JP2019093620A - Antistatic antibacterial film material - Google Patents

Abstract

To provide a static electricity countermeasure sheet having antibacterial properties which has a lower coloring property (less influence of the hue of carbon nanotubes) and is obtained by using an antistatic film using carbon nanotubes.SOLUTION: There is provided a static electricity countermeasure sheet which uses a fiber fabric as a base material and has a coating film layer on at least one surface of a thermoplastic resin coating layer of a flexible sheet having a thermoplastic resin coating layer on one or more surfaces of the base material, wherein the coating film layer contains a cyclic polyether ion complex and carbon nanotubes and especially the coating film layer is formed as a continuous body having an area occupation ratio of at least 20% to the surface of the thermoplastic resin coating layer.SELECTED DRAWING: None

Description

  The present invention relates to an antistatic technique and an antimicrobial technique for industrial material sheets, and more specifically, the present invention relates to an antistatic property used as a countermeasure against static electricity of a sensor sensing type sheet shutter device in a factory, a warehouse, a clean room or the like. And anti-bacterial and anti-dustproof film material, anti-static, anti-bacterial and anti-dust film material used for anti-static measures such as partitions, floor sheets, equipment covers and aprons, and flexible container bags etc. The present invention relates to an anti-static, antibacterial and anti-dustproof dust-proof film material used for the static electricity countermeasure of the logistics goods of

In a factory or a warehouse, a loading and unloading operation of a load by a forklift, a transfer robot, a transfer drone or the like is frequently performed, and therefore, a sheet shutter device which is opened and closed by sensor detection is provided as an entrance. These sheet shutter devices open and close the entrance and exit by taking up / rewind a sheet film material of a specification made of a synthetic resin such as polyvinyl chloride resin, but since the specification is made of a synthetic resin, it can be opened and closed at high speed. Sheet friction tends to cause static electricity, and charged film materials cause dust contamination that attracts foreign substances such as dust and dirt, and depending on the factory environment, problems that cause fires and dust explosion accidents are manifested. . Therefore, there is a demand for a sheet shutter device that takes into consideration the antistatic property, the prevention of insect pests, and the antibacterial property as a clean room specification, insect repellent and dustproof specification in a food factory, a drug factory, a precision instrument factory and the like. In such facilities, in addition to sheet shutters, there is a need for various anti-static sheets such as partitions, floor sheets, equipment covers, aprons, etc., and anti-bacterial and anti-glare sheets. Also, in the physical distribution, there has been a long-felt need for flexible containers that can reduce static electricity generated due to discharge friction of powders, particles, resin pellets, etc. from flexible containers, and those containing carbon black are technical mainstream and It has become. However, in a sheet containing a carbon black amount sufficient to obtain a sufficient antistatic effect, use of carbon black unsuitable for safety confirmation has been avoided in sheet shutters and partitions because of the black concealing property.

  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 layer having a conductive layer containing a conductive polymer and a carbon nanotube, which is excellent in antistatic property, transparency, and adhesion between a substrate and the conductive layer Transparent packaging material (Patent Document 1), a conductive polymer layer laminated on a substrate, and a carbon nanotube layer provided in contact thereon, transparent with high conductivity and light transmittance Inventions such as conductive films (Patent Document 2) have been proposed, but these are colored with carbon nanotubes (for example, black-blue type, black-purple type, etc.) and with conductive polymers (doping type) (for example blue-green It has the fault which makes the appearance dark under the influence of the system, the reddish purple etc.). Therefore, in applications such as sheet shutters, partitions, floor sheets, equipment covers, and aprons, there has been a demand for an anti-electrostatic sheet that is less affected by the hue of the conductive material, and a sheet having antibacterial and anti-corrosion properties.

JP 2005-81766 A JP, 2009-2119, A JP, 2013-189562, A

  The present invention is an anti-static sheet (sheet shutter, partition, floor sheet, equipment cover, apron, etc.) using an antistatic film using carbon nanotubes, but with low coloring property with little influence of the hue of carbon nanotubes, An object is to provide an anti-static sheet having antibacterial properties.

  As a result of repeating researches and studies in view of the above-mentioned present conditions, the present invention uses at least one surface thermoplastic resin of a flexible sheet having a thermoplastic resin coating layer on at least one surface thereof using a fiber fabric as a base material By having a coating layer on the covering layer, and the coating layer containing cyclic polyether ion complexes and carbon nanotubes, it is possible to prevent sufficient charging while using a small amount of carbon nanotubes, which is difficult in the above prior art. It has been found that an effect can be obtained, an anti-electrostatic and anti-electrostatic sheet can be obtained with low colorability (less affected by the hue of carbon nanotubes), and the present invention has been completed.

  That is, the antistatic antibacterial film material of the present invention is coated on at least one surface of the flexible resin sheet having a thermoplastic resin coating layer on at least one surface of the fibrous woven fabric as a base material. A membrane layer, the coating layer comprising cyclic polyether ion complex, and carbon nanotubes, and the coating layer having an area occupancy of at least 20% of the surface of the thermoplastic resin coating layer It is preferable that it is a continuous body. As a result, a sufficient antistatic effect can be obtained while using a small amount of carbon nanotubes, and an anti-electrostatic and anti-static antistatic sheet can be obtained with low colorability (less affected by the hue of the carbon nanotubes).

  In the antistatic antimicrobial film material of the present invention, at least one selected from the cyclic polyether group of the cyclic polyether ion complex is selected from crown ether, aza crown ether, thia crown ether, azathia crown ether, cryptand, and the like. And an ionic complex based on at least one selected from a group of derivatives in which a functional group and / or a substituent is introduced into the cyclic polyether group, and a group of polymers having the cyclic polyether structure as a repeating unit. Is preferred. Due to the presence of cyclic polyether ion complex, a sufficient antistatic effect can be obtained while using a small amount of carbon nanotubes, and an antistatic and anti-static sheet with low coloring (with little influence of the color of carbon nanotubes) You can get

  In the antistatic antibacterial film material of the present invention, the above-mentioned ion complex comprises a silver ion complex, a copper ion complex, a zinc ion complex, an aluminum ion complex, a lithium ion complex, a nickel ion complex, a potassium ion complex, and a cobalt ion complex It is preferable that it is one or more selected. Due to the presence of such an ion complex, a sufficient antistatic effect can be obtained while using a small amount of carbon nanotubes, and an antistatic and anti-static antistatic sheet with low coloring (with less influence of the hue of carbon nanotubes). You can get

  The antistatic antibacterial film material of the present invention is characterized in that the carbon nanotubes are single-walled carbon nanotubes, double-walled carbon nanotubes, multi-walled carbon nanotubes, cup-stacked carbon nanotubes, oxidized carbon nanotubes, functionalized carbon nanotubes (terminal modification and / or It is preferable that it is at least one selected from sidewall modification) and metal (vapor deposition or sputtering) carbon nanotubes. Due to the presence of such carbon nanotubes, a sufficient antistatic effect can be obtained with a smaller amount of addition than conventional carbon black, and an antistatic sheet with low colorability (less affected by the hue of carbon nanotubes) can be obtained. .

  In the antistatic antibacterial film material of the present invention, the coating film layer contains a binder resin, and the content of the cyclic polyether ion complex and the carbon nanotube relative to the coating film layer is 0.1 to 6 It is preferable that it is mass%. As a result, a sufficient antistatic effect can be obtained while using a small amount of carbon nanotubes, and an anti-electrostatic and anti-static sheet can be obtained with low colorability (less affected by the hue of carbon nanotubes).

  In the antistatic antibacterial film material of the present invention, the coating layer is one or more nanoparticles selected from silica, titanium oxide, zinc oxide, tin oxide, zirconium oxide, cerium oxide, and alumina, and silane It is preferable to further contain a 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 further enhanced, and a sufficient antistatic effect can be obtained while using a small amount of carbon nanotubes, and low colorability (less affected by the hue of the carbon nanotubes) In addition, it is possible to obtain an anti-electrostatic and anti-static sheet.

  In the antistatic antibacterial film material of the present invention, the coating film is formed of polypyrroles, polythiophenes, polyacetylenes, polyphenylenes, polyphenylene vinylenes, polyanilines, polyacenes, polythiophene vinylenes, polyethylene dioxithiophene, It is preferable to further include one or more π electron conjugated conductive polymers selected from the group consisting of the following: and the content thereof is 1 to 25% by mass with respect to the coating layer. By further including a π electron conjugated conductive polymer in the coating layer, the antistatic effect is further enhanced, and a sufficient antistatic effect can be obtained while using a small amount of carbon nanotubes, and the low coloring property (the influence of the hue of carbon nanotubes In addition, it is possible to obtain an anti-static sheet that is antibacterial and antifungal.

  In the antistatic antibacterial film material of the present invention, at least one nanoparticle selected from the group consisting of silica, titanium oxide, zinc oxide, tin oxide, zirconium oxide, cerium oxide, and alumina, and the coating layer is a silane Nanoparticle network with compound and at least one π selected from polypyrroles, polythiophenes, polyacetylenes, polyphenylenes, polyphenylene vinylenes, polyanilines, polyacenes, polythiophene vinylenes, and copolymers thereof An electron conjugated conductive polymer is further contained, and the content of the nanoparticles and the π electron conjugated conductive polymer is 1 to 25% by mass with respect to the coating layer, and the content ratio is 2: 1 It is preferable that it is-1: 5. By further including nanoparticles and a π electron conjugated conductive polymer in the coating layer in a specific ratio, the antistatic effect is further enhanced, and a sufficient antistatic effect can be obtained while using a small amount of carbon nanotubes, and low colorability ( It is possible to obtain an anti-electrostatic sheet that is resistant to the influence of the color of the carbon nanotube), and is also antibacterial and antifungal.

  According to the present invention, although it is an antistatic sheet using an antistatic film utilizing carbon nanotubes, a sufficient antistatic effect can be obtained, and the coloring property is low (the influence of the hue of carbon nanotubes is small), and the antibacterial・ We can obtain antistatic protective sheet. Since a less colored anti-bacterial and anti-static sheet can be obtained, it can be suitably used as a sheet shutter, partition, floor sheet, equipment cover, apron, and the like.

  The antistatic antibacterial film material of the present invention is a coated film layer on at least one surface of a thermoplastic resin coated layer of a flexible sheet having a thermoplastic resin coated layer on at least one surface of a fibrous woven fabric as a substrate. The coating layer contains cyclic polyether ion complexes and carbon nanotubes, and in particular, the coating layer contains a binder resin, and the content of the cyclic polyether ion complex and the carbon nanotubes is in the coating layer. In contrast, at 0.1 to 6% by mass, the coating layer is a continuous body having an area occupancy of at least 20% with respect to one surface of the thermoplastic resin coating layer (the area of the target surface on which the coating layer is provided) It is.

  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 fixing, adhesive application, etc. 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 multifilament or short fiber spinning to ensure flexibility of the membrane material and tear strength. (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 (elliptic or flat in cross section) or twisted yarn 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 substrate for the antistatic antibacterial film material, with a shot 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 heat-laminated on preferably both sides of a multi-filament yarn woven fabric (porosity 7.5-30%) to form a thermoplastic resin coating layer, and short fiber spinning In the case of a cloth (span), preferably, on both sides of a staple fiber spun cloth (span) having a porosity of 0 to 5%, coating with a liquid thermoplastic resin-heat treatment or dipping-heat treatment of a thermoplastic resin coating layer Suitable for forming.

The thermoplastic resin coating layer is formed from a soft vinyl chloride resin composition (containing a plasticizer), and coating with polyvinyl chloride resin (emulsion polymerization type) or film formation by dipping to gelation heat treatment, or straight Particularly preferred is film formation from a vinyl chloride resin film (sheet) that has been calendered or T-die-extruded using a vinyl chloride resin (suspension polymerization type). 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 plasticizers include phthalic acid ester plasticizers, isophthalic acid ester plasticizers, terephthalic acid ester plasticizers, cyclohexanedicarboxylic acid ester plasticizers, cyclohexene dicarboxylic acid ester plasticizers, chlorinated paraffinic plasticizers, and polyester resins. Plasticizer, ethylene-vinyl acetate-carbon monoxide terpolymer resin, ethylene- (meth) acrylic acid ester-carbon monoxide terpolymer resin, etc. can be used, and in particular, it is possible to use an ether bond in the alkyl chain 1 The plasticizer contained above is excellent in conductivity and is preferable. In addition, in the thermoplastic resin coating layer, olefin resin (PE, PP), olefin elastomer, ethylene-vinyl acetate copolymer resin, ethylene- (meth) acrylic acid (ester) copolymer resin, urethane elastomer, acrylic 100 to 1000 g / m ² , in particular 200 per layer, obtained by calendering or T-die extrusion using a single elastomer, a styrene elastomer, a polyester elastomer, a fluoroelastomer, a silicone elastomer and the like alone or in combination A film or sheet of -500 g / m < ² > can be used, and a tarpaulin laminated with these thermoplastic resin coating layers is preferred.

  In particular, a flame retardant can be added to the thermoplastic resin coating layer to ensure flame resistance conforming to the Fire Service Act, and furthermore, it can be made a non-combustible material (incombustible film material for tent structure) approved by the Minister of Land, Infrastructure, Transport and Tourism . Specifically, 100 to 100 parts by mass of a flame retardant such as a phosphorus-containing compound, a nitrogen-containing compound, or an inorganic compound may be added to 100 parts by mass of a thermoplastic resin. ) Phosphate, (metal) organic phosphate, ammonium polyphosphate and the like, and as nitrogen-containing compounds, (iso) cyanurate compounds, (iso) cyanuric acid compounds, guanidine compounds, urea compounds Compounds and derivative compounds thereof, and as inorganic compounds, metal oxides (such as antimony trioxide and antimony pentoxide), metal hydroxides (such as aluminum hydroxide and magnesium hydroxide), metal complex oxides (such as zirconium Antimony complex oxides), metal complex hydroxides (eg, zinc hydroxystannate, hydrotalcite, etc.) and the like. These flame retardants can improve a flame retardance by using 2 or more types together.

In particular, it is preferable that the thermoplastic resin coating layer contains a mildew-proof organic compound, and as the mildew-proof organic compound, it is possible to use salmon, bacteria (gram positive, gram negative), cell walls such as fungi, cell membranes, cytoplasm, cell nuclei, etc. Specific organic compounds that exert effects such as oxidative phosphorylation inhibition, electron transport system inhibition, -SH group inhibition, DNA synthesis inhibition, cell epidermal function inhibition, lipid metabolism inhibition, chelate formation, etc. , thiazole compounds, isothiazoline compounds, pyridine compounds, triazine compounds, triazole compounds, N- haloalkylthio compounds, quaternary ammonium salt compounds, phenoxazine sialic Shin compounds such as, specifically, 10,10 ^'- oxy Bisphenoxyarsine, 2- (4-thiazolyl) -benzimidazole is particularly preferred. These flameproof organic compounds are mesoporous silica, (synthetic) zeolite, titanium zeolite, zirconium phosphate, calcium phosphate, zinc calcium phosphate, hydrotalcite, hydroxyapatite, silica alumina, calcium silicate, magnesium aluminum silicate, It is preferable to be supported by one or more kinds of inorganic porous particles selected from diatomaceous earth and treated products of these silane coupling agents. The content of the support of such a flameproof organic compound or inorganic porous particles contained in the thermoplastic resin coating layer (particularly the soft vinyl chloride resin composition) is relative to the thermoplastic resin coating layer (soft vinyl chloride resin composition) 0.01 to 5% by mass, preferably 0.1 to 1% by mass.

  In particular, calcium-zinc complex type, barium-zinc complex type, organic tin laurate, organic tin laurate, organic tin mercaptite, epoxy type stabilizer or the like may be used alone or in combination as a soft vinyl chloride resin coating layer as a soft vinyl chloride resin coating layer. By using it, heat deterioration and discoloration during the production of the antistatic antibacterial film material of the present invention are suppressed, and the weather resistance is further improved. Further, the antistatic antibacterial film material of the present invention is free of pigment coloration, and in particular, coloring such as white and pastel colors makes the contrast of ink jet printing and marking film letter insertion clear. In the thermoplastic resin coating layer, various known additives for thermoplastic resin can be added in optional amounts, and if necessary, light stabilizers (HALS), ultraviolet absorbers (benzotriazole-based, benzophenone) Systems, etc.), antioxidants (phenolic), fluorescent whitening agents, antistatic agents, hardeners (isocyanate etc.), insect repellents (pyrethroids etc.), deodorants (silicon oxide and metal oxide composites etc.) ), Thermal barrier filler (hollow particles, coarse titanium dioxide etc), fragrance, luminous pigment (strontium aluminate etc), aluminum flake pigment, pearl pigment, inorganic filler (calcium carbonate, barium sulfate etc) etc. be able to.

A coating layer is provided on the thermoplastic resin coating layer, and the coating layer contains cyclic polyether ion complexes and carbon nanotubes. In particular, the coating layer contains a binder resin, cyclic polyether ion complexes, and carbon nanotubes. The content of and is 0.1 to 6% by mass, preferably 0.3 to 3% by mass with respect to the coating layer. By containing a specific amount of cyclic polyether ion complex in the coating film layer, it becomes possible to express conductivity with a smaller amount of carbon nanotubes, thereby obtaining an antibacterial antistatic sheet with lower colorability. it can. In particular, the coating layer is a continuous body having an area occupancy of 20% or more, particularly 35% or more, to the surface of one thermoplastic resin coating layer, and is 0.05 to 20 g / m ² , particularly 0.5 to 10 g / M < ² > is preferable and the coating film layer may be provided on the thermoplastic resin coating layer of front and back. The amount of binder contained in the coating layer is 95 to 99.99% by mass, preferably 97.5 to 99.9% by mass, based on the coating layer. The binder may be any of an organic compound, an inorganic compound, and a mixture of an organic compound and an inorganic compound. As the organic compound, (meth) acrylic resin, (meth) acrylic copolymer resin, radical polymer of (meth) acrylate (ultraviolet curing resin), urethane resin, acrylic modified urethane resin, silicon modified urethane resin, polyester based Resin, vinyl acetate resin, vinyl chloride resin, vinyl chloride-vinyl acetate copolymer resin, fluorine-containing copolymer resin (polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene copolymer, polyvinylidene fluoride-hexafluoropropylene- Tetrafluoroethylene copolymer etc. can be illustrated. The inorganic compounds are exemplified by sol-gel thin films mainly composed of metal oxide gel and / or metal hydroxide gel such as silica sol, alumina sol, zirconia sol, niobium oxide sol, and silicon compound such as polysiloxane, colloidal silica and silica. it can.

  The cyclic polyether ion complex includes at least one member selected from the cyclic polyether group such as crown ether, aza crown ether, thia crown ether, azathia crown ether, cryptand, etc., and functional groups for these cyclic polyether groups And / or an ionic complex based on at least one selected from a group of derivatives into which a substituent is introduced and a group of polymers having these cyclic polyethers as repeating units, and these cyclic polyether ion complexes are antibacterial It develops sex and flock. The antibacterial activity is mainly based on the effect of suppressing the growth of Staphylococcus aureus, Escherichia coli, Klebsiella pneumoniae, Pseudomonas aeruginosa, methicillin resistant Staphylococcus aureus, enterohemorrhagic Escherichia coli and the like. That is, cyclic polyether ion complexes are cyclic polyether silver ion complexes, cyclic polyether copper ion complexes, cyclic polyether zinc ion complexes, cyclic polyether aluminum ion complexes, cyclic polyether lithium ion complexes, cyclic polyether nickel ion complexes, Specifically, cyclic polyether ion complexes which are one or more selected from cyclic polyether potassium ion complexes and cyclic polyether cobalt ion complexes are crown ether silver ion complexes, crown ether copper ion complexes, crown ether zinc ions Crowns such as complexes, crown ether aluminum ion complexes, crown ether lithium ion complexes, crown ether nickel ion complexes, crown ether potassium ion complexes, crown ether cobalt ion complexes, etc. Ether system, aza crown ether silver ion complex, aza crown ether copper ion complex, aza crown ether zinc ion complex, aza crown ether aluminum ion complex, aza crown ether lithium ion complex, aza crown ether nickel ion complex, aza crown ether potassium ion Aza crown ether system such as complex and aza crown ether cobalt ion complex, thia crown ether silver ion complex, thia crown ether copper ion complex, thia crown ether zinc ion complex, thia crown ether aluminum ion complex, thia crown ether lithium ion Complex, thia crown ether nickel ion complex, thia crown ether potassium ion complex, and thia crown ether cobalt ion complex Azathia crown ether silver ion complex, azathia crown ether copper ion complex, azathia crown ether zinc ion complex, azathia crown ether aluminum ion complex, azathia crown ether lithium ion complex, azathia crown Azathia crown ether systems such as ether nickel ion complex, azathia crown ether potassium ion complex, and azathia crown ether cobalt ion complex, cryptand silver ion complex, cryptand copper ion complex, cryptand zinc ion complex, cryptand aluminum ion complex , Cryptand lithium ion complex, cryptand nickel ion complex, cryptand potassium ion complex, and cryptand cobalt ion complex, etc. Putando system, one or more selected from, preferably contains at least silver ion complex.

  Crown ether is 9-crown-3, 12-crown-4, 15-crown-5, 18-crown-6, 21-crown-7, 24-crown-8, 27-crown-9, 30-crown- [(9 + 3n) -crown- (3 + n)] formula: n is a cyclic polyether represented by an integer of 1 or more, such as 10, 33-crown-11, 36-crown-12, etc .; The numbers represent the total number of atoms, and the numbers at the end represent the number of oxygen atoms. Also, as benzo crown ethers, at least one benzene ring is covalently bonded to the two carbon atoms of the crown ether to these [(9 + 3 n) -crown- (3+ n)] crown ethers. For example, in the case of 18-crown-6, benzo18-crown-6, dibenzo18-crown-6, tribenzo18-crown-6 and hexabenzo18-crown-6 can be exemplified. In addition, as a cyclohexano crown ether, at least one cyclohexane ring is covalently bonded to two carbon atoms of the crown ether in these [(9 + 3 n) -crown- (3+ n)] crown ethers. For example, in the case of 18-crown-6, for example, cyclohexano 18-crown-6, dicyclohexano 18-crown-6, tricyclohexano 18-crown-6, hexacyclohexano 18-crown 6 Can be illustrated. The aza crown ether, benzo aza crown ether, and cyclohexano aza crown ether correspond to those obtained by replacing part or all of the oxygen atoms of the aforementioned crown ether group with a nitrogen atom (NH). Similarly, thia crown ether, benzothia crown ether and cyclohexanothia crown ether correspond to those obtained by replacing a part or all of the oxygen atoms of the above-mentioned crown ether group with a sulfur atom (S). Similarly, in the azathiacrown ether, benzoazathiacrown ether and cyclohexanoazathiacrown ether, some or all of the oxygen atoms of the above-mentioned crown ether group are substituted by nitrogen atom (NH) and sulfur atom (S) Is the equivalent.

Further, as the crown ether derivative group, those obtained by introducing a functional group and / or a substituent to the crown ether described in paragraph [0026], and as the functional group, for example, a hydroxy group, a vinyl group, an acryloyl group, an acyl group, acetyl Group, carboxyl group, sulfonic group, carbonyl group, epoxy group, amino group, imino group, cyano group, azo group, isocyanate group, sulfo group, nitro group, thiol group etc., and examples of the substituent include alkyl Groups, vinyl groups, allyl groups, aryl groups, phenyl groups, naphthyl groups, aralalkyl groups, benzyl groups, cycloalkyl groups, alkoxy groups, methoxy groups, ethoxy groups and the like. The terminal and / or side chain of these substituents may have the above-mentioned functional group. Further, as a polymer group having cyclic polyether as a repeating unit, a dimer, a trimer of a crown ether derivative group, a bicyclic cryptand [2.2] which is a three-dimensional structure of a plurality of crown ethers, a tricyclic cryptand [2.2.2] and polymers (polymers) or dendrimers, in particular, the polymers are known polymers of a monomer A having a cyclic polyether structure and a monomer B capable of addition reaction with the monomer A. These include polyester resins (-COOH + -OH), polyamide resins (-COOH + -NH ₂ ), polyurethane resins (-NCO + -OH), polyketone resins (-COOH + dibenzo crown ether: free Acrylic resin, vinyl resin, etc. by homopolymerization of monomer A, such as Del-Crafts reaction) Monomer A having a cyclic polyether structure in a straight chain or in a side chain, in particular having a cyclic polyether structure, is a cyclic polyether silver ion complex, a cyclic polyether copper ion complex, a cyclic polyether zinc ion complex in advance Preferably, any of cyclic polyether aluminum ion complex, cyclic polyether nickel ion complex, and cyclic polyether cobalt ion complex is formed, and addition reaction or homopolymerization is carried out in the state of cyclic polyether ion complex. The cyclic polyether ion complex used in the present invention has a form in which one metal atom (ion) is surrounded by a plurality of cyclic polyethers (crown ether), and two cyclic polys per one metal atom (ion). Including an embodiment sandwiching with ether (crown ether).

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 paragraphs [0029] and [0030]), etc. It can also be used as a binder. 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. As another example of combined use, when the conductive network containing the π electron conjugated conductive polymer is A and the conductive network containing carbon nanotubes is B, 2 of “A / B” and “B / A” The combined use of layers, triple combination of "A / B / A" and "B / A / B" etc. also dramatically improves the conductivity. In addition, the conductivity is dramatically improved by using carbon nanotubes and fullerene in combination at a mass ratio of 100: 1 to 2: 1. As the fullerene, C ₆₀ fullerene, organically modified fullerene, inorganically modified fullerene, hydrogen-containing fullerene, metal-containing fullerene and the like can be used.

  The coating layer contains a binder resin, and the content of the cyclic polyether ion complex and the carbon nanotube with respect to the coating layer is 0.1 to 6% by mass, that is, the binder resin contained in the coating layer is a coating 94 to 99% by weight with respect to the layer is preferred. The mass ratio of the cyclic polyether ion complex to the carbon nanotube is preferably 5: 1 to 1: 5, particularly 2: 1 to 1: 2. Examples of the binder resin include acrylic resins, acrylic-silicon resins, urethane resins, polyester resins, epoxy resins, fluorine resins, vinyl acetate resins, and polyvinyl chloride-vinyl acetate resins. 1) One or more types of nanoparticles selected from silica, titanium oxide, zinc oxide, tin oxide, zirconium oxide, cerium oxide, and alumina in the above-mentioned coating layer (nanoparticles when forming coating layer) It is preferable to further include a sol) and a silane compound 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 can be further enhanced, and conductivity can be expressed with a smaller amount of carbon nanotubes, thereby obtaining an antistatic sheet with lower colorability. be able to. 2) In the above-mentioned coating layer, polypyrroles, polythiophenes, polyacetylenes, polyphenylenes, polyphenylene vinylenes, polyanilines, polyacenes, polythiophene vinylenes, polyethylene dioxythiophene, and doped bodies thereof (polystyrene (polystyrene) And further containing at least one π electron conjugated conductive polymer selected from sulfonic acid, p-toluenesulfonic acid and the like as a doping agent), and the content thereof is 1 to 25% by mass with respect to the coating layer It is preferable to do. By further including a π electron conjugated conductive polymer 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, an antistatic sheet with lower colorability can be obtained. You can get In addition, 3) the above-mentioned coating layer may simultaneously contain the above nanoparticle (a nanoparticle sol is used when forming a coating layer) and a nanoparticle network of a silane compound and the above-mentioned π electron conjugated conductive polymer. The content of the nanoparticle nanoparticle network and the π electron conjugated conductive polymer is preferably 1 to 25% by mass with respect to the coating layer, and the contained mass ratio is preferably 1:10 to 1: 1. . By further including a nanoparticle nanoparticle network and a π electron conjugated conductive polymer in a specific ratio in the coating layer, the antistatic effect can be further enhanced, and conductivity can be expressed with a smaller amount of carbon nanotubes. Thus, it is possible to obtain an antistatic sheet with lower colorability. 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.

  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.

  Each of the above-mentioned coating layers is a continuum having an area occupancy of at least 20% with respect to the surface of the thermoplastic resin coating layer (the area of the target surface on which the coating layer is provided), an area occupancy of up to 100% It is preferable that it is a continuous body having By forming a coating film layer having such an area occupancy rate as a continuum, a network capable of expressing conductivity with a smaller amount of carbon nanotubes is made possible, so that an antistatic antistatic sheet with lower colorability is obtained. Can. If the area ratio of the coating layer is less than 20%, the antistatic property and the antimicrobial property of the resulting film material may be insufficient. Therefore, the area ratio of the coating layer is 25 to 50%, and It is preferable that it is a continuous body. 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. In the case of the π electron conjugated conductive polymer, a thickness of 0.05 μm to 15 μm and in the case of a carbon nanotube, a thickness of 0.001 μm to 0.5 μm are preferable.

  In order to process the antistatic antibacterial film material of the present invention into a sheet shutter, a partition, a floor sheet, an equipment cover, a flexible container, etc., bonding of the antistatic antibacterial film materials of the present invention In the end-to-end overlap bonding), bonding can be performed by high-frequency vibration using a high-frequency welder, specifically, a film material is placed between two electrodes (one electrode is a weld bar), and welding is performed. By applying a potential difference oscillating at a high frequency (1 to 200 MHz) while pressing with a bar, the thermoplastic resin coating layer of the film material fuses by being brought into a melted and softened state by molecular frictional heat, and is cooled and solidified in that state Obtain a conjugate. 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 a hot plate fusion method or the like in which an adherend is pressure-bonded and fused using a mold (a trowel) heated at a temperature higher than the melting temperature of the thermoplastic resin coating 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 thermoplastic resin coating layer is poor, or the temperature difference of the softening temperature is large. Since the adhesive force at the time of joining the film materials to be obtained becomes insufficient, the area occupancy of the coating film layer is 25 to 50%, and the area other than the coating film layer, that is, the thermoplastic resin coating exposed on the surface It is desirable that the layer and the thermoplastic resin-coated layer on the back surface of the other membrane material be at least heat-melted to provide a firmly bondable state.

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 antistatic antibacterial film material 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, the antistatic property was evaluated on the premise of having the "low colorability" which is the subject of the present invention. .
As a standard of antistatic property as an example, one having a surface resistivity of 10 ⁵ Ω / sq to 10 ⁹ Ω / sq and a surface resistivity of 10 ¹⁰ Ω / sq or less is set as a 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) Antibacterial: (. The number of inoculated was 10 ⁴⁾ (JIS Z2801 2010 years compliant) dropwise general Foundation family constitution test center entrusted specimen bacterial suspension on the surface of the sheet was inoculated, obtained above The bacterial solution and the sheet were brought into close contact with each other so that the sheet was in contact with the bacterial solution, and the mixture was cultured for 24 hours ± 1 hour in an environment of 35 ° C ± 1 ° C and a relative humidity of 90% or more. Thereafter, the test piece sheet is washed away, the number of viable bacteria per 1 cm ^{2 of} the test piece sheet is measured, and the antibacterial activity value (value obtained by subtracting the bacteria count logarithm of the sheet manufactured in the example from the bacteria count logarithm of the target section) Was calculated. The target section was a sheet to which the cyclic polyether ion complex was not added. A cell suspension adjusting solution used a 1/200 NB medium. The bacterial species used are shown below. The numerical value in the table is the number of viable cells per 1 cm ² of the test piece, and “ND” is not detected (Not Detected) of viable cells.
Staphylococcus aureus "Staphylococcus aureus subsp. Aureus 12732"
E. coli "Escherichia coli NBRC 3972"
(3) Antifungal property (JIS Z2911 culture test)
Inoculate the spore of the below-mentioned test sputum on the test piece sheet of width 3 cm x length 3 cm, place on a potato dextrose agar medium, observe the development of sputum at 28 ° C for 7 days in a petri dish, and It evaluated by the criterion.
1: No growth of mycelium is observed in the inoculated part of the test piece 2: The area of mycelial growth part found in the inoculated part of the test piece does not exceed 1/3 of the total area 3: Recognized in the inoculated part of the test piece The area of the growth portion of the mycelium to be grown is more than 1/3 of the total area. <Test stain> (A) + (B) + (C)
(A) Aspergillus niger NBRC 105649 (Ebony)
(B) Penicillium citrinum NBRC 6352 (blue)
(C) Cladosporium cladosporioides NBRC 6348 (Krokawa moth)
(4) 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

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 ) A thermoplastic resin coated layer / a thermoplastic resin coated layer having a thickness of 0.2 mm made of the following soft vinyl chloride resin composition (1) as a thermoplastic resin coated layer as a base material by bridge melting lamination by thermocompression bonding A laminated film material (terporin) having a thickness of 0.65 mm and a mass of 680 g / m ² was obtained, which was composed of a base fabric / thermoplastic resin coating layer.
<Soft vinyl chloride resin composition (1)>
Vinyl chloride resin (polymerization degree 1300) 100 parts by mass 4-cyclohexene-1,2-dicarboxylic acid bis (2-ethylhexyl)
(Plasticizer) 50 parts by mass Tricresyl phosphate (flame retardant plasticizer) 10 parts by mass Epoxidized soybean oil (stabilizer and plasticizer) 5 parts by mass Barium / zinc composite stabilizer 2 parts by mass Antimony trioxide (flame retardant) 10 Mass part Rutile type titanium oxide (white pigment) 5 mass parts Benzotriazole skeleton compound (ultraviolet light absorber) 0.3 mass parts The following coating on the thermoplastic resin coating layer on the surface side of the above laminated film material (terporin) A grid-like continuum (grating having an area occupancy of 55.5%) by coating 120 mesh square grid pattern gravure roll using a coating liquid (solid content concentration 16.9 mass%) for layer (1) A coating film layer (1) having a width of 5 mm and square holes of 10 mm × 10 mm) was formed to obtain an antistatic antibacterial film material (terpoline) having a mass of 682 g / m ² .
Solution for Coating Layer (1)
Methyl methacrylate resin (acrylic resin) 100 parts by mass 18-monoazathia crown ether-5 silver (cyclic polyether ion complex)
1 part by mass * Silver ions are supported in a cavity formed by ringing-(CH ₂ CH ₂ S) ₅ CH ₂ CH ₂ NH- Single-walled carbon nanotubes (diameter 1.5 to 2.5 nm) 0.5 parts by mass * Cyclic polyether ion complex: Carbon nanotube content ratio 2: 1
※ Cyclic polyether ion complex to coating layer: Carbon nanotube content ratio 1.47% 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 solution for coating layer (1) of Example 1, 1 part by mass of 18-monoazathiacrown ether-5 silver (cyclic polyether ion complex) is added to 18-diazacrown ether-4 copper (cyclic polyether ion) Complex) An antistatic antibacterial film material (terpolin) having a thickness of 0.65 mm and a mass of 682 g / m ² was obtained in the same manner as in Example 1 except that 1 part by mass of the complex was substituted to form a coating film layer (2).
※ 18-Diaza crown ether-4 copper:
A ring of-[(CH ₂ CH ₂ NH (CH ₂ CH ₂ O) ₂ ] _2- carries a copper ion

[Example 3]
An antistatic antibacterial agent having a thickness of 0.65 mm and a mass of 682 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 (3). A membrane material (tarpaulin) was obtained.
<Solution for coating layer (3)>
Poly (3,4-ethylenedioxythiophene) * polythiophene 20 parts by mass methyl methacrylate resin (acrylic resin) 80 parts by mass 18-monoazathiacrown ether-5 silver (cyclic polyether ion complex)
0.5 parts by mass ※-(CH ₂ CH ₂ S) ₅ CH ₂ CH ₂ NH-in a ring-shaped cavity with silver ions supported Single-walled carbon nanotubes (diameter 1.5 to 2.5 nm) 1.5 mass Part * Cyclic polyether ion complex: Carbon nanotube content ratio 1: 3
※ Cyclic polyether ion complex to coating layer: Carbon nanotube content 1.95% 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 4
In the solution for the coating layer (3) of Example 3, 0.5 parts by mass of 18-monoazathiacrown ether-5 silver (cyclic polyether ion complex) is added to 18-diazacrown ether-4 copper (cyclic poly Ether ion complex) In the same manner as in Example 3 except that the coating film layer (4) was replaced with 0.5 parts by mass, an antistatic antibacterial film material (terporin) having a thickness of 0.65 mm and a mass of 682 g / m ² I got

[Example 5]
The solution for the coating layer (1) of Example 1 is changed to the solution for the coating layer (5), and the thickness is the same as in Example 1 except that the coating layer (5) containing the nanoparticle network is used. An antistatic antibacterial film material (terporin) having a weight of 682 g / m ² was obtained.
<Solution for coating layer (5)>
Methyl methacrylate resin (acrylic resin) 100 parts by mass Dibenzo 18-crown-6 silver (cyclic polyether ion complex) 1 part by mass ※ -C ₆ H ₄ (CH ₂ CH ₂ O) 0 (CH ₂ CH ₂ O) C ₆ H ₄ (CH ₂ CH ₂ O) 0 (CH ₂ CH ₂ O—) with a cyclic portion supporting silver ions supported single-walled carbon nanotubes (diameter 1.5 to 2.5 nm) 0.5 parts by mass organosilica sol (Nanoparticles of silica) 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 ※ nano ratio of silica sol and methyltriethoxysilane 3: 2 in mass ratio Particle network formed in the coating layer * Cyclic polyether ion complex: Carbon nanotube content ratio 2: 1
※ Cyclic polyether ion complex to coating layer: Carbon nanotube content 1.23 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 6]
In the solution for the coating film layer (5) of Example 5, 1 part by mass of dibenzo 18-crown-6 silver (cyclic polyether ion complex) and 1 part by mass of dibenzo 18-crown-6 copper (cyclic polyether ion complex) An antistatic antibacterial film material (turporin) having a thickness of 0.65 mm and a weight of 682 g / m ² was obtained in the same manner as in Example 5 except that the coating film layer (6) was substituted.

[Example 7]
The thickness was 0.65 mm in the same manner as in Example 3 except that the solution for the coating layer (3) in Example 3 was changed to the solution for the coating layer (7) containing a π electron conjugated polymer and a nanoparticle network. , An antistatic antibacterial film material (terpoline) having a mass of 682 g / m ² .
Solution for Coating Layer (7)
Poly (3,4-ethylenedioxythiophene) * polythiophene 20 parts by mass methyl methacrylate resin (acrylic resin) 80 parts by mass 18-monoazathiacrown ether-5 silver (cyclic polyether ion complex)
0.5 parts by mass ※-(CH ₂ CH ₂ S) ₅ CH ₂ CH ₂ NH-in a ring-shaped cavity with silver ions supported Single-walled carbon nanotubes (diameter 1.5 to 2.5 nm) 1.5 mass Part * Cyclic polyether ion complex: Carbon nanotube content ratio 1: 3
※ Cyclic polyether ion complex to coating layer: Carbon nanotube content ratio 1.63 mass%
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]
In the solution for coating layer (7) of Example 7, 0.5 parts by mass of 18-monoazathiacrown ether-5 silver (cyclic polyether ion complex) is added to 18-diazacrown ether-4 copper (cyclic poly Ether ion complex) In the same manner as in Example 7 except that the coating film layer (8) containing a π electron conjugated polymer and a nanoparticle network was substituted by 0.5 parts by mass, the thickness was 0.65 mm, mass 682 g / An m ² antistatic antibacterial film material (terporin) was obtained.

[Effects of Embodiments 1 to 8]
The film materials of Examples 1 to 8 containing a cyclic polyether ion complex and a carbon nanotube in a mass ratio of 2: 1 to 1: 5 have antistatic properties superior to the surface resistivity of 10 ¹⁰ Ω / □, and It has antibacterial and antifungal properties and has low colorability. In particular, the film materials of Examples 5 to 8 additionally containing the nanoparticle network in the coating film layer are superior in antistatic property to the film materials of Examples 1 to 4 and, in particular, π electron conjugated conductive in the coating film layer The film materials of Examples 3, 4, 7 and 8 additionally containing a hydrophobic polymer are superior in antistatic property to the film materials of Examples 1, 2 and 5 and, the amount of carbon nanotubes used is large. Is excellent in antistatic property (Examples 3, 4, 7 and 8), low in color despite the antistatic property of the surface resistivity 10 ⁵ to 10 ⁶ Ω / □ level, and cyclic polyether further The film materials of Examples 1, 2 and 5 containing a large amount of ion complex were superior in antibacterial and antifungal properties to the film materials of Examples 3, 4, 7 and 8.

Comparative Example 1
The thickness is 0.65 mm as in Example 1 except that 1 part by mass of 18-monoazathiacrown ether-5 silver (cyclic polyether ion complex) is omitted from the solution for the coating layer (1) of Example 1. A tarpaulin (9) having a mass of 682 g / m ² was obtained. The antibacterial property of the obtained tarpaulin was significantly inferior to that of the tarpaulin (1) of Example 1, and the antistatic property was also somewhat inferior.

Comparative Example 2
A tarpaulin (10) having a thickness of 0.65 mm and a mass of 682 g / m ^{2 was} prepared in the same manner as in Example 1 except that 0.5 parts by mass of single-walled carbon nanotubes was omitted from the solution for coating layer (1) of Example 1. Obtained. The resulting tarpaulin had high brightness and good appearance but did not have antistatic properties.

Comparative Example 3
The solution for the coating film layer (1) of Example 1 was the same as Example 1 except that 0.5 parts by mass of single-walled carbon nanotubes was replaced with 0.5 parts by mass of carbon black, and the thickness 0.65 mm, mass 682 g A tarpaulin (11) / m ² was obtained. The resulting tarpaulin had a low lightness, a black appearance, and a poor antistatic property.

Comparative Example 4
In the solution for the coating film layer (1) of Example 1, 1 part by mass of 18-monoazathiacrown ether-5 silver (cyclic polyether ion complex) is replaced with 1 part by mass of zeolite silver, and Similarly, a tarpaulin (12) having a thickness of 0.65 mm and a mass of 682 g / m ² was obtained. The obtained tarpaulin had high lightness and antibacterial properties, but was inferior in antistatic properties.

As is clear from the above-described Examples and Comparative Examples, according to the present invention, the anti-electrostatic sheet using an antistatic film utilizing carbon nanotubes, but the electrostatic and anti-static electrostatic of lower colorability Since a countermeasure sheet can be obtained, it can be suitably used as a sheet shutter, partition, floor sheet, equipment cover, apron, and the like.

Claims (8)

  A film layer is formed on at least one surface of the flexible resin coated layer having a thermoplastic resin coated layer on at least one surface of the fiber fabric as a base material, and the coated layer is annular. An antistatic antibacterial film material comprising a polyether ion complex and a carbon nanotube, and being a continuous body having an area occupancy of at least 20% with respect to the surface of the thermoplastic resin coating layer.   The cyclic polyether ion complex includes at least one member selected from the cyclic polyether group of crown ether, aza crown ether, thia crown ether, azathia crown ether, cryptand, and a functional group and / or the cyclic polyether group. Or an ion complex comprising, as a substrate, at least one selected from a group of derivatives having a substituent introduced therein, and a group of polymers having the cyclic polyether structure as a repeating unit. Material.   The ion complex is one or more selected from silver ion complex, copper ion complex, zinc ion complex, aluminum ion complex, lithium ion complex, nickel ion complex, potassium ion complex, and cobalt ion complex. Antistatic antibacterial film material described in 4.   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) The antistatic antibacterial film material according to any one of claims 1 to 3, which is at least one selected from carbon nanotubes.   The said coating film layer contains binder resin, The content with the said cyclic polyether ion complex and the said carbon nanotube is 0.1-6 mass% with respect to the said coating film layer, The any one of Claims 1-4 Antistatic antibacterial film material as described in 1 or 2.   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 antistatic antibacterial film material according to claim 5, which comprises a nanoparticle network of 0.1 to 5% by mass.   At least one selected from the group consisting of polypyrroles, polythiophenes, polyacetylenes, polyphenylenes, polyphenylenes, polyphenylene vinylenes, polyanilines, polyacenes, polythiophene vinylenes, polyethylene dioxythiophenes, and doped bodies thereof. The antistatic antimicrobial film material according to claim 5, further comprising a π electron conjugated conductive polymer of a content of 1 to 25% by mass with respect to the coating film layer.   The coating film layer is composed of at least one nanoparticle selected from silica, titanium oxide, zinc oxide, tin oxide, zirconium oxide, cerium oxide, and alumina, a nanoparticle network of a silane compound, and polypyrroles. And at least one π electron conjugated conductive polymer selected from polythiophenes, polyacetylenes, polyphenylenes, polyphenylene vinylenes, polyanilines, polyacenes, polythiophene vinylenes, and copolymers thereof, The content of the nanoparticles and the π electron conjugated conductive polymer is 1 to 25% by mass with respect to the coating layer, and the content mass ratio is 1:10 to 1: 1. Anti-static antibacterial film material.