JP6575893B2 - Conductive resin composition and transparent conductive laminate - Google Patents

Description

The present invention relates to a conductive resin composition and a transparent conductive laminate, and further relates to a printing ink, a method for producing a transparent conductive laminate, a touch panel, and a touch sensor.

In recent years, there has been an increasing demand for transparent conductive laminates used as transparent electrodes, which are essential components for touch panels and display elements of various electronic devices. The transparent conductive laminate has a structure in which a transparent conductive film is laminated on a transparent base material using a conductive resin containing a conductive polymer. Known methods for producing the transparent conductive film include screen printing, offset printing, pad printing, and the like.

Since these printing methods do not require complicated steps, they can be patterned easily at low cost, and are extremely excellent in productivity. On the other hand, the ink used requires a high viscosity. Patent Document 1 discloses a solution or dispersion of a complex of poly (3,4-ethylenedioxythiophene) [PEDOT] and polystyrene sulfonic acid [PSS] ([PEDOT] / [PSS]) as a conductive polymer. A solution or dispersion having a content of [PEDOT] / [PSS] of less than 2% by weight is concentrated to more than 2% by weight, and optionally a binder, a thickening agent, and a filler are blended. A resin composition having a viscosity of 1 to 200 dPa · s is disclosed. Patent Document 2 discloses a resin composition in which crosslinkable polyacrylic acid is blended as a thickener in the aqueous dispersion of [PEDOT] / [PSS].

Special table 2002-500408 gazette Special Table 2004-532307

However, the method described in Patent Document 1 requires a step of concentrating the conductive polymer, which increases the cost of the conductive resin composition. In addition, in the method described in Patent Document 2, although the viscosity of the composition increases, the dispersion stability of the conductive polymer deteriorates due to the influence of the liquid property change due to the addition of the thickener, resulting in a liquid resin composition. Precipitates were observed, and the transparent conductive film obtained by coating the resin composition on the base material had problems such as marks on the coating bar and inferior transparency.

As a result of intensive studies to solve the above problems, the present inventors have observed precipitates in a conductive resin composition containing an aqueous dispersion of a conductive polymer having a higher viscosity than the conventional conductive polymer. The transparent conductive film obtained from the composition was found to have good appearance and excellent transparency, and the present invention was completed.

That is, the conductive resin composition of the present invention is
It contains (A) a conductive polymer, (B) a conductivity improver, and (C) a binder, and has a viscosity of 10 to 1000 dPa · s at 25 ° C.

The conductive resin composition of the present invention preferably has a thixotropy index of 1 to 15 at 25 ° C.

The conductive resin composition of the present invention preferably has a yield value at 25 ° C. of 2 to 500 Pa.

The conductive resin composition of the present invention preferably has no flash point.

In the conductive resin composition of the present invention, the conductive polymer (A) is preferably a composite of poly (3,4-ethylenedioxythiophene) and polystyrenesulfonic acid.

In the conductive resin composition of the present invention, the binder (C) is at least one selected from the group consisting of polyester resins, polyurethanes, epoxy resins, acrylic resins, alkoxysilane oligomers, and polyolefin resins. preferable.

The printing ink of the present invention is characterized by including the conductive resin composition of the present invention.

The transparent conductive laminate of the present invention is obtained by printing the printing ink of the present invention on a substrate, and exhibits a surface resistivity of 0.1 to 1000Ω / □ and a total light transmittance of 50% or more. It is characterized by that.

The transparent conductive laminate of the present invention is preferably printed by at least one means selected from the group consisting of screen printing, offset printing and pad printing.

The manufacturing method of the transparent conductive laminated body of this invention is characterized by including the process of printing the printing ink of this invention on a base material.

In the method for producing a transparent conductive laminate of the present invention, printing is preferably performed by at least one means selected from the group consisting of screen printing, offset printing, and pad printing.

The touch panel or touch sensor of the present invention is characterized by using the transparent conductive laminate of the present invention.

In the conductive resin composition of the present invention, since a highly viscous conductive polymer is contained, no precipitate is observed, and the obtained transparent conductive film has a good appearance and excellent transparency. .

The conductive resin composition of the present invention is
A conductive resin composition containing (A) a conductive polymer, (B) a conductivity improver, and (C) a binder and having a viscosity at 25 ° C. of 10 to 1000 dPa · s.

<(A) Conductive polymer>
(A) A conductive polymer is a compound for providing electroconductivity to a transparent conductive film. (A) The conductive polymer 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. Is mentioned. 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. (A) The conductive polymer 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. In addition, when the conductive resin composition is poly (3,4-disubstituted thiophene) or a composite of poly (3,4-disubstituted thiophene) and polyanion (dopant), the temperature is low and short. A transparent conductive film can be formed in time, and 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 conductive polymer 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 composition cannot be ensured, and the conductivity for the transparent conductive laminate 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).

(A) The composite of the conductive polymer and the polyanion is a composite of poly (3,4-ethylenedioxythiophene) and polystyrene sulfonic acid because it is particularly excellent in transparency and conductivity. Is preferred.

(A) The conductivity of the conductive polymer 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 conductive film. More preferably.

The content of the conductive polymer (A) in the conductive resin composition is not particularly limited, and when the transparent conductive laminate is formed, an amount of 0.01 to 50.0 mg / m ² is preferable, An amount of 10.0 mg / m ² is more preferable. If it is less than 0.01 mg / m ² , the proportion of the conductive polymer (A) in the transparent conductive film decreases, and the conductivity of the transparent conductive film may not be sufficiently secured. If it exceeds / m ² , the proportion of the conductive polymer (A) in the transparent conductive film increases, which may cause a negative effect on the strength and film formability of the coating film.

(A) The viscosity of the conductive polymer is preferably 5 to 500 dPa · s, preferably 10 to 500 dPa · s in a 1 to 5 wt% aqueous dispersion, preferably 2 to 5 wt% aqueous dispersion at 25 ° C. Is more preferable. If it is less than 5 dPa · s, the viscosity required for the composition cannot be ensured, and if it exceeds 500 dPa · s, problems such as foaming at the time of blending and inability to mix uniformly tend to occur. In the present specification, the viscosity is a value measured using a B-type viscometer.

(A) The thixotropic index (Ti) of the conductive polymer is preferably 0.1 to 10 in a 1 to 5 wt% aqueous dispersion, preferably 2 to 5 wt% aqueous dispersion at 25 ° C. Is more preferably from 10 to 10, and even more preferably from 1 to 8. (A) When a conductive polymer has a thixotropy index within the above range, a thixotropy index described later can be achieved when a composition is used. In this specification, the thixotropy index is a ratio of the viscosity η ₁ at a shear rate of 1 (1 / s) and the viscosity η ₁₀ at a shear rate of 10 (1 / s) at 25 ° C. using a rheometer (Ti value). = Η ₁ / η ₁₀ ).

(A) The yield value of the conductive polymer is preferably 1 to 100 Pa and preferably 2 to 100 Pa in a 1 to 5 wt% aqueous dispersion, preferably 2 to 5 wt% aqueous dispersion at 25 ° C. Is more preferable. (A) When a conductive polymer has a yield value in the above range, a yield value described later can be achieved when a composition is used. Yield value was measured using a rheometer, changing the shear rate in the range of 0.01 (1 / s) to 100 (1 / s) at 25 ° C., and Casson's approximate expression (√stress = √viscosity velocity × √shear rate + √yield value).

(A) As an example of a method for producing a conductive polymer, a method for producing an aqueous dispersion of a complex of polythiophene and a dopant represented by formula (I) will be described. 3,4-dialkoxythiophene represented by the following formula (II)

(Wherein R ³ and R ⁴ each independently represent a hydrogen atom or a C _1-4 alkyl group, or, when R ³ and R ⁴ are bonded, a C _1-4 alkylene) The alkyl group of C _1-4 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 ³ and R ⁴ 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, 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 groups, etc. Among these, , Methylene group, 1,2-ethylene, 1,3-propylene group are preferred, 1,2-ethylene group is more preferred alkyl groups _{.C 1-4,} and _an alkylene group of _{C 1-4,} the A part of hydrogen may be substituted.)
Is produced through a step of oxidative polymerization in an aqueous solvent using an oxidizing agent in the presence of a dopant.

In the production of polythiophene, a monomer is oxidatively polymerized by a chemical polymerization method using various oxidizing agents. Since the chemical polymerization method is simple and capable of mass production, it is a method suitable for an industrial production method as compared with the conventional electrolytic polymerization method.

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

The amount of dopant such as polyanion used is preferably in the range of 50 to 2000 parts by weight, more preferably in the range of 100 to 1000 parts by weight with respect to 100 parts by weight of 3,4-dialkoxythiophene.

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

The conductive polymer (A) having the above viscosity has a higher reaction temperature, lowers the pH of the reaction system, lowers the stirring speed, and lowers the dissolved oxygen concentration, compared with the conductive polymer production conditions generally used in general. It can be produced by controlling the conditions in terms of increasing the reaction concentration. By controlling these conditions, it is considered that the above-mentioned viscosity and further the thixotropy index / yield value can be achieved by increasing the molecular weight or agglomerating the obtained conductive polymer.

The temperature of the oxidative polymerization reaction is preferably 0 to 40 ° C, more preferably 5 to 35 ° C. If it is less than 0 ° C, the polymerization reaction of the conductive polymer does not proceed sufficiently and the conductivity may be insufficient. If it exceeds 40 ° C, the polymerization reaction tends to proceed excessively and the dispersion stability tends to deteriorate. .

The pH during polymerization is preferably from 0.1 to 5.0, more preferably from 0.1 to 3.0. If it is less than 0.1, the polymerization reaction may proceed excessively and the dispersion stability may deteriorate, and if it exceeds 5.0, the polymerization reaction of the conductive polymer does not proceed sufficiently and the conductivity tends to be insufficient. There is.

100-1000 rpm is preferable and, as for the stirring speed of the reaction liquid mixture at the time of superposition | polymerization, 200-500 rpm is more preferable. If it is less than 100 rpm, the polymerization reaction may proceed excessively and dispersion stability may deteriorate, and if it exceeds 1000 rpm, the polymerization reaction of the conductive polymer does not proceed sufficiently and the conductivity tends to be insufficient.

1-10% is preferable and, as for the reaction concentration of the reaction liquid mixture at the time of superposition | polymerization, 1-6% is more preferable. If it is less than 1%, the polymerization reaction of the conductive polymer does not proceed sufficiently, and the conductivity may be insufficient. If it exceeds 10%, the polymerization reaction proceeds excessively and the dispersion stability tends to deteriorate. .

The conductive polymer (A) obtained by the above production method has an average particle diameter of 60 to 10000 nm, preferably 70 to 5000 nm, due to high molecular weight or secondary aggregation. Here, an average particle diameter means what is measured by a dynamic light scattering method (DLS).

In the present invention, the aqueous dispersion of the conductive polymer (A) produced in the above step can be used as a blending raw material without going through the concentration step.

<(B) Conductivity improver>
(B) The conductivity improver is added for the purpose of improving the conductivity of the transparent conductive film formed using the conductive resin composition of the present invention. (B) The conductivity improver evaporates by heating when forming the transparent conductive film, and (A) improves the conductivity of the transparent conductive film by controlling the orientation of the conductive polymer. Presumed. In addition, when (B) the conductivity improver is used, the amount of the (A) conductive polymer can be reduced while maintaining the surface resistivity as compared with the case where (B) the conductivity improver is not used. , There is an advantage that can improve transparency.

(B) The conductivity improver may be at least one selected from the group consisting of (i) to (vii) below from the viewpoint of ensuring the necessary conductivity for the use of the transparent conductive film. preferable.
(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 two or more 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 higher 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 two or more 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, inmitol, 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 (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.

(B) When the boiling point of the conductivity improver is equal to or higher than a specific temperature, (B) the conductivity improver gradually volatilizes by heating during the formation of the transparent conductive film. ) It is considered that the orientation of the conductive polymer is controlled to an orientation advantageous for the conductivity, and as a result, the conductivity is improved. On the other hand, if the boiling point of the (B) conductivity improver is less than the specific temperature, the (B) conductivity improver suddenly evaporates, so that the (A) conductive polymer is sufficiently oriented. It is considered that the conductivity is not improved without being controlled.

Further, (B) the conductivity improver is not particularly limited, but has an SP value of δD = 12-30, δH = 3-30, δP = 5-30, and δD + δH + δP = 35-70. It is more preferable to have an SP value of δD = 15 to 25, δH = 10 to 25, δP = 10 to 25, and δD + δH + δP = 35 to 70.

In this specification, the SP value refers to Hansen's solubility parameter, and the solubility of a substance is expressed by three parameters: a dispersion term δD, a polar term δH, and a hydrogen bond term δP. By adding the (B) conductivity improver having an SP value within the above range, it is considered that (A) the conductive polymer is pseudo-dissolved and the alignment is promoted in the evaporation process. On the other hand, the (B) conductivity improver having an SP value outside the above range is less likely to interact with the (A) conductive polymer, and therefore cannot obtain a sufficient conductivity improvement effect by controlling the arrangement. Sometimes.
In addition, since the (B) conductivity improver having an SP value within the above range has a high affinity with (A) the conductive polymer, the stability of the dispersion of the (A) conductive polymer can be improved. .

The SP value is δD = 12-30, δH = 3-30, δP = 5-30, and δD + δH + δP = 35-70. (B) The conductivity improver is not particularly limited, but for example, isocyanate ( δD = 15.8, δH = 10.5, δP = 13.6), methyl isothiocyanate (δD = 17.3, δH = 16.2, δP = 10.1), trimethyl phosphate (δD = 15. 7, δH = 10.5, δP = 10.2), 2-methyl lactonitrile (δD = 16.6, δH = 12.2, δP = 15.5), ephedrine (δD = 18.0, δH = 10.7, δP = 24.1), thiourea (δD = 20.0, δH = 19.4, δP = 14.8), carbamonitrile (δD = 15.5, δH = 27.6, δP) = 16.8), ethylene cyanohydrin (δD = 17.2, δH = 18.8, δP = 17.6), pyrazole (δD = 20.2, δH = 10.4, δP = 12.4) and the like. These may be used alone or in combination of two or more.

Moreover, (B) As the conductivity improver, those having the above-mentioned (i) to (vii) and an SP value within the above range can also be used.

Although content of (B) electroconductivity improver is not specifically limited, 5-2000 weight part is preferable with respect to 100 weight part of solid content of (A) conductive polymer, and 10-1500 weight part is more preferable. If the amount is less than 5 parts by weight, the conductivity improving effect due to the addition of the conductivity improver (B) may not be fully enjoyed. On the other hand, when the amount exceeds 2000 parts by weight, the content of the conductive polymer (A) in the conductive resin composition of the present invention is relatively reduced, and sufficient conductivity cannot be obtained when a transparent conductive film is obtained. Sometimes.

<(C) Binder>
(C) The binder is added for the purpose of bonding the compounds in the conductive resin composition of the present invention to form a transparent conductive film (including a conductive pattern) more reliably. The (C) a binder is not particularly limited, for example, polyester resin, polyurethane, epoxy resin, A Turkey silane oligomer, and at least is one selected from the group consisting of polyolefin-based resin.

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 alkoxysilane oligomer is, for example, a high molecular weight alkoxysilane formed by condensation of alkoxysilane monomers represented by the following formula (III), and has a siloxane bond (Si—O—Si). Examples include oligomers having one or more in one molecule.
SiR ₄ (III)
(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 structure of the alkoxysilane oligomer is not particularly limited, and may be linear or branched. Moreover, as an alkoxysilane oligomer, the compound represented by Formula (III) may be used independently, and 2 or more types may be used together. Although the weight average molecular weight of an alkoxysilane oligomer is not specifically limited, It is preferable that it is larger than 152 and 4000 or less, It is more preferable that it is 500-2500, It is more preferable that it is 500-1500. Here, the weight average molecular weight is a value measured by gel permeation chromatography (GPC).

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.

(C) Content of a binder is not specifically limited, However, 0.1-1000 weight part is preferable with respect to 100 weight part of (A) solid content of a conductive polymer, and 5-500 weight part is more preferable. When the amount is less than 0.1 part by weight, the strength of the transparent conductive laminate may be weakened. When the amount exceeds 1000 parts by weight, the content of the conductive polymer (A) in the conductive resin composition is small. In some cases, the conductivity is relatively small and sufficient conductivity cannot be ensured when a transparent conductive film is formed.

<(D) Thickener>
The conductive resin composition of the present invention preferably contains substantially no (D) thickener in order to avoid the formation of precipitates. Here, “substantially does not contain” means that in the conductive resin composition of the present invention, (A) the content of the thickener is 10 with respect to 100 parts by weight of the solid content of the conductive polymer. It means not more than parts by weight, preferably not more than 5 parts by weight, more preferably not more than 1 part by weight.

In this specification, the (D) thickener means polyacrylic acid resin, cellulose ether resin, polyvinyl pyrrolidone, carboxyvinyl polymer, and polyvinyl alcohol. Examples of commercially available thickeners include CARBOPOL ETD-2623 (crosslinkable polyacrylic acid, manufactured by BF Goodrich), GE-167 (N-vinylacetamide / acrylic acid copolymer, Showa Denko KK). Manufactured), dirimer (polyacrylic acid, manufactured by Nippon Pure Chemicals Co., Ltd.), polyvinylpyrrolidone K-90 (polyvinylpyrrolidone, manufactured by Nippon Shokubai Co., Ltd.), and the like.

<Optional component>
The conductive resin composition of the present invention optionally contains other components in addition to (A) the conductive polymer, (B) the conductivity improver, and (C) the binder as long as the object of the present invention is not impaired. It may be. Examples of other components include a solvent, a crosslinking agent, a catalyst, a surfactant and / or a leveling agent, a water-soluble antioxidant, a metal nanowire, an antifoaming agent, a rheology control agent, and a neutralizing agent.

The solvent is not particularly limited. For example, water; alcohols such as methanol, ethanol, 2-propanol, 1-propanol, and glycerin; ethylene glycols such as ethylene glycol, diethylene glycol, triethylene glycol, and tetraethylene glycol; ethylene Glycol ethers such as glycol monomethyl 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 Propylene glycols such as coal; 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 Propylene glycol ethers such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, etc .; tetrahydrofuran; acetone Acetonitrile. These solvents may be used alone or in combination of two or more.

The solvent is preferably water or a mixture of water and an organic solvent. When the conductive resin composition of the present invention contains water as a solvent, the content of water is not particularly limited, but (A) 20 to 1,000,000 parts by weight with respect to 100 parts by weight of the solid content of the conductive polymer. Preferably, 200 to 500000 parts by weight is more preferable. If the water content is less than 20 parts by weight, the viscosity may increase and handling may be difficult. If it exceeds 1000000 parts by weight, the concentration of the solution becomes too low and the thickness of the transparent conductive film can be adjusted. It can be difficult.

When the solvent contains a mixture of water and an organic solvent, the organic solvent is at least one selected from the group consisting of methanol, ethanol, 2-propanol, glycerin, ethylene glycol, diethylene glycol, triethylene glycol, and tetraethylene glycol. It is preferable that Content of an organic solvent is not specifically limited, 20-700000 weight part is preferable with respect to 100 weight part of solid content of a conductive polymer, and 200-350,000 weight part is more preferable. The ratio of water to the organic solvent (water: organic solvent) is preferably 100: 0 to 5:95, more preferably 100: 0 to 30:70, by weight.

It is preferable that the solvent does not remain in the transparent conductive laminate formed using the conductive resin composition. In the present specification, a distinction is made between those in which all components of the conductive resin composition are completely dissolved (ie, “solvent”) and those in which insoluble components are dispersed (ie, “dispersion medium”). Without being described as “solvent”.

By blending the crosslinking agent, the binder (C) can be crosslinked, and the strength of the transparent conductive film formed using the conductive resin 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 it contains a crosslinking agent, the content is not particularly limited, but (A) 0.1 to 17000 parts by weight is preferable and 1 to 1000 parts by weight is more preferable with respect to 100 parts by weight of the solid content of the conductive polymer. . When the content of the crosslinking agent is less than 0.1 parts by weight, the strength of the transparent conductive film may be insufficient. On the other hand, when the content exceeds 17000 parts by weight, the (A) conductive polymer in the transparent conductive film. In some cases, the conductivity of the transparent conductive film cannot be sufficiently ensured.

When it contains a crosslinking agent, (C) As a catalyst for crosslinking the binder, an acidic group of the dopant may be used, or an organic acid or an inorganic acid may be newly added. Moreover, you may add a heat sensitive acid generator, a radiation sensitive acid generator, an electromagnetic wave sensitive acid generator, etc.

The catalyst is not particularly limited, and for example, a photopolymerization initiator or a thermal polymerization initiator that is usually used in the field can be used. (C) When using an acrylic resin as a binder, it is preferable to use a photoinitiator as a catalyst.

Although content of a catalyst is not specifically limited, It is preferable that it is 0.01-100 weight part with respect to 100 weight part of (C) binder, and it is more preferable that it is 0.1-10 weight part. When the content of the catalyst is less than 0.01 parts by weight, the function as a catalyst may not be sufficient. When the content exceeds 100 parts by weight, the proportion of the conductive polymer (A) decreases, and the transparent conductive film This is because sufficient conductivity may not be ensured.

By adding a surfactant and / or a leveling agent, the leveling property of the conductive resin composition can be improved, and a uniform transparent film can be formed by forming a transparent conductive film using the conductive resin composition. A conductive film can be obtained. In the present invention, one compound may correspond to both a surfactant and a leveling agent.

The surfactant is not particularly limited as long as it has an effect of improving leveling properties, and specific examples thereof include, for example, polyether-modified polydimethylsiloxane, polyether-modified siloxane, polyetherester-modified hydroxyl group-containing polydimethyl Siloxane compounds such as siloxane, polyether-modified acrylic group-containing polydimethylsiloxane, polyester-modified acrylic group-containing polydimethylsiloxane, perfluoropolydimethylsiloxane, perfluoropolyether-modified polydimethylsiloxane, perfluoropolyester-modified polydimethylsiloxane; Fluorine-containing organic compounds such as fluoroalkyl carboxylic acid and perfluoroalkyl polyoxyethylene ethanol; polyoxyethylene alkyl phenyl ether, propylene ether Polyether compounds such as side polymers and ethylene oxide polymers; carboxylic acids such as coconut oil fatty acid amine salts and gum rosins; castor oil sulfates, phosphate esters, alkyl ether sulfates, sorbitan fatty acid esters, sulfonate esters, succinates Ester compounds such as acid esters; sulfonate compounds such as alkyl aryl sulfonate amine salts and dioctyl sodium sulfosuccinate; phosphate compounds such as sodium lauryl phosphate; amide compounds such as coconut oil fatty acid ethanolamide; acrylic compounds Etc. These surfactants may be used alone or in combination of two or more.
Among these, a siloxane compound and a fluorine-containing organic compound are preferable because a leveling property improvement effect is remarkably obtained.

Commercially available products can also be used as the surfactant. Specific examples thereof include BYK-301, BYK-302, BYK-307, BYK-331, BYK-333, BYK-337, and BYK-341. , BYK-375, BYK-378, BYK-380N, BYK-340, BYK-DYNWET800 (all manufactured by Big Chemie Japan Co., Ltd.), NIKKOL AM-101, NIKKOL AM-301, NIKKOL AM-3130N (all Japanese surfactant) Industrial Co., Ltd.), Asahi Guard AG-8025, Asahi Guard MA-91 (both by Meisei Chemical Industry Co., Ltd.), Amipol AS-8 (Nikka Chemical Co., Ltd.), Amorgen AOL, Amorgen CB-C, Amorgen CB -H, Amorgen LB-C, A Gen No. 8, Amorgen S, Amorgen S-H (all manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Amphithol series (manufactured by Kao Corporation), Amphora 35N, Amphora 50, Amphora 50-SF (all Miyoshi oil and fat Manufactured by Co., Ltd.), Plus Coat RY-2 (manufactured by Kanayo Chemical Co., Ltd.), Energy Coal C-30 B (manufactured by Lion Co., Ltd.), Obazoline 662N, Katchinal AOC (all manufactured by Toho Chemical Co., Ltd.), Offnon D (Manufactured by Yushiro Chemical Co., Ltd.), Crink A-27 (manufactured by Yoshimura Oil Chemical Co., Ltd.), Genagen B 1566 (manufactured by Clariant Japan Co., Ltd.), KF-351, KF-352, KF-354L, KF-355A, KF -618, KF-6011, X-22-4272 (all manufactured by Shin-Etsu Silicone Co., Ltd.), CA PSTONE FS-3100 (manufactured by DuPont) and the like.

The leveling agent 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 Siloxane compounds such as polydimethylsiloxane, perfluoropolydimethylsiloxane, perfluoropolyether-modified polydimethylsiloxane, and perfluoropolyester-modified polydimethylsiloxane; fluorine-containing organic materials such as perfluoroalkylcarboxylic acid and perfluoroalkylpolyoxyethyleneethanol Compound: Polyether compound such as polyoxyethylene alkylphenyl ether, propylene oxide polymer, ethylene oxide polymer Carboxylic acids such as coconut oil fatty acid amine salt and gum rosin; castor oil sulfate esters, phosphate esters, alkyl ether sulfates, sorbitan fatty acid esters, sulfonate esters, succinate esters and other ester compounds; alkyl aryl sulfonate amines Examples thereof include salts, sulfonate compounds such as dioctyl sodium sulfosuccinate; phosphate compounds such as sodium lauryl phosphate; amide compounds such as coconut oil fatty acid ethanolamide; acrylic compounds and the like. These leveling agents may be used independently and may use 2 or more types together.

Commercially available products can also be used as the leveling agent. Specific examples thereof include BYK-325, BYK-345, BYK-346, BYK-347, BYK-348, BYK-349, BYK-UV3500, BYK-381, BYKEOL-AQ, BYKETOL-WS (all manufactured by Big Chemie Japan Co., Ltd.), Polyflow WS, Polyflow WS-30, Polyflow WS-314 (all manufactured by Kyoeisha Chemical Industry Co., Ltd.), and the like.

By mix | blending a water-soluble antioxidant, the heat resistance of the transparent conductive film formed using the said composition for transparent conductive film formation, and heat-and-moisture resistance can be improved.

The water-soluble antioxidant is not particularly limited, and examples thereof include a reducing water-soluble antioxidant and a non-reducing water-soluble antioxidant.
Examples of the reducing water-soluble antioxidant include L-ascorbic acid, sodium L-ascorbate, potassium L-ascorbate, D (-)-isoascorbic acid (erythorbic acid), sodium erythorbate, and erythorbic acid. Compounds having a lactone ring substituted with two hydroxyl groups such as potassium; monosaccharides or disaccharides (excluding sucrose) such as maltose, lactose, cellobiose, xylose, arabinose, glucose, fructose, galactose, mannose; , Flavonoids such as rutin, myricetin, quercetin, kaempferol, sanmerin (registered trademark) Y-AF; phenolic hydroxyl groups such as curcumin, rosmarinic acid, chlorogenic acid, hydroquinone, 3,4,5-trihydroxybenzoic acid, tannic acid Compounds having two or more; cysteine, glutathione, a compound having a pentaerythritol tetrakis (3-mercapto butyrate) thiol groups, such as and the like.
Examples of the non-reducing water-soluble antioxidant include oxidation of phenylimidazolesulfonic acid, phenyltriazolesulfonic acid, 2-hydroxypyrimidine, phenyl salicylate, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid sodium, and the like. Examples include compounds that absorb ultraviolet rays that cause deterioration.
These water-soluble antioxidants may be used alone or in combination of two or more.

Among these, at least one compound selected from the group consisting of a compound having a lactone ring substituted with two hydroxyl groups and a compound having two or more phenolic hydroxyl groups is preferred, and D (-)- Isoascorbic acid or Sanmerin (registered trademark) Y-AF is more preferred.

When the conductive resin composition of the present invention contains the water-soluble antioxidant, the content thereof is not particularly limited, but (A) 0.001 to 500 weights with respect to 100 weight parts of the solid content of the conductive polymer. Part is preferable, 0.01 to 250 parts by weight is more preferable, and 0.05 to 100 parts by weight is further preferable.
If the content of the water-soluble antioxidant is less than 0.001 part by weight, the heat resistance and moist heat resistance of the transparent conductive film formed using the conductive resin composition may not be sufficiently improved. On the other hand, when the amount exceeds 500 parts by weight, the proportion of the conductive polymer (A) in the transparent conductive film formed using the conductive resin composition decreases, and the conductivity of the transparent conductive film is sufficiently ensured. May not be possible.

By mix | blending metal nanowire, the electroconductivity at the time of using the conductive resin composition of this invention as a transparent conductive film can be improved.
As metal nanowire, what consists of a metal simple substance or a metal containing compound is mentioned.
Although it does not specifically limit as said metal simple substance, For example, silver, copper, silver, iron, cobalt, nickel, zinc, ruthenium, rhodium, palladium, cadmium, osmium, iridium, platinum etc. are mentioned, As said metal containing compound, Although there is no particular limitation, examples include those containing these metals. These metal nanowires may be used alone or in combination of two or more.

The metal nanowire is preferably at least one selected from the group consisting of silver nanowires, copper nanowires, and gold nanowires. This is because the free electron concentration is high and the conductivity is high compared to other metal nanowires.

Although the diameter of metal nanowire is not specifically limited, It is preferable that it is 1-1000 nm, and it is more preferable that it is 1-100 nm. When the diameter of the metal nanowire is less than 1 nm, the wire itself may be easily cut, and when it exceeds 1000 nm, the haze value of the coating film may be increased.
Although the length of metal nanowire is not specifically limited, It is preferable that it is 1-1000 micrometers, and it is more preferable that it is 1-100 micrometers. When the length of the metal nanowire is less than 1 μm, it may cause a decrease in the conductivity of the coating film, and when it exceeds 1000 μm, the stability of the metal nanowire dispersion may be deteriorated.

The aspect ratio of the metal nanowire is not particularly limited, but is preferably 50 to 10,000, and more preferably 70 to 7000.
This is because when the aspect ratio of the metal nanowire is less than 50, the conductivity of the coating film is lowered, and when it exceeds 10,000, the stability of the metal nanowire dispersion is deteriorated.
In the present invention, the aspect ratio represents the ratio of the length to the diameter of the metal nanowire.

Since the conductive resin composition of the present invention is acidic, a basic compound can be used as the neutralizing agent. The basic compound is not particularly limited, and examples thereof include hydroxides and carbonates such as alkali metals and alkaline earth metals, ammonium compounds such as ammonia, and amines. These may be used alone or in combination of two or more.

In the conductive resin composition of the present invention, the viscosity at 25 ° C. is 10 to 1000 dPa · s, preferably 20 to 1000 dPa · s, and more preferably 60 to 800 dPa · s. If it is less than 10 dPa · s, the adhesion to the substrate becomes poor due to poor drying.
The viscosity measurement conditions are as described above.

In the conductive resin composition of the present invention, the thixotropy index (Ti) at 25 ° C. is preferably 0.2 to 15, more preferably 1 to 15, and further preferably 1 to 10. If the ratio is less than 0.2, the lines and characters are likely to blur due to liquid dripping, making it difficult to use in applications such as printing ink.
The measurement conditions for the thixotropy index are as described above.

In the conductive resin composition of the present invention, the yield value at 25 ° C. is preferably 2 to 500 Pa, and more preferably 5 to 500 Pa. If it is less than 2 Pa, fluidity is exhibited even when it is left standing, and printing cannot be performed because it cannot remain on the plate.
The measurement conditions for the yield value are as described above.

The conductive resin composition of the present invention preferably has no flash point. When there is no flash point, the risk of fire is greatly reduced, and handling is very easy in terms of transportation, storage and disposal, and safety is high.

The water content of the conductive resin composition of the present invention is not particularly limited, but is preferably 30% by weight or more, more preferably 40% by weight or more, and further preferably 50% by weight or more. When the water content is 30% by weight or more, the film performance is not affected by the type of the organic solvent, and the degree of freedom in blending is high.

The printing ink of the present invention contains the conductive resin composition of the present invention and is suitably used for printing means such as screen printing, offset printing, and pad printing. Since these printing means do not require a complicated process, patterning can be performed easily at low cost. Since the printing ink of the present invention contains a high-viscosity conductive polymer, it can be suitably applied to screen printing that requires a high viscosity. Moreover, the obtained coating film has a good external appearance and excellent transparency.

The transparent conductive laminate of the present invention is obtained by printing a printing ink containing the above conductive resin composition on a substrate, and has a surface resistivity of 0.1 to 1000Ω / □ and a total of 50% or more. The light transmittance is shown. By printing, a transparent conductive film can be formed on the substrate.

A transparent substrate is preferable as the substrate. The material of the transparent substrate is not particularly limited as long as it is transparent. For example, glass, polyethylene terephthalate (PET), polyethylene naphthalate, modified polyester and other polyester resins, polyethylene (PE) resin, and polypropylene (PP) resin. , Polyolefin resins such as polystyrene resin and cyclic olefin resin, 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, and the like.

Although the thickness of a transparent base material 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 transparent substrate is not particularly limited, but is preferably 60% or more, and more preferably 80% or more.

The surface resistivity of the transparent conductive laminate is not particularly limited, but is preferably 1000Ω / □ or less, more preferably 900Ω / □ or less, and further preferably 800Ω / □ or less. If it exceeds 1000Ω / □, sufficient conductivity may not be ensured. In addition, since the said surface resistivity is so preferable that it is small, the minimum is not specifically limited, For example, it is 0.1 ohm / square.

The total light transmittance of the transparent conductive laminate 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 not particularly limited.

The manufacturing method of the transparent conductive laminated body of this invention includes the process of printing the printing ink of this invention on a base material. Specifically, for example, it can be obtained by (I) a coating step by printing and (II) a forming step, which will be described later. By printing, patterning can be performed, a non-conductive portion and a conductive portion can be provided, and the conductive portion can be a conductor pattern.
The printing ink of the present invention is preferably applied onto the substrate by printing means such as screen printing, offset printing and pad printing, and the printing ink of the present invention may be directly applied to the substrate. However, after forming a layer such as a primer layer on the substrate in advance, the printing ink of the present invention may be applied on the layer formed on the substrate.
Further, if necessary, the above-mentioned (I) printing step may be performed after surface treatment is performed on the surface of the substrate in advance. Examples of the surface treatment include corona treatment, plasma treatment, itro treatment, flame treatment, and the like.

(II) A formation process can form a transparent conductive film in the at least 1 surface of a base material by heat-processing what was screen-printed on the base material at the temperature of 150 degrees C or less. 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. In addition, (I) When the ink used at a printing process contains a solvent, a solvent is removed by heat processing.

The heat treatment is performed under a temperature condition of 150 ° C. or lower. When the temperature of the heat treatment exceeds 150 ° C., the type of base material to be used is limited. For example, base materials generally used for transparent electrode films such as PET film, polycarbonate film, and acrylic film cannot 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 transparent conductor 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 use of the transparent conductive laminate of the present invention is not particularly limited as long as transparency and conductivity are required. For example, various display systems such as liquid crystal, plasma, field emission, etc. Examples include touch panels and touch sensors of various electronic devices, and transparent electrodes in display elements. Moreover, the said transparent conductive laminated body can also be used for uses, such as a transparent electrode in a solar cell, an electromagnetic wave shielding material, electronic paper, an electroluminescent light control element, a transparent heating element, and an electroplating primer. Among these applications, touch panels for various electronic devices, transparent electrodes for driving liquid crystals, transparent electrodes for driving EL, transparent electrodes for driving electrochromic elements, electromagnetic shielding materials, transparent heating elements, or electrolytic plating primers It is preferable to be used. Especially, it can use suitably for the touch panel and touch sensor of various electronic devices.

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.

Production Example 1 (conductive polymer)
In a 10 L reaction vessel equipped with a stirrer and a nitrogen inlet, 5508 g of ion-exchanged water and 492 g of an aqueous solution of 12.8 wt% polystyrene sulfonic acid (PSS) (Mw = 56000) were placed and kept at 25 ° C. while blowing nitrogen. 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%, 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. Hereinafter, the average particle size is described as the particle size)).

Production Example 2 (conductive polymer)
Except for changing the pH to 0.5, 4500 g of dark blue high-viscosity PEDOT / PSS was obtained by the method described in Production Example 1 (solid content 2.4%, viscosity 93 dPa · s, thixotropy index). 4.1, yield value 10.3 Pa, particle size 410 nm).

Production Example 3 (Conductive polymer)
Except that the stirring speed was 250 rpm, 4400 g of dark blue high-viscosity PEDOT / PSS was obtained by the method described in Preparation Example 1 (solid content 3.9%, viscosity 130 dPa · s, thixotropy index 3 .9, yield value 12.5 Pa, particle size 680 nm).

Production Example 4 (conductive polymer)
Except that the temperature was 28 ° C., 5500 g of dark blue high-viscosity PEDOT / PSS was obtained by the method described in Production Example 1 (solid content 4.3%, viscosity 250 dPa · s, thixotropy index 6 .3, yield value 8.9 Pa, particle size 1050 nm).

Production Example 5 (conductive polymer)
Except for adjusting the amount of ion-exchanged water so that the reaction concentration was 5%, 5950 g of dark blue high-viscosity PEDOT / PSS was obtained by the method described in Production Example 1 (solid content 4. 8%, viscosity 290 dPa · s, thixotropy index 6.5, yield value 15.5 Pa, particle size 2500 nm).

Production Example 6 (conductive polymer)
In a 10 L reaction vessel equipped with a stirrer and a nitrogen inlet, 2437 g of ion-exchange water, 244 g of 12.8 wt% polystyrene sulfonic acid (PSS) (Mw = 56000) aqueous solution were placed, and kept at 25 ° C. while blowing nitrogen. 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 0.5, and the stirring speed was 250 rpm [Nick process unit using an Impro 6000 series O ₂ sensor. 73O ₂ (measured using METTLER TOLEDO Co., Ltd.)]. Then 12.7 g (89 mmol) 3,4-ethylenedioxythiophene (EDOT), 0.225 g Fe ₂ (SO ₄ ) ₃ .3H ₂ O, 211 g 10 wt% H ₂ S ₂ O ₈ An aqueous solution was added to initiate the polymerization reaction. After reacting for 12 hours at 25 ° C., an additional 35 g of 10 wt% H ₂ S ₂ O ₈ was added. After an additional reaction time of 12 hours, 1800 g of dark blue high-viscosity PEDOT / PSS was obtained by treatment with ion exchange resins Lewatit S100H and Lewatit MP62 (solid content 1.1%, viscosity 45 dPa · s, thixotropy index 2 .1, yield value 2.5 Pa, particle size 80 nm).

In the following Examples and Comparative Examples, the following materials were used in addition to the high-viscosity PEDOT / PSS aqueous dispersion obtained in Production Examples 1 to 6.
-(A) Conductive polymer poly (3,4-ethylenedioxythiophene) polystyrene sulfonic acid (manufactured by Heraeus Co., Ltd., Clevios PH500, conductivity: 300 S / cm, solid content: 1.0%, viscosity: 0.3 dPa · s or less , Thixotropy index 1, yield value 0.5 Pa or less, particle size 55 nm)
Poly (3,4-ethylenedioxythiophene) polystyrene sulfonic acid (Agfa, freeze-dried product, solid content 90%)
Polyaniline sulfonic acid (Mitsubishi Rayon Co., Ltd., AQUAPASS, solid content 5.0%, viscosity 10 dPa · s, thixotropy index 1.5, yield value 1 Pa, particle size 500 nm)
-(B) Conductivity improver ethylene cyanohydrin (manufactured by Tokyo Chemical Industry Co., Ltd.)
Pyrazole (manufactured by Tokyo Chemical Industry Co., Ltd.)
Ethylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd.)
-(C) Binder polyester (manufactured by Nagase ChemteX Corporation, Gabsen ES-210, solid content 25%)
Methyl silicate oligomer (Mitsubishi Chemical Co., Ltd., MKC silicate MS57, solid content 100%)
Polyolefin (Toyobo Co., Ltd., Hardren EZ-2001, solid content 30%)
(D) Thickener water-soluble polyacrylic acid (manufactured by Nippon Shokubai Co., Ltd., Aquaric (registered trademark) L, H)
・ Antioxidant tannic acid (manufactured by Ajinomoto Omnichem)
L-ascorbic acid (manufactured by Wako Pure Chemical Industries, Ltd.)
・ Surfactant Fluorosurfactant (manufactured by DuPont, CAPSTONE FS-3100)
Coconut oil fatty acid amidopropyl betaine (Amogen CB-H, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
Polyether-modified polydimethylsiloxane (Shin-Etsu Silicone Co., Ltd., KF-6011)
・ Solvent IPA (isopropyl alcohol) (manufactured by Wako Pure Chemical Industries, Ltd.)
Ethylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd.)

Examples 1-15, Comparative Examples 1-3
Each component was mixed by the weight ratio shown in the following Table 1, and the conductive resin composition was produced.

For the high viscosity PEDOT / PSS aqueous dispersions obtained in Production Examples 1 to 6, the conductive resin compositions obtained in Examples 1 to 15 and Comparative Examples 1 to 3, the viscosity, thixotropy index, and yield value are as follows: It was measured by the method shown. Moreover, about the conductive resin composition obtained in Examples 1-15 and Comparative Examples 1-3, liquid appearance, moisture content, flash point, coating film appearance, surface resistivity (SR), total light transmittance (Tt ) / Haze value, adhesion, resolution, and heat resistance were measured by the following methods. The results are shown in Table 2.

Viscosity Viscosity was measured with a B-type viscometer (B-type viscometer BM: manufactured by Toki Sangyo Co., Ltd., rotational speed 6 rpm, No. 4 rotor) while being kept in a thermostatic bath at 25C.

Thixotropic index Using a rheometer (AR-G2, manufactured by TA Instruments Inc.), at 25 ° C., a viscosity η _{1 at} a shear rate of 1 (1 / s) and a shear rate of 10 (1 The ratio (Ti value = η ₁ / η ₁₀ ) with the viscosity η ₁₀ in / s) was calculated.

Yield value Using a rheometer (AR-G2, manufactured by TA Instruments Inc.), at 25C, the shear rate was 0.01 (1 / s) to 100 (1 / s). The stress was measured while changing the range, and the stress was calculated from Casson's approximate expression (√stress = √viscosity velocity × √shear rate + √yield value).

Liquid appearance The conductive resin 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

Water content Calculated from the blending amount of each component.

The flash point was measured according to the method described in JIS K 2265.

Appearance of coating film Illumination for visual inspection was arranged on the back surface of the transparent conductor, and the appearance characteristics of the transparent conductive laminate were evaluated in the following two stages.
○: A smooth coating film is uniformly formed.
(Triangle | delta): The aggregate and repellency exist in a coating film, and are non-uniform | heterogenous.

Surface resistivity (SR)
The conductive resin composition was coated on a base material (type: blue plate glass (manufactured by Sekiya Rika Co., Ltd., 100 × 100 × 2 mm, total light transmittance 91.0%)) with a bar coater, and 130 using a blower oven. By heating at 0 degreeC for 5 minutes, the transparent conductive film was formed in the one surface of a base material, and the transparent conductive laminated body was obtained. Using the conductive laminate, the surface resistance was measured using a resistivity meter (Mitsubishi Chemical Corporation, Lorester GP MCP-T600).

Total light transmittance (Tt) / Haze value Using the above-mentioned transparent conductive laminate, measurement was performed using a haze computer HGM-2B manufactured by Suga Test Instruments Co., Ltd. according to JIS K 7150.

Adhesion (cross cut test)
A cross-cut peel test was performed according to JIS K 5400.

Resolution Using a conductive resin composition, on a blue plate glass substrate (Sekiya Rika Co., Ltd., 100 × 100 × 2 mm, total light transmittance 91.0%) by screen printing, 0 Each wiring pattern was printed in a range of 0.02 to 10 mm, the drawn pattern was observed with a microscope, and the smallest line width drawn without a defect was taken as the resolution.

Heat resistance With respect to the transparent conductive film of the transparent conductive laminate, the initial surface resistivity and the surface resistivity after being stored at 80C for 240 hours were measured by the method for measuring the surface resistivity described above. The surface resistivity increase magnification after storage (surface resistivity after storage / initial surface resistivity) was calculated and evaluated in the following three stages.
◯: Surface resistivity increase ratio is less than 1.5 Δ: Surface resistivity increase ratio is 1.5 or more and less than 2.0 x: Surface resistivity increase ratio is 2.0 or more

From the results of Production Examples 1 to 6, it was revealed that PEDOT / PSS showing a predetermined viscosity, thixotropy index, and yield value can be synthesized by changing the conditions of pH, stirring speed, temperature, and concentration.

From the results of Examples 1 to 15 and Comparative Examples 1 to 3, it is clear that the transparent conductive laminates of the examples are superior in terms of appearance / haze, adhesion, and resolution as compared with the comparative examples. It was.

In addition, since the conductive resin composition of the present invention does not contain a thickener, no precipitates due to the addition of the thickener, no repelling during coating, and a low haze value compared to the comparative example. .
Since the conductive resin composition of the present invention has good viscosity characteristics, it has been clarified that drying after coating proceeds promptly, good adhesion is obtained, and handling properties are excellent.
Since the conductive resin composition of the present invention has good thixotropy, it does not sag and is excellent in leveling properties, so that the coating film appearance is good.
Since the conductive resin composition of the present invention has a good yield value, it has high resolution.

The conductive resin composition of the present invention is suitably used for the production of a transparent conductive laminate.

Claims (11)

A conductive resin composition containing (A) a conductive polymer, (B) a conductivity improver, and (C) a binder and having a viscosity at 25 ° C. of 10 to 800 dPa · s ,
Conductive resin composition in which binder (C) is at least one selected from the group consisting of polyester resins, polyurethanes, epoxy resins, alkoxysilane oligomers, and polyolefin resins (however, those containing a thickener) except). The conductive resin composition of Claim 1 whose thixotropy index in 25 degreeC is 1-15. The conductive resin composition of Claim 1 or 2 whose yield value in 25 degreeC is 2-500 Pa. The conductive resin composition according to claim 1, which has no flash point. The conductive resin composition according to any one of claims 1 to 4, wherein the conductive polymer (A) is a composite of poly (3,4-ethylenedioxythiophene) and polystyrenesulfonic acid. Printing ink containing the conductive resin composition of any one of Claims 1-5 . A transparent conductive laminate obtained by printing the printing ink according to claim 6 on a substrate and exhibiting a surface resistivity of 0.1 to 1000 Ω / □ and a total light transmittance of 50% or more. The transparent conductive laminate according to claim 7 , wherein the printing is performed by at least one means selected from the group consisting of screen printing, offset printing, and pad printing. The method for producing a transparent conductive laminate according to claim 7 , comprising a step of printing the printing ink according to claim 6 on a substrate. The manufacturing method according to claim 9 , wherein the printing is performed by at least one means selected from the group consisting of screen printing, offset printing, and pad printing. A touch panel or a touch sensor using the transparent conductive laminate according to claim 7 or 8 .