JP2017082187A - Coating composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coating composition excellent in printability for forming an over coat layer and a primer layer excellent in adhesion to a resin film, a transparent electrode and a connecting part, transparency, ultraviolet light resistance, sulfur resistance, heat resistance, water resistance, moisture heat resistance or the like.SOLUTION: There is provided a coating composition for an electrode structure of an electrostatic capacitance type switch, which contains (a) a thermoplastic resin with Tg of 30°C or more, (b) an ultraviolet absorber and (c) an organic solvent and can be applied by printing.SELECTED DRAWING: None

Description

The present invention relates to a coating composition for an electrode structure of a capacitive switch, an electrode structure of a capacitive switch obtained by using the coating composition, and a method for manufacturing the same.

Electrodes of capacitive switches such as touch switches are layered in order: a resin film as a base material, a transparent electrode formed on the resin film, and a connection part formed so as to be in contact with part of the transparent electrode Has a structured. In order to protect the surfaces of the resin film, the transparent electrode, and the connecting portion, an overcoat layer is formed so as to cover at least a part of the transparent electrode and the connecting portion. Moreover, in order to improve the adhesiveness of a resin film and a transparent electrode, a primer layer may be formed on a resin film. Such an overcoat layer or primer layer is required to be excellent in adhesion to a resin film, a transparent electrode and a connection part, transparency, ultraviolet resistance, sulfidation resistance, heat resistance, water resistance, moisture heat resistance, and the like. . Moreover, the composition (coating composition) for forming an overcoat layer or a primer layer is required to be excellent in printability.

Patent Document 1 discloses that a transparent conductor including a substrate and a conductive layer on the substrate including a plurality of metal nanowires further includes a protective film on the conductive layer. As a material for the protective film, a general thermoplastic resin such as polyester has been proposed. Patent Document 2 discloses an electrode structure including a film made of an insulating material, a transparent electrode made of a conductive polymer placed on the film, and a conductive paste printed so as to be in contact with the transparent electrode. It is disclosed that a protective member that covers a part of the transparent electrode and the conductive paste is provided, and that a transparent insulating sheet made of PET is used as the protective member.

However, since the protective film of Patent Document 1 is made of a general thermoplastic resin such as polyester, there is a problem that it is inferior in sulfidation resistance. Moreover, since the protective member of Patent Document 2 is a transparent insulating sheet, patterning by printing cannot be performed, and a dedicated thermocompression bonding apparatus is required when forming the protective member.

Special table 2009-505358 JP 2007-52975 A

The present invention is for forming an overcoat layer and a primer layer that are excellent in adhesion to a resin film, a transparent electrode and a connection portion, transparency, ultraviolet resistance, sulfidation resistance, heat resistance, water resistance, moisture heat resistance, etc. It aims at providing the coating composition which is excellent in printability.

As a result of intensive studies, the present inventors have improved the sulfur resistance by using a coating composition containing a thermoplastic resin having a specific Tg, and have improved adhesion, transparency, ultraviolet resistance, and sulfur resistance. The present inventors have found that an overcoat layer and a primer layer excellent in heat resistance, water resistance, wet heat resistance and the like can be formed, and that the coating composition is excellent in printability.

That is, the present invention
(A) a thermoplastic resin having a Tg of 30 ° C. or higher,
(B) an ultraviolet absorber, and
(C) The present invention relates to a coating composition for an electrode structure of a capacitive switch, which contains an organic solvent and can be applied by printing.

In the coating composition of the present invention, (a) the thermoplastic resin is preferably a polyester having a weight average molecular weight of 2,000 to 200,000 and an acid value of 50 mgKOH / g or less.

In the coating composition of the present invention, it is preferable that (b) the ultraviolet absorber is benzotriazole or triazine.

In the coating composition of the present invention, the water contact angle of the coating layer formed by printing is preferably 65 ° or less.

The coating composition of the present invention preferably further comprises (j) a hydrophilicity-imparting agent, and (j) the hydrophilicity-imparting agent comprises a polyether-modified urethane compound, a polyether-modified acrylate compound, and a polyether-modified compound. It is preferably at least one selected from the group consisting of silicone compounds.

In the coating composition of the present invention, (a) the water contact angle of the thermoplastic resin is preferably 65 ° or less.

The coating composition of the present invention preferably further comprises (d) an inorganic fine particle slip agent as a slip agent.

The present invention also provides
Resin film (A),
A transparent electrode (B) formed on the resin film (A) using (f) a conductive composition containing a conductive polymer;
A connection part (C) formed so as to be in contact with a part of the transparent electrode (B), and
Overcoat layer (D) formed using the coating composition of the present invention so as to cover at least a part of the transparent electrode (B) and the connecting portion (C)
It is related with the electrode structure of the electrostatic capacitance type switch characterized by comprising.

In the electrode structure of the present invention, the conductive composition preferably further includes (g) a thermoplastic resin having a Tg of 0 ° C. or higher.

In the electrode structure of the present invention, it is preferable that the resin film (A) contains at least one resin selected from the group consisting of a polyester resin, a polycarbonate resin, and an acrylic resin.

In the electrode structure of the present invention, (f) the conductive polymer is poly (3,4-disubstituted thiophene) or a complex of poly (3,4-disubstituted thiophene) and polyanion. preferable.

In the electrode structure of the present invention, the connecting portion (C) is preferably formed using at least one conductive paste selected from the group consisting of silver paste, copper paste, and carbon paste.

The electrode structure of the present invention preferably further comprises a primer layer (E) between the resin film (A) and the transparent electrode (B), and the primer layer (E) uses the coating composition of the present invention. It is preferable to be formed.

The present invention also provides
A method for manufacturing the electrode structure of the present invention, comprising:
The present invention relates to a method for producing an electrode structure comprising the following steps (2) to (4) (a method for producing an electrode structure of the first invention).
(2) A step of forming a transparent electrode (B) by printing a conductive composition containing a conductive polymer (f) on the resin film (A),
(3) a step of forming a connection part (C) by printing a conductive paste so as to be in contact with a part of the transparent electrode (B); and
(4) A step of forming the overcoat layer (D) by printing the coating composition of the present invention so as to cover at least a part of the transparent electrode (B) and the connecting portion (C).

The present invention also provides
A method for producing an electrode structure of the present invention comprising a primer layer (E),
The present invention relates to a method for producing an electrode structure comprising the following steps (1) to (4) (a method for producing an electrode structure of the second invention).
(1) A step of forming a primer layer (E) by printing on the resin film (A),
(2) On the primer layer (E), (f) a step of forming a transparent electrode (B) by printing a conductive composition containing a conductive polymer;
(3) a step of forming a connection part (C) by printing a conductive paste so as to be in contact with a part of the transparent electrode (B); and
(4) A step of forming the overcoat layer (D) by printing the coating composition of the present invention so as to cover at least a part of the transparent electrode (B) and the connecting portion (C).

In the second method for producing an electrode structure of the present invention, it is preferable to form the primer layer (E) using the coating composition of the present invention in the step (1).

The present invention also provides
(F) a conductive polymer, and
(G) A conductive composition for forming a transparent electrode (B) in the electrode structure of the present invention, which comprises a thermoplastic resin having a Tg of 0 ° C. or more and can be applied by printing. .

In the conductive composition of the present invention, the (g) thermoplastic resin is preferably a polyester having a weight average molecular weight of 2,000 to 200,000 and an acid value of 50 mgKOH / g or less.

In the conductive composition of the present invention, (f) the conductive polymer is poly (3,4-disubstituted thiophene) or a complex of poly (3,4-disubstituted thiophene) and a polyanion. It is preferable.

Since the coating composition of the present invention contains a thermoplastic resin having a specific Tg, the sulfidation resistance is improved, and adhesion, transparency, ultraviolet resistance, sulfidation resistance, heat resistance, water resistance, and heat and moisture resistance are improved. It is possible to form an overcoat layer and a primer layer that are excellent in the above, and excellent printability. Therefore, it can be suitably used for forming the overcoat layer and the primer layer in the electrode structure of the capacitive switch.

<< Coating composition >>
First, the coating composition of the present invention will be described in detail.
The coating composition of the present invention comprises:
(A) a thermoplastic resin having a Tg of 30 ° C. or higher,
(B) an ultraviolet absorber, and
(C) A coating composition for an electrode structure of a capacitive switch, which contains an organic solvent and can be applied by printing.
By using the coating composition of the present invention, an overcoat layer and a primer layer necessary for forming an electrode structure of a capacitive switch (hereinafter, the overcoat layer and the primer layer are collectively referred to as a coating layer). Can also be obtained).

<(A) Thermoplastic resin>
It is extremely important that the coating composition of the present invention contains (a) a thermoplastic resin having a Tg of 30 ° C. or higher (hereinafter, also simply referred to as “component (a)”). The sulfidation resistance of the resulting coating layer is improved.

The component (a) is not particularly limited as long as Tg is 30 ° C. or higher, and examples thereof include thermoplastic resins such as polyester, polyurethane, acrylic resin, and olefin resin. In these, polyester is preferable from a viewpoint of adhesiveness and transparency. These (a) components may be used independently and may use 2 or more types together.

The Tg of the component (a) is not particularly limited as long as it is 30 ° C. or higher, but is preferably 35 ° C. or higher, and more preferably 40 ° C. or higher. When Tg is less than 30 ° C., the sulfidation resistance may deteriorate. Although the upper limit of Tg is not specifically limited, For example, it is 110 degreeC. If it exceeds 110 ° C., the flexibility is lost, and defects such as cracks may occur.

Although the weight average molecular weight of (a) component is not specifically limited, It is preferable that it is 2,000-200,000, and it is more preferable that it is 2,500-100,000. If the weight average molecular weight is less than 2,000, bleeding may occur after the coating layer is formed, and if it exceeds 200,000, stringing is likely to occur and printability may be deteriorated.

Although the acid value of (a) component is not specifically limited, It is preferable that it is 50 mgKOH / g or less, and it is more preferable that it is 30 mgKOH / g or less. When the acid value exceeds 50 mgKOH / g, stringing is likely to occur and printability may be deteriorated. Although the minimum of an acid value is not specifically limited, For example, it is 0.1 mgKOH / g.

Although the water contact angle of (a) component is not specifically limited, It is preferable that it is 65 degrees or less, and it is more preferable that it is 60 degrees or less. When the water contact angle of the component (a) is 65 ° or less, the water contact angle of the coating layer formed by printing can be 65 ° or less. On the other hand, when the water contact angle of the component (a) exceeds 65 °, the printability of the conductive composition on the coating layer may be deteriorated.

The content of component (a) (solid content of component (a) contained) is not particularly limited, but is preferably 10 to 70% by weight in the coating composition of the present invention, and is 20 to 60% by weight. It is more preferable that When the content is less than 10% by weight, the viscosity is low and the printability is deteriorated, or even if printing is possible, the film resistance of the coating layer may be insufficient. When the content exceeds 70% by weight, Viscosity may increase and printability may deteriorate.

<(B) UV absorber>
(B) Although it does not specifically limit as a ultraviolet absorber (henceforth only (b) component), For example, a benzotriazole, a triazine, a benzophenone etc. are mentioned. Among these, benzotriazole and triazine are preferable because they are difficult to bleed out and have excellent ultraviolet resistance. These (b) components may be used independently and may use 2 or more types together.

Although content of (b) component is not specifically limited, It is preferable that it is 0.1-20 weight% in the coating composition of this invention, and it is more preferable that it is 1-10 weight%. When the content is less than 0.1% by weight, the UV resistance may be insufficient. When the content exceeds 20% by weight, bleeding may occur after the coating layer is formed.

<(C) Organic solvent>
(C) Although it does not specifically limit as an organic solvent (henceforth only (c) component), For example, alcohols, such as methanol, ethanol, 2-propanol, 1-propanol, glycerol; Ethylene glycol, diethylene glycol, triglyceride Ethylene glycols such as ethylene glycol and tetraethylene glycol; glycol ethers such as ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, ethylene glycol diethyl ether and diethylene glycol dimethyl ether; ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether Glycol ether acetates such as acetate; propylene glycol Propylene glycols such as dipropylene glycol and tripropylene glycol; ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether , Propylene glycol ethers such as propylene glycol diethyl ether and dipropylene glycol diethyl ether; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate Propylene glycol ether acetates such as methyl acetate; methyl ethyl ketone, methyl isobutyl ketone, isophorone, cyclohexanone, propylene carbonate, γ-butyrolactone, β-butyrolactone, 1,3-dimethyl-2-imidazolidinone, diacetone alcohol, acetone, etc. Ketones; hydrocarbons such as toluene, xylene (o-, m-, or p-xylene), benzene, hexane, heptane; esters such as ethyl acetate and butyl acetate; chloromethane (methyl chloride), dichloromethane (salt) Methylene), trichloromethane (chloroform), halogens such as tetrachloromethane (carbon tetrachloride); tetrahydrofuran; N-methylpyrrolidone; acetonitrile and the like. Among these, from the viewpoint of drying on the printing plate, the boiling points of methyl isobutyl ketone, isophorone, cyclohexanone, propylene carbonate, γ-butyrolactone, 1,3-dimethyl-2-imidazolidinone, diacetone alcohol, etc. Is preferably a ketone having a temperature of 100 ° C. or higher. These (c) components may be used independently and may use 2 or more types together.

Although content of (c) component is not specifically limited, It is preferable that it is 1 to 60 weight% in the coating composition of this invention, and it is more preferable that it is 2 to 40 weight%. If the content is less than 1% by weight, the viscosity of the coating composition may increase and printability may deteriorate, and if it exceeds 60% by weight, the viscosity of the coating composition may decrease and printability may deteriorate. is there.

<Optional component>
The coating composition of the present invention may optionally contain other components in addition to the components (a) to (c). Other components include, but are not limited to, (d) slip agent, (e) surfactant, antifoaming agent, adhesion improver, cross-linking agent, thermosetting resin, photocurable resin, (j) hydrophilic And a property-imparting agent.

When the coating composition of the present invention is used for forming the overcoat layer (D), the coating composition of the present invention may contain (d) a slip agent. (D) The slip agent (hereinafter also simply referred to as component (d)) is not particularly limited, and examples thereof include inorganic fine particle slip agents, silicon slip agents, and fluorine slip agents. In these, since an antiblocking property is favorable, an inorganic fine particle type slip agent is preferable. These (d) components may be used independently and may use 2 or more types together.

The inorganic fine particle slip agent is not particularly limited, and examples thereof include silica fine particles, alumina fine particles, titanium oxide fine particles, and zirconia oxide fine particles. Among these, silica fine particles and alumina fine particles are preferable from the viewpoints of transparency and dispersibility. These inorganic fine particle slip agents may be used alone or in combination of two or more.

Although it does not specifically limit as a silicon-type slip agent, For example, polyether modified polydimethylsiloxane, polyester modified polydimethylsiloxane, etc. are mentioned. These silicone slip agents may be used alone or in combination of two or more.

Although it does not specifically limit as a fluorine-type slip agent, For example, a perfluoroalkyl ethylene oxide adduct etc. are mentioned. These fluorine-based slip agents may be used alone or in combination of two or more.

When the coating composition of the present invention contains the component (d), the content is not particularly limited, but is preferably 0.01 to 10% by weight in the coating composition of the present invention, 0.05 to More preferably, it is 5% by weight. When the content is less than 0.01% by weight, the anti-blocking property may be deteriorated, and when it exceeds 10% by weight, the transparency may be deteriorated.

(E) Surfactant (hereinafter, also simply referred to as component (e)) is not particularly limited and a known surfactant can be used. From the viewpoint of surface tension reducing ability, a siloxane compound, At least one selected from the group consisting of fluorine compounds and acrylic compounds is preferred. These (e) components may be used independently and may use 2 or more types together.

The siloxane compound is not particularly limited. For example, polyether-modified polydimethylsiloxane, polyether-modified siloxane, polyetherester-modified hydroxyl group-containing polydimethylsiloxane, polyether-modified acrylic group-containing polydimethylsiloxane, polyester-modified acrylic group-containing Examples thereof include polydimethylsiloxane, perfluoropolydimethylsiloxane, perfluoropolyether-modified polydimethylsiloxane, and perfluoropolyester-modified polydimethylsiloxane. Of these, polyether-modified polydimethylsiloxane is preferred from the viewpoint of surface tension reducing ability. These siloxane compounds may be used alone or in combination of two or more.

Although it does not specifically limit as a fluorine-type compound, For example, perfluoroalkyl carboxylic acid, perfluoroalkyl polyoxyethylene ethanol, etc. are mentioned. These fluorine compounds may be used alone or in combination of two or more.

Although it does not specifically limit as an acryl-type compound, For example, an acryl-type copolymer etc. are mentioned. These acrylic compounds may be used alone or in combination of two or more.

When the coating composition of the present invention contains the component (e), the content is not particularly limited, but is preferably 0.01 to 10% by weight in the coating composition of the present invention, 0.05 to More preferably, it is 5% by weight. When the content is less than 0.01% by weight, the surface tension lowering ability may not be obtained, and when it exceeds 10% by weight, the dispersibility may be deteriorated.

By adding an antifoaming agent to the coating composition of the present invention, foaming and foaming of the coating composition can be prevented. Although it does not specifically limit as an antifoamer, For example, silicone resin, polydimethylsiloxane, silicone resin, etc. are mentioned. These may be used alone or in combination of two or more. When the coating composition of the present invention contains an antifoaming agent, the content is not particularly limited, but is preferably 0.005 to 20% by weight in the coating composition of the present invention, and 0.01 to 10 More preferably, it is% by weight.

The adhesion improver is not particularly limited, but for example, an imidazole adhesion improver, a thiazole adhesion improver, a triazole adhesion improver, a silane coupling agent, a titanium coupling agent, a zirconia coupling agent, An aluminum coupling agent etc. are mentioned. These may be used alone or in combination of two or more. When the coating composition of the present invention contains an adhesion improver, the content is not particularly limited, but is preferably 0.1 to 20% by weight in the coating composition of the present invention, 0.5 to More preferably, it is 10% by weight.

By mix | blending a crosslinking agent with the coating composition of this invention, (a) component can be bridge | crosslinked and the intensity | strength of the coating layer formed using a coating composition can further be improved. Although it does not specifically limit as a crosslinking agent, For example, crosslinking agents, such as a melamine type, a polycarbodiimide type, a polyoxazoline type, a polyepoxy type, a polyisocyanate type, a polyacrylate type, are mentioned. These crosslinking agents may be used independently and may use 2 or more types together. When the coating composition of the present invention contains a crosslinking agent, the content thereof is not particularly limited, but is preferably less than 70 parts by weight and more preferably less than 50 parts by weight with respect to 100 parts by weight of the solid content of the coating composition. preferable. When the content of the crosslinking agent is 70 parts by weight or more, the adhesion may be deteriorated.

Although it does not specifically limit as a thermosetting resin, For example, an isocyanate resin, a melamine resin, a silicate resin, an epoxy resin, a phenol resin etc. are mentioned. These thermosetting resins may be used alone or in combination of two or more.

The photocurable resin is not particularly limited as long as it can be crosslinked and cured by irradiation with ultraviolet light. For example, epoxy acrylate resin, urethane (meth) acrylate resin, bifunctional or higher polyester acrylate, polyether Examples include acrylate resins typified by acrylates and carboxyl-modified reactive polyacrylates, bifunctional or higher polybutadiene acrylates, silicon acrylates, aminoplast resin acrylates, and organic-inorganic hybrid resins. These photocurable resins may be used alone or in combination of two or more.

When the coating composition of the present invention is used for forming the primer layer (E), the coating composition of the present invention may contain (j) a hydrophilicity-imparting agent. (J) By containing a hydrophilicity imparting agent, the water contact angle of the primer layer formed by printing can be made 65 ° or less.

(J) The hydrophilicity-imparting agent (hereinafter also simply referred to as component (j)) is not particularly limited, and examples thereof include polyether-modified urethane compounds, polyether-modified acrylate compounds, and polyether-modified silicone compounds. Can be mentioned. These may be used alone or in combination of two or more. Among these, from the viewpoint of dispersibility and adhesion between the primer layer and the conductive composition, a group consisting of a polyether-modified urethane compound, a polyether-modified acrylate compound, and a polyether-modified silicone compound. It is preferable to use at least one selected from the above.

When the coating composition of this invention contains (j) component, the content is not specifically limited, but (a) It is 0.01-5.0 weight part with respect to 100 weight part of thermoplastic resins. Is more preferable, and it is more preferable that it is 0.05-3.0 weight part. When the content is less than 0.01 parts by weight, the water contact angle may not be lowered. When the content exceeds 5.0 parts by weight, the dispersibility is deteriorated, and the primer layer (E) and the conductive composition. Adhesion failure may occur.

The solid content concentration of the coating composition of the present invention is not particularly limited, but is preferably 10 to 70% by weight, and more preferably 20 to 60% by weight. If the solid content concentration is less than 10% by weight, the viscosity of the coating composition may be low and printability may be deteriorated. There is.

Although the viscosity of the coating composition of this invention is not specifically limited, It is preferable that it is 1-100 dPa * s, and it is more preferable that it is 5-50 dPa * s. When the viscosity is less than 1 dPa · s, the printability may deteriorate, and when it exceeds 100 dPa · s, the printability may deteriorate.

The surface tension of the coating composition of the present invention is not particularly limited, but is preferably 1 to 50 mN / m, and more preferably 10 to 30 mN / m. If the surface tension is less than 1 mN / m, bleeding may occur during printing, and if it exceeds 50 mN / m, repelling may occur during printing.

The coating composition of the present invention can be applied by printing. Here, the specific method of printing is not particularly limited, and examples thereof include offset printing such as screen printing, pad printing, and gravure offset printing.

<< Electrode structure >>
Next, the electrode structure of the present invention will be described in detail.
The electrode structure of the present invention includes a resin film (A),
A transparent electrode (B) formed on the resin film (A) using (f) a conductive composition containing a conductive polymer;
A connection part (C) formed so as to be in contact with a part of the transparent electrode (B), and
Overcoat layer (D) formed using the coating composition of the present invention so as to cover at least a part of the transparent electrode (B) and the connecting portion (C)
It is an electrode structure of the electrostatic capacitance type switch characterized by comprising.

<Resin film (A)>
The material of the resin film (A) is not particularly limited. Polyester resin such as polyethylene terephthalate (PET), polyethylene naphthalate, and modified polyester, polyethylene (PE) resin, polypropylene (PP) resin, polystyrene resin, cyclic olefin type Polyolefin resins such as resins, vinyl resins such as polyvinyl chloride and polyvinylidene chloride, polyether ether ketone (PEEK) resin, polysulfone (PSF) resin, polyether sulfone (PES) resin, polycarbonate (PC) resin, Polyamide resin, polyimide resin, acrylic resin, triacetyl cellulose (TAC) resin, etc. are mentioned. The resin film (A) preferably includes at least one resin selected from the group consisting of a polyester resin, a polycarbonate resin, and an acrylic resin from the viewpoint of adhesion, and particularly includes polyethylene terephthalate (PET). preferable.

Although the thickness of a resin film (A) is not specifically limited, It is preferable that it is 10-10000 micrometers, and it is more preferable that it is 25-5000 micrometers. When the thickness is less than 10 μm, the strength of the electrode structure may be insufficient, and when it exceeds 10,000 μm, the transparency may be insufficient. Moreover, the easily bonding layer etc. may be provided in the resin film (A).

<Transparent electrode (B)>
The transparent electrode (B) is formed on the resin film (A) using a conductive composition containing (f) a conductive polymer.

(F) A conductive polymer (hereinafter also simply referred to as component (f)) is blended in the conductive composition in order to impart conductivity to the transparent electrode (B). The component (f) is not particularly limited, and a conventionally known conductive polymer can be used. Specific examples thereof include polythiophene, polypyrrole, polyaniline, polyacetylene, polyphenylene vinylene, polynaphthalene, and derivatives thereof. It is done. These may be used alone or in combination of two or more. Among these, a conductive polymer including at least one thiophene ring in the molecule is preferable in that a molecule having high conductivity can be easily formed by including a thiophene ring in the molecule. The component (f) may form a complex with a dopant such as a polyanion.

Among the conductive polymers containing at least one thiophene ring in the molecule, poly (3,4-disubstituted thiophene) is more preferable because it is extremely excellent in conductivity and chemical stability. Further, when the conductive polymer is poly (3,4-disubstituted thiophene) or a composite of poly (3,4-disubstituted thiophene) and polyanion (dopant), it can be performed at a low temperature and in a short time. The transparent electrode (B) can be formed and the productivity is also excellent. In addition, poly anion is a dopant of a conductive polymer, and the content thereof will be described later.

Poly (3,4-disubstituted thiophene) is particularly preferably poly (3,4-dialkoxythiophene) or poly (3,4-alkylenedioxythiophene). As poly (3,4-dialkoxythiophene) or poly (3,4-alkylenedioxythiophene), the following formula (I):

A polythiophene in a cationic form consisting of repeating structural units represented by
Here, R ¹ and R ² each independently represent a hydrogen atom or a C _1-4 alkyl group, or when R ¹ and R ² are bonded, a C _1-4 alkylene group. Represents. The C _1-4 alkyl group is not particularly limited, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a t-butyl group. .
In addition, when R ¹ and R ² are bonded, the C _1-4 alkylene group is not particularly limited, and examples thereof include a methylene group, a 1,2-ethylene group, a 1,3-propylene group, 1, 4-butylene group, 1-methyl-1,2-ethylene group, 1-ethyl-1,2-ethylene group, 1-methyl-1,3-propylene group, 2-methyl-1,3-propylene group, etc. Can be mentioned. Among these, a methylene group, 1,2-ethylene group, and 1,3-propylene group are preferable, and a 1,2-ethylene group is more preferable. In the C _1-4 alkyl group and the C _1-4 alkylene group, a part of hydrogen may be substituted. As the polythiophene having a C _1-4 alkylene group, poly (3,4-ethylenedioxythiophene) is particularly preferable.

The weight average molecular weight of the component (f) is preferably in the range of 500 to 100,000, more preferably in the range of 1000 to 50000, and most preferably in the range of 1500 to 20000. When the weight average molecular weight is less than 500, the viscosity required for the conductive composition may not be ensured, and the conductivity of the transparent electrode (B) may be lowered.

The dopant is not particularly limited, but a polyanion is preferable. The polyanion forms a complex by forming an ion pair with the polythiophene (derivative), and the polythiophene (derivative) can be stably dispersed in water. Although it does not specifically limit as a poly anion, For example, carboxylic acid polymers (for example, polyacrylic acid, polymaleic acid, polymethacrylic acid, etc.), sulfonic acid polymers (for example, polystyrene sulfonic acid, polyvinyl sulfonic acid, polyisoprene) Sulfonic acid etc.). These carboxylic acid polymers and sulfonic acid polymers are also copolymers of vinyl carboxylic acids and vinyl sulfonic acids with other polymerizable monomers such as aromatic vinyl compounds such as acrylates, styrene, vinyl naphthalene, etc. It may be. Among these, polystyrene sulfonic acid is particularly preferable.

The polystyrene sulfonic acid preferably has a weight average molecular weight of 20,000 to 500,000, more preferably 40,000 to 200,000. If polystyrene sulfonic acid having a molecular weight outside this range is used, the dispersion stability of the polythiophene conductive polymer in water may be lowered. The weight average molecular weight is a value measured by gel permeation chromatography (GPC).

(F) When using a complex with a polyanion as a component, since it is particularly excellent in transparency and conductivity, use a complex of poly (3,4-ethylenedioxythiophene) and polystyrenesulfonic acid. Is preferred.

The conductivity of the component (f) is not particularly limited, but is preferably 0.01 S / cm or more and 0.05 S / cm or more from the viewpoint of imparting sufficient conductivity to the transparent electrode (B). More preferably.

In the conductive composition, the content of the component (f) is not particularly limited. For example, when the transparent electrode (B) is used, an amount of 0.01 to 50.0 mg / m ² is preferable. An amount of ˜10.0 mg / m ² is more preferred. If it is less than 0.01 mg / m ² , the proportion of the component (f) in the transparent electrode (B) decreases, and the conductivity of the transparent electrode (B) may not be sufficiently secured. If it exceeds 0.0 mg / m ² , the proportion of the component (f) in the transparent electrode (B) increases, which may cause adverse effects on the strength and film formability of the coating film.

The conductive composition may optionally contain other components in addition to the component (f). Other components include, but are not limited to, (g) a thermoplastic resin having a Tg of 0 ° C. or higher, (h) a binder, (i) a conductivity improver, an antioxidant, (e) a surfactant, Examples include foaming agents, (d) slip agents, adhesion improvers, thickeners, crosslinking agents, solvents, and the like. In addition, (e) surfactant, antifoaming agent, (d) slip agent, adhesion improver, and crosslinking agent are the same as those in the above-described coating composition.

From the viewpoint of film strength and tackiness, the conductive composition preferably further comprises (g) a thermoplastic resin having Tg of 0 ° C. or higher (hereinafter also simply referred to as component (g)).
The component (g) is not particularly limited as long as Tg is 0 ° C. or higher, and examples thereof include thermoplastic resins such as polyester, polyurethane, acrylic resin, and olefin resin. Moreover, you may use the (a) component mentioned above as a (g) component. Among these, polyester is preferable from the viewpoint of adhesion to the resin film (A) and transparency. These (g) components may be used independently and may use 2 or more types together.

(G) Although Tg of a component is not specifically limited as long as it is 0 degreeC or more, it is preferable that it is 10 degreeC or more, and it is more preferable that it is 20 degreeC or more. When Tg is less than 0 ° C., the strength of the transparent electrode (B) may be deteriorated or tack may be generated. Although the upper limit of Tg is not specifically limited, For example, it is 110 degreeC. If it exceeds 110 ° C., the flexibility is lost, and defects such as cracks may occur.

Although the weight average molecular weight of (g) component is not specifically limited, It is preferable that it is 2,000-200,000, and it is more preferable that it is 2,500-100,000. When the weight average molecular weight is less than 2,000, bleeding out may occur when the transparent electrode (B) is used. When the weight average molecular weight exceeds 200,000, the liquid stability of the conductive composition may deteriorate, Viscosity increases too much and applicability may decrease.

(G) Although the acid value of a component is not specifically limited, It is preferable that it is 50 mgKOH / g or less, and it is more preferable that it is 30 mgKOH / g or less. When the acid value exceeds 50 mgKOH / g, the liquid stability of the electrically conductive composition may be deteriorated, or the viscosity may be excessively increased to lower the coating property. Although the minimum of an acid value is not specifically limited, For example, it is 0.1 mgKOH / g.

When the conductive composition contains the component (g), the content is not particularly limited, but is preferably 0.1 to 90% by weight, and 1 to 80% by weight in the conductive composition. It is more preferable. If the content is less than 0.1% by weight, the strength of the transparent electrode (B) may decrease. If the content exceeds 90% by weight, the liquid stability of the conductive composition deteriorates or the viscosity increases excessively. In addition to the decrease in applicability, sufficient conductivity may not be obtained.

(H) The binder (hereinafter, also simply referred to as the (h) component) is used for the purpose of binding the blends in the conductive composition and forming the transparent electrode (B) (including the conductive pattern) more reliably. Added. (H) Although it does not specifically limit as a component, For example, a polyester-type resin, a polyurethane, an epoxy resin, an acrylic resin, an alkoxysilane oligomer, a polyolefin-type resin etc. are mentioned. These may be used alone or in combination of two or more.

The polyester-based resin is not particularly limited as long as it is a polymer compound obtained by polycondensation of a compound having two or more carboxyl groups in the molecule and a compound having two or more hydroxyl groups. Examples thereof include polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and polybutylene naphthalate. These may be used alone or in combination of two or more.

The polyurethane is not particularly limited as long as it is a polymer compound obtained by copolymerizing a compound having an isocyanate group and a compound having a hydroxyl group. For example, an ester / ether polyurethane, an ether polyurethane, a polyester polyurethane, Examples thereof include carbonate polyurethane and acrylic polyurethane. These may be used alone or in combination of two or more.

Examples of the epoxy resin include bisphenol A type, bisphenol F type, phenol novolac type, tetrakis (hydroxyphenyl) ethane type or tris (hydroxyphenyl) methane type, biphenyl type, triphenyl type, which have many benzene rings. Examples include phenol methane type, naphthalene type, ortho novolak type, dicyclopentadiene type, aminophenol type, alicyclic epoxy resin, silicone epoxy resin, and the like. These may be used alone or in combination of two or more.

The acrylic resin is not particularly limited, and examples thereof include (meth) acrylic resins and vinyl ester resins. As these acrylic resins, for example, a polymer containing a polymerizable monomer having an acid group such as a carboxyl group, an acid anhydride group, a sulfonic acid group, or a phosphoric acid group as a constituent monomer may be used. Examples thereof include a single or copolymer of a polymerizable monomer having a group, a copolymer of a polymerizable monomer having a acid group and a copolymerizable monomer, and the like. These may be used alone or in combination of two or more.

The alkoxysilane oligomer is, for example, a high molecular weight alkoxysilane formed by condensation of alkoxysilane monomers represented by the following formula (II), and has a siloxane bond (Si—O—Si). Examples include oligomers having one or more in one molecule.
SiR ₄ (II)
(In the formula, R represents hydrogen, a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, an alkyl group which may have a substituent, or a phenyl group which may have a substituent. At least one of R is an alkoxy group having 1 to 4 carbon atoms or a hydroxyl group)
The compounds represented by the formula (II) may be used alone or in combination of two or more.

The polyolefin resin is not particularly limited, and examples thereof include chlorinated polypropylene, non-chlorinated polypropylene, chlorinated polyethylene, and non-chlorinated polyethylene. These may be used alone or in combination of two or more.

(H) Although content of a component is not specifically limited, 0.1-1000 weight part is preferable with respect to 100 weight part of solid content of (f) component, and 5-500 weight part is more preferable. If it is less than 0.1 part by weight, the strength of the transparent electrode (B) may be weakened. If it exceeds 1000 parts by weight, the content of the component (f) in the conductive composition is relatively reduced. When the transparent electrode (B) is used, sufficient conductivity may not be ensured.

(I) The conductivity improver (hereinafter also simply referred to as component (i)) is added for the purpose of improving the conductivity of the transparent electrode (B) formed using the conductive composition. The component (i) evaporates by heating when forming the transparent electrode (B), and it is estimated that the conductivity of the transparent electrode (B) is improved by controlling the orientation of the component (f) at that time. Is done. Moreover, when (i) component is used, compared with the case where (i) component is not used, as a result of being able to reduce the compounding quantity of (f) component, maintaining the surface resistivity, there exists an advantage which can improve transparency. is there.

The component (i) is at least one selected from the group consisting of the following (i-1) to (i-7) from the viewpoint of surely ensuring the conductivity necessary for the use of the transparent conductive film. Is preferred.
(I-1) Compound having a boiling point of 60 ° C. or higher and having at least one ketone group in the molecule (i-2) Compound having a boiling point of 100 ° C. or higher and having at least one ether group in the molecule (i-3) Boiling point Is a compound having a boiling point of 100 ° C. or higher and a compound having at least one amide group in the molecule (i-5) having a boiling point of 50 ° C. or higher. Compound (i-6) having at least one carboxyl group therein (i-6) Boiling point of 100 ° C. or higher and compound (i-7) having two or more hydroxyl groups in the molecule Boiling point of 100 ° C. or higher and at least one in the molecule Compound having lactam group

Examples of the compound (i-1) having a boiling point of 60 ° C. or higher and having at least one ketone group in the molecule include isophorone, propylene carbonate, γ-butyrolactone, β-butyrolactone, 1,3-dimethyl-2-imidazolide. Non etc. are mentioned. These may be used alone or in combination of two or more.

Examples of the compound (i-2) having a boiling point of 100 ° C. or higher and having at least one ether group in the molecule include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, 2-phenoxyethanol, dioxane, morpholine, and 4-acryloyl. Examples include morpholine, N-methylmorpholine N-oxide, 4-ethylmorpholine, and 2-methoxyfuran. These may be used alone or in combination of two or more.

Examples of the compound (i-3) having a boiling point of 100 ° C. or higher and having at least one sulfinyl group in the molecule include dimethyl sulfoxide and the like.

Examples of the compound (i-4) having a boiling point of 100 ° C. or higher and having at least one amide group in the molecule include N, N-dimethylacetamide, N-methylformamide, N, N-dimethylformamide, acetamide, N— Examples include ethylacetamide, N-phenyl-N-propylacetamide, and benzamide. These may be used alone or in combination of two or more.

Examples of the compound (i-5) having a boiling point of 50 ° C. or higher and having at least one carboxyl group in the molecule include acrylic acid, methacrylic acid, methanoic acid, ethanoic acid, propanoic acid, butanoic acid, pentanoic acid and hexanoic acid. , Octanoic acid, decanoic acid, dodecanoic acid, benzoic acid, p-toluic acid, p-chlorobenzoic acid, p-nitrobenzoic acid, 1-naphthoic acid, 2-naphthoic acid, phthalic acid, isophthalic acid, oxalic acid, malon Examples include acid, succinic acid, adipic acid, maleic acid, fumaric acid and the like. These may be used alone or in combination of two or more.

Examples of the compound (i-6) having a boiling point of 100 ° C. or higher and having two or more hydroxyl groups in the molecule include ethylene glycol, diethylene glycol, propylene glycol, trimethylene glycol, β-thiodiglycol, triethylene glycol, Tripropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,3-butanediol, 1,6-hexanediol, neopentyl glycol, catechol, cyclohexanediol, cyclohexanedimethanol, glycerin, erythritol, immutol , Lactitol, maltitol, mannitol, sorbitol, xylitol, sucrose and the like. These may be used alone or in combination of two or more.

Examples of the compound (i-7) having a boiling point of 100 ° C. or higher and having at least one lactam group in the molecule include N-methylpyrrolidone, β-lactam, γ-lactam, δ-lactam, ε-caprolactam, laurolactam. Etc. These may be used alone or in combination of two or more.

When the boiling point of the component (i) is equal to or higher than a specific temperature, the component (i) gradually volatilizes due to the heating during the formation of the transparent electrode (B). In the process, the orientation of the component (f) Is controlled to an orientation advantageous for conductivity, and as a result, the conductivity is considered to be improved. On the other hand, if the boiling point of the component (i) is less than the specific temperature, the component (i) evaporates abruptly, so that the orientation of the component (f) is not sufficiently controlled and the conductivity is not improved. It is considered a thing.

When the conductive composition contains the component (i), the content is not particularly limited, but is preferably 5 to 2000 parts by weight, and 10 to 1500 parts by weight with respect to 100 parts by weight of the solid content of the component (f). Is more preferable. If it is less than 5 parts by weight, the effect of improving conductivity by adding component (i) may not be fully enjoyed. On the other hand, when it exceeds 2000 parts by weight, the content of the component (f) in the conductive composition is relatively reduced, and sufficient conductivity may not be obtained when the transparent electrode (B) is obtained.

Although it does not specifically limit as antioxidant, For example, a reducing water-soluble antioxidant, a non-reducing water-soluble antioxidant, etc. are mentioned. Examples of reducing water-soluble antioxidants include L-ascorbic acid, sodium L-ascorbate, potassium L-ascorbate, D (-)-isoascorbic acid (erythorbic acid), sodium erythorbate, potassium erythorbate A compound having a lactone ring substituted with two hydroxyl groups such as maltose, lactose, cellobiose, xylose, arabinose, glucose, fructose, galactose, mannose and the like monosaccharides or disaccharides (excluding sucrose); Flavonoids such as rutin, myricetin, quercetin, kaempferol, sanmerin (registered trademark) Y-AF; gallic acid, methyl gallate, propyl gallate, tannic acid, curcumin, rosmarinic acid, chlorogenic acid, hydroquinone, 3,4,5 -Birds Compounds having two or more phenolic hydroxyl group such as Dorokishi benzoic acid; cysteine, glutathione, a compound having a pentaerythritol tetrakis (3-mercapto butyrate) thiol groups, such as and the like. Non-reducing water-soluble antioxidants include, for example, oxidative degradation such as phenylimidazolesulfonic acid, phenyltriazolesulfonic acid, 2-hydroxypyrimidine, phenyl salicylate, sodium 2-hydroxy-4-methoxybenzophenone-5-sulfonate. And a compound that absorbs ultraviolet rays causing the above. These antioxidants may be used alone or in combination of two or more. When the conductive composition contains an antioxidant, the content is not particularly limited, but it is 0.001 to 500 parts by weight with respect to 100 parts by weight of the solid content of the conductive polymer (f). Preferably, it is 0.01-300 weight part.

Although it does not specifically limit as a thickener, For example, polyacrylic acid-type resin, a cellulose ether resin, polyvinylpyrrolidone, a carboxy vinyl polymer, polyvinyl alcohol etc. are mentioned. These thickeners may be used alone or in combination of two or more. When the conductive composition contains a thickener, the content thereof is not particularly limited, but (f) is preferably less than 200 parts by weight with respect to 100 parts by weight of the solid content of the conductive polymer. More preferably, it is less than part.

Examples of the solvent include, but are not limited to, water; alcohols such as methanol, ethanol, 2-propanol, and 1-propanol; ethylene glycols such as ethylene glycol, diethylene glycol, triethylene glycol, and tetraethylene glycol; ethylene glycol monomethyl Glycol ethers such as ether, diethylene glycol monomethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether; Glycol ether acetates such as ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate; propylene glycol, dipropylene glycol, Tripropylene glycol Propylene glycols such as: propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, propylene glycol diethyl ether, dipropylene glycol diethyl ether, etc. Propylene glycol ethers; propylene glycol ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate; tetrahydrofuran; acetone; Tolyl, and the like. These solvents may be used alone or in combination of two or more. When the conductive composition contains a solvent, the content is not particularly limited, but is preferably 0.01 to 99.99% by weight in the conductive composition, preferably 0.1 to 99.9% by weight. It is more preferable that

Although it does not specifically limit as a method of forming a transparent electrode (B) using an electroconductive composition, After apply | coating or printing an electroconductive composition on a resin film (A), it is 0.5 at 50-150 degreeC. The method etc. which heat-process for 15 minutes are mentioned.

Although the thickness of a transparent electrode (B) is not specifically limited, It is preferable that it is 0.1-1 micrometer, and it is more preferable that it is 0.2-0.5 micrometer. If the thickness is less than 0.1 μm, sufficient conductivity may not be obtained, and if it exceeds 1 μm, the transparency may be deteriorated.

<Connection (C)>
The connection part (C) is formed so as to contact a part of the transparent electrode (B).

The connection part (C) is preferably formed using at least one conductive paste selected from the group consisting of silver paste, copper paste, alloy paste, and carbon paste from the viewpoint of conductivity and printability. The method for forming the connection portion (C) using the conductive paste is not particularly limited, but the conductive paste is applied or printed so as to be in contact with a part of the transparent electrode (B), and then fired or heat-cured. The method of performing etc. is mentioned.
Here, the temperature conditions for firing and heat curing are not particularly limited, but firing is preferably performed at a high temperature of about 550 to 900 ° C., while the heat curing is relatively performed at room temperature (about 20 ° C.) to about 200 ° C. It is preferable to carry out at a low temperature.

<Overcoat layer (D)>
The overcoat layer (D) is formed using the coating composition of the present invention so as to cover at least a part of the transparent electrode (B) and the connection portion (C).

The method for forming the overcoat layer (D) using the coating composition of the present invention is not particularly limited. For example, the coating composition of the present invention is applied to at least the transparent electrode (B) and the connection portion (C). Examples of the method include drying, heat curing, or photocuring after coating or printing so as to cover a part.
Drying is performed by heating at 40-150 degreeC, for example, and removing a liquid component. In that case, you may dry under reduced pressure as needed, and may combine heat drying and reduced pressure drying.
When the coating composition contains a thermosetting resin, the coating composition applied or printed so as to cover at least a part of the transparent electrode (B) and the connection portion (C) is heated, and the solvent or the dispersion medium is removed. The overcoat layer (D) can be formed by evaporating and simultaneously thermosetting (drying / thermosetting). Although heating temperature is not specifically limited, Preferably it is 40-200 degreeC, More preferably, it is 50-150 degreeC.
When the coating composition contains a photocurable resin, the coating composition applied or printed so as to cover at least a part of the transparent electrode (B) and the connection portion (C) is heated, and the solvent or the dispersion medium is removed. After evaporating, the overcoat layer (D) can be formed by photocuring. The photocuring is preferably performed by irradiating ultraviolet rays, visible light, electron beams, ionizing radiation, or the like.

<Primer layer (E)>
The electrode structure of the present invention has a primer layer (E) between the resin film (A) and the transparent electrode (B) from the viewpoint of improving the printability and adhesion of the conductive composition to the resin film (A). It is preferable to further comprise. Moreover, it is preferable that a primer layer (E) is formed using the coating composition of this invention from a printable and adhesive viewpoint of the electrically conductive composition which is aqueous.

Although it does not specifically limit as a method of forming a primer layer (E) using the coating composition of this invention, For example, after apply | coating or printing the coating composition of this invention on the surface of a resin film (A), Examples include a method of drying, heat curing or photocuring.
Drying is performed by heating at 40-150 degreeC, for example, and removing a liquid component. In that case, you may dry under reduced pressure as needed, and may combine heat drying and reduced pressure drying.
When the coating composition contains a thermosetting resin, the coating composition applied or printed on the surface of the resin film (A) is heated to evaporate the solvent or the dispersion medium and simultaneously heat cure (drying / thermosetting). ), The primer layer (E) can be formed. Although heating temperature is not specifically limited, Preferably it is 40-200 degreeC, More preferably, it is 50-150 degreeC.
When the coating composition contains a photocurable resin, the coating composition applied or printed on the surface of the resin film (A) is heated to evaporate the solvent or dispersion medium, and then photocured to obtain a primer. A layer (E) can be formed. The photocuring is preferably performed by irradiating ultraviolet rays, visible light, electron beams, ionizing radiation, or the like.

The water contact angle of the primer layer (E) is not particularly limited, but is preferably 65 ° or less, and more preferably 60 ° or less. When the water contact angle of the primer layer (E) exceeds 65 °, the printability of the conductive composition on the primer layer (E) may be deteriorated.

<< Electrode Structure Manufacturing Method >>
<The manufacturing method of the electrode structure of 1st this invention>
The manufacturing method of the electrode structure of the first present invention is a method for manufacturing the electrode structure of the present invention,
It includes the following steps (2) to (4).
(2) A step of forming a transparent electrode (B) by printing a conductive composition containing a conductive polymer (f) on the resin film (A),
(3) a step of forming a connection part (C) by printing a conductive paste so as to be in contact with a part of the transparent electrode (B); and
(4) The process of forming an overcoat layer (D) by printing the coating composition of this invention so that at least one part of a transparent electrode (B) and a connection part (C) may be coat | covered.

<The manufacturing method of the electrode structure of 2nd this invention>
The method for producing an electrode structure of the second invention is a method for producing an electrode structure of the invention comprising a primer layer (E),
It includes the following steps (1) to (4).
(1) A step of forming a primer layer (E) by printing on the resin film (A),
(2) On the primer layer (E), (f) a step of forming a transparent electrode (B) by printing a conductive composition containing a conductive polymer;
(3) a step of forming a connection part (C) by printing a conductive paste so as to be in contact with a part of the transparent electrode (B); and
(4) The process of forming an overcoat layer (D) by printing the coating composition of this invention so that at least one part of a transparent electrode (B) and a connection part (C) may be coat | covered.

In the manufacturing method of the electrode structure of the second aspect of the present invention, the coating composition of the present invention is used in step (1) from the viewpoint of improving the printability and adhesion of the conductive composition to the resin film (A). It is preferable to form the primer layer (E).

<< Conductive composition >>
The conductive composition of the present invention comprises (f) a conductive polymer, and
(G) A conductive composition for forming a transparent electrode (B) in the electrode structure of the present invention, comprising a thermoplastic resin having a Tg of 0 ° C. or higher and capable of being applied by printing. is there.

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

1. Materials used The following materials were used in the following examples and comparative examples.
1-1. (A) Thermoplastic resin / thermoplastic polyester having a Tg of 30 ° C. or higher (Arakawa Chemical Industries, Arakid 7018, solid content 40% by weight, weight average molecular weight 18,000, Tg 50 ° C., acid value 3 mgKOH / g, Water contact angle 75 °)
Thermoplastic acrylic resin (manufactured by DIC Corporation, ACRYDIC A-452, solid content 40% by weight, weight average molecular weight unknown, Tg 70 ° C., acid value 3 mg KOH / g, water contact angle 73 °)
Thermoplastic polyester (Arakawa Chemical Industries, Arakid 7012, solid content 35% by weight, weight average molecular weight 25,000, Tg 51 ° C., acid value less than 1 mg KOH / g, water contact angle 75 °)
Thermoplastic polyester (by Toyobo Co., Ltd., Byron UR-1400, solid content 40% by weight, weight average molecular weight 40,000, Tg 83 ° C., acid value less than 1 mg KOH / g, water contact angle 70 °)
Thermoplastic polyester (Takamatsu Yushi Co., Ltd., Pesresin S-680EA, solid content 45% by weight, weight average molecular weight 3,000, Tg 30 ° C., acid value 60 mg KOH / g, water contact angle 62 °)
Thermoplastic polyester (Toyobo Co., Ltd., Byron UR-6100, solid content 45% by weight, weight average molecular weight 25,000, Tg-30 ° C., acid value of less than 1 mg KOH / g, water contact angle 71 °)
-Thermoplastic polyester (manufactured by Iupika Co., Ltd., Iupika Coat GV230, solid content 100% by weight, weight average molecular weight 7,900, Tg unknown, acid value 53 mgKOH / g, water contact angle 70 °)
1-2. (B) UV absorber / triazine UV absorber (Adeka Corporation, ADK STAB LA-F70)
・ Benzotriazole UV absorber (Adeka Corporation, Adeka Stab LA-36)
1-3. (C) Organic solvent / diacetone alcohol (Tokyo Chemical Industry Co., Ltd., boiling point: 168 ° C.)
・ Γ-butyrolactone (Wako Pure Chemical Industries, Ltd., boiling point: 204 ° C.)
1-4. (D) Slip agent / organosilica sol (manufactured by Nissan Chemical Co., Ltd., particle size 10-15 nm, silica concentration 30%, organic solvent dispersion)
1-5. (E) Surfactant / fluorine compound (manufactured by DuPont, CAPSTONE FS-3100)
1-6. (G) Thermoplastic resin / polyester resin having a Tg of 0 ° C. or higher (manufactured by Nagase ChemteX Corp., Gabsen ES-9020, solid content 25%, Tg 25 ° C.)
1-7. (I) Conductivity improver, dimethyl sulfoxide (DMSO) (manufactured by Tokyo Chemical Industry Co., Ltd.)
1-8. (J) Hydrophilicity imparting agent / polyether-modified urethane surface conditioner (manufactured by San Nopco, SN Clean Act 82)
-Polyether-modified acrylate (Daicel Ornex Co., Ltd., EBECRYL80)
-Polyether-modified silicone surface conditioner (Shin-Etsu Chemical Co., Ltd., KF-6011)
1-9. Thickener and cross-linkable polyacrylic acid (BF Goodrich, CARBOPOL ETD-2623)
1-10. Antioxidant and tannic acid (Wako Pure Chemical Industries, Ltd.)
1-11. Solvent, isopropyl alcohol (Wako Pure Chemical Industries, IPA)
1-12. Silver paste CA-T30 (purchased from Daiken Chemical Manufacturing and Sales Co., Ltd.)
1-13. Resin film (A)
・ PET film (Toray Industries, Lumirror T-60)
・ PC film (Teijin Limited, Pure Ace)
・ Acrylic resin film (Acryprene HBS006, manufactured by Mitsubishi Rayon Co., Ltd.)

2. (F) Production of conductive polymer (Production Example 1) Production of PEDOT / PSS polymer product In a 10 L reaction vessel equipped with a stirrer and a nitrogen inlet, 5508 g of ion-exchanged water, 492 g of 12.8 wt% polystyrene sulfonic acid An aqueous solution of (PSS) (Mw = 56000) was added, and the mixture was stirred for 1 hour while being kept at 25 ° C. while blowing nitrogen. The temperature in the solution at this time was 25 ° C., the oxygen concentration was 0.5 mg / L, the pH was 0.8, and the stirring speed was 300 rpm. The oxygen concentration was measured using a nick process unit 73O2 (manufactured by Mettler Toledo Co., Ltd.) using an Impro 6000 series O ₂ sensor. Next, 25.4 g (179 mmol) 3,4-ethylenedioxythiophene (EDOT), 0.45 g Fe ₂ (SO ₄ ) ₃ .3H ₂ O, 30 g Na ₂ S ₂ O ₈ were added, The polymerization reaction was started. After reacting for 12 hours at 25 ° C., an additional 30 g of Na ₂ S ₂ O ₈ was added. After an additional reaction time of 12 hours, 4200 g of dark blue high-viscosity PEDOT / PSS was obtained by treatment with ion exchange resins Lewatit S100H and Lewatit MP62 (solid content 2.2%, viscosity 66 dPa · s, thixotropy index 3 .3, yield value 5.5 Pa, average particle size 330 nm (measured using a Zetasizer Nano-S manufactured by Malvern)).

3. Method for producing various test films / Method for producing a test film having an electrode structure (test film (1)) Conductivity obtained by mixing each component on the resin film (A) at a weight ratio shown in Table 1 below. The composition was printed by a screen printing method and heat-treated at 100 ° C. for 10 minutes to produce a transparent electrode (B). Next, the silver paste was printed and heat-cured at 120 ° C. to form the connection portion (C). Furthermore, the coating composition obtained by mixing each component in the weight ratio shown in Table 1 below was printed and dried at 100 ° C. for 15 minutes to form an overcoat layer (D). ) Was produced. Note that the surface resistance of the transparent electrode (B) after the overcoat layer (D) is formed by leaving a non-covered portion that is not partially covered by the overcoat layer (D) in the connection portion (C). The value can be measured.

-Preparation method of sulfidation resistance test film (test film (2)) After forming the connecting portion (C) on the resin film (A) in the same manner as the test film (1), the following Table 1 The coating composition obtained by mixing each component at the weight ratio shown in FIG. 5 was printed on the entire surface by screen printing, dried at 100 ° C., and formed an overcoat layer (D). ) Was produced.

-Preparation method of anti-blocking property test film (test film (3)) A test film (3) was prepared in the same manner as the test film (2) except that the connection part (C) was not formed.

4). Evaluation Method In the following examples and comparative examples, evaluation was performed by the following method.

The dispersible appearance coating composition was put in a glass container and sealed, and visually observed after 1 hour, and the liquid appearance was evaluated according to the following evaluation criteria.
○: Precipitate is not observed ×: Precipitate is observed

Put the viscosity coating composition in a glass container and seal it, put it in a thermostatic bath and keep it at 25 ° C., and use a B-type viscometer (B-type viscometer BM: manufactured by Toki Sangyo Co., Ltd., rotational speed 6 rpm, No. 4 rotor) The viscosity was measured.

The surface tension at 25 ° C. of the surface tension coating composition was measured by a Wilhelmy method using a fully automatic surface tension meter (CBVP-Z, manufactured by Kyowa Interface Science Co., Ltd.).

The total light transmittance (Tt) and haze value test film (1) was measured according to JIS K 7150 using a haze computer HGM-2B manufactured by Suga Test Instruments Co., Ltd.

Adhesion (cross cut test)
The test film (1) was subjected to a cross cut test according to JIS K 5400 and evaluated according to the following criteria.
◎: Cross cut test is 10 points ○: Cross cut test is 9 to 8 points

The sulfidation resistance test film (2) and sulfur powder were placed in a sealed container, allowed to stand at room temperature for 24 hours, and then the color change before and after the test of the silver paste was visually confirmed and evaluated as follows.
◎: No discoloration ○: Some discoloration slightly blackish ×: Discoloration to black

With respect to the UV resistance test film (1), the surface resistivity SR (Ω / □) before and after the UV resistance test was measured to determine the SR increase rate, and evaluated according to the following criteria.
SR increase rate = (SR after UV resistance test) / (SR before UV resistance test)
A: SR increase rate is 0.95 to 1.05. O: SR increase rate is 1.05 to 1.3. X: SR resistance increase rate is 1.3 or more. The test film (1) is stored in a testing machine (manufactured by ATLAS Material Testing Technology GmbH, SUNSET CPS), and UV irradiation is continuously performed for 100 hours under conditions of an irradiance of 250 W / m ² and a temperature of 50 ° C. using a xenon lamp. Was done.
The surface resistivity SR was measured by strongly bonding the tips of the test leads of Sanwa Digital Multimeter PC5000 manufactured by Sanwa Denki Keiki Co., Ltd. to the connection portion of the test film (1).

For the heat resistance test film (1), the surface resistivity SR (Ω / □) before and after the heat resistance test was measured to determine the SR increase rate, and the evaluation was made based on the following criteria.
SR increase rate = (SR after heat resistance test) / (SR before heat resistance test)
A: SR increase rate is 0.95 to 1.05. O: SR increase rate is 1.05 to 1.3. X: SR heat increase test is 1.3 or more. 1) was placed in a blast oven and kept at a temperature of 100 ° C. for 100 hours.
The surface resistivity SR was measured by strongly bonding the tips of the test leads of Sanwa Digital Multimeter PC5000 manufactured by Sanwa Denki Keiki Co., Ltd. to the connection portion of the test film (1).

Prepare two anti-blocking test films (3) and stack them so that the overcoat layer forming surface of one test film (3) and the resin film (A) surface of the other test film (3) are in contact with each other. After standing at room temperature for 24 hours, the anti-blocking property when peeling the test film was evaluated according to the following criteria.
◎: Easy to peel without sticking ○: Slightly sticks but peels ×: Sticks and hard to peel

Primer (water contact angle)
On the resin film (A), the coating compositions obtained in Examples 1 to 14 were applied using a screen printing method, and heat-treated at 100 ° C. for 15 minutes, whereby an overcoat layer (D) (primer layer ( E)) was formed. The contact angle of the obtained overcoat layer (D) (primer layer (E)) was measured using a contact angle meter (Kyowa Interface Chemical Co., Ltd., CA-D type). In an environment of 25 ° C. and 50% RH, 25 ° C. distilled water (manufactured by Wako Pure Chemical Industries, Ltd.) was dropped onto the surface of the primer layer, and the contact angle after 10 seconds was measured.

Primer (printability)
On the overcoat layer (D) (primer layer (E)) obtained by the evaluation of the water contact angle, a 0.5 mm wiring pattern was printed by a screen printing method using the conductive composition, and the drawn pattern Were observed with a microscope, and the appearance of the pattern was evaluated according to the following criteria.
○: All wiring patterns are marked with no defects ×: There are wiring patterns with defects such as repelling and twisting

Using the pattern appearance coating composition, a 0.5 mm wiring pattern is printed on the resin film (A) by a screen printing method, the drawn pattern is observed with a microscope, and the appearance of the pattern is evaluated according to the following criteria. did.
○: All wiring patterns are drawn without defects ×: There are defective wiring patterns

A 0.5 mm wiring pattern is printed on the resin film (A) by a screen printing method using the repelling and covering composition, and the drawn pattern is observed with a microscope. evaluated.
◎: There is no unevenness in the wiring pattern, and there is no deviation. ○: There is an unevenness in the wiring pattern, and there is a deviation or wrinkle, but there is no adverse effect.

Using the stringing coating composition, a 0.5 mm wiring pattern is printed on the resin film (A) by a screen printing method, and when the screen plate and the resin film (A) are separated, the coating composition The degree of stringing was evaluated visually.
◎: No stringing is observed at all ○: Slight stringing is observed, but printability is not adversely affected

(Examples 1-14, Comparative Examples 1-3)
Each component was mixed by the weight ratio shown in following Table 1, and the coating composition and the electroconductive composition were obtained. Using the obtained coating composition and conductive composition, the physical properties (dispersion appearance, viscosity, surface tension) of the coating composition, physical properties (total light transmittance (Tt), haze ( Haze) value, adhesion, sulfidation resistance, UV resistance, heat resistance, anti-blocking properties), primer properties (water contact angle, printability), and screen printability (pattern appearance, repelling, twisting, stringing) ) Was evaluated. The results are shown in Table 1.
In addition, since the evaluation result of the dispersible appearance was bad, the coating composition of Comparative Example 3 was not evaluated for other evaluation items.

Claims (21)

(A) a thermoplastic resin having a Tg of 30 ° C. or higher,
(B) an ultraviolet absorber, and
(C) A coating composition for an electrode structure of a capacitive switch, which contains an organic solvent and can be applied by printing. The coating composition according to claim 1, wherein the (a) thermoplastic resin is a polyester having a weight average molecular weight of 2,000 to 200,000 and an acid value of 50 mgKOH / g or less. The coating composition according to claim 1 or 2, wherein the (b) ultraviolet absorber is benzotriazole or triazine. The coating composition according to any one of claims 1 to 3, wherein a water contact angle of a coating layer formed by printing is 65 ° or less. The coating composition according to claim 4, further comprising (j) a hydrophilicity-imparting agent. (J) The hydrophilicity imparting agent is at least one selected from the group consisting of a polyether-modified urethane compound, a polyether-modified acrylate compound, and a polyether-modified silicone compound. Coating composition. (A) Coating composition of any one of Claims 4-6 whose water contact angle of a thermoplastic resin is 65 degrees or less. (D) The coating composition according to any one of claims 1 to 7, further comprising an inorganic fine particle slip agent as a slip agent. Resin film (A),
A transparent electrode (B) formed on the resin film (A) using (f) a conductive composition containing a conductive polymer;
A connection part (C) formed so as to be in contact with a part of the transparent electrode (B), and
The overcoat layer (D) formed using the coating composition according to any one of claims 1 to 8, so as to cover at least a part of the transparent electrode (B) and the connection portion (C).
An electrode structure of a capacitive switch, comprising: The electrode structure according to claim 9, wherein the conductive composition further comprises (g) a thermoplastic resin having a Tg of 0 ° C or higher. The electrode structure according to claim 9 or 10, wherein the resin film (A) includes at least one resin selected from the group consisting of a polyester resin, a polycarbonate resin, and an acrylic resin. (F) Conductive polymer is a composite of poly (3,4-disubstituted thiophene) or poly (3,4-disubstituted thiophene) and polyanion. 2. The electrode structure according to item 1. The electrode structure according to any one of claims 9 to 12, wherein the connection portion (C) is formed using at least one conductive paste selected from the group consisting of silver paste, copper paste, and carbon paste. . The electrode structure according to any one of claims 9 to 13, further comprising a primer layer (E) between the resin film (A) and the transparent electrode (B). The electrode structure according to claim 14, wherein the primer layer (E) is formed using the coating composition according to any one of claims 4 to 7. A method for manufacturing the electrode structure according to any one of claims 9 to 13, comprising:
The manufacturing method of the electrode structure characterized by including following process (2)-(4):
(2) A step of forming a transparent electrode (B) by printing a conductive composition containing a conductive polymer (f) on the resin film (A),
(3) a step of forming a connection part (C) by printing a conductive paste so as to be in contact with a part of the transparent electrode (B); and
(4) The overcoat layer (D) is printed by printing the coating composition according to any one of claims 1 to 8 so as to cover at least a part of the transparent electrode (B) and the connection portion (C). ). A method for manufacturing the electrode structure according to claim 14 or 15, comprising:
A method for producing an electrode structure comprising the following steps (1) to (4):
(1) A step of forming a primer layer (E) by printing on the resin film (A),
(2) On the primer layer (E), (f) a step of forming a transparent electrode (B) by printing a conductive composition containing a conductive polymer;
(3) a step of forming a connection part (C) by printing a conductive paste so as to be in contact with a part of the transparent electrode (B); and
(4) The overcoat layer (D) is printed by printing the coating composition according to any one of claims 1 to 8 so as to cover at least a part of the transparent electrode (B) and the connection portion (C). ). The production method according to claim 17, wherein in step (1), the primer layer (E) is formed using the coating composition according to any one of claims 4 to 7. (F) a conductive polymer, and
(G) The transparent electrode (B) in the electrode structure according to any one of claims 9 to 15, which comprises a thermoplastic resin having a Tg of 0 ° C or higher and can be applied by printing. An electrically conductive composition for forming a film. (G) The electrically conductive composition according to claim 19, wherein the thermoplastic resin is a polyester having a weight average molecular weight of 2,000 to 200,000 and an acid value of 50 mgKOH / g or less. (F) The conductive polymer is poly (3,4-disubstituted thiophene) or a complex of poly (3,4-disubstituted thiophene) and a polyanion according to claim 19 or 20. Conductive composition.