JP2019072937A - Static electricity countermeasure film material for industrial material - Google Patents

Abstract

To provide a static electricity countermeasure sheet which uses one or more coloring materials selected from a carbon nanotube, a fullerene and a π-electron conjugated-based conductive polymer, and is excellent in low colorability and visibility.SOLUTION: A fabric is used as a base material, a flexible laminate having an antistatic resin layer provided on the whole surface of both surfaces or the whole surface of one surface of the base material is used as a substrate, a coating film layer containing one or more selected from a carbon nanotube, a fullerene and a π-electron conjugated-based conductive polymer is formed wholly or in a net form on at least one surface of the substrate, and an ester compound having one or more ether bonds in the molecule is contained in the antistatic resin layer.SELECTED DRAWING: None

Description

  The present invention relates to measures against static electricity in industrial material sheets. Specifically, the present invention relates to antistatic flexible film materials used in sheet shutter devices installed in factories, warehouses, clean rooms, etc., and further to partitions, floor sheets The present invention relates to an antistatic flexible film material used for equipment covers, aprons and the like, and further to an antistatic flexible film material used for powder and granular material distribution products such as container bags.

  In recent years, the application development of carbon nanotubes to heat conductive members, conductive members, antistatic members, heat generating members, heat radiating members, electromagnetic wave shielding members, etc. has progressed, and in the technical field of conductive functions, in particular, much less than carbon black. An excellent conductive effect can be obtained by the amount used, so that an antistatic film having excellent transparency and durability can be obtained although it has light colorability. Furthermore, as an application to a conventional π-based conjugated polymer, a conductive packaging material (Patent Document 1) having a conductive layer containing a conductive polymer and carbon nanotubes has been proposed. Also, a transparent conductive film having high conductivity and light transmittance, comprising a conductive polymer thin film layer laminated on a substrate and a carbon nanotube thin film layer provided in contact therewith (Patent Document 2) Such inventions have been proposed. It is true that these prior inventions are excellent in antistatic properties and transparency, but in the case of needs requiring a higher degree of antistatic properties, the concentration of the conductive polymer is increased or the blending amount of carbon nanotubes is increased. Therefore, the color masking property (for example, blue-green type, red-purple type, etc.) of the conductive polymer (doping type) is increased, or / and the color-masking property by carbon nanotubes (for example, black blue type, black purple type) And the like, and it has a drawback that it has a dark brown appearance and a poor visibility. Furthermore, the cost is increased. Therefore, sheet shutters, partitions, floor sheets, equipment covers can be obtained if it is easy to obtain a high degree of antistatic properties without extremely increasing the concentration of the conductive polymer or increasing the compounding amount of carbon nanotubes indiscriminately. Can be widely used and deployed in applications such as aprons.

JP 2005-81766 A JP, 2009-2119, A

  The present invention relates to an antistatic sheet (sheet shutter, partition, floor sheet, equipment cover, apron, etc.) using one or more coloring materials selected from carbon nanotubes, fullerenes, and π electron conjugated conductive polymers. An object of the present invention is to provide an anti-static film material for industrial materials which has low colorability and is excellent in visibility.

  As a result of repeating researches and studies in view of the above-mentioned present conditions, the present invention uses a woven fabric as a substrate, and a flexible laminate having an antistatic resin layer provided on the entire both surfaces or one surface of this substrate. And forming a coating layer including at least one selected from carbon nanotubes, fullerenes, and a π electron conjugated conductive polymer on at least one surface of the base, or forming a network on the substrate, and an antistatic resin layer However, by incorporating an ester compound having one or more ether bonds in the molecule, it is possible to use a coloring material such as a carbon nanotube or a π electron conjugated conductive polymer, which was difficult in the above prior art. The present invention has been accomplished by finding that an antistatic sheet excellent in low colorability can be obtained.

In the antistatic material for industrial materials of the present invention, it is preferable that the liquid compound having an ether bond is one or more selected from [Chemical Formula 1] and [Chemical Formula 2]. By using the conductivity of the liquid compound having these ether bonds, the effect as an antistatic resin layer can be realized, and the amount of use of coloring materials such as carbon nanotubes, fullerenes, and π electron conjugated conductive polymers, etc. Since it is possible to comprehensively obtain an excellent antistatic effect without extremely increasing the above, it is possible to make an antistatic film material for industrial materials less coloring and concealing.

[Formula 1]
R (AO) _n OOC-X-COO (AO) _m R
(Wherein, X is: C ₆ H ₄ , C ₆ H ₈ , C ₆ H ₁₀ , C ₂ H _{4 to} C ₈ H ₁₆ ,
R is: C _3-15 linear or branched alkyl group (R is the same as or different from each other),
A is an alkylene group of _{2 to 4} carbons, m and n are integers of 1 to 10 (the same or different from each other)
Compounds represented by

[Formula 2]
R ₁ CO (OCH ₂ CH-R ₂ ) _n COOR ₃
(Wherein, R ₁ and R ₃ are: C _3-15 linear or branched alkyl group, or alkenyl group, R ₂ is: H, CH ₃ , C ₂ H ₅ , n is 3 to 20 Compounds represented by integers)

  In the antistatic material film material for industrial materials of the present invention, the coating film layer is made of an acrylic resin, a polyurethane resin, a polyester resin, a styrene resin, an epoxy resin, a vinyl acetate resin, a vinyl chloride resin as a binder resin. It is preferable that one or more types selected from silicon-based resins and fluorine-based resins are included, and the content thereof is 50 to 99.9% by mass with respect to the coating film layer. By this, the adhesiveness with a flexible laminated body (antistatic resin layer) or adhesiveness can be increased, and at the same time, the abrasion resistance and flex resistance of the coating film layer itself can be enhanced.

  In the antistatic material for industrial materials of the present invention, the coating layer contains the π electron conjugated conductive polymer, and the carbon nanotubes and the fullerene are used in combination at a mass ratio of 100: 1 to 2: 1. Is preferred. By this combined use, an excellent antistatic effect can be obtained with a smaller addition amount.

  The anti-electrostatic film material for industrial materials of the present invention comprises the single-walled carbon nanotube, double-walled carbon nanotube, multi-walled carbon nanotube, cup-stacked carbon nanotube, oxidized carbon nanotube, functionalized carbon nanotube (terminal modification and / or Or at least one selected from metal (vapor deposition or sputtering) carbon nanotubes, and the content thereof is preferably 0.1 to 5% by mass with respect to the coating layer. By the presence of such carbon nanotubes, an excellent antistatic effect can be obtained with a smaller addition amount.

The anti-electrostatic film material for industrial materials of the present invention is one or more selected from the group consisting of C ₆₀ fullerene, C ₇₀ fullerene, organically modified fullerene, inorganically modified fullerene, nonmetal atom endohedral fullerene, and metal endohedral fullerene. It is preferable that the content is 0.1-5 mass% with respect to the said coating film layer. By the presence of such a fullerene, an excellent antistatic effect can be obtained with a smaller addition amount.

  The anti-electrostatic film material for industrial materials of the present invention is characterized in that the π electron conjugated conductive polymer is polypyrroles, polythiophenes, polyacetylenes, polyphenylenes, polyphenylene vinylenes, polyanilines, polyacenes, polythiophene vinylenes, polyethylene geo It is preferable that it is 1 or more types chosen from xthiophene and these doping bodies, and that the content is 1-25 mass% with respect to the said coating film layer. By the presence of such a π electron conjugated conductive polymer, an excellent antistatic effect can be obtained with a smaller addition amount.

  The antistatic film material for industrial materials of the present invention is characterized in that the coating layer is at least one kind of nanoparticles selected from silica, titanium oxide, zinc oxide, tin oxide, zirconium oxide, cerium oxide, and alumina, It is preferable to further contain a silane compound and to constitute a nanoparticle network of 0.1 to 5% by mass with respect to the coating layer. By further including a nanoparticle nanoparticle network in the coating layer, the antistatic effect is enhanced, and the amount of carbon nanotubes, and / or less fullerene, and / or less π electron conjugated conductive polymer can be reduced. By expressing the antistatic property with the above, it is possible to obtain a less colored antistatic material for industrial materials.

  In the antistatic material for industrial materials of the present invention, preferably, the coating layer is a continuous body having an area occupancy of at least 20% with respect to the surface of the antistatic resin layer. The coating layer having such an area occupancy ratio forms a continuum, thereby preventing charging with a smaller amount of carbon nanotubes, and / or a smaller amount of fullerene, and / or a smaller amount of π electron conjugated conductive polymer By developing the property, it is possible to obtain a less colored electrostatic protection film material for industrial materials.

  According to the present invention, although it is an anti-static film material utilizing one or more coloring materials selected from carbon nanotubes, fullerenes, and π electron conjugated conductive polymers, it has lower coloring properties and excellent charging. Since the prevention effect can be obtained, it can be widely used as a film material for industrial materials, such as a sheet shutter, a partition, a floor sheet, an equipment cover, an apron, and the like.

  The antistatic protective film material for industrial materials according to the present invention comprises a fabric as a substrate and a flexible laminate having an antistatic resin layer provided on the entire both surfaces or one surface of the substrate as a substrate A coating layer containing one or more selected from carbon nanotubes, fullerenes, and a π electron conjugated conductive polymer is formed on the entire surface or reticulated on at least one side of In the aspect containing an ester compound having one or more ether bonds, in particular, the coating layer is a continuum having an area occupancy of at least 20% with respect to the surface of the antistatic resin layer.

  The fiber fabric as a base material used in the present invention can be used in any form such as woven fabric, knitted fabric, non-woven fabric, etc. As a woven fabric, plain woven fabric (a minimum structural unit using at least two warp and weft) , Basket fabrics (eg 2 × 2, 3 × 3, 4 × 4, etc. regular basket weave, 3 × 2, 4 × 2, 4 × 3, 5 × 3, 2 × 3, 2 × 4, 3) Irregular basket weave such as × 4, 3 × 5, etc., twill weave (with both warp and weft yarns each having a minimum of 3 units): 3 sheets, 4 sheets, 4 sheets, 5 sheets, 6 sheets Swash, 8 sheets, etc.), satin weave (a minimum of 5 warps and wefts each have minimum structural units: 2 fly, 3 fly, 4 fly, 5 fly, etc.), and change plain weave , Change 綾 fabric, change 朱 such as woven fabric, also honeycomb fabric, 子 ground fabric, 、 斜 織物, day and night 朱 織物 fabric, 織物 織物 (紗 fabric , Twill weaves, sewn weaves, double weaves, etc., but plain weaves and 2 × 2 basket weaves are particularly preferred because of their excellent balance of longitudinal and physical properties. The above-mentioned woven fabric is subjected to one or more of known fiber processing such as scouring, bleaching, dyeing, softening, water repellency, waterproofing, water proofing, flame proofing, baking, calendering, binder fixation, adhesive application It can also be used.

  The yarn constituting the fiber fabric may be any of synthetic fibers, natural fibers, semi-synthetic fibers, inorganic fibers or mixed fibers composed of two or more of them, but polypropylene fibers, polyethylene fibers, polyvinyl alcohol fibers, polyesters (PET, PBT, PNT) fiber, wholly aromatic polyester fiber, nylon fiber, wholly aromatic polyamide fiber, aromatic heterocyclic polymer (polybenzimidazole, polybenzoxazole, polybenzothiazole etc.) fiber, acrylic fiber, polyurethane fiber Alternatively, synthetic fibers such as these mixed fibers can be used, and polyester (PET: polyethylene terephthalate) fibers are particularly preferable. Aspects of these yarns are monofilaments, multifilaments, short fiber spinning (span), splits, tapes, etc., but multifilaments or short fibers to obtain the appearance, flex resistance and tear strength of the membrane material. Fiber spinning (span) is preferred. In addition, multifilament yarns such as glass fibers, silica fibers, alumina fibers, silica alumina fibers, carbon fibers can also be used, and these inorganic fibers are particularly nonflammable materials approved by the Minister of Land, Infrastructure, Transport and Tourism (incombustible film materials for tent structures) Suitable for use, in particular glass fiber multifilament yarns are preferred.

The fiber fabric used in the present invention is preferably a fabric comprising multifilament yarns, or a staple fiber spun fabric (span), and the multifilament yarns have a range of 250 to 3000 denier (277 to 3333 dtex), particularly 500 to 2000 denier (555 to 2222 dtex) is preferable, and if necessary, non-twisted yarn (elliptical or flat in cross section), twisted yarn, Taslan yarn, Wooly yarn and the like can be used. The staple fiber spun yarn is in the range of 10 counts (591 dtex) to 60 counts (97 dtex), in particular 10 counts (591 dtex), 14 counts (422 dtex), 16 counts (370 dtex), 20 counts (295 dtex), 24 counts (24 246 dtex), 30 count yarn (197 dtex), etc., these single yarns, or double yarns (one-twist yarns), double-twist yarns with two or more single yarns (ply twist yarns), etc. are preferable. There are no limitations on the density of the warp and weft threads of the fabric, and any design is possible depending on the thickness (denier, count) of the yarn used, but the porosity of the fabric (perforated) is 0 to 30%. A woven fabric having a weight per unit area of 100 to 500 g / m ² is suitable as a base material of the antistatic film material for industrial materials, with a driving density in the range of The porosity can be determined as a percentage of the area of the yarn occupied in the unit area of the fiber fabric and can be determined as a value subtracted from 100. Suitable for production in which a thermoplastic resin film is thermally laminated on both sides of a multi-filament yarn woven fabric (porosity 7.5-30%) to form an antistatic resin layer, and short fiber spinning In the case of a cloth (span), preferably an antistatic resin layer formed by coating with a liquid thermoplastic resin or heat treatment or dipping-heat treatment on both sides of a staple fiber spun cloth (span) with a porosity of 0-5% Suitable for forming.

The antistatic resin layer is a paste having a thickness of 0.03 to 1.0 mm formed of a soft vinyl chloride resin composition (containing 35 to 100 parts by mass of plasticizer with respect to 100 parts by mass of vinyl chloride resin) Coating using vinyl chloride resin (emulsion polymerization type) or film formation by dipping-gelation heat treatment, or straight vinyl chloride resin (suspension polymerization type), calendered or T-die extruded vinyl chloride resin film The formation of a soft film by (sheet) is particularly preferred. Paste vinyl chloride resin is suitable for the covering layer of canvas, straight vinyl chloride resin is suitable for the covering layer of tarpaulin. The plasticizer is preferably an ester compound having one or more ether bonds in the alkyl chain because of its excellent conductivity. Such a conductive plasticizer is one or more selected from [Chemical formula 1] and [chemical formula 2], and in the case of the antistatic resin layer by the soft vinyl chloride resin composition, relative to the mass of the antistatic resin layer The amount of the plasticizer is preferably 10 to 50% by mass, and the occupancy ratio of the conductive plasticizer [Formula 1] and / or [formula 2] to the amount of the plasticizer is preferably 50 to 100% by mass.

[Formula 1]
R (AO) _n OOC-X-COO (AO) _m R
(Wherein, X is: C ₆ H ₄ , C ₆ H ₈ , C ₆ H ₁₀ , C ₂ H _{4 to} C ₈ H ₁₆ ,
R is: C _3-15 linear or branched alkyl group (R is the same as or different from each other),
A is an alkylene group of _{2 to 4} carbons, m and n are integers of 1 to 10 (the same or different from each other)
Compounds represented by

[Formula 2]
R ₁ CO (OCH ₂ CH-R ₂ ) _n COOR ₃
(Wherein, R ₁ and R ₃ are: C _3-15 linear or branched alkyl group, or alkenyl group, R ₂ is: H, CH ₃ , C ₂ H ₅ , n is 3 to 20 Compounds represented by integers)

  The dicarboxylic acid used for producing the ester compound of the above formula (I) is preferably a dicarboxylic acid such as adipic acid, azelaic acid, sebacic acid, succinic acid, brassic acid, tetrahydrophthalic acid or phthalic acid, and the above (II) The carboxylic acid used for producing the ester compound of the formula is a monocarboxylic acid, a trivalent or higher polyvalent carboxylic acid, or a bivalent carboxylic acid having an epoxycyclohexane ring. These carboxylic acids may have a substituent containing an alkyl group such as a methyl group or an ethyl group, a hydroxyl group, or a heteroatom such as oxygen, silicon or halogen. The monocarboxylic acid is preferably an aliphatic monocarboxylic acid having 2 to 22 carbon atoms, and more preferably an aliphatic, alicyclic or aromatic polybasic acid comprising a carboxylic acid residue having 3 to 8 carbon atoms. Aliphatic polybasic carboxylic acids such as citric acid, aconitic acid, butanetricarboxylic acid and butanetetracarboxylic acid, alicyclic carboxylic acids such as epoxyhexahydrophthalic acid, and aromatic polyvalent acids such as trimellitic acid and pyromellitic acid It is possible to use a carboxylic acid having a valence, an acid anhydride of these carboxylic acids and the like. The ester compounds of the above-mentioned formula (I) and the above-mentioned formula (II) are those using the above-mentioned carboxylic acid alone or a mixture of two or more kinds.

  Specifically, such conductive plasticizers [Chemical formula 1] are diethyl cellosolve phthalate, dibutyl cellosolve phthalate, diethyl cellosolve adipate, dibutyl cellosolve adipate, diethyl cellosolve azelate, dibutyl cellosolve azelate, diethyl cellosolve sebacate The reaction products of dicarboxylic acid alkylcellosolve-based ester compounds such as dibutyl cellosolve sebacate and the like and dicarboxylic acids such as adipic acid and phthalic acid and mono- and poly-alkylene glycol monoalkyl ethers are listed. Mono- and poly-alkylene glycol monoalkyl ethers are adducts of alcohols with ethylene oxide such as propanol, butanol, hexanol, heptanol, octanol, nonanol, addition compounds of alcohol and propylene oxide, addition compounds of alcohol and butylene oxide Or an adduct of an alcohol and two or more alkylene oxides selected from alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, etc. Specifically, these are ethylene glycol monooctyl ether, diethylene glycol monomethyl ether, diethylene glycol Monobutyl ether, diethylene glycol monoheptyl ether, triethylene glycol monomethyl ether, tri (Mono-poly) alkylene glycol monoalkyl ethers such as ethylene glycol monopropyl ether, tetraethylene glycol monoethyl ether, propylene glycol monoethyl ether, propylene glycol monooctyl ether, dipropylene glycol monobutyl ether, butylene glycol monoethyl ether, etc. In addition, diethylene glycol di-2-ethyl hexonate, tetraethylene glycol di-2-ethyl hexonate, hexaethylene glycol di-2-ethyl hexonate, triethylene glycol diethyl butyrate, polyethylene glycol diethyl butyrate, polypropylene Glycol diethyl hexonate, triethylene glycol dibenzoate, tetraethylene glycol dibe Zoeto, polyethylene glycol dibenzoate, polypropylene glycol dibenzoate or polyethylene glycol-2-ethylhexonate benzoate, and the like. The conductive plasticizer [Chemical formula 2] includes caprylic ester of triethylene glycol, octyl ester of tetraethylene glycol, diester of polyethylene glycol and 2-ethyl acetic acid, diester of polyester glycol and 2-ethyl hexic acid, etc. can give.

  Although the plasticizer having conductivity shown in the above [Chemical Formula 1] and [Chemical Formula 2] preferably accounts for 100% by mass of the total plasticizer used, the plasticizer used in combination with a known general-purpose plasticizer 10-50 mass% of the whole can also be used as a general purpose plasticizer. General-purpose plasticizers include adipic acid ester plasticizers, sebacic acid ester plasticizers, phthalic acid ester plasticizers, isophthalic acid ester plasticizers, terephthalic acid ester plasticizers, cyclohexanedicarboxylic acid ester plasticizers, cyclohexene dicarboxylic acid Acid ester plasticizer, chlorinated paraffin plasticizer, polyester plasticizer, ethylene-vinyl acetate-carbon monoxide ternary resin, ethylene- (meth) acrylic acid ester-carbon monoxide ternary copolymer It is resin etc.

  The antistatic resin layer has not only a vinyl chloride resin, but also a vinyl chloride-vinyl acetate copolymer resin, a vinyl chloride-acrylic acid ester copolymer resin, and a vinyl acetate component in a side chain with vinyl chloride as a main chain Or graft resin having an acrylic ester component or having a urethane component, polymer alloy of vinyl chloride resin and urethane elastomer, polymer alloy of vinyl chloride resin and polyester elastomer, polymer alloy of vinyl chloride resin and styrene elastomer, etc. In the case of the antistatic resin layer made of these resins, the amount of plasticizer relative to the mass of the antistatic resin layer is 1 to 35% by mass, and the conductive plasticizer [conversion to this amount of plasticizer] The occupancy of 1] and / or [Chemical formula 2] is preferably 50 to 100% by mass. In addition, various additives can be added to the antistatic resin layer in any desired amount, and if necessary, pigments (inorganic, organic, aluminum flake pigments, pearl pigments, fluorescent dyes, luminous pigments, etc.) Metal complex stabilizers, inorganic flame retardants, phosphate ester flame retardants, light stabilizers (HALS), UV absorbers (benzotriazole, benzophenone etc.), antioxidants (phenolic), antistatic agents (positive) Ion surfactant, quaternary ammonium cation etc.), curing agent (isocyanate series etc.), insect repellent (pyrethroid series etc.), deodorant (silicon oxide / metal oxide complex etc.), heat shield filler (hollow particles, Coarse-grained titanium oxide etc., inorganic fillers (calcium carbonate, barium sulfate etc.) etc. can be contained in arbitrary amounts.

A flexible laminate is formed on at least one side of the substrate (on the antistatic resin layer), on the entire surface, a coating layer containing one or more selected from carbon nanotubes, fullerenes and π electron conjugated conductive polymers, or It is reticulated. In particular, acrylic resin, polyurethane resin, polyester resin, styrene resin, epoxy resin, vinyl acetate resin, vinyl chloride resin, silicon resin, and fluorine resin as a binder resin for the coating layer It is preferable that it contains one or more selected, and the content thereof is 50 to 99.9% by mass with respect to the coating layer. Accordingly, the content of carbon nanotube, fullerene, and π electron conjugated conductive polymer is 0.1 to 50% by mass with respect to the coating film layer, and 0.1 to 3% by mass with respect to the content of carbon nanotube and fullerene, respectively. The content of the π electron conjugated conductive polymer is 10 to 50% by mass. In particular, the coating layer is a continuum having an area occupancy of 20% or more, preferably 35% or more, of the surface of the antistatic resin layer, and preferably 0.05 to 20 g / m ² , preferably 0.5 to 0.5 It is a coating of 10 g / m ² . The binder may contain an inorganic compound, and a metal oxide gel and / or a metal hydroxide gel such as silica sol, alumina sol, zirconia sol and niobium oxide sol, and a silicon compound such as polysiloxane, colloidal silica and silica The sol-gel body which makes a main body can be illustrated.

  The carbon nanotubes may be those having an average fiber diameter of 0.5 to 100 nm and an aspect ratio of 50 to 5000, and may be aligned or randomly arranged. Specifically, single-walled carbon nanotubes with a diameter of 0.4 nm to 5 nm, double-walled carbon nanotubes with a diameter of 1.5 nm to 5 nm, multi-walled carbon nanotubes with a diameter of 3 nm to 50 nm, cup-stacked carbon nanotubes, oxidized carbon nanotubes, functionalization One or more types selected from carbon nanotubes (end modification and / or sidewall modification), metal (vapor deposited or sputtered) carbon nanotubes, and having a hexagonal arrangement (chiral index) of (n, n) constituting carbon nanotubes It may be an armchair type, an (n, 0) zigzag type, or an (n, m) helical type. Moreover, conductivity can be improved by using these carbon nanotubes in combination with other electroactive materials. Examples of the electroactive material include oxides of transition metals such as Ru, Ir, W, Mo, Mn, Ni, and Co, and in particular, a π electron conjugated conductive polymer (described in paragraph [0028]) and the like can also be used as a binder. It can also be used. In particular, metal (vapor deposited or sputtered) carbon nanotubes are carbon nanotubes whose surface is metallized by vapor deposition or sputtering with Au, Ag, Cu, Al, Zn, Ti etc. The conductivity of Au / Ti, Ag / Ti, and Cu / Ti is dramatically improved.

One of the preferred embodiments of the coating layer contains a π electron conjugated conductive polymer, and the carbon nanotube and the fullerene are used in combination at a mass ratio of 100: 1 to 2: 1, preferably 10: 1 to 1: 1. It is In addition, as an example of an embodiment of the multilayer, “A / B” and “B / A” when the conductive network containing the π electron conjugated conductive polymer is A and the conductive network containing carbon nanotubes is B The combined use of two layers, combined use of "A / B / A" and "B / A / B" also dramatically improves the conductivity. Similarly, when the conductive network containing fullerenes is C, the combination of two layers of "A / C" and "C / A", the combination of three layers of "A / C / A" and "C / A / C" are used. Etc. also dramatically improve the conductivity. In addition, the combined use of "A / B / C", "A / C / B", and "B / A / C" together etc. also dramatically improves the conductivity. As the fullerene, C ₆₀ fullerene, C ₇₀ fullerene, organically modified fullerene, inorganicly modified fullerene, nonmetal atom contained fullerene, metal atom contained fullerene, and the like can be used. And C ₆₀ fullerene 6-membered ring 20 surface, at 5-membered ring 12 surface 32 surface at configured a soccer ball-shaped cage body, organically modified fullerene, C ₆₀ or one or more on the surface of the C _{70 fullerene,} It is a polymer having a substituent and / or one or more functional groups, or a polymer-substituted fullerene grafted on a polymer side chain. Endohedral metallofullerenes are atoms of Li, Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Ba, Ra, Sc, Y, Ti, Zr, lanthanoids, actinoids, or any of the above fullerenes Metal ions are taken in. The nonmetal atom-containing fullerene may be any of the above fullerenes, such as hydrogenated fullerene containing H, carbonized fullerene containing C, nitrogenated fullerene containing N, oxygenated fullerene containing O, sulfurized fullerene containing S, etc. is there.

  Specifically, the π electron conjugated conductive polymers are mainly composed of polypyrroles, polythiophenes, polyacetylenes, polyphenylenes, polyphenylene vinylenes, polyanilines, polyacenes, polythiophene vinylenes, and copolymers and derivative polymers thereof. The chain is composed of a π conjugated system, and there is no particular limitation on its side chain, presence or absence of substituent, side chain, type of substituent, but polypyrrole, polythiophene, poly (N-methylpyrrole), poly (3-methylthiophene Polypyrrole and polythiophene are particularly preferred, such as poly (3-methoxythiophene), poly (3,4-ethylenedioxythiophene), etc., particularly poly (N-methylpyrrole), poly (3-methylthiophene) and the like. Alkyl-substituted compounds are preferred because of their excellent solubility in organic solvents. In addition, the π electron conjugated conductive polymer is doped with a polymeric carboxylate (polyacrylic acid, polymethacrylic acid, polymaleic acid, etc.), or a polymeric sulfonic acid (polyvinylsulfonic acid, polystyrene sulfonic acid, polyisoprene sulfone) Acid, polyacrylic acid ethyl sulfonic acid, poly acrylic acid butyl sulfonic acid, poly (2-acrylamido-2-methyl-1-propane sulfonic acid) etc. or doping with polymeric carboxylic acid salt and polymeric sulfone The conductivity can be further enhanced by co-doping with an acid in a mass ratio of 2: 1 to 1: 5. The ratio of the π electron conjugated conductive polymer to the polymeric carboxylate is 10: 1. 1: 1, the ratio of π electron conjugated conductive polymer to polymeric carboxylate and polymeric sulfonic acid is 5: 1 1: 1 is preferable, and the polymeric carboxylate, or the polymeric carboxylate and the polymeric sulfonic acid coexist with the monomer of the π electron conjugated conductive polymer at the time of the π electron conjugated conductive polymer synthesis. What is doped in the π electron conjugated conductive polymer at the time of oxidative polymerization of the π electron conjugated conductive polymer synthesis is preferable.

  The above-mentioned coating layer further contains one or more kinds of nanoparticles selected from silica, titanium oxide, zinc oxide, tin oxide, zirconium oxide, cerium oxide, and alumina, and a silane compound, and a coating layer Preferably, 0.1 to 5% by mass of the nanoparticle network is configured. By further including a nanoparticle nanoparticle network in the coating layer, the antistatic effect can be further enhanced, and by making it possible to express conductivity with a smaller amount of carbon nanotubes or a smaller amount of fullerene, lower colorability can be achieved. Thus, it is possible to obtain an anti-static film material for industrial materials which is excellent in visibility. In particular, the above-mentioned coating layer contains a π electron conjugated conductive polymer, and the content thereof is preferably 1 to 25% by mass with respect to the coating layer. By including a π electron conjugated conductive polymer in the coating layer, the antistatic effect is further enhanced, and conductivity is exhibited with a smaller amount of carbon nanotubes or a smaller amount of fullerene, resulting in lower colorability and visibility. An excellent antistatic material for industrial materials can be obtained. In particular, the above-mentioned coating layer may simultaneously contain the above nanoparticle (a nanoparticle sol is used when forming the coating layer), a nanoparticle network of a silane compound, and the above-mentioned π electron conjugated conductive polymer. The content of the particle nanoparticle network and the π electron conjugated conductive polymer is preferably 1 to 25% by mass and the contained mass ratio is 1:10 to 1: 1 with respect to the coating film layer. By enhancing the antistatic effect by containing the nanoparticle nanoparticle network and the π electron conjugated conductive polymer in a specific ratio in the coating layer, the conductivity is expressed with a smaller amount of carbon nanotubes or a smaller amount of fullerenes. Thus, it is possible to obtain an electrostatic protection film material for industrial materials which has lower colorability and excellent visibility. As the silane compound, methyltrimethoxysilane, methyltriethoxysilane and the like can be used. The mixing ratio of the nanoparticles to the silane compound or the hydrolysis product thereof is preferably 90%: 10% to 40%: 60% by mass.

  Each of the above-mentioned coating layers is preferably a continuous body having an area occupancy of at least 20% with respect to the surface of the antistatic resin layer. By forming a coating film layer having such an area occupancy rate as a continuum, a network is formed to express conductivity with a smaller amount of carbon nanotubes or a smaller amount of fullerenes, so that the colorability is lower and the visibility is excellent. It is possible to obtain the anti-static film material for industrial materials. If the area ratio of the coating layer is less than 20%, the antistatic property of the resulting film material may be insufficient. Therefore, the area ratio of the coating layer is 25 to 50%, and is a continuous body. Is preferred. Such a continuum (network) is a regular continuum such as a square lattice, triangular lattice, honeycomb, round hole punching, mesh, etc., or an irregular continuum, or a single-stroke character or pattern, A lottery ticket, etc. are illustrated. If the area occupancy rate of the coating film layer is 100%, the antistatic property and the antimicrobial property of the film material will be sufficient, but the adhesion at the time of superposition bonding of the film materials may be insufficient. Specifically, such a coating layer (conductive network) solubilizes or finely disperses a π electron conjugated conductive polymer obtained by chemical oxidation polymerization of a monomer constituting the π electron conjugated polymer in a solvent Printing with a gravure roll as a paint, or as a paint containing a dispersion of 0.05 to 5% by mass of carbon nanotubes in a dispersion medium such as water, alcohol, or an organic solvent; Or it is formed by printing by a rotary screen. A thickness of 0.05 μm to 15 μm is preferable in the case of a π electron conjugated conductive polymer, and a thickness of 0.001 μm to 0.5 μm is preferable in the case of carbon nanotubes and fullerenes.

  In order to process the antistatic material film for industrial materials of the present invention into a sheet shutter, a partition, a floor sheet, an equipment cover, an anti-static container, etc., bonding of the antistatic materials for industrial materials of the present invention Aligned edge overlap bonding) can be joined by high frequency vibration using a high frequency welder machine, specifically, the film material between two electrodes (one electrode is a weld bar) Place and apply a potential difference oscillating at a high frequency (1 to 200 MHz) while pressing with a weld bar to fuse the antistatic resin layer of the film material into a melt-softened state by molecular friction heat, and cool in that state Solidify to obtain a bonded body. In addition, ultrasonic fusion method or heater electric that performs the fusion by amplifying the amplitude of the ultrasonic energy (16 to 30 KHz) generated from the ultrasonic transducer and using the frictional heat generated at the boundary surface of the film material Hot air fusion method in which hot air set steplessly at 100 to 700 ° C by control is blown through the nozzle between the membrane material to melt and soften the surface of the membrane material, and the membrane material is pressure bonded immediately after passing through the nozzle. Bonding can be performed by, for example, a hot plate fusion method in which an adherend is pressure-bonded and fused using a mold (hot tip) incorporated with a heater and heated to a temperature higher than the melting temperature of the antistatic resin layer. In the above bonding method, when the area ratio of the coating layer is 90 to 100%, the compatibility between the binder resin of the coating layer and the antistatic resin layer is poor, or the temperature difference of the softening temperature is large. The adhesion of the resulting film materials to each other is insufficient, and the area occupancy of the coating layer is 25% to 50%. It is desirable to provide a state in which the layer and the antistatic resin layer on the back surface of the other film material are at least thermally melted to allow firm adhesion.

EXAMPLES The present invention will next be described in more detail by way of examples and comparative examples, which should not be construed as limiting the scope of the present invention. In the following examples and comparative examples, the effect of the anti-static film material for industrial materials was evaluated by surface resistivity.
(1) Surface resistivity measurement (JIS K 7194 compliant)
After leaving a piece of film material to stand at 23 ° C. and relative humidity 50% RH for 24 hours, the surface resistivity was measured three times using the following resistivity meter (in accordance with JIS K 7194), and the average value was taken as the surface resistivity. However, since the quality of the surface resistivity depends on the amount of the conductive material, it is antistatic based on the premise that the "low colorability" and "visibility" are both problems of the present invention. Good and bad were evaluated.
The preferred range of antistatic properties in the following examples is a surface resistivity of 10 ⁷ Ω / □ to 10 ⁹ Ω / □ (a surface resistivity exceeding 10 ⁷ Ω / □ is even better), a surface resistivity less than that The thing below 10 ¹⁰ ohms / square was made into the comparative example.
1) High resistance, resistivity meter, Inc. Mitsubishi Chemical Analytech Co., Ltd. “Hiresta UP MCP-HT800 (range 10 ³ to 10 ¹⁴ Ω)”
2) Low-resistance resistivity meter, manufactured by Mitsubishi Chemical Analytech Co., Ltd. "Loresta GX MCP-T700 (range 10 ^-4 to 10 ⁷ Ω)"
(2) Low colorability
Judgment criteria of colorability using color difference ΔE of JIS Z8729 (blank is a white plate of barium sulfate)
ΔE = 0 to 7.9: 1 = low colorability
ΔE = 8 to 14.9: 2 = colored and appearance is dark
ΔE = 15 to 3: 3 = dark in color and black in appearance
(3) Visibility In the tent warehouse of Hiraoka Ori-Dan Co., Ltd. in Soka City, Saitama Prefecture (sheet shutter device installed, illuminance in the warehouse: JIS Z9110: 1979 40-60 lx) at 5:00 pm September 2017 A paper panel with black Gothic text printed on a thick paper with a size of 10 cm in size, woven, woven, printed, and printed on a cardboard sheet is randomly placed at a position 30 cm behind the test membrane inside the tent warehouse. 10 observers simultaneously judged "weave", "fiber", "job", and "paper" paper panels individually from the position of 1 m outside the front through the membrane material. The paper panel's identification score of 100% is “1”, identification score of 75% “2”, identification score of 50% “3”, identification score of 25% “4”, identification score of 0% Was rated at five levels of “5”, “1” was rated good, and “5” was rated bad.

Example 1
Polyester fiber plain weave base fabric (warp 1111 dtex multifilament yarn: yarn density 22 / 2.54 cm × weft 1111 dtex multifilament yarn: yarn density 24 / 2.54 cm: porosity 21%: mass 165 g / m ² ) As a substrate, a 0.2 mm-thick calendar molded film consisting of the following soft vinyl chloride resin composition (1) on both surfaces thereof is used as an antistatic resin layer by bridge melting lamination by thermocompression bonding. A laminated film material (1) having a thickness of 0.75 mm and a mass of 785 g / m ² was obtained, which was composed of a base fabric / antistatic resin layer ".
<Soft vinyl chloride resin composition (1)>
Vinyl chloride resin (polymerization degree 1300) 100 parts by mass Conductive plasticizer (1) 30 parts by mass ※ Adipic acid diester by reaction of adipic acid with alcohol obtained by adding ethylene oxide to n-octanol: (ester having two ether bonds Compound [Chemical Formula 1]
Equivalent to
4-cyclohexene-1,2-dicarboxylic acid bis (2-ethylhexyl) (plasticizer)
20 parts by mass Tricresyl phosphate (flameproof plasticizer) 10 parts by mass Epoxidized soybean oil (stabilizer / plasticizer) 5 parts by mass Barium / zinc composite stabilizer 2 parts by mass Antimony trioxide (flame retardant) 10 parts by mass Rutile type Titanium oxide (white pigment) 5 parts by mass Benzotriazole skeleton compound (ultraviolet light absorber) 0.3 parts by mass On the antistatic resin layer on the surface side of the above laminated film material (1), the following coating layer (1) A grid-like continuum (lattice width 5 mm, square) having an area occupancy rate of 55.5% using a coating solution (solid content concentration 16.8 mass%) for coating and square grid pattern gravure roll coating of 120 mesh The coating film layer (1) having a hole size of 10 mm × 10 mm) was formed to obtain a 787 g / m ² mass of an anti-static material for industrial materials (terporin).
Solution for Coating Layer (1)
Methyl methacrylate resin (acrylic resin) 100 parts by mass Single-walled carbon nanotubes (diameter 1.5 to 2.5 nm) 0.5 parts by mass ※ Content rate of carbon nanotubes to coating layer 0.5% by mass
Benzotriazole backbone compound (UV absorber) 0.3 parts by mass Methyl ethyl ketone (dilution solvent) 250 parts by mass Toluene (dilution solvent) 250 parts by mass

Example 2
In the laminated film material (1) of Example 1, 30 parts by mass of the conductive plasticizer (1) of the soft vinyl chloride resin composition (1) is obtained by the reaction of phthalic anhydride with alcohol obtained by adding ethylene oxide to n-octanol. Phthalate diester: as in Example 1 except that 30 parts by mass is substituted for conductive plasticizer (2): (corresponding to an ester compound having two ether bonds [Chemical formula 1]) and 30 parts by mass. As a result, an antistatic film (tarpaulin) for industrial materials having a thickness of 0.75 mm and a mass of 787 g / m ² was obtained.

[Example 3]
In the laminated film material (1) of Example 1, 30 parts by mass of the conductive plasticizer (1) of the soft vinyl chloride resin composition (1) is obtained by the reaction of an alcohol obtained by adding propylene oxide to n-octanol and sebacic acid Sebacic acid diester: Conductive plasticizer (3): (equivalent to an ester compound having two ether bonds [Chemical formula 1]), 30 parts by mass as in Example 1 except that it is replaced by a laminated film material (3) As a result, an antistatic film (tarpaulin) for industrial materials having a thickness of 0.75 mm and a mass of 787 g / m ² was obtained.

Example 4
In the laminated film material (1) of Example 1, 30 parts by mass of the conductive plasticizer (1) of the soft vinyl chloride resin composition (1), and octylate of tetraethylene glycol: Conductive plasticizer (4): (Equivalent to an ester compound having three ether bonds [Chemical formula 2]) and 30 parts by mass to obtain a laminated film material (4) in the same manner as in Example 1 with a thickness of 0.75 mm and a mass of 787 g / m Obtained the anti-static film material (Taporin) for industrial materials of ² .

[Example 5]
Static electricity for industrial materials having a thickness of 0.75 mm and a mass of 787 g / m ^{2 in} the same manner as in Example 1 except that the solution for the coating layer (1) of Example 1 was changed to the solution for the coating layer (2). Obtained a countermeasure membrane material (tarpaulin).
Solution for Coating Layer (2)
Poly (3,4-ethylenedioxythiophene) * polythiophene 20 parts by mass Methyl methacrylate resin (acrylic resin) 80 parts by mass Single-walled carbon nanotubes (diameter 1.5 to 2.5 nm) 0.5 parts by mass ※ Coating layer Content of carbon nanotubes to 0.5% by mass
Benzotriazole skeleton compound (ultraviolet absorber) 0.3 parts by mass Cyclopentanone (dilution solvent) 100 parts by mass Toluene (dilution solvent) 200 parts by mass Methyl ethyl ketone (dilution solvent) 200 parts by mass

[Example 6]
Static electricity for industrial materials having a thickness of 0.75 mm and a mass of 787 g / m ^{2 in} the same manner as in Example 1 except that the solution for coating layer (1) in Example 1 was changed to the solution for coating layer (3) Obtained a countermeasure membrane material (tarpaulin).
<Solution for coating layer (3)>
Methyl methacrylate resin (acrylic resin) 100 parts by mass Single-walled carbon nanotubes (diameter 1.5 to 2.5 nm) 0.5 parts by mass Organosilica sol (silica nanoparticles) 40 parts by mass ※ Particle diameter 10 to 15 nm: solid content 30% by mass: methyl ethyl ketone solvent methyltriethoxysilane (silane compound) 8 parts by mass ※ A nanoparticle network of silica sol and methyltriethoxysilane in a mass ratio of 3: 2 is formed in the coating layer ※ inclusion of carbon nanotubes in the coating layer 0.4 mass%
Benzotriazole skeleton compound (UV absorber) 0.3 parts by mass Toluene (dilution solvent) 250 parts by mass Methyl ethyl ketone (dilution solvent) 250 parts by mass

[Example 7]
Static electricity for industrial materials having a thickness of 0.75 mm and a mass of 787 g / m ^{2 in} the same manner as in Example 1 except that the solution for the coating layer (1) of Example 1 was changed to the solution for the coating layer (4). Obtained a countermeasure membrane material (tarpaulin).
<Solution for coating layer (4)>
Poly (3,4-ethylenedioxythiophene) * polythiophene 20 parts by mass Methyl methacrylate resin (acrylic resin) 80 parts by mass Single-walled carbon nanotubes (diameter 1.5 to 2.5 nm) 0.5 parts by mass ※ Coating layer Content of carbon nanotubes relative to
Organosilica sol (silica nanoparticles) 40 parts by mass ※ Particle size 10 to 15 nm: solid content 30% by mass: methyl ethyl ketone solvent methyltriethoxysilane (silane compound) 8 parts by mass ※ mass ratio of silica sol to methyltriethoxysilane 3: 2 Of nanoparticle network in coating layer benzotriazole skeleton compound (ultraviolet absorber) 0.3 parts by mass cyclopentanone (dilution solvent) 100 parts by mass toluene (dilution solvent) 200 parts by mass methyl ethyl ketone (dilution solvent) 200 parts Department

[Example 8]
The coating layer (1) for 0.5 parts by single-walled carbon nanotubes using a solution of Example 1, C ₆₀ but substituting the fullerene 0.5 parts by weight, same as to the thickness of Example 1 0. A 75 mm, 787 g / m ² mass anti-static film (tarpaulin) for industrial materials was obtained.

[Effects of Embodiments 1 to 8]
The base material of the membrane material for industrial materials contains an ester compound (conductive plasticizer) having one or more ether bonds in the molecule, and contains a carbon nanotube or fullerene in the coating film layer in Examples 1 to 8 The film materials had antistatic properties each having a surface resistivity of about 10 ⁹ Ω / □ or more, and were low in coloring properties and excellent in visibility. In particular, the film material of Example 5 in which a π electron conjugated conductive polymer and carbon nanotubes are used in combination in the coating layer has a surface resistivity of 10 ⁷ Ω / □, and an embodiment in which the carbon nanotube and nanoparticle network are used in combination with the coating layer. The film material No. 6 has antistatic properties with a surface resistivity of 10 ⁸ Ω / □, low colorability, excellent visibility, and a π electron conjugated conductive polymer and carbon nanotube in the coating layer, and The film material of Example 7 in which the nanoparticle network was used in combination had excellent antistatic properties such as a surface resistivity of 10 ⁷ Ω / □, and was low in colorability.

Comparative Example 1
In the laminated film material (1) of Example 1, 30 parts by mass of the conductive plasticizer (1) of the soft vinyl chloride resin composition (1) was added to bis (2-ethylhexyl) 4-cyclohexene-1,2-dicarboxylate 30 parts by mass, the plasticizer in the soft vinyl chloride resin composition is 50 parts by mass of bis (2-ethylhexyl) 4-cyclohexene-1,2-dicarboxylate, and contains a plasticizer having an ether bond in the molecule A tarpaulin having a mass of 787 g / m ² was obtained in the same manner as in Example 1 except that the above was carried out. The antistatic property of the obtained tarpaulin was inferior to that of the antistatic material film material for industrial materials of Example 1.

Comparative Example 2
A solution for a coating film layer (1) of Example 1, except that 0.5 parts by mass of single-walled carbon nanotubes is replaced by 0.5 parts by mass of carbon black, is the same as Example 1, and a tarpaulin having a mass of 787 g / m ² Obtained. The obtained tarpaulin increased the strength of the black appearance, the visibility was inferior to the tarpaulin of Example 1, and the antistatic property was also inferior.

Comparative Example 3
In coating layer (1) solution of Example 1, the mass 787 g / m ² tarpaulin and 0.5 parts by mass of single-walled carbon nanotubes as similarly but replacing the carbon black 0.8 parts by weight as in Example 1 Obtained. In Comparative Example 2, 0.5 parts by mass of carbon black was increased to 0.8 parts by mass, and a tarpaulin having antistatic performance equivalent to that of the anti-static film material for industrial materials of Example 1 was obtained. Certainly, if the amount of carbon black is increased, the level of antistatic performance is also improved along with the increase, but the tarpaulin obtained further increases the coloring strength of the black appearance, and the visibility is larger than that of the tarpaulin of Example 1. It became inferior.

Comparative Example 4
In order to obtain the antistatic performance equivalent to that of Example 5 with the composition in which 0.5 parts by mass of single-walled carbon nanotubes is omitted in the solution for the coating film layer (2) of Example 5, poly (3,4-ethylenedi) 20 parts by mass of oxythiophene) was increased to 100 parts by mass, and 80 parts by mass of methyl methacrylate resin was omitted. The obtained tarpaulin further increased the coloring strength of the black appearance, and the visibility became significantly inferior to the tarpaulin of Example 5.

  As apparent from the above-described Examples and Comparative Examples, according to the present invention, measures against static electricity utilizing a coloring material such as a carbon nanotube and / or a fullerene and / or a π electron conjugated conductive polymer Although it is a film material, an excellent antistatic effect can be obtained with lower colorability, and therefore, it can be widely used as a film material for industrial materials such as a sheet shutter, a partition, a floor sheet, an equipment cover, and an apron.

Claims (9)

  Using a woven fabric as a substrate, a flexible laminate having an antistatic resin layer provided on the entire both surfaces or one surface of this substrate as a substrate, carbon nanotubes, fullerenes and π on at least one surface of this substrate A coating film layer containing one or more selected from electron conjugated conductive polymers is formed on the entire surface or in a network, and the antistatic resin layer is an ester compound having one or more ether bonds in the molecule An antistatic film material for industrial materials, characterized in that it contains. The electrostatic protection film material for industrial materials according to claim 1, wherein the liquid compound having an ether bond is at least one selected from the group consisting of Chemical Formula 1 and Chemical Formula 2.

[Formula 1]
R (AO) _n OOC-X-COO (AO) _m R
(Wherein, X is: C ₆ H ₄ , C ₆ H ₈ , C ₆ H ₁₀ , C ₂ H _{4 to} C ₈ H ₁₆ ,
R is: C _3-15 linear or branched alkyl group (R is the same as or different from each other),
A is an alkylene group of _{2 to 4} carbons, m and n are integers of 1 to 10 (the same or different from each other)
Compounds represented by

[Formula 2]
R ₁ CO (OCH ₂ CH-R ₂ ) _n COOR ₃
(Wherein, R ₁ and R ₃ are: C _3-15 linear or branched alkyl group, or alkenyl group, R ₂ is: H, CH ₃ , C ₂ H ₅ , n is 3 to 20 Compounds represented by integers)
  The coating film layer is selected from an acrylic resin, a polyurethane resin, a polyester resin, a styrene resin, an epoxy resin, a vinyl acetate resin, a vinyl chloride resin, a silicon resin, and a fluorine resin as a binder resin. The anti-static film material for industrial materials according to claim 1 or 2, which contains at least one selected from the group consisting of 50 to 99.9% by mass of the coating layer.   The said coating film layer contains the said (pi) electron conjugated system conductive polymer, And the said carbon nanotube and the said fullerene are used together by 100: 1-2: 1 mass ratio, The any one of Claims 1-3 Antistatic film for industrial materials.   The carbon nanotubes are single-walled carbon nanotubes, double-walled carbon nanotubes, multi-walled carbon nanotubes, stacked carbon nanotubes, oxidized carbon nanotubes, functionalized carbon nanotubes (terminal modification and / or sidewall modification), and metals (vapor deposition or sputtering) It is 1 or more types chosen from the carbon nanotube, The content is 0.1-5 mass% with respect to the said coating film layer, The electrostatic countermeasure against industrial materials in any one of Claims 1-4. Membrane material. The fullerene is one or more selected from C ₆₀ fullerene, C ₇₀ fullerene, organically modified fullerene, inorganicly modified fullerene, nonmetal atom endohedral fullerene, and metal endohedral fullerene, and the content thereof is in the coating layer It is 0.1-5 mass% with respect to it, The electrostatic protection film material for industrial materials in any one of Claims 1-5.   The π electron conjugated conductive polymer is selected from polypyrroles, polythiophenes, polyacetylenes, polyphenylenes, polyphenylene vinylenes, polyanilines, polyacenes, polythiophene vinylenes, polyethylene dioxythiophene, and a doping body thereof The anti-static material for industrial materials according to any one of 1 to 6, which is one or more kinds, and the content thereof is 1 to 25% by mass with respect to the coating film layer.   The coating layer further includes one or more nanoparticles selected from silica, titanium oxide, zinc oxide, tin oxide, zirconium oxide, cerium oxide, and alumina, and a silane compound, and the coating layer The anti-static film material for industrial materials according to any one of claims 1 to 7, which comprises a nanoparticle network of 0.1 to 5% by mass.   The antistatic film according to any one of claims 1 to 8, wherein the coating layer is a continuous body having an area occupancy of at least 20% with respect to the surface of the antistatic resin layer. Material.