, a conductive laminate film was obtained in the same manner as in Example 1-1.

(Example 2-2)
An anchor coating agent composition paint (f ′) was obtained in the same manner as in Example 2-1, except that 10 parts of HCIC was used instead of 100 parts of HCIC, and an anchor coat layer ( f) was formed. Furthermore, using the conductive resin composition paint 1-1 prepared in Example 1-1, a conductive laminate film was obtained in the same manner as in Example 1-1.

(Example 2-3)
An anchor coat agent composition paint (g ′) was obtained in the same manner as in Example 2-1, except that 100 parts of ADH was used instead of 100 parts of HCIC, and an anchor coat layer ( g) was formed. Furthermore, using the conductive resin composition paint 1-1 prepared in Example 1-1, a conductive laminate film was obtained in the same manner as in Example 1-1.

(Example 2-4)
An anchor coat agent composition paint (h ′) was obtained in the same manner as in Example 2-1, except that 10 parts of ADH was used instead of 100 parts of HCIC, and an anchor coat layer ( h) was formed. Furthermore, using the conductive resin composition paint 1-1 prepared in Example 1-1, a conductive laminate film was obtained in the same manner as in Example 1-1.

(Example 3)
An anchor coating agent composition paint (i ′) was prepared in the same manner as in Example 1-1 except that 10 parts of PAA-1 (polyallylamine: manufactured by Nitto Boseki Co., Ltd.) was used instead of 100 parts of HCIC. An anchor coat layer (i) was formed on the substrate (A). Furthermore, using the conductive resin composition paint 1-1 prepared in Example 1-1, a conductive laminate film was obtained in the same manner as in Example 1-1.

Example 4
An anchor was operated in the same manner as in Example 1-1 except that 10 parts of PAS-J-81L (acrylamide / diallyldimethylammonium chloride copolymer: Nitto Boseki Co., Ltd.) was used instead of 100 parts of HCIC. A coating composition (j ′) was obtained, and an anchor coat layer (j) was formed on the substrate (A). Furthermore, using the conductive resin composition paint 1-1 prepared in Example 1-1, a conductive laminate film was obtained in the same manner as in Example 1-1.

(Example 5)
An anchor coating agent was prepared in the same manner as in Example 1-1 except that 10 parts of PAS-92A (diallylamine acetate / sulfur dioxide copolymer: manufactured by Nitto Boseki Co., Ltd.) was used instead of 100 parts of HCIC. A composition paint (k ′) was obtained, and an anchor coat layer (k) was formed on the substrate (A). Furthermore, using the conductive resin composition paint 1-1 prepared in Example 1-1, a conductive laminate film was obtained in the same manner as in Example 1-1.

(Example 6-1)
10.4 parts (in terms of solid content) of an aqueous dispersion of a complex of poly (3,4-ethylenedioxythiophene) and polystyrenesulfonic acid, 48 parts of N-methylformamide, a small amount of surfactant, a small amount And 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 6-1. Next, using the substrate (A) on which the anchor coat layer (a) obtained in Example 1-1 was formed, the conductive resin composition paint 6-1 was applied on the anchor coat layer (a). The conductive laminated body film which has a conductive layer which consists of a conductive resin composition was obtained by drying and heating in 130 degreeC oven.

(Example 6-2)
Using the base (A) on which the anchor coat layer (b) obtained in Example 1-2 was formed, the conductive resin composition paint 6- prepared in Example 6-1 was formed on the anchor coat layer (b). 1 was applied, dried, and heated in an oven at 130 ° C. to obtain a conductive laminate film having a conductive layer made of a conductive resin composition.

(Example 6-3)
Using the substrate (A) on which the anchor coat layer (c) obtained in Example 1-3 was formed, the conductive resin composition paint 6- prepared in Example 6-1 was formed on the anchor coat layer (c). 1 was applied, dried, and heated in an oven at 130 ° C. to obtain a conductive laminate film having a conductive layer made of a conductive resin composition.

(Example 6-4)
Using the substrate (A) on which the anchor coat layer (d) obtained in Example 1-4 was formed, the conductive resin composition paint 6- prepared in Example 6-1 was formed on the anchor coat layer (d). 1 was applied, dried, and heated in an oven at 130 ° C. to obtain a conductive laminate film having a conductive layer made of a conductive resin composition.

(Example 7-1)
Using the substrate (A) on which the anchor coat layer (e) obtained in Example 2-1 was formed, the conductive resin composition paint 6- prepared in Example 6-1 was formed on the anchor coat layer (e). 1 was applied, dried, and heated in an oven at 130 ° C. to obtain a conductive laminate film having a conductive layer made of a conductive resin composition.

(Example 7-2)
Using the substrate (A) on which the anchor coat layer (f) obtained in Example 2-2 was formed, the conductive resin composition paint 6- prepared in Example 6-1 was formed on the anchor coat layer (f). 1 was applied, dried, and heated in an oven at 130 ° C. to obtain a conductive laminate film having a conductive layer made of a conductive resin composition.

(Example 7-3)
Using the base (A) on which the anchor coat layer (g) obtained in Example 2-3 was formed, the conductive resin composition paint 6- prepared in Example 6-1 was formed on the anchor coat layer (g). 1 was applied, dried, and heated in an oven at 130 ° C. to obtain a conductive laminate film having a conductive layer made of a conductive resin composition.

(Example 7-4)
Using the substrate (A) on which the anchor coat layer (h) obtained in Example 2-4 was formed, the conductive resin composition paint 6- prepared in Example 6-1 was formed on the anchor coat layer (h). 1 was applied, dried, and heated in an oven at 130 ° C. to obtain a conductive laminate film having a conductive layer made of a conductive resin composition.

(Comparative Example 1)
An anchor coat agent composition paint (l ′) containing 2.0% Evaphanol (registered trademark) HA-15 was obtained in the same manner as Example 1-1 except that HCIC was not used. An anchor coat layer (l) was formed on the substrate (A) using this anchor coat agent (l ′). Furthermore, using the conductive resin composition paint 1-1 prepared in Example 1-1, a conductive laminate film was obtained in the same manner as in Example 1-1.

(Comparative Example 2)
An anchor coat agent composition paint (m ′) containing 2.0% of Vylonal (registered trademark) MD-1500 was obtained in the same manner as in Example 2-1, except that HCIC was not used. Using this anchor coat agent (m ′), an anchor coat layer (m) was formed on the substrate (A). Furthermore, using the conductive resin composition paint 1-1 prepared in Example 1-1, a conductive laminate film was obtained in the same manner as in Example 1-1.

  In the conductive laminate of the present invention, the anchor coat layer (B) is blended with a substance having a cationic functional group, thereby electrostatically forming between the conductive layer (C) and the anchor coat layer (B). A strong attractive force was produced, and a strong adhesion could be obtained. Thereby, in the abrasion resistance test which is a durability test under a condition where a repeated force is applied, Examples 1-1 to 1-4, Examples 2-1 to 2-4, and Examples 3 to 5 are used. Compared with Comparative Examples 1 and 2, the scratch resistance was superior. Moreover, the result excellent in abrasion resistance was obtained also in Examples 6-1 to 6-4 and Examples 7-1 to 7-4 in which the conductive layer (C) does not contain a binder resin and a crosslinking agent. From this, the adhesion that can withstand the condition of applying a repeated force acting between the conductive layer (C) and the anchor coat layer (B) exists in the composite contained in the conductive layer (C). This is considered to be an interaction between the acceptor and the substance having a cationic functional group contained in the anchor coat layer (B). It turned out that the electroconductive laminated body of this invention is used suitably for the touch screen etc. which a repeated force is loaded.

  The conductive laminate of the present invention includes a touch screen, a capacitor, a secondary battery, a conductive connection member, a polymer semiconductor element, an antistatic film, a display, an energy conversion element, a resist, e-paper, a solar battery, and the like. It is suitably used in the field.

It is a schematic cross section which shows one aspect | mode of the electroconductive laminated body of this invention.

Explanation of symbols

1 Transparent resin substrate 2 Anchor coat layer 3 Conductive layer

Claims (8)

A transparent resin substrate (A), an anchor coat layer (B) provided on at least one surface of the transparent resin substrate (A), and a conductive layer (C) provided on the surface of the anchor coat layer (B) A conductive laminate having
The anchor coat layer (B) comprises an anchor coat agent composition containing a binder resin and a substance having a cationic functional group, and the conductive layer (C) comprises a π-conjugated conductive polymer and an acceptor as a dopant. The conductive laminated body which consists of a conductive resin composition containing a composite_body | complex with.   The conductive laminate according to claim 1, wherein the π-conjugated conductive polymer is polyalkyldioxythiophene, and the acceptor is polystyrene sulfonic acid.   The conductive laminate according to claim 1, wherein the binder resin is a polyester resin or a polyurethane resin.   4. The conductive laminate according to claim 1, wherein the substance having a cationic functional group is a compound having an amino group, a compound having a hydrazino group, or a derivative thereof. 5.   The conductive laminate according to claim 4, wherein the compound having an amino group, the compound having a hydrazino group, or a derivative thereof has a weight average molecular weight of 100 to 50,000.   The compound having an amino group, the compound having a hydrazino group, or a derivative thereof is carbohydrazide, succinic acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, dodecanedioic acid dihydrazide, isophthalic acid dihydrazide, hydrazino isocyanurate, polyallylamine The conductive laminate according to claim 4 or 5, which is at least one selected from the group consisting of: a diallylamine acetate / sulfur dioxide copolymer, and an acrylamide / diallyldimethylammonium chloride copolymer. A step of applying an anchor coat agent composition paint containing a binder resin and a substance having a cationic functional group onto the transparent resin substrate (A) and drying to form an anchor coat layer (B);
A step of applying a conductive resin composition paint containing a complex of a π-conjugated conductive polymer and an acceptor as a dopant onto the anchor coat layer (B) and drying to form a conductive layer (C) The manufacturing method of the electroconductive laminated body of any one of Claim 1 to 6 including these.   A resistive film switch film comprising a conductive laminate obtained by the method of claim 7.

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