JP7013693B2 - Conductive wiring sheet and manufacturing method of wiring sheet - Google Patents

Description

The present invention relates to a wiring sheet having conductive wiring arranged on a sheet.

In recent years, conductive paints and conductive adhesives using a conductive resin composition have been increasing from the viewpoints of reducing the weight of products, considering the environment, and suppressing manufacturing costs. In such applications, high conductivity is required, and metal is often used as the conductive filler. Until now, rigid wiring boards with copper wiring on glass epoxy boards and flexible wiring with copper wiring on polyimide have been used. Printed circuit boards (FPCs) were common. These are obtained by attaching a photosensitive dry film to the copper layer of a copper-clad laminate, patterning the dry film by photoresist, etching copper, and then peeling off the dry film. Alternatively, there is a wire harness in which a plurality of electric wires are tied together with a binding band, a tube, an adhesive tape, or the like, and a multi-core connector capable of connecting a plurality of electric wires at one time is attached to the end. Rigid wiring boards and flexible printed circuits form a copper pattern by etching, so naturally there is a lot of wasted copper and the cost is high. Moreover, if a copper wiring board is used outdoors, it will be affected by salt, acid, alkali, etc. If there is, there is a drawback that copper becomes non-conductive and conduction cannot be obtained. Furthermore, since the wiring basically uses metal plated with copper, silver, lead solder, nickel, gold, etc. for the connection part, when used outdoors, the wiring material deteriorates and non-conductors are formed on the surface. There was a concern that the conductivity would deteriorate over time. Wire harnesses are used in car engine rooms, etc., but they are not used for mounting IC chips or sensors on wiring boards, but are used for connecting parts, etc., but the copper wiring part is covered with vinyl chloride resin. Although it is relatively stable because it is broken, there is a problem that the connector part basically has a part where metal is exposed, and the harness itself is a bundle of wiring, so that it is bulky from the top of the wiring layout.
In applications where long-term reliability is required, corrosion resistance is required, and in such applications, wiring using these metals cannot be used, so conductive carbon-based fillers are used, but compared to metals. Since the conductivity is inferior, the use is limited, and the carbon-based filler has a lighter specific gravity than the metal, and the amount of the carbon-based filler in the composition increases in order to exhibit high conductivity. , There is a problem that printing coating by screen printing or the like becomes difficult.
Patent Document 1 includes an example in which a metallic conductive filler is dispersed in a carboxyl group-containing polyurethane resin and printed with a film thickness of less than 20 μm. However, since these use a metallic conductive filler, the conductive filler is used. It is considered that the conductivity is reduced due to the corrosion of the metal, and it cannot withstand outdoor use for a long period of time.
Patent Document 2 has an example in which graphite powder having an average particle diameter of 1 to 100 μm is dispersed in a polyolefin-based thermoplastic resin to obtain a conductive molded body, which can be used for patterning on a substrate on a sheet. It requires actions such as cutting and adhering the molded body, and it cannot be printed, and its productivity is significantly inferior to that of a wiring board or a wiring sheet.
Patent Document 3 proposes a conductive sheet in which a conductive filler is dispersed in a thermosetting resin and is in a semi-cured state, but this is also unsuitable for patterning wiring such as printing, and productivity is remarkably high. Inferior.
As a resin composition in which expanded graphite having an average particle diameter of 20 μm or less is dispersed, Patent Documents 4 and 5 propose as an electromagnetic wave shielding material in which expanded graphite is dispersed in a thermoplastic resin, but these are also suitable for patterning. do not have.

JP 2016-173933 JP 2016-172850 Patent No. 4900396 JP-A-3-7740 Japanese Patent Application Laid-Open No. 6-100727

An object of the present invention is that a wiring sheet and a conductive wiring forming step having good corrosion resistance, exhibiting high conductivity, and having excellent weather resistance in various outdoor environments are at least a patterning step and a hot pressing step. It is to provide the manufacturing method of the wiring sheet which has.
If a carbon-based conductive material can be used for the conductive wiring, there is no concern about deterioration of the carbon material itself, and the conductivity does not decrease. Therefore, the conductive wiring can withstand long-term use in units of several decades. Can be provided.

As a result of diligent studies to solve the above problems, the present inventors have good corrosion resistance and high conductivity according to the following forms, and form various patterns by printing, coating, or the like. We have found that we can provide a wiring sheet having possible conductive wiring, and have completed the present invention.

That is, the present invention is a wiring sheet having a sheet-like base material and conductive wiring arranged on the sheet-like base material.
The conductive wiring contains at least a binder resin (A) and a conductive carbon material (B).
The amount of the conductive carbon material (B) contained in 100% by mass of the conductive wiring is 50 to 90% by mass.
The thickness of the conductive wiring is 30 to 200 μm, and the thickness is 30 to 200 μm.
The volume resistivity value of the conductive wiring is 1 × 10 ^-3 to 2 × 10 ^-2- Ω · cm.
Regarding the wiring sheet.

The present invention also relates to the wiring sheet, wherein the conductive carbon material contains expanded graphite (B1) having an average particle size of 10 μm to 200 μm.

Further, the present invention is characterized in that the binder resin contains at least one resin selected from urethane resin, polyester resin, polyamide resin, acrylic resin, fluororesin, epoxy resin, and styrene elastomer. Regarding.

The present invention also relates to the wiring sheet, wherein the sheet-like substrate contains at least one sheet selected from polyethylene terephthalate, polyimide, polyphenylene sulfide, polyvinyl chloride, and fluororesin.

Further, the present invention is a wiring sheet in which a film is laminated on the conductive wiring and the conductive wiring is sealed, and the film is an acrylic resin, a fluororesin, an epoxy resin, and the like. And a wiring sheet comprising at least one resin selected from polyamide resins.
A method for manufacturing a wiring sheet having a sheet-shaped base material and conductive wiring arranged on the sheet-shaped base material.
The conductive wiring contains at least a binder resin (B) and a conductive carbon material (C).
The amount of the conductive carbon material (C) contained in 100% by mass of the conductive wiring is 40 to 90% by mass.
The thickness of the conductive wiring is 30 to 200 μm, and the thickness is 30 to 200 μm.
The volume resistivity value of the conductive wiring is 2 × 10 ^-2-1 × 10 ^-3 Ω · cm.
The present invention relates to a method for manufacturing a wiring sheet, wherein the step of forming the conductive wiring includes at least a patterning step and a hot pressing step.

The present invention further relates to a method for manufacturing the wiring sheet, which comprises a step of laminating a film and sealing the conductive wiring.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a wiring sheet having conductive wiring having good corrosion resistance, exhibiting excellent conductivity, and capable of forming various patterns by printing.
By printing with a screen plate or metal mask, or by patterning the conductive composition into a wiring sheet by slit coating with a comma coater, die coater, etc., it can be used for several decades even in a highly corrosive environment. It can withstand and can stably fulfill roles such as power supply and signal transmission.

In the conductive wiring sheet of the present invention, a conductive wiring sheet can be obtained by applying a conductive composition on a sheet-like substrate by various methods to form a conductive layer.

In order to form the conductive wiring, at least the binder (A) and the conductive carbon material (B) are contained on the sheet-like base material, and the conductive carbon material contained in 100% by mass of the conductive wiring is contained. A conductive composition having an amount of (B) of 50 to 90% by mass is used.

<Conductive composition>
The conductive composition contains at least the binder resin (A) and the conductive carbon material (B).
<Binder resin (A)>
The binder resin is selected from the group consisting of polyurethane-based, polyamide-based, acrylonitrile-based, acrylic-based, butadiene-based, polyvinyl butyral-based, polyolefin-based, polyester-based, polystyrene-based, EVA-based, polyvinylidene fluoride-based, and silicon-based resins. It can contain one or more species. However, it is not limited to these resins. The binder resin may be used alone or in combination of two or more. In particular, it is preferable that the binder resin contains at least one resin selected from urethane resin, polyester resin, polyamide resin, acrylic resin, fluororesin, epoxy resin, and styrene elastomer.
The binder resin can also be a curable resin that undergoes a curing (crosslinking) reaction after the binder resin is applied to the substrate.
That is, the binder resin is selected to be self-curing or combined with a curing agent described later, and the conductive composition is printed or coated on the substrate and then cured (crosslinked). Can be done.

As the binder resin, a polyurethane resin is preferable from the viewpoint of volume resistance, adhesion to a substrate, and durability. The volume resistance value is a good result because the resin component in the hot press tends to flow.
When the conductive composition is printed or coated on a substrate and then hot-pressed, the resin component softens, and while maintaining the flat pattern shape of the conductive film during printing and coating, while maintaining the flat pattern shape of the conductive film during printing and coating. When it flows in the thickness direction, the voids can be reduced and the contact between the conductivity-imparting agents (C) can be increased, so that the volume resistance value of the obtained conductive film can be expected to decrease. Therefore, as the binder resin, one that moderately softens and flows during hot pressing is preferable.

<Polyurethane resin>
The method for synthesizing the polyurethane resin (A1) is not particularly limited, but for example, a polyol compound (a) and a diisocyanate (b) may be reacted, or a polyol compound (a), a diisocyanate (b) and a diol compound having a carboxyl group may be reacted. (C) may be reacted to obtain a urethane prepolymer (d) having an isocyanate group, or the urethane prepolymer (d) may be further reacted with a polyamino compound (e), or in the above three cases, it is necessary. Examples thereof include those obtained by reacting a reaction terminator.

As the polyol compound (a), various polyether polyols, polyester polyols, polycarbonate polyols, polybutadiene glycols, or a mixture thereof, which are generally known as polyol components constituting the polyurethane resin, can be used.

Examples of the polyether polyols include polymers or copolymers of ethylene oxide, propylene oxide, tetrahydrofuran and the like.
Examples of polyester polyols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, pentanediol, 3-methyl-1, Saturated and unsaturated low molecular weight diols such as 5-pentanediol, hexanediol, octanediol, 1,4-butylenediol, diethyleneglycol, triethyleneglycol, dipropyleneglycol, dimerdiol, and n-butylglycidyl ether, 2 -Alkyl glycidyl ethers of ethylhexyl glycidyl ethers, monocarboxylic acid glycidyl esters such as versatic acid glycidyl esters, adipic acid, phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, succinic acid, oxalic acid, Dicarboxylic acids such as malonic acid, glutaric acid, pimelli acid, suberic acid, adipic acid, and sebacic acid, or anhydrides thereof are dehydrated and condensed to obtain polyester polyols or cyclic ester compounds by ring-opening polymerization. Examples thereof include the obtained polyester polyols.

As the polycarbonate polyols, 1) a reaction product of diol or bisphenol and carbonic acid ester, and 2) a reaction product of diol or bisphenol with phosgene in the presence of alkali can be used. Examples of the carbonic acid ester include dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate, propylene carbonate and the like. The diols include ethylene glycol, propylene glycol, dipropylene glycol, diethylene glycol, triethylene glycol, butylene glycol, 3-methyl-1,5-pentanediol, 2-methyl-1,8-octanediol, 3,3. '-Dimethylol heptane, polyoxyethylene glycol, polyoxypropylene glycol, propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9 -Nonandiol, neopentyl glycol, octanediol, butylethylpentanediol, 2-ethyl-1,3-hexanediol, cyclohexanediol, 3,9-bis (1,1-dimethyl-2-hydroxyethyl, 2,2) , 8,10-Tetraoxospiro [5.5] Undecane and the like. Examples of the bisphenol include bisphenol A and bisphenol F, and bisphenols obtained by adding alkylene oxides such as ethylene oxide and propylene oxide to bisphenols. Can be mentioned.

The number average molecular weight (Mn) of the polyol compound is appropriately determined in consideration of the solubility of the polyurethane resin in producing the conductive composition, the durability of the conductive film formed, the adhesive strength to the substrate, and the like. However, it is usually preferably in the range of 580 to 8000, and more preferably 1000 to 5000. When Mn is less than 580, the number of urethane bonds in the polyurethane resin becomes too large, the flexibility of the polymer skeleton tends to decrease, and the adhesion to the substrate tends to deteriorate. When Mn exceeds 8000, the cross-linking point tends to be deteriorated. The intermolecular weight becomes large, and there is a tendency that sufficient coating strength cannot be obtained after hot pressing.
The above-mentioned polyol compound may be used alone or in combination of two or more. Further, as long as the performance of the polyurethane resin is not lost, a part of the polyol compound can be replaced with low molecular weight diols, for example, various low molecular weight diols used for producing the polyol compound.

As the diisocyanate compound (b), aromatic diisocyanate, aliphatic diisocyanate, alicyclic isocyanate, or a mixture thereof can be used, but isophorone diisocyanate is particularly preferable. Examples of the aromatic diisocyanate include 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-benzyl isocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, and 1, , 3-Phenylene diisocyanate, 1,4-Phenylene diisocyanate, Tolylene diisocyanate, Xylylene diisocyanate and the like.

Examples of the aliphatic diisocyanate include butane-1,4-diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and lysine diisocyanate.
Examples of the alicyclic diisocyanate include cyclohexane-1,4-diisocyanate, isophorone diisocyanate, norbornane diisocyanatomethyl, bis (4-isocyanatecyclohexyl) methane, 1,3-bis (isocyanatemethyl) cyclohexane, and methylcyclohexanediisocyanate. Be done.

Examples of the diol compound (c) having a carboxyl group include dimethylol alkanoic acid such as dimethylol acetic acid, dimethylol propionic acid, dimethylol butanoic acid and dimethylol pentanoic acid, dihydroxysuccinic acid and dihydroxybenzoic acid. In particular, dimethylolpropionic acid and dimethylolbutanoic acid are preferable from the viewpoint of reactivity and solubility.
The conditions for reacting the polyol compound (a) with the diisocyanate (b) and the diol compound (c) having a carboxyl group to obtain the urethane prepolymer (d) having an isocyanate group are other than making the isocyanate group excessive. Although not particularly limited, the isocyanate group / hydroxyl group equivalent ratio is preferably in the range of 1.05 / 1 to 3/1. More preferably, it is 1.2 / 1 to 2/1. The reaction is usually carried out between room temperature and 150 ° C., and is preferably carried out between 60 and 120 ° C. in terms of production time and control of side reactions.

The polyamino compound (e) acts as a chain extender, and includes ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, isophoronediamine, dicyclohexylmethane-4,4'-diamine, norbornandiamine, and 2 -Amines having hydroxyl groups such as (2-aminoethylamino) ethanol, 2-hydroxyethylethylenediamine, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, and di-2-hydroxypropylethylenediamine can also be used. can. Among them, isophorone diamine is preferably used.

When synthesizing a polyurethane resin by reacting a urethane prepolymer (d) having an isocyanate group with a polyamino compound (e), a reaction terminator can be used in combination in order to adjust the molecular weight of the obtained polyurethane resin. As the reaction terminator, dialkylamines such as di-n-butylamine, dialkanolamines such as diethanolamine, and alcohols such as ethanol and isopropyl alcohol can be used.

The conditions for reacting the urethane prepolymer (d) having an isocyanate group with the polyamino compound (e) and, if necessary, a reaction terminator are not particularly limited, but the free isocyanates at both ends of the urethane prepolymer are not particularly limited. When the number of groups is 1 equivalent, the total equivalent of the polyamino compound (e) and the amino groups in the reaction terminator is preferably in the range of 0.5 to 1.3. More preferably, it is in the range of 0.8 to 0.995.
The weight average molecular weight of the polyurethane resin is preferably in the range of 5000 to 200,000. When the molecular weight is less than 5000, a good resin viscosity cannot be obtained in the conductive composition containing this as a binder, and the coatability deteriorates. If it exceeds 200,000, the viscosity of the resin solution itself is high and the handleability is lowered, which is not preferable.

When synthesizing a polyurethane resin, one or two selected from ester-based solvents, ketone-based solvents, glycol ether-based solvents, aliphatic solvents, aromatic solvents, alcohol-based solvents, carbonate-based solvents, water, etc. The above can be used in combination.
Examples of the ester solvent include ethyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, amyl acetate, ethyl lactate and the like.
Examples of the ketone solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone benzene, diisobutyl ketone, diacetone alcohol, isophorone, cyclohexanenone and the like.
Examples of the glycol ether-based solvent include ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, and acetates of these monoethers, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, and propylene. Examples thereof include glycol monomethyl ethers, propylene glycol monoethyl ethers, and acetates of these monoethers.
Examples of the aliphatic solvent include n-heptane, n-hexane, cyclohexane, methylcyclohexane, ethylcyclohexane and the like.
Examples of the aromatic solvent include toluene, xylene and the like.
Examples of the alcohol solvent include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, cyclohexanol and the like.
Examples of the carbonate solvent include dimethyl carbonate, ethylmethyl carbonate, di-n-butyl carbonate and the like.

<Polyester resin>
The polyester resin (A2) used in the present invention is preferably a polyester containing a polyvalent carboxylic acid component and a polyvalent alcohol component as a copolymerization component, and more preferably a dicarboxylic acid component and a glycol component as a copolymerization component. preferable.
The dicarboxylic acid component constituting the polyester resin (A2) is not particularly limited, and examples thereof include aromatic dicarboxylic acid, aliphatic dicarboxylic acid, and alicyclic dicarboxylic acid, and in particular, aromatic dicarboxylic acid and aliphatic dicarboxylic acid are used in combination. It is preferable to do so.

The copolymerization amount of the aromatic dicarboxylic acid is preferably 50 mol% or more, more preferably 60 mol% or more, when the total amount of the carboxylic acid components is 100 mol%. If the amount is too small, the ester group concentration becomes too high, and the polyester resin (A) having excellent moisture and heat resistance may not be obtained. Further, 90 mol% or less is preferable, and 80 mol% or less is more preferable. If it is too large, the storage elastic modulus at 60 ° C. may become too large and the adhesiveness to the substrate may decrease.
Specific examples of the aromatic dicarboxylic acid are not particularly limited, but are terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalic acid, 2,6-naphthalic acid, 4,4'-diphenyldicarboxylic acid, 2,2. ′ -Diphenyldicarboxylic acid, 4,4′-diphenyletherdicarboxylic acid and the like can be mentioned, and these can be used alone or in combination of two or more. Of these, it is particularly preferable to use terephthalic acid and isophthalic acid from the viewpoint of moisture and heat resistance.

The aliphatic dicarboxylic acid is not particularly limited, but it is preferable to use an aliphatic dicarboxylic acid having 4 or more and 10 or less carbon atoms. The aliphatic dicarboxylic acid has more preferably 5 or more carbon atoms, and more preferably 6 or more carbon atoms. Further, it is more preferable that the number of carbon atoms is 10 or less. By using an aliphatic dicarboxylic acid having a carbon number in the above range, it can be expected that a polyester resin (A2) having a good ester group concentration can be obtained. The copolymerization amount of the aliphatic dicarboxylic acid is preferably 50 mol% or less, more preferably 40 mol% or less, when the total amount of the carboxylic acid components is 100 mol%. Further, it is preferably 10 mol% or more, more preferably 20 mol% or more. If it is too small, the storage elastic modulus at 60 ° C. may become too large and the adhesiveness to the substrate may decrease. If it is too large, the ester group concentration may become too high and a polyester resin (A2) having excellent moisture and heat resistance may not be obtained.
Specific examples of the aliphatic dicarboxylic acid include, but are not limited to, adipic acid, azelaic acid, sebacic acid, dodecandionic acid, octadecandionic acid and the like, and these may be used alone or in combination of two or more. Can be done. Of these, it is particularly preferable to use adipic acid and sebacic acid from the viewpoint of availability.

The copolymerization amount of the alicyclic dicarboxylic acid is preferably 50 mol% or less, more preferably 40 mol% or less, still more preferably 30 mol% or less, when the total amount of the carboxylic acid components is 100 mol%. Yes, particularly preferably 20 mol% or less, most preferably 10 mol% or less, and 0 mol% may be used. If it is too much, it may not be possible to obtain a polyester resin having excellent moisture and heat resistance. Specific examples of the alicyclic dicarboxylic acid are not particularly limited, but are 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 4-methyl-1,2-cyclohexanedicarboxylic acid. Examples thereof include acid, dimer acid and the like, and these can be used alone or in combination of two or more. In particular, it is preferable to use 1,4-cyclohexanedicarboxylic acid among them from the viewpoint of availability.

Anhydrous polyvalent carboxylic acid can be used for the purpose of imparting an acid value or branching to the polyester resin (A2). By imparting an acid value or branching, it can be expected that the reactivity with the polyisocyanate (B) will be improved and the adhesiveness to a substrate such as aluminum will be improved. The anhydrous polyvalent carboxylic acid is not particularly limited, but is aromatic anhydrous such as anhydrous phthalic acid, anhydrous pyromellitic acid, anhydrous trimellitic acid, ethylene glycol bis (anhydrotrimeritate), and glycerol tris anhydrotrimeritate. Polyvalent carboxylic acid; aliphatic anhydrous polyvalent carboxylic acid such as fumaric acid anhydride, maleic acid anhydride, succinic acid anhydride, itaconic acid anhydride, dodecenyl succinic acid anhydride; phthalic acid anhydride, 4-methylhexahydrophthalic acid anhydride, etc. An alicyclic anhydrous polyvalent carboxylic acid can be mentioned. These can be used alone or in combination of two or more.

Among the anhydrous polyvalent carboxylic acids, aromatic anhydrous polyvalent carboxylic acids are preferable because they have higher acid value and branching effect than aliphatic anhydrous polyvalent carboxylic acids and alicyclic anhydrous polyvalent carboxylic acids. Of these, trimellitic anhydride, ethylene glycol bis (anhydrotrimellitic acid), and glycerol tris anhydrotrimellitic acid are preferable, and trimellitic anhydride is more preferable from the viewpoint of availability.
The method for imparting branching is not particularly limited, but a trifunctional or higher anhydrous polyvalent carboxylic acid is used as a copolymerization component of the polyester resin (A2) and is subjected to a dehydration esterification step together with other polyvalent carboxylic acids and polyhydric alcohols. There is a method of polymerization. The method for imparting the acid value is not particularly limited, and examples thereof include a method in which the polyester resin (A) is polymerized and then a trifunctional or higher anhydrous polyvalent carboxylic substance is added into the system to impart the acid value. The copolymerization amount of the anhydrous polyvalent carboxylic acid is preferably 5 mol% or less, more preferably 2 mol% or less, and 1 mol% or less when the total amount of the carboxylic acid components is 100 mol%. Is more preferable. If it is too large, the mechanical properties of thin films and the like may deteriorate, and gelation may occur during polymerization.

The acid value of the polyester resin (A2) may be 0 equivalent / ^{106 g or more, preferably 0.5 equivalent / 10 6 g} or more, and more preferably 1 equivalent / ¹⁰⁶ g or more. It is more preferably 5 equivalents / 10 ⁶ g or more. On the other hand, it is preferably 200 equivalents / 10 ⁶ g or less, more preferably 180 equivalents / 10 ⁶ g or less, further preferably 160 equivalents / 10 ⁶ g or less, and 140 equivalents / 10 ⁶ g or less. Is particularly preferable. If it is too high, the polyester resin (A) may be hydrolyzed and the moisture and heat resistance may decrease.
The polyhydric alcohol component constituting the polyester resin (A2) used in the present invention is not particularly limited, and examples thereof include aliphatic glycols, aromatic glycols and alicyclic glycols, and it is particularly preferable to use aliphatic glycols. ..

The aliphatic glycol may be either a linear aliphatic glycol or a branched aliphatic glycol. The aliphatic glycol is not particularly limited, but a glycol having 2 or more and 10 or less carbon atoms is preferable. The more preferable number of carbon atoms of the aliphatic glycol is 2 or more. The number of carbon atoms is preferably 9 or less, more preferably 8 or less, further preferably 7 or less, and particularly preferably 6 or less. The copolymerization amount of the aliphatic glycol is preferably 40 mol% or more, more preferably 50 mol% or more, still more preferably 60 mol% or more, and more preferably, when the total amount of the glycol components is 100 mol%. It is more preferably 70 mol% or more, particularly preferably 80 mol% or more, most preferably 90 mol% or more, and may be 100 mol% or more. If the copolymerization amount of the aliphatic glycol is too small, the glass transition temperature rises and the flexibility decreases, so that the adhesiveness to the substrate may decrease.
Specific examples of the aliphatic glycol are not particularly limited, but are ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,2-butanediol, neopentyl glycol, and methyl. Examples thereof include pentandiol, pentandiol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, and dodecanediol, which can be used alone or in combination of two or more. Of these, ethylene glycol, neopentyl glycol, 1,4-butanediol, and 1,6-hexanediol are particularly preferable.
The alicyclic glycol is not particularly limited, and examples thereof include cyclohexanediol, cyclohexanedimethanol, and hydrogenated xylylene glycol. The aromatic glycol is not particularly limited, and examples thereof include xylylene glycol and the like.

The number average molecular weight of the polyester resin (A2) is preferably 5000 or more, more preferably 6000 or more, further preferably 7000 or more, particularly preferably 8000 or more, and particularly preferably 10,000 or more. Is the most preferable. Further, it is preferably 50,000 or less, more preferably 45,000 or less, further preferably 40,000 or less, particularly preferably 35,000 or less, and most preferably 30,000 or less. When the number average molecular weight is 5000 or more, sufficient adhesiveness to the substrate, processability, and moisture heat resistance can be obtained. When the number average molecular weight is 50,000 or less, the viscosity of the ink is good.

<Polyamide resin>
As the binder resin, the polyamide resin (A3) is preferable from the viewpoint of the volume resistance value and the adhesion to the substrate. The volume resistance value is a good result because the resin component in the hot press easily flows.
The polyamide resin used in the present invention is basically a general term for polymers having an amide bond obtained by various reactions such as polycondensation of dibasic acid and diamine, polycondensation of aminocarboxylic acid, or ring-opening polymerization of lactam. This is a mixture of various modified polyamides, products manufactured with a partially hydrogenated reactant, products with a partial copolymerization of other monomers, or other substances such as various additives. It is a broad concept that includes things.

The polyamide resin used in the present invention is not particularly limited as long as the above conditions are satisfied, but a dimer acid-modified polyamide resin obtained by condensation polymerization of a dibasic acid containing dimer acid as a main component and polyamines is preferable. .. Dimer acid As the dimer acid for producing the modified polyamide resin, dimer acid obtained by polymerizing natural monobasic unsaturated fatty acids contained in tall oil fatty acid, soybean oil fatty acid, etc. is widely used industrially, but in principle. May be various dicarboxylic acids such as saturated fatty acid, unsaturated fatty acid, alicyclic, or aromatic.
Examples of commercially available products of the dimer acid include Hari Dimer 200, 300 (manufactured by Harima Chemicals, Inc.), Versa Dime 228, 216, Empole 1018, 1019, 1061, 1062 (manufactured by Cognis Co., Ltd.) and the like. Further, hydrogenated dimer acid can also be used, and examples of commercially available hydrogenated dimer acid include Prepole 1009 (manufactured by Claude Japan Co., Ltd.) and Empole 1008 (manufactured by Cognis Co., Ltd.).
In addition to the dimer acid, various dicarboxylic acids can be used as the dibasic acid in order to obtain a polyamide resin having appropriate flexibility. Specific examples of the dicarboxylic acid include oxalic acid, malonic acid, (anhydrous) succinic acid, (anhydrous) maleic acid, glutaric acid, adipic acid, bimeric acid, suberic acid, azelaic acid, sebacic acid, terephthalic acid, and isophthalic acid. Acids, phthalic acids, naphthalenedicarboxylic acids, 1,3- or 1,4-cyclohexanedicarboxylic acids, 1,18-octadecanedicarboxylic acids, 1,16-hexadecanedicarboxylic acids and the like are used.

Further, a dibasic acid having a phenolic hydroxyl group can also be used. By using a dibasic acid having a phenolic hydroxyl group, the phenolic hydroxyl group can be introduced into the side chain of the polyamide resin and can be used for the reaction with the curing agent.
As a dibasic acid having a phenolic hydroxyl group,
Hydroxyisophthalic acids such as 2-hydroxyisophthalic acid, 4-hydroxyisophthalic acid, 5-hydroxyisophthalic acid,
Dihydroxyisophthalic acid such as 2,5-dihydroxyisophthalic acid, 2,4-dihydroxyisophthalic acid, 4,6-dihydroxyisophthalic acid,
Dihydroxyterephthalic acid such as 2-hydroxyterephthalic acid, 2,3-dihydroxyterephthalic acid, 2,6-dihydroxyterephthalic acid,
Hydroxyphthalic acid such as 4-hydroxyphthalic acid and 3-hydroxyphthalic acid,
Examples thereof include dihydroxyphthalic acids such as 3,4-dihydroxyphthalic acid, 3,5-dihydroxyphthalic acid, 4,5-dihydroxyphthalic acid and 3,6-dihydroxyphthalic acid.
Further, these acid anhydrides and ester derivatives such as polybasic acid methyl ester can also be mentioned.
Of these, 5-hydroxyisophthalic acid is preferable from the viewpoint of copolymerizability and easy availability.

Further, various monocarboxylic acids are used as needed in order to obtain a polyamide resin having appropriate fluidity when heated. Specifically, as the monocarboxylic acid, propionic acid, acetic acid, caprylic acid (octanoic acid), stearic acid, oleic acid and the like are used.
The polyamines as a reaction product in producing the dimer acid-modified polyamide resin are, for example, various diamines such as aliphatic, alicyclic and aromatic, triamine and polyamine.
Specific examples of the above diamines include ethylenediamine, propanediamine, butanediamine, triethylenediamine, tetraethylenediamine, hexamethylenediamine, p- or m-xylene diamine, 4,4'-methylenebis (cyclohexylamine), and 2,2-bis. -(4-Cyclohexylamine), polyglycoldiamine, isophoronediamine, 1,2-, 1,3- or 1,4-cyclohexanediamine, 1,4-bis- (2'-aminoethyl) benzene, N-ethyl Amino piperazine, piperazine and the like can be mentioned.
Further, examples of the triamine include diethylenetriamine, and examples of the polyamine include triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine. Further, a dimer diamine obtained by converting a dimerized aliphatic nitrile group and reducing it with hydrogen can also be used.

Examples of the polyamine compound include a compound obtained by converting a carbosyl group of a polybasic acid compound having a cyclic or acyclic hydrocarbon group having 20 to 48 carbon atoms into an amino group, and examples of commercially available products include croaders. Examples thereof include "Priamine 1071", "Priamine 1073", "Priamine 1074" and "Priamine 1075" manufactured by Japan Co., Ltd. and "Versamine 551" manufactured by Cognis Japan Co., Ltd.
Alkanolamine may be used in combination with the diamine. Examples of alkanolamines include ethanolamine, propanolamine, diethanolamine, butanolamine, 2-amino-2-methyl-1-propanol, 2- (2-aminoethoxy) ethanol and the like.
Further, a polyether diamine having oxygen in its skeleton can be used. This polyether has the general formula H ₂ N-R _1- (RO) _n -R ₂ -NH ₂ (in the formula, n is 2 to 100, and R ₁ and R ₂ have 1 to 14 carbon atoms. An alkyl group or an alicyclic hydrocarbon group, where R is an alkyl group or an alicyclic hydrocarbon group having 1 to 10 carbon atoms. The alkyl group may be linear but branched. It may be expressed by). Examples of this ether diamine include polyoxypropylene diamine and the like, and commercial products include Jeffamines (manufactured by San Techno Chemical Co., Ltd.). Further, bis- (3-aminopropyl) -polytetrahydrofuran can also be mentioned.
The polyamines and dimer acid or various dicarboxylic acids are heat-condensed by a conventional method, and various polyamide resins including dimer acid-modified polyamide resin are produced by an amidation step accompanied by dehydration. Generally, the reaction temperature is about 100 to 300 ° C., and the reaction time is about 1 to 8 hours.

<Acrylic resin>
The acrylic resin (A4) is an acrylic copolymer (f), and is obtained from an acrylic copolymer having a hydroxyl group or an acrylic copolymer having no hydroxyl group.

The acrylic copolymer (f) can be obtained by copolymerizing a monomer having a hydroxyl group or another monomer having no hydroxyl group. That is, the acrylic copolymer is a copolymer composed of a unit derived from a monomer having a hydroxyl group and a unit derived from another monomer.

Examples of the monomer having one hydroxyl group include hydroxyalkyl (meth) acrylate and a compound in which ε-caprolactone is added to the hydroxyalkyl (meth) acrylate, and hydroxyalkyl (meth) acrylate is preferable.

Specific examples of hydroxyalkyl (meth) acrylates include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 4-. Examples thereof include hydroxyalkyl (meth) acrylates having an alkyl group having 1 to 4 carbon atoms such as hydroxybutyl (meth) acrylate.
Specific examples of the compound obtained by adding ε-caprolactone to hydroxyalkyl (meth) acrylate include 1 mol adduct of ε-caprolactone of 2-hydroxyethyl (meth) acrylate and 2 mol of ε-caprolactone of 2-hydroxyethyl (meth) acrylate. Examples of the adduct include an ε-caprolactone adduct of a hydroxyalkyl (meth) acrylate having 1 to 4 carbon atoms such as a ε-caprolactone 3 mol adduct of 2-hydroxyethyl (meth) acrylate. It is not limited to such an example. These hydroxyl group-containing monomers may be used alone or in combination.

Examples of the monomer having two or more hydroxyl groups include 1,1-dihydroxymethyl (meth) acrylate, 1,2-dihydroxyethyl (meth) acrylate, 2,2-dihydroxyethyl (meth) acrylate, and 2,3-. Dihydroxypropyl (meth) acrylate or a (meth) acryloyl-based monomer having an epoxy group in one molecule is reacted with a compound or water having one functional group in one molecule and a hydroxyl group capable of reacting with the epoxy group. Examples thereof include a monomer obtained by opening a ring of an epoxy group, but the present invention is not limited to such an example. These hydroxyl group-containing monomers may be used alone or in combination.

The hydroxyl value of the acrylic copolymer is preferably 5 to 210 mgKOH / g. When the hydroxyl value of the acrylic copolymer is 5 mgKOH / g or more, the durability of the cured film can be ensured, and when it is 210 mgKOH / g or less, the moldability of the cured film can be ensured. From the viewpoint of adhesion to the substrate, the hydroxyl value of the acrylic copolymer (A4) is preferably 50 mgKOH / g or less. When the hydroxyl value is 50 mgKOH / g, the hard coat layer and the polycarbonate-based base material layer are in good contact with each other. Further, when using another base material, it is more preferably 150 mgKOH / g or less.

Examples of other acrylic monomers having no hydroxyl group include various monomers as shown below. Examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and sec-butyl (meth). Acrylate, tert-butyl (meth) acrylate, isoamyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isononyl (meth) acrylate, isodecil (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, Examples thereof include alkyl (meth) acrylates such as tert-butylhexyl (meth) acrylates, 2-acetoacetoxyethyl (meth) acrylates, and phenoxyethyl (meth) acrylates.

Examples of the monomer having an alicyclic hydrocarbon group include cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, cyclododecyl (meth) acrylate, bornyl (meth) acrylate, and isobornyl (meth) acrylate. Examples thereof include dicyclopentenyl (meth) acrylate and dicyclopentanyl (meth) acrylate.

Examples of the monomer having an epoxy group include glycidyl (meth) acrylate, α-methylglycidyl acrylate, α-methylglycidyl methacrylate, 3,4-epoxycyclohexylmethylacrylate, and 3,4-epoxycyclohexylmethylmethacrylate.

The acrylic copolymer (f) having a hydroxyl group is preferably one obtained by polymerizing a methacrylate-based monomer among the various monomers described above.

Examples of the method for polymerizing the monomer include a solution polymerization method, a bulk polymerization method, a suspension polymerization method, an emulsion polymerization method, and the like, but the present invention is not limited to such a polymerization method. Among these polymerization methods, the solution polymerization method is preferable because the obtained reaction mixture can be used as it is.

Hereinafter, an embodiment in the case of preparing an acrylic copolymer (f) having a hydroxyl group by solution-polymerizing the monomer will be described. However, the present invention is not limited to the embodiment thereof.

Examples of the solvent used for solution polymerization of the monomer include aromatic solvents such as toluene and xylene; alcohol solvents such as n-butyl alcohol, propylene glycol monomethyl ether, diacetone alcohol, and ethyl cellosolve; ethyl acetate, Esther-based solvents such as butyl acetate and cellosolve acetate; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; dimethylformamide and the like can be mentioned, but the present invention is not limited thereto. The amount of the solvent is preferably appropriately determined according to the concentration of the monomer mixture, the molecular weight of the target acrylic copolymer and the like.

Examples of the polymerization initiator include 2,2'-azobis- (2-methylbutyronitrile), tert-butylperoxy-2-ethylhexanoate, 2,2'-azobisisobutyronitrile, and benzoyl. Examples thereof include peroxides and di-tert-butyl peroxides, but the present invention is not limited to such examples. The amount of the polymerization initiator is usually preferably 0.01 to 30 parts by mass, and more preferably 0.05 to 10 parts by mass per 100 parts by mass of the monomer mixture. When the mass average molecular weight (Mw) is 100,000 or more as in the present invention, the amount of the polymerization initiator is preferably 0.05 to 0.1 parts by mass.

The polymerization temperature at which the monomer is polymerized is usually preferably 40 to 200 ° C, more preferably 40 to 160 ° C. When the mass average molecular weight (Mw) is 100,000 or more as in the present invention, the polymerization temperature is preferably 90 ° C. or lower.

Since the polymerization time of the monomer varies depending on the polymerization temperature, the composition of the monomer mixture, the type and amount of the polymerization initiator, and the like, it cannot be unconditionally determined. Therefore, it is preferable to appropriately determine the monomer according to them.

The acrylic copolymer (f) may have an acid value. Having an acid value promotes the reaction between the hydroxyl group and isocyanate, so that a highly durable cured film can be obtained. When imparting an acid value, the acid value of the acrylic copolymer (f) is preferably 20 mgKOH / g or less. When the acid value is 20 mgKOH / g or less, durability can be imparted. The acid value is more preferably 15 mgKOH / g or less.
As a method of imparting an acid value to the acrylic copolymer (f), it can be obtained by copolymerizing a monomer having an acid value with another monomer. Monomers having an acid value include (meth) acrylic acid, maleic anhydride, 2- (meth) acryloyloxyethyl-succinic acid, 2- (meth) acryloyloxyethyl-hexahydrophthalic acid, and 2- (meth). ) Acryloyloxyethyl-phthalic acid, 2- (meth) acryloyloxyethyl acid phosphate and the like can be mentioned, and among them, (meth) acrylic acid is preferably used.

The acrylic copolymer (f) preferably has a glass transition temperature of −40 to 95 ° C. When the glass transition temperature is −40 ° C. or higher, adhesion to the substrate can be obtained, and when it is 95 ° C. or lower, good flexibility can be obtained. The glass transition temperature of the acrylic copolymer (f) is determined by the composition ratio of the hydroxyl group-containing monomer and the other monomer copolymerized with the acidic functional group-containing monomer.

Acrylic copolymer (bb)
Further, among acrylic polymers, polyethers and polyesters having a functional group capable of reacting with an isocyanate group in the main chain of a vinyl-based polymer obtained by polymerizing a monomer having an ethylenically unsaturated double bond. , Polyester, Polyester, Polyester, Polybutadiene, or Polybutadiene-grafted acrylic copolymer (bb) with at least one structure introduced as a side chain is more preferred.

Examples of the functional group capable of reacting with the isocyanate group include a hydroxyl group, an amino group, a carboxyl group, an epoxy group, an N-methylol group, an N-alkoxymethyl group and the like, and a hydroxyl group is preferable in terms of reactivity.
The method for introducing the side chain is not particularly limited, but for example, a copolymer of an unsaturated dibasic acid and another monomer having an ethylenically unsaturated double bond is synthesized to form a copolymer. At least one selected from polyether, polyester, polycarbonate, or polybutadiene having a carboxylic acid or anhydrous carboxylic acid moiety of (f), a functional group capable of reacting with a carboxyl group, and a functional group capable of reacting with an isocyanate group. It can be introduced by subjecting the carboxyl group of the above to a reactive functional group by a condensation reaction.
In addition, when used in applications that require higher toughness and durability, it is possible to introduce a functional group capable of reacting with isocyanate directly into the main chain of the vinyl-based polymer in order to obtain a higher crosslink density. desirable. In that case, the polymer is unsaturated dibasic acid (f1), a monomer (f2) other than (f1) having a functional group capable of reacting with isocyanate and an ethylenically unsaturated double bond, and ethylenically unsaturated. It has a copolymer (f) of a monomer (f3) other than (f1) and (f2) having a double bond, a functional group capable of reacting with a carboxyl group, and a functional group capable of reacting with an isocyanate group. , Polyether, polyester, polycarbonate, or polybutadiene, can be obtained by a condensation reaction with at least one selected (g).

Examples of unsaturated dibasic acids (f1) that can be used to synthesize the copolymer (f) are maleic acid, maleic anhydride, fumaric acid, mesaconic acid, citraconic acid, itaconic acid, crotonic acid, diphenylmethane-di. -Γ-Ketocrotonic acid and the like can be mentioned.
The unsaturated dibasic acid (f1) can be used alone or in combination of two or more depending on the required performance. The proportion of the unsaturated dibasic acid (f1) in the monomer that is the raw material of the copolymer (f) is preferably 0.01 to 30% by weight, more preferably 0.05 to 10% by weight. be. When the proportion of unsaturated dibasic acid (f1) exceeds 30% by weight, the stability of the obtained polymer (A1) decreases, and when it is less than 0.01% by weight, the flexibility of the coating film is inadequate. It becomes sufficient and the adhesion to the substrate deteriorates.
Examples of the monomer (f2) other than (f1) having a functional group capable of reacting with isocyanate and an ethylenically unsaturated double bond include a (meth) acrylic monomer having a functional group capable of reacting with an isocyanate group. Vinyl monomers and the like can be used. Of these, (meth) acrylic monomers are preferable in terms of reactivity.
Examples of the functional group capable of reacting with the isocyanate group include a hydroxyl group, an amino group, a carboxyl group, an epoxy group, an N-methylol group, an N-alkoxymethyl group and the like, and a hydroxyl group is preferable in terms of reactivity.

Examples of the (meth) acrylic monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 1-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. Examples thereof include polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and polytetramethylene glycol mono (meth) acrylate.
Examples of the (meth) acrylic monomer having an amino group include methylaminoethyl (meth) acrylate, ethylaminoethyl (meth) acrylate, butylaminoethyl (meth) acrylate, and t-butylaminoethyl (meth) acrylate. N, N-dialkylamino such as monoalkylaminoalkyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylamino (meth) acrylate, N, N-dibutylaminoethyl (meth) acrylate Alkyl (meth) acrylate and the like can be mentioned.
Examples of the (meth) acrylic monomer having a carboxyl group include acrylic acid and methacrylic acid.
Examples of the (meth) acrylic monomer having an epoxy group include glycidyl (meth) acrylate.
Examples of the (meth) acrylic monomer having an N-methylol group include N-methylol (meth) acrylamide and the like.
Examples of the (meth) acrylic monomer having an N-alkoxymethyl group include N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, N-propoxymethyl (meth) acrylamide, and N-butoxymethyl ( (Meta) acrylamide having N-monoalkoxymethyl group such as meta) acrylamide, N, N-dimethylol (meth) acrylamide, N, N-di (methoxymethyl) (meth) acrylamide, N, N-di (ethoxymethyl) ) (Meta) acrylamide, N, N-di (propoxymethyl) (meth) acrylamide, N, N-di (butoxymethyl) (meth) acrylamide, etc. (meth) acrylamide having N, N-dialkoxymethyl groups, etc. Can be mentioned.

Examples of the vinyl monomer include hydroxystyrene and vinyl alcohol.
The monomer (f2) other than (f1) having a functional group capable of reacting with isocyanate and an ethylenically unsaturated double bond may be used alone or in combination of two or more depending on the required performance. can. The proportion of the monomer (f2) in the monomer that is the raw material of the copolymer (f) is preferably 0.01 to 50% by weight, more preferably 0.1 to 20% by weight, and particularly preferably. Is 0.1 to 10% by weight.

Examples of the monomer (f3) other than (f1) and (f2) having an ethylenically unsaturated double bond include a (meth) acrylic monomer, an aromatic vinyl monomer, and an olefin hydrocarbon monomer. , Vinyl ether monomer and the like can be used.
Examples of the (meth) acrylic monomer include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and stearyl (meth) acrylate. Examples thereof include alkyl (meth) acrylate and benzyl (meth) acrylate.
Examples of the aromatic vinyl monomer include styrene, methylstyrene, ethylstyrene and the like.
Examples of the olefin hydrocarbon monomer include ethylene, propylene, butadiene, isobutylene, isoprene, 1,4-pentadiene and the like.
Examples of vinyl ether monomers include vinyl methyl ether.
The monomers other than (f1) and (f2) having an ethylenically unsaturated double bond can be used alone or in admixture of two or more depending on the required performance.

The copolymer (f) can be obtained by a known method, for example, solution polymerization. Solvents include alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol methyl ether and diethylene glycol methyl ether, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether and the like. Ethers, hydrocarbons such as hexane, heptane, and octane, aromatics such as benzene, toluene, xylene, and cumene, and esters such as ethyl acetate and butyl acetate can be used. Two or more kinds of solvents may be mixed and used.
The concentration of the monomer charged at the time of synthesis is preferably 0 to 80% by weight.
Examples of the polymerization initiator include peroxides or azo compounds such as benzoyl peroxide, azoisobutylvaleronitrile, azobisisobutyronitrile, dit-butyl peroxide, t-butylperbenzoate, and t-butylperoctate. Kumen hydroxyperoxide and the like can be used, and the polymerization temperature is preferably 50 to 200 ° C, particularly preferably 70 to 140 ° C.

The polystyrene-equivalent weight average molecular weight of the copolymer (f) is preferably 5,000 to 500,000, more preferably 10,000 to 100,000. When the weight average molecular weight of the copolymer (a) is 500,000 or less, the dispersibility of the obtained carbon is good, and when it is 5,000 or more, sufficient coating film strength can be obtained after hot pressing.

Examples of the compound (g) include a polyether and a polyester having one or more functional groups capable of reacting with a carboxyl group and one or more functional groups capable of reacting with an isocyanate group at a linear end or a branched end. Polyester or polybutadiene can be used. Above all, polyester is preferable in order to obtain sufficient coating film strength after hot pressing.
Examples of the functional group capable of reacting with the carboxyl group of the compound (g) include a hydroxyl group, an epoxy group, an amino group, an isocyanate group and the like, and a hydroxyl group is preferable in terms of reactivity. Examples of the functional group capable of reacting with the isocyanate group of the compound (g) include a hydroxyl group, an amino group, a carboxyl group, an epoxy group, an N-methylol group, an N-alkoxymethyl group and the like, but in terms of reactivity. A hydroxyl group is suitable. The functional group capable of reacting with the carboxyl group of the compound (g) and the functional group capable of reacting with the isocyanate group may be the same functional group or different functional groups.

Examples of the polyester include a terminal hydroxyl group-containing ester compound obtained by esterifying at least one dicarboxylic acid and at least one polyol such as a polyhydric alcohol, a polyhydric phenol, or an alkoxy-modified product thereof, and a terminal. Examples thereof include an ester compound obtained by modifying the hydroxyl group of the above to an amino group, a carboxyl group, an epoxy group, an N-methylol group, or an N-alkoxymethyl group.
Examples of dicarboxylic acids include terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalic acid, p-oxybenzoic acid, p- (hydroxy) benzoic acid, 1,4-cyclohexanedicarboxylic acid, succinic acid, adipic acid. , Dicarboxylic acids such as azelaic acid, sebacic acid and dodecanedicarboxylic acid.

Examples of polyhydric alcohols are 1,3-propanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, 2-methyl-1,4-butanediol, 1,2-dimethyl-. 1,4-Butanediol, 2-ethyl-1,4-butanediol, 1,5-pentanediol, 2-methyl-1,5-pentanediol, 3-methyl-1,5-pentanediol, 2,2 , 4-trimethyl-1,3-pentanediol, 3-ethyl-1,5-pentanediol, 1,6-hexanediol, 2-methyl-1,6-hexanediol, 3-methyl-1,6-hexane Glycol, 1,7-heptanediol, 2-methyl-1,7-heptanediol, 3-methyl-1,7-heptanediol, 4-methyl-1,7-heptanediol, 1,8-octanediol, 2 -Methyl-1,8-octanediol, 2-ethyl-1,8-octanediol, 3-methyl-1,8-octanediol, 4-methyl-1,8-octanediol, 1,9-nonanediol, Ethylene Glycol, Propylene Glycol, Neopentyl Glycol, Diethylene Glycol, Dipropylene Glycol, Cyclohexanedimethanol, Polyethylene Glycol, Polypropylene Glycol, Polytetramethylene Glycol, Trimethylol Propane, 1,1,1-Trimethylol Propane Ethylene Glycol, Glycerin, Erythritol , Xylitol, sorbitol, mannitol and the like.

Examples of polyhydric phenols include catechol, resorcin, hydroquinone, hexylresorcin, trihydroxybenzene, dimethylolphenol and the like.
Examples of commercially available polyesters (polyester polyols) having two or more hydroxyl groups include Kuraray polyols P-510, P-1010, P-1510, P-2010, P-3010, and P-4010 manufactured by Kuraray Co., Ltd. P-5010, P-6010, P-2011, P-2013, P-520, P-1020, P-2020, P-1012, P-2012, P-530, P-1030, P-2030, PMHC- 2050, PMHC-2050R, PMHC-2070, PMHC-2090, PMSA-1000, PMSA-2000, PMSA-3000, PMSA-4000, F-2010, F-3010, N-2010, PNOA-1010, PNOA-2014, O-2010, Desmophen 650MPA, 651MPA / X, 670, 670BA, 680X, 680MPA, 800, 800MPA, 850, 1100, 1140, 1145, 1150, 1155, 1200, 1300X, 1652, 1700, manufactured by Sumitomo Bayer Urethane Co., Ltd. Examples thereof include 1800, RD181, RD181X, C200, Byron 200, 560, 600, GK130, GK860, GK870, 290, GK590, GK780, GK790 manufactured by Toyo Spinning Co., Ltd.

Examples of the polyether include polyalkylene glycols such as polyethylene glycol, polypropylene glycol and polytetramethylene glycol, and terminal hydroxyl groups such as amino group, carboxyl group, epoxy group, N-methylol group or N-alkoxymethyl group. Examples include modified ether compounds. Examples of commercially available polyethers having two or more hydroxyl groups (polyether polyols) include Desmophen 250U, 550U, 1600U, 1900U, 1915U, 1920D manufactured by Sumitomo Bayer Urethane Co., Ltd.

Examples of the polycarbonate include a polycarbonate diol represented by the following general formula, and a carbonate compound in which the terminal hydroxyl group is modified to an amino group, a carboxyl group, an epoxy group, an N-methylol group or an N-alkoxymethyl group. ..
H- (OR-OCO-) nR-OH
(R: alkylene chain, diethylene glycol, etc.)
Examples of commercially available polycarbonates having two or more hydroxyl groups include Kuraray polyols PNOC-1000, PNOC-2000, PMHC-2050, PMHC-2050R, PMHC-2070, PMHC-2070R, PMHC-2090R, C manufactured by Kuraray Co., Ltd. -2090 and the like can be mentioned.
Examples of polybutadiene include α, ω-polybutadiene glycol, α, β-polybutadiene glycol, and butadiene in which the terminal hydroxyl group is modified to an amino group, a carboxyl group, an epoxy group, an N-methylol group or an N-alkoxymethyl group. Examples include compounds.
As commercially available polybutadiene having two or more hydroxyl groups, for example, NISSO-PBG-1000, G-2000, G-3000, GI-1000, G manufactured by Nippon Soda Corporation.
Examples thereof include I-2000, GI-3000, GQ-1000, and GQ-2000.
Examples of commercially available polybutadiene having two or more epoxy groups include NISSO-PBBF-1000, EPB-13, EPB-1054 manufactured by Nippon Soda Corporation.

The polystyrene-equivalent weight average molecular weight of compound (g) is preferably 500 to 25,000, more preferably 1,000 to 10,000. When the weight average molecular weight of the compound (g) exceeds 25,000, the solubility in a solvent, the compatibility with the copolymer (f), and the reactivity with the copolymer (f) are lowered, and the reactivity with the copolymer (f) is lowered. Sufficient coating strength cannot be obtained after hot pressing. On the other hand, if it is less than 500, sufficient flexibility cannot be imparted to the sheet, and the adhesion to the base material is lowered.

The polymer (fb) uses a known method, for example, a compound (g), in which a carboxylic acid or anhydrous carboxylic acid moiety of the copolymer (f) and a functional group capable of reacting with the carboxyl group of the compound (g) are used. The functional group capable of reacting with the carboxyl group of) is a hydroxyl group, an epoxy group can be esterified, an amino group can be amidated, and an isocyanate group can be imidized. As the solvent, the solvent at the time of synthesizing the copolymer (f) can be used as it is, and further, another solvent may be added or the solvent may be removed depending on the conditions at the time of synthesis, the conditions at the time of coating and the like. It doesn't matter.
As the reaction catalyst, for example, tertiary amines such as triethylamine, triethanolamine, and ethylenediamine are used, and the reaction temperature is preferably 50 to 300 ° C.
The reaction ratio between the copolymer (f) and the compound (g) is such that 1 mol of the carboxylic acid or the anhydrous carboxylic acid of the copolymer (f) has a functional group capable of reacting with the carboxyl group of the compound (g). , 0.01 to 10 mol, more preferably 0.1 to 5 mol, still more preferably 0.5 to 2 mol. When the reaction ratio of the compound (g) exceeds 10 mol, the coatability of the resin composition is impaired, and when it is less than 0.01 mol, the flexibility of the obtained sheet decreases, so that the base material is used. Adhesion with and is reduced.
Further, it is not necessary to use one type each of the copolymer (f) and the compound (g), and a plurality of types may be used depending on the purpose and required physical properties.
The polystyrene-equivalent weight average molecular weight of the polymer is preferably 5,000 to 500,000, more preferably 10,000 to 100,000. When the weight average molecular weight of the polymer (A1) exceeds 500,000, the solubility in a solvent decreases, and when it is less than 5,000, sufficient coating film strength cannot be obtained after hot pressing.

<Fluororesin>
The fluororesin (A5) is a fluorine-containing polyol polyisocyanate having two or more hydroxyl groups in one molecule. The fluoropolypoly having two or more hydroxyl groups in one molecule is not limited, but is preferably a polymer compound, for example, a copolymer of a fluoroolefin and a vinyl ether, or a copolymer of a fluoroolefin and a vinyl ester. Examples thereof include a copolymer of a fluoroolefin and a (meth) acrylic acid ester, and those that can be dissolved in a solvent are preferable.
Specifically, Lumiflon LF100, LF200, LF400, LF600, 800 of Asahi Glass Co., Ltd., Zeffle GK500, GK510, GK550, GK570, GK580 of Central Glass Co., Ltd. 705 and DIC's Fluonate K-700, K-702, K-704. The same K-705, the same K-707, the same WZQ-660 and the like can be used. One type of fluorine-containing polyol may be used alone, or two or more types may be used in combination.

<Epoxy resin>
As the epoxy resin (A6), various conventionally known polyepoxy compounds can be used. For example, bis (4-hydroxyphenyl) propan diglycidyl ether and bis (4-hydroxy-3,5-dibromophenyl) propan diglycidyl ether can be used. , Bis (4-hydroxyphenyl) ethane diglycidyl ether, bis (4-hydroxyphenyl) methane diglycidyl ether, resorcinol diglycidyl ether, fluoroglycinol triglycidyl ether, trihydroxybiphenyl triglycidyl ether, tetraglycidyl benzophenone, bisresorcinol Tetraglycidyl ether, tetramethylbisphenol A diglycidyl ether, bisphenol C diglycidyl ether, bisphenol hexafluoropropane diglycidyl ether, 1,3-bis [1- (2,3-epoxypropoxy) -1-trifluoromethyl- 2,2,2-trifluoroethyl] benzene, 1,4-bis [1- (2,3-epoxypropoxy) -1-trifluoromethyl-2,2,2-trifluoromethyl] benzene, 4, Aromatic glycidyl ether compounds such as 4'-bis (2,3-epoxypropoxy) octafluorobiphenyl and phenol novolac type bisepoxy compounds, alicyclic diepoxy acetal, alycyclic diepoxy adipate, alycyclic diepoxy Alicyclic polyepoxy compounds such as carboxylate and vinyl cyclohexene dioxide, diglycidyl phthalate, diglycidyl tetrahydrophthalate, diglycidyl hexahydrophthalate, dimethylglycidyl phthalate, dimethylglycidyl hexahydrophthalate, diglycidyl-p-oxybenzoate, diglycidyl Cyclopentane-1,3-dicarboxylate, glycidyl ester compounds such as dimer acid glycidyl ester, diglycidyl aniline, diglycidyl toluidine, triglycidyl aminophenol, tetraglycidyl diaminodiphenylmethane, diglycidyl tribromoaniline and other glycidyl amine compounds, Examples thereof include heterocyclic epoxy compounds such as diglycidyl hydantin, glycidyl glycidoxyalkyl hydantin, and triglycidyl isocyanurate, and oligomer compounds thereof.

<Elastomer>
The styrene-based elastomer (A7) that can be used as a binder contains styrene units as a constituent unit of the main chain, and the content of the styrene units is 10% by weight or more and 90% by weight or less, and the weight average molecular weight is 10. It may be in the range of 000 or more and 200,000 or less.

As used herein, the term "constituent unit" refers to a structure derived from a single molecule in the structure constituting an elastomer which is a polymer.

As used herein, the term "styrene unit" refers to a constituent unit derived from styrene contained in the polymer when styrene is polymerized.

The binder resin has a styrene unit content of 10% by weight or more and 90% by weight or less, and an elastomer having a weight average molecular weight of 10,000 or more and 200,000 or less.
The content of the styrene unit is more preferably more than 50% by weight. Further, the more preferable range of the weight average molecular weight of the elastomer is 20,000 or more, and the more preferable range is 150,000 or less.

As the elastomer, various elastomers are used as long as the content of the styrene unit is in the range of 10% by weight or more and 90% by weight or less and the weight average molecular weight of the elastomer is in the range of 10,000 or more and 200,000 or less. be able to. Specifically, for example, polystyrene-poly (ethylene / propylene) block copolymer (SEP), styrene-isoprene-styrene block copolymer (SIS), styrene-butadiene-styrene block copolymer (SBS), styrene-butadiene-butylene-styrene. Block Copolymer (SBBS) and its hydrogenated products; Styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-ethylene-propylene-styrene block copolymer (styrene-isoprene-styrene block copolymer) (SEPS), styrene -Ethethylene-ethylene-propylene-styrene block copolymer (SEEPS) and the like can be mentioned, and those having a styrene unit content and a weight average molecular weight within the above ranges can be used.

The elastomer is more preferably hydrogenated. When the elastomer is a hydrogenated product, the stability against heat is improved, deterioration such as decomposition and polymerization is unlikely to occur, and the solubility in a hydrocarbon solvent and the resistance to a resist solvent are excellent.

Further, among the above-mentioned elastomers, elastomers in which both ends of the molecule are styrene moieties are more preferable. Elastomers exhibit higher heat resistance by having styrene moieties with high thermal stability as block structures at both ends.

Further, the elastomer is more preferably hydrogenated from block copolymers of styrene and conjugated diene, where both ends of the molecule are styrene moieties. As a result, the stability against heat is improved and deterioration such as decomposition and polymerization is less likely to occur, and the solubility and resistance to hydrocarbon solvents are excellent, and the styrene moiety having high thermal stability is blocked at both ends. By having it as, it shows higher heat resistance.

Further, the elastomer may have at least one functional group-containing atomic group in the molecule, if necessary. The elastomer can be obtained, for example, by attaching a functional group-containing atomic group to a known block copolymer using a denaturing agent.

A functional group-containing atomic group refers to an atomic group containing one or more functional groups. Examples of the functional group contained in the functional group-containing atomic group include an amino group, an acid anhydride group (preferably maleic anhydride group), an imide group, a urethane group, an epoxy group, an imino group, a hydroxyl group, a carboxyl group and a silanol group. And an alkoxysilane group (the alkoxysilane group preferably has 1 to 6 carbon atoms). When the elastomer has at least one functional group-containing atomic group in the molecule, the flexibility and adhesiveness of the adhesive composition are further improved.

Commercially available products that can be used as the above elastomer include, for example, "Septon (trade name)" manufactured by Kuraray Corporation, "Hybler (trade name)" manufactured by Kuraray Corporation, "Tough Tech (trade name)" manufactured by Asahi Kasei Corporation, and JSR Corporation. Company-made "Dynaron (trade name)" and the like can be mentioned.

(Hardener)
The conductive composition used for the conductive wiring of the present invention includes an isocyanate-based curing agent, an epoxy-based curing agent, a metal chelate-based curing agent, and an oxetane group-containing compound for the purpose of improving the adhesion of the binder to the curing agent or the substrate. It can contain an aziridine group-containing compound, a carbodiimide group-containing compound, a benzoxazine compound, a β-hydroxyalkylamide group-containing compound, a sulfur-containing compound, and the like, but is not particularly limited. In addition, an ultraviolet absorber, a hindered amine light stabilizer, an antioxidant, an antioxidant, etc. may be contained for the purpose of imparting durability such as weather resistance and heat resistance.
It is important that the isocyanate-based curing agent (g) has two or more isocyanate groups in one molecule, and examples thereof include aromatic isocyanates, aliphatic isocyanates, and alicyclic isocyanates. Above all, it is preferable to use an aliphatic isocyanate-based curing agent from the viewpoint of preventing yellowing of the molded decorative sheet. The isocyanate-based curing agent (g) may be used alone or in combination of two or more types. Further, a curing agent that reacts with other hydroxyl groups may be used as long as it does not affect the physical properties of the decorative sheet of the present invention.

The aromatic isocyanates include 1,3-phenylenedi isocyanate, 4,4'-diphenyldiisocyanate, 1,4-phenylenediisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, and 2,6-tolylene diisocyanate. Isocyanate, 4,4'-toluene diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, dianisidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4', 4 "- Examples thereof include triphenylmethane triisocyanate.

Examples of the aliphatic isocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylenediocyanate, 1,3-butylenediocyanate, and dodecamethylene diisocyanate. Examples thereof include 2,4,4-trimethylhexamethylene diisocyanate.

Examples of the alicyclic isocyanate include 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (IPDI), 1,3-cyclopentane diisocyanate, 1,3-cyclohexanediisocyanate, 1,4-cyclohexanediisocyanate, and methyl-2. , 4-Cyclohexanediisocyanate, methyl-2,6-cyclohexanediisocyanate, 4,4'-methylenebis (cyclohexylisocyanate), 1,4-bis (isocyanatemethyl) cyclohexane and the like.

These isocyanate-based curing agents further include an adduct of the isocyanate and a polyol compound such as trimethylolpropane, a bullet or isocyanurate of the isocyanate, and further, a polyether polyol, a polyester polyol, or an acrylic polyol known as the isocyanate. It is preferable to use it as an adduct with a polybutadiene polyol, a polyisoprene polyol, or the like.

Among these isocyanate-based curing agents (g), low-yellowing aliphatic or alicyclic isocyanates are preferable from the viewpoint of design, and adducts are preferable from the viewpoint of film strength of the cured film. More specifically, an adduct of hexamethylene diisocyanate (HDI) and an adduct of 3-isocyanatemethyl-3,5,5-trimethylcyclohexylisocyanate (IPDI) are preferable. In addition, a mixture of these is also preferably used.

Further, in the present invention, a blocked isocyanate curing agent may be used. As the blocked isocyanate curing agent, those obtained by blocking the above-mentioned unblocked isocyanate curing agent with various blocking agents are used, and as the blocking agent, those that dissociate at a relatively low temperature of about 80 ° C to 120 ° C are used. preferable. When a non-blocking isocyanate curing agent is used, the acrylic copolymer (f) having a hydroxyl group and the isocyanate-based curing agent (g) are packaged separately and mixed immediately before use. Is preferably used.

The acrylic resin has at least one structure selected from polyether, polyester, polycarbonate, or polybutadiene having a functional group capable of reacting with an isocyanate group from the viewpoint of volume resistance, adhesion to a substrate, and durability. It is also preferable to include a vinyl-based polymer having a side chain. The volume resistance value is a good result because the resin component in the hot press tends to flow.

<Conductivity imparting agent (B)>
The conductive carbon material (B) in the present invention is not particularly limited as long as it is a conductive carbon material, but graphite, carbon black, and conductive carbon fibers (carbon nanotubes, carbon nanofibers, carbon). Fiber), fullerene, etc. can be used alone or in combination of two or more. From the viewpoint of conductivity, it is preferable to use graphite.

As the graphite, for example, artificial graphite, natural graphite, or the like can be used. Artificial graphite is made by artificially orienting irregularly arranged micrographite crystals by heat treatment of amorphous carbon, and is generally manufactured using petroleum coke or coal-based pitch coke as the main raw material. To. As the natural graphite, scaly graphite, lump graphite, earth graphite and the like can be used. It is also possible to use expanded graphite (also referred to as expandable graphite) obtained by chemically treating scaly graphite, or expanded graphite obtained by heat treatment and expansion of expanded graphite and then miniaturization or pressing. You can. Among these graphites, when used for the conductive layer of the wiring sheet, expanded graphite is preferable from the viewpoint of conductivity.

(Expanded graphite (B1))
As described above, the expanded graphite used in the present invention is expanded graphite obtained by chemically treating scaly graphite (also referred to as expansive graphite; Expandable Graphite), which is heat-treated to expand and then refined. be. It also includes expanded graphite powder obtained by crushing a graphite sheet that has been rolled before miniaturization.
The expanded graphite can be appropriately selected from conventionally known expanded graphite. Commercially available expanded graphite may be used. Examples of commercially available expanded graphite include EC1500, EC1000, EC500, EC300, EC100, and EC50 manufactured by Ito Graphite Industry Co., Ltd. (all are trade names).
The shape of the expanded graphite is not particularly limited. For example, flaky expanded graphite processed into flakes can be mentioned.
Expanded graphite can exhibit high conductivity with a small amount of content as compared with other graphites. For example, it tends to exhibit higher conductivity in a smaller amount than general scaly graphite.
The average particle size of the expanded graphite is preferably 10 μm to 200 μm, more preferably 25 to 150 μm. If it is 10 μm or more, sufficient conductivity can be obtained, and if it is 200 μm or less, the adhesion of the conductive composition to the substrate and the coatability are good, which is preferable.
Further, it is preferable that the difference in particle size between D10 (μm) and D90 (μm) is 60 μm or more.

The "average particle size" in the present invention means the particle size at an integrated value of 50% in the particle size distribution obtained by the laser diffraction / scattering method. D10 (μm) and D90 (μm) mean particle sizes of integrated values of 10% and 90%.
The measurement shall be performed under the following conditions.
Measuring equipment: Microtrack MT3300EX2 (Microtrack Bell Co., Ltd.)
Measurement sample preparation method: After adding 0.63 g of graphite and 11.87 g of toluene to a mayonnaise bottle (M-70), planetary stirring (manufactured by Shinky Co., Ltd .: Awatori Rentaro, stirring time: 3 minutes) is performed to disperse the dispersion. And carry out the measurement.

When the solid content of the conductive composition is 100% by weight, the content of the conductivity-imparting agent (B1) is 40% by weight to 90% by weight, more preferably 55% by weight to 85% by weight. .. If it is less than 50% by weight, the conductivity is not sufficient, and if it exceeds 90% by weight, the adhesion to the substrate and the coatability are insufficient.

(Carbon black (B2))
As the conductivity-imparting agent of the present invention, it is preferable to further use carbon black in combination. By using expanded graphite and carbon black in combination, carbon black plays a role of connecting the conductive paths of expanded graphite, and tends to exhibit high conductivity without going through a hot pressing process.
As the carbon black, conventionally known conductive carbon such as acetylene black, ketjen black, and furnest black can be used.

As the specific surface area of the carbon black used increases, the contact points between the carbon black particles increase, which is advantageous for lowering the internal resistance of the electrode. Specifically, the specific surface area (BET) obtained from the amount of nitrogen adsorbed is 20 m2 / g or more, 1500 m2 / g or less, preferably 50 m2 / g or more, 1500 m2 / g or less, and more preferably 100 m2 / g or more.
It is desirable to use one of 1500 m2 / g or less. Sufficient conductivity can be obtained by using carbon black having a specific surface area of 20 m2 / g or more, and if it is 1500 m2 / g or less, carbon black can be easily obtained as a commercially available material.

The particle size of the carbon black used is preferably 0.005 to 1 μm in primary particle size, and particularly preferably 0.01 to 0.2 μm. However, the primary particle diameter referred to here is an average of the particle diameters measured by an electron microscope or the like.

Examples of commercially available carbon black include Tokai Carbon's Talker Black # 4300, # 4400, # 4500, # 5500, Degusa's Printex L, Colombian's Raven7000, 5750, 5250, 5000ULTRAIII, 5000ULTRA, etc. Conductex SC ULTRA, Conductex 975 ULTRA, PUERBLACK100, 115, 205, # 2350, # 2400B, # 2600B, # 30050B, # 3030B, # 3230B, # 3350B, # 3400B, # 5400B, manufactured by Mitsubishi Chemical Co., Ltd. MONARCH1400, 1300, 900, VulcanXC-72R, BlackPearls2000, Ensaco250G, Ensaco260G, Ensaco350G, Furness Black such as SuperP-Li manufactured by TIMCAL), EC-300J, EC-600JD manufactured by Lion, etc. Examples thereof include acetylene blacks such as Denka Black, Denka Black HS-100, and FX-35 manufactured by Kogyo Co., Ltd., but the present invention is not limited to these, and two or more types may be used in combination.

The weight composition ratio of expanded graphite (B1) and carbon black (B2) is 60 to 90 weight when the total weight of expanded graphite and carbon black is 100% by weight from the viewpoint of conductivity. %, Carbon black is preferably 10 to 40% by weight.

(Conductive carbon fiber)
As the conductive carbon fiber, one obtained by firing from a raw material derived from petroleum is preferable, but one obtained by firing from a raw material derived from a plant can also be used. Further, the carbon nanotubes include a single-walled carbon nanotube in which a graphene sheet forms a tube having a diameter in a nanometer region, and a multi-walled carbon nanotube in which the graphene sheet is a multi-walled layer. Therefore, the diameter of the multi-walled carbon nanotube shows a large value of 30 nm with respect to 0.7-2.0 nm of a typical single-walled carbon nanotube.

Examples of commercially available conductive carbon fibers and carbon nanotubes include vapor-phase carbon fibers such as VGCF manufactured by Showa Denko Co., Ltd., EC1.0, EC1.5, EC2.0, EC1.5-P manufactured by Meijo Nanocarbon Co., Ltd., etc. Examples thereof include single-walled carbon nanotubes manufactured by CNano, FloTube9000, FloTube9100, FloTube9110, FloTube9200, NC7000 manufactured by Nanocyl, and 100T manufactured by Knano.

<Organic solvent>
Organic solvents include alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol methyl ether and diethylene glycol methyl ether, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether and the like. Suitable for the composition of the conductive composition from among ethers, hydrocarbons such as hexane, heptane and octane, aromatics such as benzene, toluene, xylene and cumene, and esters such as ethyl acetate and butyl acetate. Can be used. Further, two or more kinds of solvents may be used.
When a printing coating method that requires an ink composition having a viscosity of a certain level or higher, such as screen printing, is adopted, the viscosity of the organic solvent at 25 ° C. is preferably 30 mPa · s to 75,000 mPa · s. When it is 30 mPa · s or more, high conductivity is exhibited, so that even if the resin content is small, good dispersibility of the viscosity and conductivity-imparting agent suitable for coating can be obtained, and the coating property becomes good, 75,000 mPa. When it is s or less, the dispersibility of the conductivity-imparting agent (B1) becomes good. For example, tarpineol, dihydroterpineol, 2,4-diethyl-1,5-pentanediol, 1,3-butylene glycol, isobornylcyclohexanol can be mentioned. Two or more kinds of high-viscosity solvents shown here may be used, or they may be used in combination with low-viscosity solvents such as methyl ethyl ketone, toluene, and isopropyl alcohol whose viscosity at 25 ° C. is less than 30 mPa · s. It is possible.

The viscosity shown here means a numerical value obtained by the following measuring method.
The measurement was performed using a leometer (MCR302) manufactured by Anton Paar Japan. As a measurement method, the measurement sample is measured under the following conditions after installation, and the numerical value 60 seconds after the start of shearing is read.
Measuring jig: Cone plate CP25-2 (If measurement is not possible with this jig, use cone plate CP50-1)
Rotation speed: 1000 (1 / sec)
Plate temperature: 25 ° C

<Other ingredients>
The conductive composition of the present invention contains, if necessary, an ultraviolet absorber, an ultraviolet stabilizer, a radical catching agent, a filler, a thixotropic agent, an antistatic agent, and an antioxidant, as long as the effects of the present invention are not impaired. Agents, antistatic agents, flame retardants, thermal conductivity improvers, plasticizers, anti-sag agents, antifouling agents, preservatives, disinfectants, defoamers, leveling agents, anti-blocking agents, hardeners, thickeners, Various additives such as a pigment dispersant and a silane coupling agent may be added.

<Manufacturing of conductive composition>
The conductive composition of the present invention can be produced by using the above-mentioned binder resin and carbon material as essential components, and further adding an organic solvent and other components as necessary, and then uniformly dispersing them.
The dispersion method is carried out by dissolving the binder resin in a solvent, adding a conductive filler, and then stirring the planet, using a three-roll, two-roll, scandex, or bead mill. The solvent used is not particularly limited as long as it dissolves the binder resin. A dispersion method other than the above may be used as long as the physical properties are not deteriorated. However, when a curing agent is used, the curing agent shall be added after the conductive composition is dispersed. After adding the curing agent, the mixture is appropriately mixed by planetary stirring, a mix rotor, a disper, or the like. The mixing method is not particularly limited.

(Conductive wiring sheet)
The conductive wiring sheet of the present invention has a conductive layer formed from a conductive composition on a sheet-like substrate.

(Sheet-like base material)
The shape of the sheet-like base material used for the conductive wiring sheet is not particularly limited, but an insulating resin film is preferable, and one suitable for various uses can be appropriately selected.

As the sheet-like base material, a material having particularly low conductivity and capable of withstanding the heat of drying and the heat of the heat pressing process in order to form the conductive wiring is selected. The sheet-like base material (A) is preferably a plastic base material having a thickness of 25 to 500 μm, and is particularly preferably a sheet made of at least one selected from polyethylene terephthalate, polyimide, polyphenylene sulfide, polyvinyl chloride, and fluororesin.

As the shape, a film on a flat plate is generally used, but a film having a roughened surface, a primer-treated film, a perforated film, and a mesh-like substrate can also be used.

The method for coating the conductive composition on the sheet-like substrate is not particularly limited, and a known method can be used.

Specific examples include a die coating method, a dip coating method, a roll coating method, a doctor coating method, a knife coating method, a spray coating method, a gravure coating method, a screen printing method, an electrostatic coating method, and the like, and drying. As the method, a stand-alone dryer, a blower dryer, a warm air dryer, an infrared heater, a far-infrared heater, and the like can be used, but the method is not particularly limited thereto.
Further, after coating, rolling processing may be performed by a lithographic press, a calendar roll, or the like.

(Thickness of conductive layer)
The thickness of the conductive layer of the present invention is 30 to 200 μm, more preferably 50 to 150 μm.

(Volume resistance value of conductive layer)
The volume resistance value of the conductive layer of the present invention is 2 × 10 ^-2-1 × 10 ^-3 Ω · cm. When the volume resistance value is 2 × 10 ^-2 Ω · cm or less, it can be used as wiring for electronic devices and the like.

(Composition of conductive layer)
The proportion of the binder resin (A) in the conductive layer of the present invention is less than 50% by mass, preferably 10 to 50% by mass, and more preferably 20 to 35% by mass. If the amount of the binder resin (A) is too small, the surface texture and adhesion of the conductive layer may not be maintained, while if the amount of the binder resin (A) is too large, the conductivity of the conductive layer may decrease. ..
The proportion of the conductive carbon material (B) in the conductive layer of the present invention is 50 to 90% by weight, more preferably 65 to 80% by mass. If the amount of the conductive carbon material (B) is too small, the conductivity of the conductive layer may be insufficient, while if the amount of the conductive carbon material (B) is too large, the adhesion of the conductive layer deteriorates. May be done.

(Wiring sealing)
The wiring sheet of the present invention can also seal conductive wiring by laminating a film.
Examples of the film used for laminating include acrylic resin, fluororesin, epoxy resin, and polyamide resin.
As a laminating method, a film made of acrylic resin, fluororesin, epoxy resin, polyamide resin, etc. is appropriately heated from room temperature to 250 ° C. on one or both of the two heating rolls, and passed through the nip between the heat rolls to form a wiring sheet. Just stick them together.
Even if one side of the film is heat-sealed and pasted, the wiring pattern of the wiring sheet is provided after applying an acrylic adhesive or a polyester-based, acrylic-based, or epoxy-based dry laminating adhesive to one side of the film. It is also possible to stack the film on the side with the wiring pattern sandwiched between them, pass it through the nip between the thermal rolls, and bond them together.
Alternatively, the wiring sheet and the film or the film provided with the adhesive on one side of the film may be stacked between the hot presses of the flat plate so as to sandwich the side of the wiring sheet provided with the wiring pattern between the films.

Hereinafter, the present invention will be described in more detail by way of examples, but the following examples do not limit the scope of rights of the present invention in any way. In addition, "part" in an Example and a comparative example represents a "mass part".

<Measurement method of weight average molecular weight (Mw)>
For the measurement of Mw, GPC (gel permeation chromatography) "HPC-8020" manufactured by Tosoh Corporation was used. GPC is a liquid chromatography in which a substance dissolved in a solvent (THF; tetrahydrofuran) is separated and quantified according to the difference in molecular size. In the measurement in the present invention, two "LF-604" (manufactured by Showa Denko KK: GPC column for rapid analysis: 6 mm ID x 150 mm size) are connected in series to the column, the flow rate is 0.6 ml / min, and the column temperature is set. It was carried out under the condition of 40 ° C., and the weight average molecular weight (Mw) was determined in terms of polystyrene.

<Measurement of acid value>
Precisely weigh about 1 g of the sample in an Erlenmeyer flask with a stopper, and add 100 ml of a toluene / ethanol (volume ratio: toluene / ethanol = 2/1) mixture to dissolve the sample. Phenolphthalein test solution is added to this as an indicator and held for 30 seconds. Then, titrate with 0.1N alcoholic potassium hydroxide solution until the solution turns pink. The acid value was calculated by the following formula (unit: mgKOH / g). Acid value (mgKOH / g) = (5.611 × a × F) / S
However,
S: Sample collection amount (g)
a: Consumption of 0.1N alcoholic potassium hydroxide solution (ml)
F: Potency of 0.1N alcoholic potassium hydroxide solution

<Measurement method of hydroxyl value>
The hydroxyl value is the amount of hydroxyl group contained in 1 g of a hydroxyl group-containing resin expressed by the amount of potassium hydroxide (mg) required to neutralize acetic acid bonded to the hydroxyl group when the hydroxyl group is acetylated. Is. The hydroxyl value was measured according to JIS K0070. In the present invention, when calculating the hydroxyl value, the acid value is taken into consideration as shown in the following formula.

<Measurement of hydroxyl value>
Precisely weigh about 1 g of the sample in an Erlenmeyer flask with a stopper, and add 100 ml of a toluene / ethanol (volume ratio: toluene / ethanol = 2/1) mixture to dissolve the sample. Further, exactly 5 ml of an acetylating agent (a solution in which 25 g of acetic anhydride was dissolved in pyridine to make a volume of 100 ml) was added, and the mixture was stirred for about 1 hour. Phenolphthalein test solution is added to this as an indicator and lasts for 30 seconds. Then, titrate with 0.1N alcoholic potassium hydroxide solution until the solution turns pink.
The hydroxyl value was calculated by the following formula (unit: mgKOH / g).
Hydroxy group value (mgKOH / g) = [{(ba) × F × 28.05} / S] + D
However,
S: Sample collection amount (g)
a: Consumption of 0.1N alcoholic potassium hydroxide solution (ml)
b: Consumption (ml) of 0.1N alcoholic potassium hydroxide solution in the blank experiment
F: Potency of 0.1N alcoholic potassium hydroxide solution D: Acid value (mgKOH / g)

<Measurement method of glass transition temperature>
The binder resin from which the solvent was dried and removed was measured by using "DSC-1" manufactured by METTLER TOLEDO Co., Ltd. and raising the temperature from -80 to 150 ° C. at 2 ° C./min.

[Adjustment of binder resin]
<Synthesis of binder resin A-1>
Polyester polyol (manufactured by Kuraray Co., Ltd.) obtained from terephthalic acid, adipic acid and 3-methyl-1,5-pentanediol in a reaction vessel equipped with a stirrer, a thermometer, a reflux cooler, a dropping device, and a nitrogen introduction tube. "Kurare Polyol P-2011", Mn = 2011) 455.5 parts, dimethylol butanoic acid 16.5 parts, isophorone diisocyanate 105.2 parts, and toluene 140 parts were charged and reacted at 90 ° C. for 3 hours under a nitrogen atmosphere. Toluene was added in an amount of 360 parts to obtain a urethane prepolymer solution having an isocyanate group. Next, a urethane prepolymer solution having an isocyanate group obtained by mixing 19.9 parts of isophorondiamine, 0.63 parts of di-n-butylamine, 294.5 parts of 2-propanol, and 335.5 parts of toluene. 969.5 parts were added and reacted at 50 ° C for 3 hours followed by 70 ° C for 2 hours, diluted with 126 parts of toluene and 54 parts of 2-propanol, Mw = 61,000, acid value = 10 mgKOH / g, urethane pre. A solution of polyurethane resin A-1 was obtained in which the total equivalent of the polyamino compound and the amino groups in the reaction terminator was 0.98 with respect to the free isocyanate groups at both ends of the polymer.

<Preparation of binder resin A-2>
Toyobo's polyester resin "Byron 200" was dissolved in a mixed solvent of MEK and toluene (mixing ratio 1: 1) so as to have a solid content of 30% to obtain a solution of the binder resin A-2.
<Preparation of binder resin A-3>
Toyobo's polyester resin "Byron 240" was dissolved in a mixed solvent of MEK and toluene (mixing ratio 1: 1) so as to have a solid content of 30% to obtain a solution of the binder resin A-3.
<Preparation of binder resin A-4>
Acrylic resin "Dianal 80" manufactured by Mitsubishi Rayon was dissolved in a mixed solvent of MEK and toluene (mixing ratio 1: 1) so as to have a solid content of 30% to obtain a solution of binder resin A-4.
<Binder resin A-5>
Taisei Fine Chemical's acrylic polyol "6AN-5001" (solid content 40%, hydroxyl value 15 mg (KOH) / g) was used.
<Binder resin A-6>
Asahi Glass's fluorine-containing polyol "LF200" (solid content 60%, hydroxyl value 31 mg (KOH) / g) was used.
<Binder resin A-7>
Asahi Glass's fluorine-containing polyol "LF600X" (solid content 50%, hydroxyl value 27 mg (KOH) / g) was used.
<Binder resin A-8>
<Binder resin A-9> using water-based acrylic emulsion NEOCRYL A-655 (Kusumoto Kasei Co., Ltd., solid content 45%)
A water-based urethane emulsion NeoRez R966 (Kusumoto Kasei Co., Ltd.) with a solid content of 33% was used.
<Preparation of binder resin A-10>
Henkel white water polyamide resin "Macromelt 6202" was dissolved in toluene and isopropyl alcohol (mixing ratio 1: 1) to obtain a solution of binder resin A-10.
<Preparation of binder resin A-11>
Henkel white water polyamide resin "Macromelt 6238" was dissolved in toluene and isopropyl alcohol (mixing ratio 1: 1) to obtain a solution of binder resin A-11.
<Preparation of binder resin A-12>
Asahi Kasei's SEBS hydrogenated styrene elastomer resin "Tuftec M1913" was dissolved in toluene) to obtain a solution of the binder resin A-12.

<Creation of encapsulant>
A laminated film was prepared as a sealing material for sealing the conductive wiring.
The adhesive a for the encapsulant was synthesized and adjusted by the following method.
<Synthesis of adhesive a>
70 parts of n-butyl acrylate, 20 parts of methyl acrylate, 2-ethyl in a reaction vessel (hereinafter, simply referred to as "reaction vessel") equipped with a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen introduction tube. After charging 4 parts of hexyl acrylate, 6 parts of acrylic acid, 72 parts of ethyl acetate and 0.13 part of 2,2'-azobis (2-methylbutyronitrile) and replacing the air in this reaction vessel with nitrogen gas. The reaction solution was reacted at reflux temperature for 8 hours in a nitrogen atmosphere with stirring. After completion of the reaction, the mixture was diluted with ethyl acetate to obtain a solution of an acrylic copolymer a1 having a non-volatile content concentration of about 30% and a weight average molecular weight of Mw of 1.05 million.
100 parts of toluene was charged in the reaction vessel, 95 parts of n-butyl methacrylate and 5 parts of N, N-dimethylaminoethyl methacrylate were charged in the dropping device, and the air in the reaction vessel was replaced with nitrogen gas and then stirred. While the mixture was added dropwise in a nitrogen atmosphere for 1 hour, the reaction solution was reacted at a reflux temperature for 8 hours. After completion of the reaction, the mixture was diluted with ethyl acetate to obtain a solution of an acrylic copolymer a2 having a non-volatile content concentration of about 30% and a weight average molecular weight of Mw of 50,000.
75 parts by weight of acrylic copolymer solution a1 and 25 parts by weight of acrylic copolymer solution a2 were added, and 0.021 parts of N, N, N', N'-tetraglycidyl-m-xylylenediamine were added as epoxy cross-linking agents. The mixture was uniformly stirred to obtain a pressure-sensitive adhesive a.
A PET film separator 50 μm (SP-PET01-50BU: manufactured by Mitsui Chemicals Tohcello) treated with peelable silicone is coated so that the coating amount is 30 g / m ² (dry), dried at 90 ° C. for 1 minute, and the substrate is used. Acrylic resin film "Sanduren SD001" manufactured by Kaneka Corporation was attached by roll laminating and aged at room temperature for 1 week to obtain a sealing material C-1.
DX film 14S2250 (manufactured by Denka Co., Ltd.) is attached to the adhesive dried by the same method as C-1, except that Sanduren SD001 is changed to the polyvinylidene fluoride film "DX film 14S2250", and the sealing material C-2 is applied. Obtained.
Furthermore, except that Sanduren SD001 was changed to ethylene tetrafluoroethylene "Aflex 100NS", Aflex 100NS (manufactured by Asahi Glass Co., Ltd.) was attached to the adhesive dried by the same method as C-1, and the sealing material C was used. I got -3.

<Wiring sheet>
(Example 1)
20 parts of Banider resin (A-1) in terms of solid content, 80 parts of B-1: LEP (Nippon Graphite Industry) as a conductive carbon material, 400 parts of propylene glycol monomethyl ether acetate (PGMAC) as a solvent. It was put into a mixer and mixed, and further put into a sand mill for dispersion to obtain a conductive composition (1).
Then, this conductive composition (1) is applied on a moisture-resistant polyethylene terephthalate film X10S (manufactured by Toray Film Processing) having a thickness of 125 μm as a sheet-like substrate using a doctor blade, and then at 130 ° C. for 30 minutes. It was heated and dried. Furthermore, a PET film separator 50 μm (SP-PET01-50BU: manufactured by Mitsui Chemicals Tohcello) is placed in a wiring pattern, and a hydraulic roll laminator NP-500S manufactured by Taisei Laminator (hydraulic pressure 2 MPa, speed 0.5 m / min, press temperature 150 ° C.). A wiring sheet (1) having a thickness of the conductive layer of 35 to 40 μm was produced by roll pressing with the above.
Further, the sealing material C-1 was peeled off from the separator, and the sealing material was attached to the wiring pattern surface of the wiring sheet with a roll to obtain a wiring sheet.
The obtained wiring sheet was evaluated by the following method. The evaluation results are shown in Table 1.
In the following evaluations, the evaluation of the volume resistance value of the conductive layer was performed using the wiring sheet before the encapsulant was attached.

(Volume resistance value of conductive layer)
The volume resistance value of the conductive layer was determined by measuring (JIS-K7194) by the 4-terminal method using Loresta GP (manufactured by Mitsubishi Chemical Analytech Co., Ltd.). The evaluation results are shown in Table 1.
⊚: “Volume resistance value is 1.0 × 10 ^-3 Ω ・ cm or more and 5 × 10 ^-3 Ω ・ cm or less (extremely good)”
◯: “Volume resistance value exceeds 5 × 10 ^-3 Ω ・ cm and is 1 × 10 ^-2 Ω ・ cm or less (good)”
Δ: “Volume resistance value exceeds 1 × 10 − ² Ω · cm and is 2 × 10 − ² Ω · cm or less (usable)”
×: “Volume resistance value exceeds 2 × 10 ^-1 Ω · cm (defective)”
(Adhesion of conductive layer)
In the conductive layer prepared above, a knife was used to make cuts from the surface of the conductive layer to the depth reaching the base material in 6 grids in each of the vertical and horizontal directions at intervals of 2 mm. An adhesive tape was attached to this notch and immediately peeled off, and the degree of detachment of the conductive layer was visually determined. The evaluation results are shown in Table 1, and the evaluation criteria are shown below.
○: "No peeling (level without practical problem)"
○ △: "Slight peeling (problem but usable level)"
△: "Peeling about half"
×: "Peeling in most parts"

(Acid resistance of conductive layer)
For the acid resistance of the conductive layer, prepare a 0.1% hydrochloric acid aqueous solution in a 900 ml mayonnaise bottle, immerse the wiring sheet (1) in a strip of 5 x 10 cm, and immerse it in an oven at 80 ° C. The appearance was observed after 1000 hours had passed.
○: "No change in appearance (level without practical problems)"
○ △: "There is a slight change in peeling, foaming, etc. (although there is a problem, it can be used)"
△: "There is a change in appearance by about half"
×: "Peeling in most parts"

(Alkali resistance of conductive layer)
The alkali resistance of the conductive layer is 80 ° C. by preparing a 1% saturated aqueous solution of calcium hydroxide in a 900 ml mayonnaise bottle, immersing the wiring sheet (1) in a strip of 5 × 10 cm, and immersing it in it. The appearance was observed after 1000 hours in the oven.
○: "No change in appearance (level without practical problems)"
○ △: "There is a slight change in peeling, foaming, etc. (although there is a problem, it can be used)"
△: "There is a change in appearance by about half"
×: "Peeling in most parts"

(Light resistance of conductive layer)
The weather resistance of the conductive layer was measured by Iwasaki Electric's ultra-accelerated weather resistance tester Eye UV Tester SUV-W161 (metal halide lamp type). The test conditions are as follows.
Irradiation time 10 hours, rest time 2 hours, shower time 10 seconds, shower interval time 1 minute, irradiation temperature 63 ° C, irradiation humidity 70%, rest temperature 70 ° C, rest humidity 70%, ultraviolet illuminance 100 mW / cm2 in a 12-hour cycle

⊚: Appearance changes in 1000 to 1500 hours ○: Appearance changes in 500 to 1000 hours Δ: Appearance changes in 300 to 500 hours ×: Appearance changes in 300 hours or less

(Examples 2 to 16, Examples 19 to 25, Examples 27 to 31, Comparative Examples 1 to 4)
With the composition ratios shown in Table 1, the conductive compositions (2) to (16), (19) to (22), (25) and (26) to the same method as those for the conductive composition (1). (30) was obtained. Further, Examples were carried out in the same manner as in the wiring sheet (1) except that the encapsulant was changed as shown in Table 1 and the coating amount and pressing conditions of the conductive composition were changed so as to have the thickness shown in Table 1. And the wiring sheets (2) to (16), (19) to (22), (25) and (27) to (33) of the comparative example were obtained.
(Examples 17, 18, 26)
Since water-based resins were used in Examples 17, 18 and 26, 400 parts of water was used instead of the PGMAC of Example 1, and the other conductive compositions (17) to (18) were obtained in the same manner.
Further, Examples were carried out in the same manner as in the wiring sheet (1) except that the encapsulant was changed as shown in Table 1 and the coating amount and pressing conditions of the conductive composition were changed so as to have the thickness shown in Table 1. The wiring sheets (17), (18), and (26) of the above were obtained.
(Example 23)
Using moisture-resistant polyethylene terephthalate X-10S (manufactured by Toray Film Processing) as the base material, apply adhesive a so that the coating amount is 30 g / m2 (dry), dry at 90 ° C. for 1 minute, and white PVC. A film (manufactured by RIKEN TECHNOS) DNFC1312-80WS was attached with a roll laminate and aged at room temperature for 1 week to obtain a laminated film DNFC1312-80WS (hereinafter referred to as DN) / X-10S. The conductive composition (13) was obtained by the same method as that of the conductive composition (1) at the composition ratios shown in Table 1. Further, the wiring sheet (1) except that the base material and the encapsulant were changed as shown in Table 1, the conductive composition was provided on the vinyl chloride film side so as to have the thickness shown in Table 1, and the coating amount and the pressing conditions were changed. The wiring sheet (23) was obtained by the same method as in the above.

(Example 24)
The base material is ethylene tetrafluoroethylene 100NS (manufactured by Asahi Glass) coated with adhesive a so that the coating amount is 30 g / m2 (dry), dried at 90 ° C. for 1 minute, and white vinyl chloride film (manufactured by Riken Technos) DNFC1312. -80WS was attached with a roll laminate and aged at room temperature for 1 week to obtain a film DN / ETFE laminate. The conductive composition (14) was obtained by the same method as that of the conductive composition (1) at the composition ratios shown in Table 1. Further, the wiring sheet (1) except that the base material and the encapsulant were changed as shown in Table 1, the conductive composition was provided on the vinyl chloride film side so as to have the thickness shown in Table 1, and the coating amount and the pressing conditions were changed. The wiring sheet (24) was obtained by the same method as in the above.

The materials used in the examples are shown below.
<Conductivity imparting agent (B)>
(Expanded graphite (B1))
B-1: LEP (Nippon Graphite Industry): Average particle size 137 μm
B-2: CMX-40 (Nippon Graphite Industry): Average particle size 60 μm

(Additive)
・ JER1001: Bisphenol A type epoxy resin (Mitsubishi Chemical)
・ Chemitite PZ-33: Aziridine compound (Nippon Shokubai)
・ LA-1: Polyester resin modifier (manufactured by Nisshinbo)
-Stabaxol P: Polymer carbodiimide (Hiroizumi Hiraizumi)

(Base material)
-X10S (manufactured by Toray Film Processing Co., Ltd.): Moisture-resistant polyethylene terephthalate film-DX film 14S2250 (manufactured by Denka Co., Ltd.): Polyvinylidene fluoride resin, thickness 50 μm transparent-# 50-3030 (manufactured by Toray Film Processing Co., Ltd.) ): Polyphenylene sulfide film 50 μm
75N-MX11 (manufactured by Toray Film Processing Co., Ltd.): Moisture resistant polyethylene terephthalate film 75 μm
100NS (manufactured by Asahi Glass Co., Ltd.): Ethylene tetrafluoroethylene 100 μm
・ Kapton 500H (manufactured by Toray DuPont Co., Ltd.): Polyimide film 125 μm

According to this embodiment, a wiring sheet having excellent acid resistance, alkali resistance, and light resistance could be provided. In particular, by using an ethylene tetrafluoroethylene fluororesin for the base material and the encapsulant, a wiring sheet with further excellent acid resistance, alkali resistance, and light resistance can be obtained, and a carbon-based conductive material for the conductive wiring. By using the above, it has become possible to provide a wiring sheet that can withstand long-term use in units of several decades without fear of deterioration of the carbon material itself.

Claims (6)

A wiring sheet having a sheet-shaped base material and conductive wiring arranged on the sheet-shaped base material.
The conductive wiring contains at least a binder resin (A) and a conductive carbon material (B).
The amount of the conductive carbon material (B) contained in 100% by mass of the conductive wiring is 40 to 90% by mass.
The conductive carbon material contains expanded graphite (B1) having an average particle size of 10 μm to 200 μm.
The thickness of the conductive wiring is 30 to 200 μm, and the thickness is 30 to 200 μm.
A wiring sheet having a volume resistivity value of 1 × 10 ^-3 to 5 × 10 ^-3 Ω · cm of the conductive wiring. The wiring sheet according to claim 1, wherein the binder resin contains at least one resin selected from a urethane resin, a polyester resin, a polyamide resin, an acrylic resin, a fluorine-based resin, an epoxy resin, and a styrene-based elastomer. .. The wiring sheet according to claim 1 or 2, wherein the sheet-like substrate comprises at least one sheet selected from polyethylene terephthalate, polyimide, polyphenylene sulfide, polyvinyl chloride, and fluororesin. Further, the wiring sheet is characterized in that a film is laminated on the conductive wiring and the conductive wiring is sealed.
The wiring sheet according to any one of claims 1 to 3, wherein the film contains at least one resin selected from an acrylic resin, a fluororesin, an epoxy resin, and a polyamide resin. A method for manufacturing a wiring sheet having a sheet-shaped base material and conductive wiring arranged on the sheet-shaped base material.
The conductive wiring contains at least a binder resin (A) and a conductive carbon material (B), and the amount of the conductive carbon material (B) contained in 100% by mass of the conductive wiring is 40 to 40. 90% by mass,
The conductive carbon material contains expanded graphite (B1) having an average particle size of 10 μm to 200 μm.
The thickness of the conductive wiring is 30 to 200 μm, and the thickness is 30 to 200 μm.
The volume resistivity value of the conductive wiring is 1 × 10 ^-3 to 5 × 10 ^-3 Ω · cm.
A method for manufacturing a wiring sheet, wherein the conductive wiring forming step includes at least a patterning step and a hot pressing step. The method for manufacturing a wiring sheet according to claim 5, further comprising a step of laminating a film and sealing the conductive wiring.