JP6617949B2 - Conductive laminate - Google Patents

Description

The present invention relates to a conductive laminate.

As a noise cut film and a polarizing plate in a liquid crystal display, a conductive laminate having a structure in which a conductive layer is laminated on a substrate is widely used. Such a conductive laminate is produced by disposing a conductive composition on a base material and heat-curing it by baking to form a conductive layer.

Although one using a conductive polymer is known as one of the conductive compositions for forming the conductive layer, the heat resistance is not sufficient, and the haze value and surface resistivity are maintained after being kept under high temperature conditions. There has been a problem that increases.

An object of this invention is to provide the electrically conductive laminated body which has the electrically conductive layer which was excellent in heat resistance and the raise of the haze value and surface resistivity after hold | maintaining on high temperature conditions was suppressed.

As a result of intensive studies to solve the above problems, the present inventors have found that a conductive layer formed using a conductive composition containing a specific amount of antioxidant has excellent heat resistance and is maintained under high temperature conditions. The inventors found that the subsequent increase in haze value and surface resistivity was suppressed, and completed the present invention.

That is, the conductive laminate of the present invention is
A conductive laminate having a conductive layer (B) on at least one surface of a substrate (A),
The conductive layer (B) is formed using a conductive composition containing a conductive polymer (b-1), an antioxidant (b-2), and a binder (b-3).
The content of the antioxidant (b-2) is 50 to 400 parts by weight with respect to 100 parts by weight of the conductive polymer (b-1),
The haze value after holding at 100 ° C. for 24 hours is not more than 5 times the haze value before holding.

In the conductive laminate of the present invention, the binder (b-3) is preferably at least one selected from the group consisting of a polyester resin, an acrylic resin, a urethane resin, an epoxy resin, a silicate resin, an acrylate, and a melamine resin. .

In the conductive laminate of the present invention, it is preferable that the binder (b-3) is at least one selected from the group consisting of a polyester resin, an acrylic resin, and a urethane resin, and Tg is 0 ° C. or higher.

In the conductive laminate of the present invention, the antioxidant (b-2) is preferably a compound having a lactone ring substituted with two hydroxyl groups and / or a compound having two or more phenolic hydroxyl groups. .

In the conductive laminate of the present invention, the pKa of the antioxidant (b-2) is preferably 6 or less.

In the conductive laminate of the present invention, the conductive layer (B) preferably has a surface resistivity after holding at 100 ° C. for 100 hours that is not more than 5 times the surface resistivity before holding.

In the conductive laminate of the present invention, the surface resistivity of the conductive layer (B) is preferably 10 ⁵ Ω / □ or less.

In the conductive laminate of the present invention, the conductive polymer (b-1) is preferably a composite of poly (3,4-alkylenedioxythiophene) and polystyrene sulfonic acid.

In the conductive laminate of the present invention, the conductive composition further includes a conductivity improver (b-4),
The conductivity improver (b-4) is preferably a compound having a boiling point of 100 ° C. or higher and having at least one sulfinyl group, at least one amide group, or at least two hydroxyl groups in the molecule.

The conductive composition of the present invention is used for forming the conductive layer (B) in the conductive laminate of the present invention.

Since the conductive laminate of the present invention includes a conductive layer formed using a conductive composition containing a specific amount of an antioxidant, it has excellent heat resistance and haze value and surface resistance after being held under high temperature conditions. The rate increase is suppressed.

<< Conductive laminate >>
The conductive laminate of the present invention is a conductive laminate having a conductive layer (B) on at least one surface of the substrate (A),
The conductive layer (B) is formed using a conductive composition containing a conductive polymer (b-1), an antioxidant (b-2), and a binder (b-3).
The content of the antioxidant (b-2) is 50 to 400 parts by weight with respect to 100 parts by weight of the conductive polymer (b-1),
The haze value after holding at 100 ° C. for 24 hours is not more than 5 times the haze value before holding.

<Base material (A)>
The material of the base material (A) is not particularly limited. For example, glass, polyethylene terephthalate (PET), polycarbonate (PC), triacetyl cellulose (TAC), polymethyl methacrylate (PMMA), cycloolefin polymer (COP) ), Polypropylene (PP), polyethylene (PE), polyvinyl alcohol (PVA), polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), polystyrene (PS), polyacrylonitrile (PAN), ethylene vinyl acetate copolymer ( EVA), ethylene-vinyl alcohol copolymer (EVOH), ethylene-methacrylic acid copolymer (EMAA), polyamide (PA) and the like. Among these, from the viewpoint of hardness, transparency, adhesion and heat resistance of the conductive layer (B), selected from the group consisting of glass, polyethylene terephthalate, polycarbonate, triacetyl cellulose, polymethyl methacrylate and cycloolefin polymer. It is preferable to include at least one material. These materials may be used alone or in combination of two or more.

The arithmetic average roughness (Ra) of the surface of the substrate (A) is not particularly limited, but is preferably 20 nm or less, and more preferably 15 nm or less. When the arithmetic average roughness exceeds 20 nm, transparency may be impaired. In the present invention, the arithmetic average roughness (Ra) means that measured by an atomic force microscope (AFM).

Although the thickness of a base material (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. Further, the total light transmittance of the substrate (A) is not particularly limited as long as it is 60% or more, but it is preferably 70% or more, and more preferably 80% or more. Although the haze value of a base material (A) is not specifically limited, It is preferable that it is 3% or less, and it is more preferable that it is 1% or less. In addition, although the minimum of a haze value is not specifically limited, For example, it is 0.01%.

<Conductive layer (B)>
The conductive layer (B) is formed using a conductive composition containing a conductive polymer (b-1), an antioxidant (b-2), and a binder (b-3). Hereinafter, each component contained in the conductive composition will be described.

(Conductive polymer (b-1))
The conductive polymer (b-1) is a compound for imparting conductivity to the conductive layer (B). It does not specifically limit as a conductive polymer (b-1), A conventionally well-known conductive polymer can be used, For example, polythiophene, polypyrrole, polyaniline, polyacetylene, polyphenylene vinylene, polynaphthalene, And derivatives thereof. 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 conductive polymer (b-1) may form a complex with a dopant such as a polyanion.

Among 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. When the conductive composition contains poly (3,4-disubstituted thiophene) or a complex of poly (3,4-disubstituted thiophene) and polyanion (dopant), the temperature is low and the time is short. Thus, the conductive layer (B) can be formed and the productivity is also excellent. The polyanion is a dopant for the conductive polymer (b-1), 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, 1,2-ethylene group, 1,3-propylene group, 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.

Although the weight average molecular weight of a conductive polymer (b-1) is not specifically limited, It is preferable that it is 500-100000, It is more preferable that it is 1000-50000, It is most preferable that it is 1500-20000. When the weight average molecular weight is less than 500, the viscosity required when the conductive composition is used cannot be secured, and the conductivity of the conductive layer (B) when the conductive laminate is formed decreases. There is.

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-based conductive polymer in water may decrease. The weight average molecular weight is a value measured by gel permeation chromatography (GPC).

As a complex of the conductive polymer (b-1) and the polyanion, since it is particularly excellent in transparency and conductivity, a complex of poly (3,4-ethylenedioxythiophene) and polystyrenesulfonic acid. It is preferable that

The conductivity of the conductive polymer (b-1) is not particularly limited, but is preferably 0.01 S / cm or more from the viewpoint of imparting sufficient conductivity to the conductive layer (B). More preferably, it is 05 S / cm or more.

Although content of the conductive polymer (b-1) in a conductive composition is not specifically limited, When it is set as a conductive layer (B), the quantity used as 0.01-50.0 mg / m < ² > is preferable, 0 More preferable is an amount of ¹ to 10.0 mg / m ² . If it is less than 0.01 mg / m ² , the proportion of the conductive polymer (b-1) in the conductive layer (B) decreases, and the conductivity of the conductive layer (B) may not be sufficiently secured. On the other hand, if it exceeds 50.0 mg / m ² , the proportion of the conductive polymer (b-1) in the conductive layer (B) increases, which adversely affects the strength and film formability of the conductive layer (B). It is because it may be a cause to give.

(Antioxidant (b-2))
By blending the antioxidant (b-2) with the conductive composition, the heat and moisture resistance of the conductive layer (B) formed using the conductive composition is improved, and the conductive layer (B) is changed over time. It is possible to moderate the progress of the conductive deterioration. It does not specifically limit as antioxidant (b-2), A reducing water-soluble antioxidant, a non-reducing water-soluble antioxidant, etc. are mentioned. These may be used alone or in combination of two or more.

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. The compound which absorbs the ultraviolet rays which cause this is mentioned.

Among these, a compound having a lactone ring substituted with two hydroxyl groups and / or a compound having two or more phenolic hydroxyl groups is preferable, and L-ascorbic acid, sodium L-ascorbate, L-ascorbic acid More preferred is at least one selected from the group consisting of potassium, D (-)-isoascorbic acid, gallic acid, methyl gallate, propyl gallate and tannic acid.

The conductive laminate of the present invention needs to have high transparency and good appearance. Among the antioxidants (b-2), a compound having a lactone ring substituted with two hydroxyl groups, phenolic A compound having two or more hydroxyl groups is preferably used because it interacts with the polythiophene-based conductive polymer and the binder (b-3), so that it tends to stay in the conductive layer (B) and hardly deteriorates in appearance due to bleed-out. Is done.

Although pKa of antioxidant (b-2) is not specifically limited, It is preferable that it is 6 or less, and it is more preferable that it is 5 or less. When the pKa exceeds 6, hydrogen ions are hardly released from the acid, and the radical trap which is an antioxidant mechanism is difficult to function, so that the effect as an antioxidant may be weakened.

Although content of antioxidant (b-2) is not specifically limited as long as it is 50-400 weight part with respect to 100 weight part of conductive polymers (b-1), It is 75-400 weight part. Preferably, it is 100-400 weight part. When the content is less than 50 parts by weight, the effect of improving wet heat resistance may not be sufficiently obtained. When the content exceeds 400 parts by weight, the antioxidant (b-2) is formed after forming the conductive layer (B). May bleed out.

(Binder (b-3))
By mix | blending a binder (b-3) with an electroconductive composition, the compound in an electroconductive composition can be couple | bonded and a conductive layer (B) can be formed more reliably. Although it does not specifically limit as a binder (b-3), For example, a polyester resin, an acrylic resin, a urethane resin, an epoxy resin, a silicate resin, an acrylate, a melamine resin, a phenol resin, an olefin resin etc. are mentioned. Among these, from the viewpoint of substrate adhesion and dispersibility, at least one selected from the group consisting of polyester resin, acrylic resin, urethane resin, epoxy resin, silicate resin, acrylate and melamine resin is preferable. From the viewpoint of adhesion, at least one selected from the group consisting of a polyester resin, an acrylic resin, and a urethane resin is preferable. These binders (b-3) may be used alone or in combination of two or more.

The polyester 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 include terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and polybutylene naphthalate. 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. The acrylic resin may be a polymer containing a polymerizable monomer having an acid group such as a carboxyl group, an acid anhydride group, a sulfonic acid group, and a phosphoric acid group as a constituent monomer. Or a copolymer of a polymerizable monomer having an acid group and a copolymerizable monomer. These may be used alone or in combination of two or more.

The (meth) acrylic resin may be polymerized with a copolymerizable monomer as long as it contains a (meth) acrylic monomer as a main constituent monomer (for example, 50 mol% or more). It is sufficient that at least one of the (meth) acrylic monomer and the copolymerizable monomer has an acid group. Examples of the (meth) acrylic resin include an acid group-containing (meth) acrylic monomer [(meth) acrylic acid, sulfoalkyl (meth) acrylate, sulfonic acid group-containing (meth) acrylamide, etc.] or a combination thereof. Polymer, (meth) acrylic monomer optionally having acid group, and other polymerizable monomer having acid group [other polymerizable carboxylic acid, polymerizable polyvalent carboxylic acid or anhydride Vinyl aromatic sulfonic acid, etc.] and / or copolymerizable monomers [for example, (meth) acrylic acid alkyl ester, glycidyl (meth) acrylate, (meth) acrylonitrile, aromatic vinyl monomer, etc.] Polymer, other polymer monomer having an acid group and (meth) acrylic copolymerizable monomer [for example, (meth) acrylic acid alkyl ester, hydroxyalkyl (meth) acrylate, Rishijiru (meth) acrylate, copolymers of (meth) acrylonitrile, etc.], rosin-modified urethane acrylate, special modified acrylic resins, urethane acrylates, epoxy acrylates, and urethane acrylates emulsion and the like.

Among these (meth) acrylic resins, (meth) acrylic acid- (meth) acrylic acid ester polymers (acrylic acid-methyl methacrylate copolymer etc.), (meth) acrylic acid- (meth) acrylic acid An ester-styrene copolymer (such as acrylic acid-methyl methacrylate-styrene copolymer) is preferred.

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

The epoxy resin is not particularly limited. For example, a bisphenol A type, a bisphenol F type, a phenol novolak type, a tetrakis (hydroxyphenyl) ethane type or a tris (hydroxyphenyl) methane type which is a polyfunctional type having a large number of benzene rings. , Biphenyl type, triphenolmethane type, naphthalene type, orthonovolak 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.

Although it does not specifically limit as silicate resin, For example, it is the alkoxysilane made into high molecular weight formed by condensation of the monomers of the alkoxysilane represented by following formula (II), and a siloxane bond (Si-O). Examples include oligomers having at least one -Si) in one molecule.
SiR ³ ₄ (II)
(In the formula, R ³ is 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 3 is an alkoxy group having 1 to 4 carbon atoms or a hydroxyl group)
The structure of the alkoxysilane oligomer is not particularly limited, and may be linear or branched. Moreover, the alkoxysilane oligomer may use the compound represented by Formula (II) independently, and may use 2 or more types together.

Although it does not specifically limit as acrylate, For example, polyfunctional (meth) acrylate, urethane (meth) acrylate resin, etc. are mentioned. Examples of the polyfunctional (meth) acrylate include epoxy (meth) acrylate resin, bifunctional or higher polyester (meth) acrylate, polyether (meth) acrylate, carboxyl-modified reactive poly (meth) acrylate, and the like. Examples of the urethane (meth) acrylate resin include compounds obtained by reacting a hydroxy group-containing (meth) acrylate with a polyisocyanate. Examples of the hydroxy group-containing (meth) acrylate include 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, hydroxyhexyl (meth) acrylate, pentaerythritol triacrylate, diester Examples include pentaerythritol pentaacrylate and trimethylolpropane diacrylate. These may be used alone or in combination of two or more.

Although it does not specifically limit as a melamine resin, For example, the compound represented by the following general formula (III) is mentioned.

In the formula, R ^{4 to} R ⁹ are represented by H or CH ₂ OR ¹⁰ , and R ¹⁰ represents H or a C _1-4 alkyl group.

The melamine resin in which all the substituents R ^{4 to} R ⁹ are hydrogen atoms is an imino type melamine resin, the melamine resin in which all the substituents R ^{4 to} R ⁹ are CH ₂ OH is a methylol type melamine resin, and the substituent R A melamine resin having a structure in which ^{4 to} R ⁹ are all CH ₂ OR ¹⁰ and R ¹⁰ is substituted with a C _1-4 alkyl group is a full ether melamine resin. Melamine resins having a structure in which two of the three substituents are mixed in one molecule are classified into iminomethylol type, methylol ether type, or imino ether type, and the melamine resin in which all are mixed is an iminomethylol ether type. . When R ^{4 to} R ⁹ are represented by CH ₂ OR ¹⁰ and R ¹⁰ is a C _1-4 alkyl group, _examples of the C _1-4 alkyl group include a methyl group, an ethyl group, a propyl group, and butyl. There are groups. The melamine resin may be an oligomer self-condensed with formula (III) as a basic skeleton. These melamine resins may be used alone or in combination of two or more.

Although Tg of a binder (b-3) is not specifically limited, It is preferable that it is 0 degreeC or more, and it is more preferable that it is 20 degreeC or more. When Tg is less than 0 ° C., the antioxidant (b-2) may bleed out from the conductive layer (B) after the conductive layer (B) is formed.

Although content of a binder (b-3) is not specifically limited, It is preferable that it is 5-90 weight% in solid content of an electroconductive composition, and it is more preferable that it is 10-80 weight%. When the content is less than 5% by weight, poor curing may occur or adhesion may be insufficient. When the content exceeds 90% by weight, dispersibility deteriorates and the viscosity becomes too high, and the conductive composition. The applicability of the coating may deteriorate.

In addition to the conductive polymer (b-1), the antioxidant (b-2), and the binder (b-3), the conductive composition may optionally include other components as long as the object of the present invention is not impaired. It may contain. Examples of other components include, but are not limited to, conductivity improvers (b-4), metal nanowires, solvents, crosslinking agents, catalysts, surfactants and / or leveling agents, antifoaming agents, rheology control agents, A thickener, a neutralizing agent, etc. are mentioned.

(Conductivity improver (b-4))
By mix | blending electroconductivity improver (b-4) with an electroconductive composition, the electroconductivity of the conductive layer (B) formed using the electroconductive composition can be improved. The conductivity improver (b-4) evaporates by heating when forming the conductive layer (B). At that time, the conductive layer (B-1) is controlled by controlling the orientation of the conductive polymer (b-1). ) Is estimated to improve the conductivity. Moreover, when using a conductive improvement agent (b-4), compared with the case where a conductive improvement agent (b-4) is not used, a conductive polymer (b-1), maintaining surface resistivity. As a result, the blending amount can be reduced, and there is an advantage that transparency can be improved.

The conductivity improver (b-4) is at least one selected from the group consisting of (i) to (vii) below from the viewpoint of ensuring the conductivity required for the conductive layer (B). Preferably there is.
(I) a compound having a boiling point of 60 ° C. or more and having at least one ketone group in the molecule (ii) a compound having a boiling point of 100 ° C. or more and having at least one ether group in the molecule (iii) a molecule having a boiling point of 100 ° C. or more Compound (iv) having at least one sulfinyl group in it (iv) Compound having a boiling point of 100 ° C. or more and at least one amide group in the molecule (v) Compound having a boiling point of 50 ° C. or more and having at least one carboxyl group in the molecule (Vi) a compound having a boiling point of 100 ° C. or more and having at least two hydroxyl groups in the molecule (vii) a compound having a boiling point of 100 ° C. or more and having at least one lactam group in the molecule

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

Examples of the compound (ii) 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, 4-acryloylmorpholine, N-methylmorpholine N-oxide, 4-ethylmorpholine, 2-methoxyfuran and the like can be mentioned. These may be used alone or in combination of two or more.

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

Examples of the compound (v) having a boiling point of 50 ° C. or more 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, hexanoic acid, and octane. 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, malonic acid, Examples include 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 (vi) having a boiling point of 100 ° C. or more and having at least two hydroxyl groups in the molecule include ethylene glycol, diethylene glycol, propylene glycol, trimethylene glycol, β-thiodiglycol, triethylene glycol, and tripropylene glycol. 1,4-butanediol, 1,5-pentanediol, 1,3-butanediol, 1,6-hexanediol, neopentyl glycol, catechol, cyclohexanediol, cyclohexanedimethanol, glycerin, erythritol, glycerin, immutol, Examples include lactitol, maltitol, mannitol, sorbitol, xylitol, and sucrose. These may be used alone or in combination of two or more.

Examples of the compound (vii) 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 and the like. Can be mentioned. These may be used alone or in combination of two or more.

The conductivity improver (b-4) has a boiling point of 100 ° C. or higher from the viewpoint of volatility and dispersibility, and has at least one sulfinyl group, at least one amide group or at least two hydroxyl groups in the molecule. It is preferable that it is a compound which has this.

When the boiling point of the conductivity improver (b-4) is equal to or higher than a specific temperature, the conductivity improver (b-4) is gradually volatilized by heating during the formation of the conductive layer (B). In the process, the orientation of the conductive polymer (b-1) is controlled to an orientation advantageous for the conductivity, and as a result, the conductivity is considered to be improved. On the other hand, when the boiling point of the conductivity improver (b-4) is less than the specific temperature, the conductivity improver (b-4) is suddenly evaporated, and thus the conductive polymer (b-1). ) Is not sufficiently controlled, and it is considered that the conductivity is not improved.

When the conductive composition contains the conductivity improver (b-4), the content is not particularly limited, but is 0.01 to 100 parts by weight with respect to 100 parts by weight of the solid content of the conductive polymer (b-1). 100000 parts by weight is preferred, 0.1 to 10,000 parts by weight is more preferred, and 1 to 5000 parts by weight is even more preferred.

(Metal nanowires)
By mix | blending metal nanowire with a conductive composition, the electroconductivity of the conductive layer (B) formed using the conductive composition can be improved.

(solvent)
The solvent is not particularly limited. For example, 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, Such as tripropylene glycol Propylene glycols; propylene 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 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; diethyl ether, diisopropyl ether Ethers such as methyl-t-butyl ether and tetrahydrofuran; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; Carbonization such as toluene, xylene (o-, m-, or p-xylene), benzene, hexane, heptane, etc. Hydrogen: Esters such as ethyl acetate and butyl acetate: Halogens such as chloromethane (methyl chloride), dichloromethane (methylene chloride), trichloromethane (chloroform), tetrachloromethane (carbon tetrachloride), acetonitrile, water and these And a mixed solvent (hydrous organic solvent) with two or more organic solvents, and a mixed solvent of two or more organic solvents. These solvents may be used alone or in combination of two or more.

The solvent is preferably water, an organic solvent, or a mixed solvent of water and an organic solvent. When the conductive composition contains water as a solvent, the content of water is not particularly limited, but is preferably 70% by weight or less, and more preferably 50% by weight or less in the conductive composition. When content exceeds 70 weight%, a viscosity will fall and the applicability | paintability of an electroconductive composition may fall.

It is preferable that the solvent does not remain in the conductive layer (B) formed using the conductive composition. In the present specification, there is a particular distinction between those in which all components of the conductive composition are completely dissolved (ie, “solvent”) and those in which insoluble components are dispersed (ie, “dispersion medium”). All are described as “solvent”.

(Crosslinking agent)
By blending the crosslinking agent, the binder (b-3) can be crosslinked, and the strength of the conductive layer (B) formed using the conductive composition can be further 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 conductive composition contains a cross-linking agent, the content is not particularly limited, but is preferably 30% by weight or less, more preferably 20% by weight or less in the solid content of the conductive composition.

(catalyst)
When the conductive composition contains a binder (b-3) and a crosslinking agent, the catalyst for crosslinking the binder (b-3) is not particularly limited. For example, a photopolymerization initiator or a thermal polymerization initiator is used. Etc. When the conductive composition contains an acrylic resin as the binder (b-3), it is preferable to use a photopolymerization initiator.

(Surfactant and / or leveling agent)
By blending a surfactant and / or a leveling agent, the leveling property of the conductive composition can be improved, and a uniform conductive layer (B) is formed by using such a conductive composition. Can do.

(Thickener)
By mix | blending a thickener with an electroconductive composition, the viscosity and rheological characteristic of an electroconductive composition can be adjusted. Although it does not specifically limit as a thickener, For example, polyacrylic acid-type resin, a cellulose ether resin, polyvinylpyrrolidone, a polyurethane, a carboxy vinyl polymer, polyvinyl alcohol etc. are mentioned. These may be used alone or in combination of two or more.

The method for forming the conductive layer (B) using the conductive composition is not particularly limited, but the method of applying the conductive composition on the substrate (A) and then performing heat treatment, light irradiation treatment, etc. Is mentioned. A method for applying the conductive composition on the substrate (A) is not particularly limited, and examples thereof include a roll coating method, a bar coating method, a dip coating method, a spin coating method, a blade coating method, a curtain coating method, and a spray. A coating method, a doctor coating method, screen printing, offset printing, gravure offset printing, pad printing, or the like can be used. Of these, spray coating and screen printing are particularly preferred.

When applying a conductive composition on a base material (A), layers, such as a primer layer, may be previously formed on a base material (A), and a conductive composition may be apply | coated on the layer. Moreover, you may apply | coat an electroconductive composition, after giving surface treatment to the surface of a base material (A) previously as needed. The surface treatment is not particularly limited, and examples thereof include corona treatment, plasma treatment, itro treatment, and flame treatment.

The conductive layer (B) can be formed on the substrate (A) by subjecting the conductive composition applied on the substrate (A) to heat treatment, light irradiation treatment, or the like. The heat treatment is not particularly limited and may be performed by a known method. For example, the heat treatment may be performed using a blow oven, an infrared oven, a vacuum oven, or the like. Note that when the conductive composition contains a solvent, the solvent is removed by heat treatment.

Although heat processing is not specifically limited, It is preferable to perform on 150 degreeC or less temperature conditions. When the temperature of the heat treatment exceeds 150 ° C., the material of the base material (A) to be used is limited. For example, the base material (A) made of a material generally used for a transparent electrode film such as a PET film, a polycarbonate film, or an acrylic film. Can no longer be used. In this invention, even if it is heat processing on 150 degreeC or less temperature conditions, it has an advantage which can obtain the electrically conductive laminated body which has sufficient transparency and electroconductivity. The temperature of the heat treatment is preferably 50 to 140 ° C, and more preferably 60 to 130 ° C. Although the processing time of heat processing is not specifically limited, It is preferable that it is 0.1 to 60 minutes, and it is more preferable that it is 0.5 to 30 minutes.

The light irradiation treatment is not particularly limited, but mainly ultraviolet rays, visible light, electron beams, ionizing radiation, etc. are used. In the case of ultraviolet curing, ultraviolet rays emitted from a light source such as an ultra-high pressure mercury lamp, a high-pressure mercury lamp, a low-pressure mercury lamp, a carbon arc, a xenon arc, or a metal halide lamp can be used. Here, the irradiation amount of the energy ray source is about 50 to 5000 mJ / cm ² as an integrated exposure amount at an ultraviolet wavelength of 365 nm.

In the conductive laminate of the present invention, the surface resistivity of the conductive layer (B) is not particularly limited, but is preferably 10 ⁵ Ω / □ or less, and more preferably 10 ⁴ Ω / □ or less. In addition, since it is so preferable that a surface resistivity is small, the minimum is not limited, For example, it is 0.1 ohm / square. When the surface resistivity exceeds 10 ⁵ Ω / □, performance as an electrode may not be exhibited.

The surface resistivity of the conductive layer (B) after being held at 100 ° C. for 100 hours is not particularly limited, but is preferably 5 times or less of the surface resistivity before holding, and more preferably 3 times or less. preferable. If the surface resistivity after holding exceeds 5 times the surface resistivity before holding, the transparency may be insufficient.

The total light transmittance of the conductive laminate of the present invention is not particularly limited, but is preferably 50% or more, more preferably 60% or more, and further preferably 80% or more. On the other hand, the upper limit is 100%.

The haze value of the conductive laminate of the present invention is not particularly limited, but is preferably 1.0% or less, more preferably 0.8% or less, and further preferably 0.5% or less. The smaller the haze value is, the better. Therefore, the lower limit is not particularly limited, but is 0.01%, for example.

About the electrically conductive laminated body of this invention, the haze value after hold | maintaining for 24 hours at 100 degreeC is not specifically limited as long as it is 5 times or less of the haze value before holding | maintenance, but it is preferable that it is 2 times or less. If the haze value after holding exceeds 5 times the haze value before holding, the transparency may be insufficient.

<< Conductive composition >>
The conductive composition of the present invention is used for forming the conductive layer (B) in the conductive laminate of the present invention. The details of the conductive composition of the present invention are as described above.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated, this invention is not limited to a following example. Hereinafter, “part” or “%” means “part by weight” or “% by weight”, respectively, unless otherwise specified.

1. Materials used 1-1. Conductive polymer / conductive polymer (shown in Production Example 1 below)
-Conductive polymer (manufactured by Heraeus, Clevios PH1000, solid content 1.0%)

(Production Example 1) Production of conductive polymer 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 (PSS) (Mw = 56000) aqueous solution were added. The mixture was kept at 25 ° C. with nitrogen blowing and stirred for 1 hour. At this time, the temperature in the solution 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 is a nick process unit using an Impro 6000 series O ₂ sensor. 73O ₂ (measured using METTLER TOLEDO Co., Ltd.)]. 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%).

1-2. Binder (b-3)
Polyester resin (Toyobo Co., Ltd., Vironal MD-1245, Tg 61 ° C., solid content 30%)
Polyester resin (manufactured by Nagase ChemteX Corporation, Gabsen ES-9020, Tg 25 ° C., solid content 25%)
・ Polyester resin (manufactured by Kyoyo Chemical Industry Co., Ltd., plus coat Z-3310, Tg-20 ° C., solid content 25%)
-Urethane resin (Daiichi Kogyo Seiyaku Co., Ltd., Superflex 150, Tg 40 ° C, solid content 30%)
-Urethane resin (manufactured by DIC Corporation, Hydran WLS-210, Tg-30 ° C, solid content 35%)
・ Silicate resin (manufactured by Fuso Chemical Industry Co., Ltd., N-POS, Tg 150 ° C. or higher, solid content 70%)
・ Silicate resin (manufactured by Shin-Etsu Chemical Co., Ltd., KBE-402, Tg 150 ° C. or higher, solid content 100%)
Acrylate (Daiichi Kogyo Seiyaku Co., Ltd., New Frontier R-1150D, Tg 150 ° C. or higher, solid content 85%)

1-3. Antioxidant (b-2)
・ Ascorbic acid (Wako Pure Chemical Industries, pKa4.1)
・ Tannic acid (Wako Pure Chemical Industries, pKa3.0)
・ Gallic acid (Wako Pure Chemical Industries, pKa4.4)
Hydroquinone (Wako Pure Chemical Industries, pKa9.9)
・ Glucose (Wako Pure Chemical Industries, pKa12.0)

1-4. Conductivity improver (b-4)
・ Dimethyl sulfoxide (DMSO) (manufactured by Wako Pure Chemical Industries, Ltd.)
・ Dioxane (manufactured by Wako Pure Chemical Industries, Ltd.)
・ Ethylene glycol (Wako Pure Chemical Industries, Ltd.)

2. Evaluation Method The conductive laminates obtained in the respective examples and comparative examples were evaluated as follows.

2-1. Initial surface resistivity (SR)
The surface resistivity of the conductive layer (B) was measured using a resistivity meter (manufactured by Mitsubishi Chemical Corporation, Lorester GP MCP-T600).

2-2. Heat resistance (haze value)
The haze value immediately after the formation of the conductive laminate and the haze value after being kept at 100 ° C. for 24 hours using a blower constant temperature dryer (manufactured by Tokyo Rika Kikai Co., Ltd., model WFO-401) are used in accordance with JIS K7150. It was measured using HGM-2B) manufactured by Suga Test Instruments Co., Ltd., and the heat resistance (haze value) was evaluated in the following three stages.
○: Haze value after holding is 2 times or less of haze value before holding Δ: Haze value after holding is larger than 2 times haze value before holding and 5 times or less x: Haze after holding The value is larger than 5 times the haze value before holding

2-3. Heat resistance (surface resistivity)
A resistivity meter (the surface resistivity immediately after the formation of the conductive laminate and the surface resistivity after being held at 100 ° C. for 100 hours using a constant air dryer (Tokyo Rika Kikai Co., Ltd., WFO-401 type)) Measured using Mitsubishi Chemical Corporation, Lorester GP MCP-T600), the heat resistance (surface resistivity) was evaluated in the following three stages.
◯: The surface resistivity after holding is 3 times or less of the surface resistivity before holding Δ: The surface resistivity after holding is larger than 3 times the surface resistivity before holding and 5 times or less.
X: The surface resistivity after holding is larger than 5 times the surface resistivity before holding

(Examples 1-47, Comparative Examples 1-13)
Each component was mixed by the weight ratio described in Tables 1-3, and the electrically conductive composition was produced. Next, the obtained conductive composition was applied onto Lumirror T-60 (manufactured by Toray Industries, Inc.) as a base material (A) using a bar coater (manufactured by Yasuda Seiki Seisakusyo Co., Ltd.), and dried at a constant air temperature. The conductive layer (B) was formed by heat-processing for 10 minutes at 130 degreeC using a machine, and the electrically conductive laminated body was obtained.

Using the conductive laminates obtained in Examples 1 to 47 and Comparative Examples 1 to 13, the initial surface resistivity (SR) was measured by the method described above, and the heat resistance (haze value) and heat resistance (surface Resistivity). The results are shown in Tables 1-3.

Claims (9)

A conductive laminate having a conductive layer (B) on at least one surface of a substrate (A),
The conductive layer (B) is formed using a conductive composition containing a conductive polymer (b-1), an antioxidant (b-2), and a binder (b-3).
The content of the antioxidant (b-2) is 50 to 400 parts by weight with respect to 100 parts by weight of the conductive polymer (b-1).
The antioxidant (b-2) is a compound having a lactone ring substituted with two hydroxyl groups, and / or a compound having two or more phenolic hydroxyl groups,
A conductive laminate, wherein a haze value after being held at 100 ° C. for 24 hours is 5 times or less of a haze value before being held. The conductive laminate according to claim 1, wherein the binder (b-3) is at least one selected from the group consisting of a polyester resin, an acrylic resin, a urethane resin, an epoxy resin, a silicate resin, an acrylate, and a melamine resin. The conductive laminate according to claim 1, wherein the binder (b-3) is at least one selected from the group consisting of a polyester resin, an acrylic resin, and a urethane resin, and Tg is 0 ° C. or higher. The electrically conductive laminated body of any one of Claims 1-3 whose pKa of antioxidant (b-2) is 6 or less. The conductive layered product according to any one of claims 1 to 4 , wherein the conductive layer (B) has a surface resistivity after being held at 100 ° C for 100 hours being 5 times or less of a surface resistivity before holding. . Conductive layer surface resistivity of the (B) is 10 ⁵ Ω / □ or less, the conductive laminate according to any one of claims 1-5. The conductive laminate according to any one of claims 1 to 6 , wherein the conductive polymer (b-1) is a composite of poly (3,4-alkylenedioxythiophene) and polystyrenesulfonic acid. The conductive composition further includes a conductivity improver (b-4),
The conductivity improver (b-4) is a compound having a boiling point of 100 ° C or higher and having at least one sulfinyl group, at least one amide group, or at least two hydroxyl groups in the molecule. conductive laminate according to any one of 7. Conductive composition characterized in that it is used to form the conductive layer (B) in the conductive laminate according to any one of claims 1-8.