JP6963298B2 - Antistatic antibacterial membrane material - Google Patents

Description

The present invention relates to an antistatic technique for an industrial material sheet and an antistatic technique. Specifically, the present invention relates to an antistatic property used for antistatic measures of a sensor-sensitive sheet shutter device in a factory, a warehouse, a clean room, or the like. Antistatic and anti-static dust-proof film material, antistatic and anti-static and anti-static dust-proof film materials used for anti-static measures such as partitions, floor sheets, equipment covers, aprons, and flexible container bags, etc. Regarding antistatic, antibacterial, and anti-static dust-proof film materials used for anti-static measures in logistics products.

The method of using a surfactant to promote the removal of static electricity has been used for a long time, and it is known that the ^{surface intrinsic resistance value should be set to 10 12 Ω or less for the purpose of preventing the adhesion of dust.} Surfactant molecules have a hydrophilic group and a lipophilic group, and when applied to the surface of a synthetic resin molded product, the lipophilic group faces the surface of the synthetic resin molded product, and the outwardly facing hydrophilic group adsorbs moisture in the air. However, the layer of water molecules leaks electric charge by exhibiting a slight electric conductivity, but the drawback is that it is humidity-dependent. To apply an antistatic agent such as a surfactant to a synthetic resin molded product, there are 1) a method of applying it to the surface of the synthetic resin molded product, and 2) a method of kneading it into the synthetic resin molded product. The antistatic agent for application (for external use) is easy to use, but has the drawback that its antistatic property is significantly reduced when the surface is wiped or washed. For kneading (internal antistatic agent), the kneaded antistatic agent gradually oozes out (bleeds out) to the surface to maintain the antistatic effect, but at temperatures below the glass transition point of the synthetic resin, It has the drawback that diffusion is unlikely to occur. On the other hand, the method of adding carbon black as a conductive filler is general-purpose, but this method is excellent in forming a conductive circuit in which carbon black densely dispersed in a synthetic resin molded product serves as a path for electric charges. It imparts electrical conductivity, and is excellent in sustainability of effect and humidity dependence. However, there is a problem that a transparent product or an arbitrary colored product cannot be obtained because the appearance of the synthetic resin molded product is black due to the influence of the black color of carbon black itself.

Therefore, as a means of imparting conductivity without using an antistatic agent such as a surfactant or carbon black, a flexible container in which soft synthetic resin layers are provided on both sides of the woven fabric is used as a soft synthetic resin. A flexible container (Patent Document 1) containing a conductive plasticizer (particularly a lithium ion-based plasticizer) in a layer has been proposed. However, the lithium-ion-based plasticizer has poor plasticizing efficiency ^{, requires a large amount to be blended in order to obtain a desired surface intrinsic resistance of 10 10} Ω or less, and also requires a considerable amount of a general-purpose plasticizer (Example 1). Because of Example 2), the soft synthetic resin layer tends to be softened and fragile, which is not practical as a flexible container. In addition, it is possible to obtain a molded product having excellent antistatic properties and maintaining high antistatic properties for a long period of time, and when packaging metals, a control for obtaining a film that does not corrode or rust contaminate the metal surface. As the electric composition, a compound or a polymer containing an ether bond and / or an ester bond, and a component obtained by adsorbing an alkali metal, an alkaline earth metal salt, or the like with hydrotalcite, an ion exchange resin, or the like (Example 1-). The antistatic composition according to 26) (Patent Document 2) is disclosed. However, as the transparent film contains a large amount of components adsorbed with hydrotalcite or an ion exchange resin as the antistatic composition, the antistatic property is improved, but the appearance of the film becomes cloudy, and the transparency and visibility are improved. There is a problem that impairs. Therefore, without using an antistatic agent such as a surfactant or carbon black, it is possible to continuously obtain a high degree of antistatic property without impairing transparency and visibility, and also has antibacterial and antistatic properties. If this is done, it will be widely used and deployed in applications such as seat shutters, partitions, floor sheets, equipment covers, and aprons.

JP-A-2002-240884 Japanese Unexamined Patent Publication No. 2003-277622

The present invention is for antistatic sheets (seat shutters, partitions, floor sheets, equipment covers, aprons, etc.) with better antibacterial and antistatic properties without using antistatic agents such as surfactants and carbon black. Providing is an issue.

The present invention has been studied and studied in view of the above-mentioned current situation, and as a result, the antistatic resin layer contains a liquid ester compound having one or more ether bonds in the molecule and a chelate complex. The present invention is completed by finding that an antistatic sheet having better antibacterial and anti-mold properties can be obtained without using an antistatic agent such as a surfactant or carbon black, which has been difficult in the prior art. It came to.

That is, the antistatic antibacterial film material of the present invention is a flexible laminate having a woven fabric as a base material and having at least one antistatic resin layer provided on the base material, and the antistatic resin. The layer contains a liquid ester compound having one or more ether bonds in the molecule, and a chelate complex, wherein the chelate complex is a silver ligand, a copper ligand, a zinc ligand, an aluminum ligand, and the like. It is preferably one or more selected from a nickel ligand, a lithium ligand, and a cobalt ligand. As a result, it is possible to obtain a more excellent antibacterial and antifungal antistatic sheet without using an antistatic agent such as a surfactant or carbon black.

In the antistatic antibacterial film material of the present invention, it is preferable that the ester compound is at least one selected from [Chemical formula 1] and [Chemical formula 2]. Due to the presence of such a liquid ester compound, an antistatic sheet having more excellent antistatic properties can be obtained.

[Chemical 1]
R (AO) _n OOC-X-COO (AO) _m R
(In the formula, 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 to ₁₅ linear or branched alkyl group (R). Are the same or different from each other), A is: _{an alkylene group of C 2-4} , m and n are integers of 1 to 10 (compounds represented by the same or different from each other)

[Chemical 2]
R ₁ CO (OCH ₂ CH-R ₂ ) _n COOR ₃
(In the formula, R ₁ and R ₃ are: C _{3 to 15} linear or branched alkyl or alkenyl groups, R ₂ is: H, CH ₃ , C ₂ H ₅ , n is an integer of 3 to 20. Compound represented by)

In the antistatic antibacterial film material of the present invention, the ligands of the chelate complex are amino acids, ethylenediamine, diethylenetriamine, triethylenetetramine, pipyridine, acetylacetonate, ethylenediaminetetraacetic acid, hydroxyethylethylenediaminetriacetic acid, and dihydroxyethylethylenediaminediamine. It is preferably one or more selected from acetic acid, 1,3-propanediaminetetraacetic acid, diethyltriaminetetraacetic acid, triethylenetetramine hexaacetic acid, pyrithione, phenanthroline, porphyrin and crown ether. Due to the presence of such a chelate complex, it is possible to obtain an antistatic sheet having more excellent antistatic properties and antibacterial / antifungal properties.

In the antistatic antibacterial film material of the present invention, the combined mass ratio of the liquid ester compound and the chelate complex is preferably 100: 1 to 5: 1. Due to the presence of the liquid ester compound and the chelate complex, it is possible to obtain an antistatic sheet having more excellent antistatic properties and antibacterial / antifungal properties.

In the antistatic antibacterial film material of the present invention, a coating film layer is formed on at least one surface of the flexible laminate on the entire surface or in a network, and the coating film layer is composed of carbon nanotubes, fullerenes and π electrons. It is preferable to contain one or more selected from conjugated conductive polymers. In particular, by having a coating film layer on the antistatic resin layer, it is possible to further enhance the antistatic effect.

In the antistatic antibacterial film material of the present invention, the coating layer is composed of one or more nanoparticles selected from silica, titanium oxide, zinc oxide, tin oxide, zirconium oxide, cerium oxide, and alumina, and silane. It is preferable that the compound is further contained to form 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 film layer, it is possible to further enhance the antistatic effect.

In the antistatic antibacterial film material of the present invention, it is preferable that the coating film layer is a continuum having an area occupancy of at least 20% per one surface of the flexible laminate. By forming a continuous coating film layer having such an area occupancy, it is possible to further enhance the antistatic effect and maintain good visibility.

According to the present invention, an antibacterial and antistatic antistatic sheet having more excellent antistatic properties can be obtained without using an antistatic agent such as a surfactant or carbon black. It can be widely used for industrial material sheets such as floor sheets, equipment covers, and aprons.

The antistatic antistatic film material of the present invention is a flexible laminate having a woven fabric as a base material and having at least one antistatic resin layer provided on the base material, and the antistatic resin layer. However, in an embodiment in which a liquid ester compound having one or more ether bonds in the molecule and a chelate complex are contained in a combined mass ratio of 100: 1 to 10: 1, particularly on at least one side of the flexible laminate. It is a continuous coating film layer in which the film layer is formed on the entire surface or in a network shape, and has an area occupancy of 20% or more with respect to one surface of the antistatic resin layer.

The fiber woven fabric as the base material used in the present invention can be used in any form such as a woven fabric, a knitted fabric, and a non-woven fabric. (Has), basket fabrics (eg regular basket fabrics such as 2x2, 3x3, 4x4, 3x2, 4x2, 4x3, 5x3, 2x3, 2x4, 3 Irregular basket weaves such as x4, 3x5), twill weaves (both warp and weft have a minimum structural unit of 3 each): 3 wefts, 4 wefts, 5 wefts, 6 It has a minimum structural unit that uses at least 5 warp and weft threads (2 jumps, 3 jumps, 4 jumps, 5 jumps, etc.), and change plain fabrics. , Change Aya woven fabric, Change brocade woven fabric, Honeycomb woven fabric, Pear woven fabric, Ripped diagonal woven fabric, Day and night brocade woven fabric, Mojiri woven fabric (Gauze woven fabric, 絽 woven fabric), Sewn woven fabric, Double woven fabric, etc. In particular, plain woven fabrics and 2 × 2 basket woven fabrics are preferable because they have an excellent balance of warp and weft properties. The above woven fabrics may be subjected to one or more known fiber treatments such as scouring, bleaching, dyeing, softening, water repellency, waterproofing, flameproofing, hair burning, calendar, binder fixing, adhesive application, etc. It can also be used.

As the threads constituting the fiber woven fabric, any of synthetic fibers, natural fibers, semi-synthetic fibers, inorganic fibers or mixed fibers composed of two or more of these can be used, but polypropylene fibers, polyethylene fibers, polyvinyl alcohol fibers and polyesters can be used. (PET, PBT, PNT) fiber, total aromatic polyester fiber (polyallylate fiber), nylon fiber, total aromatic polyamide fiber, aromatic heterocyclic polymer (polybenzoimidazole, polybenzoxazole, polybenzothiazole, etc.) fiber, Synthetic fibers such as acrylic fibers, polyurethane fibers, or mixed fibers thereof can be used, and polyester (PET: polyethylene terephthalate) fibers are particularly preferable. The modes of these yarns are monofilament, multifilament, short fiber spinning (spun), split, tape, etc., but in order to ensure the flexibility and tear strength of the membrane material, multifilament or short fiber spinning (Span) is preferred. In addition, multifilament fibers such as glass fiber, silica fiber, alumina fiber, silica-alumina fiber, and carbon fiber can also be used, and these inorganic fibers are particularly non-combustible materials (film ceiling structure, tent structure) certified by the Minister of Land, Infrastructure, Transport and Tourism. , Partition structures), especially glass fiber multifilament threads are preferred.

The fiber woven fabric used in the present invention is preferably a woven fabric made of multifilament yarn or a short fiber spun cloth (spun), and the multifilament yarn is in the range of 250 to 3000 denier (277 to 3333dtex), particularly. 500-2000 denier (555-2222dtex) is preferred, and untwisted yarn (oval or flat cross section) or twisted yarn can be used as needed. The short fiber spun yarn ranges from 10th (591dtex) to 60th (97dtex), especially 10th (591dtex), 14th (422dtex), 16th (370dtex), 20th (295dtex) and 24th (295dtex). 246dtex), 30th count (197dtex) and the like, these single yarns, twin yarns (single twisted yarns), combined twisted yarns made of two or more single yarns (multi-twisted yarns) and the like are preferable. There is no limit to the driving density of the warp and weft of the woven fabric, and any design can be made according to the thickness (denier, count) of the threads used, but the void ratio (openout) of the woven fabric is 0 to 30%. ^{A woven fabric having a grain size of 100 to 500 g / m 2} with a driving density in the range of 100 to 500 g / m 2 is suitable as a base material for an antistatic antibacterial film material. The porosity can be obtained as a value obtained by subtracting the area of the yarn occupying the unit area of the fiber woven fabric as a percentage and subtracting it from 100. Suitable for the production of forming an antistatic resin layer by heat-laminating a thermoplastic resin film on both sides of a woven fabric woven with multifilament threads (void ratio 7.5 to 30%), and short fiber spinning. In the case of cloth (spun), a short fiber spun cloth (spun) having a void ratio of 0 to 5% is preferably coated on both sides with a liquid thermoplastic resin to heat treatment, or dipping to heat treatment to provide an antistatic resin layer. Suitable for formation.

The antistatic resin layer is a soft vinyl chloride resin, an olefin resin (PE, PP), an olefin elastomer, an ethylene-vinyl acetate copolymer resin, an ethylene- (meth) acrylic acid (ester) copolymer resin, and a urethane resin. Thermoplastic resins (elastomers) such as elastomers, acrylic elastomers, styrene elastomers, polyester elastomers, fluoroelastomers, and silicone elastomers are used alone or in combination with blends, and one or more ethers in the molecule are used in these resins. Using a resin composition containing an ester compound having a bond and a cyclic polyether ion complex, coating processing, calendar rolling molding, or T-die extrusion molding was performed, and 100 to 1000 ^{g / m 2} per layer, particularly 200 to 500 g / m. ^{No. 2} film or sheet can be used, and a tarpaulin in which these antistatic resin layers are laminated is preferable. In the present invention, particularly, it is formed from a soft vinyl chloride resin composition (containing an ester compound containing one or more ether bonds in an alkyl chain), and coating or dipping using a paste vinyl chloride resin (emulsion polymerization type). It is preferable to form a film by gelling heat treatment, or to form a film by a vinyl chloride resin film (sheet) that is calendar-rolled or T-die extrusion-molded using a straight vinyl chloride resin (suspension polymerization type). The paste vinyl chloride resin is suitable for the coating layer of canvas, and the straight vinyl chloride resin is suitable for the coating layer of tarpaulin. The antistatic resin layer has not only vinyl chloride resin but also vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-acrylic acid ester copolymer resin, and vinyl chloride as the main chain and a vinyl acetate component in the side chain. , Or a graft resin having an acrylic acid ester component or a urethane component, a polymer alloy of vinyl chloride resin and urethane elastomer, a polymer alloy of vinyl chloride resin and polyester elastomer, a polymer alloy of vinyl chloride resin and styrene-based elastomer, etc. It may be.

Ester compounds having one or more ether bonds in the alkyl chain act as a conductive plasticizer, and such a conductive plasticizer is one or more selected from [Chemical formula 1] and [Chemical formula 2]. be. In particular, when the antistatic resin layer is composed of a soft vinyl chloride resin composition, the amount of the plasticizer with respect to the mass of the antistatic resin layer is 10 to 60% by mass (of a thermoplastic resin other than the soft vinyl chloride resin). In the case of 1 to 10% by mass), the occupancy rate of the conductive plasticizer [Chemical formula 1] and / or [Chemical formula 2] with respect to the amount of the plasticizer is preferably 50 to 100% by mass. The plasticizers used in combination with the conductive plasticizer [Chemical formula 1] and / or [Chemical formula 2] are phthalate ester-based plasticizers, isophthalate ester-based plasticizers, terephthalate ester-based plasticizers, and cyclohexanedicarboxylic acid esters. Plasticizers, cyclohexene dicarboxylic acid ester plasticizers, chlorinated paraffin plasticizers, polyester plasticizers, ethylene-vinyl acetate-carbon monoxide ternary copolymer resin, ethylene- (meth) acrylic acid ester-monooxide Examples thereof include a carbon ternary copolymer resin.

[Chemical 1]
R (AO) _n OOC-X-COO (AO) _m R
(In the formula, 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 to ₁₅ linear or branched alkyl group (R). Are the same or different from each other), A is: _{an alkylene group of C 2-4} , m and n are integers of 1 to 10 (compounds represented by the same or different from each other)

[Chemical 2]
R ₁ CO (OCH ₂ CH-R ₂ ) _n COOR ₃
(In the formula, R ₁ and R ₃ are: C _{3 to 15} linear or branched alkyl or alkenyl groups, R ₂ is: H, CH ₃ , C ₂ H ₅ , n is an integer of 3 to 20. Compound represented by)

As the dicarboxylic acid used for producing the ester compound of the above formula [Chemical formula 1], dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, succinic acid, brassic acid, tetrahydrophthalic acid and phthalic acid are preferable. The carboxylic acid used for producing the ester compound of the formula 2] is a monocarboxylic acid, a trivalent or higher polyvalent carboxylic acid, or a divalent carboxylic acid having an epoxycyclohexane ring. These carboxylic acids may have an alkyl group such as a methyl group or an ethyl group, or a substituent containing a hetero atom such as a hydroxyl group, oxygen, silicon or halogen. The monocarboxylic acid is preferably an aliphatic monocarboxylic acid having 2 to 22 carbon atoms, and is an aliphatic, alicyclic or aromatic polybasic acid composed of carboxylic acid residues having 3 to 8 carbon atoms. Is an aliphatic polyvalent carboxylic acid such as citric acid, aconitic acid, butane tricarboxylic acid, butane tetracarboxylic acid, an alicyclic carboxylic acid such as epoxyhexahydrophthalic acid, and aromas such as trimellitic acid and pyromellitic acid. Valuable carboxylic acids and acid anhydrides of these carboxylic acids can be used. The ester compounds of the above formula [Chemical formula 1] and the above formula [Chemical formula 2] are those using the above carboxylic acid alone or a mixture of two or more kinds.

Specifically, such a conductive plasticizer [Chemical formula 1] includes diethyl cellosolve phthalate, dibutyl cellosolve phthalate, diethyl cellosolve adipic acid, dibutyl cellosolve adipic acid, diethyl cellosolve azelaide, dibutyl cellosolve azelaline, and diethyl cello sebacate. , Dibutyl cellosolve sebacate, and other dicarboxylic acid alkyl cellosolve-based ester compounds, and reactions of dicarboxylic acids such as adipic acid and phthalic acid with mono- and poly-alkylene glycol monoalkyl ethers. Mono- and poly-alkylene glycol monoalkyl ethers are alcohol-ethylene oxide addition compounds such as propanol, butanol, hexanol, heptanol, octanol, nonanol, alcohol-propylene oxide addition compounds, and alcohol-butylene oxide addition compounds. Alternatively, it is an addition compound of alcohol and two or more alkylene oxides selected from alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide, and these are specifically ethylene glycol monooctyl ether, diethylene glycol monomethyl ether, and diethylene glycol. Monobutyl ether, diethylene glycol monoheptyl ether, triethylene glycol monomethyl ether, triethylene glycol monopropyl ether, tetraethylene glycol monoethyl ether, propylene glycol monoethyl ether, propylene glycol monooctyl ether, dipropylene glycol monobutyl ether, butylene glycol monoethyl Others such as (mono-poly) alkylene glycol monoalkyl ethers such as ethers, diethylene glycol di-2-ethylhexonate, tetraethylene glycol di-2-ethylhexonate, hexaethylene glycol di-2-ethylhexonate , Triethylene glycol diethylbutyrate, polyethylene glycol diethylbutyrate, polypropylene glycol diethylhexonate, triethylene glycol dibenzoate, tetraethylene glycol dibenzoate, polyethylene glycol dibenzoate, polypropylene glycol dibenzoate, or polyethylene glycol-2-ethyl. Hexonate benzoate and the like. The conductive plasticizer [Chemical formula 2] includes caprylic acid ester of triethylene glycol, octylate ester of tetraethylene glycol, diester of polyethylene glycol and 2-ethylacetic acid, and diester of polyester glycol and 2-ethylhexic acid. can give.

The chelate complex is one or more selected from silver ligand, copper ligand, zinc ligand, aluminum ligand, nickel ligand, lithium ligand, and cobalt ligand. The effect of the chelate complex (metal ion) reacting with the SH group of the protein involved in cell permeability on the surface layer of the fungus to inhibit enzymes and proteins necessary for vital activities, or the metal ion invading the cell is the fungus. By cross-linking the main-stranded DNA and inhibiting DNA replication, the growth of molds and algae is suppressed. Silver ions are sourced from silver salts such as silver bromide, silver chloride, silver citrate, silver iodide, silver lactate, silver nitrate, silver oxide, and silver picriate, and copper ions are disodium copper citrate and triethanolamine. Copper salts such as copper, copper carbonate, cuprous ammonium carbonate, cupric hydroxide, copper chloride, cupric chloride, ethylenediamine copper complex, copper oxychloride, copper sulfate oxychloride, cuprous oxide, copper thiocyanate Zinc ions are zinc acetate, zinc oxide, zinc carbonate, zinc chloride, zinc sulfate, zinc hydroxide, zinc citrate, zinc fluoride, zinc iodide, zinc lactate, zinc oleate, zinc oxalate, phosphoric acid. Sources are zinc salts such as zinc, zinc propionate, zinc salicylate, zinc selenate, zinc silicate, zinc stearate, zinc sulfide, zinc tannate, zinc tartrate, zinc valerianate, zinc gluconate, and zinc undecylate. Aluminum ions are supplied from aluminum salts such as aluminum oxide, aluminum hydroxide, aluminum chloride, aluminum phosphate, and aluminum sulfate, and nickel ions are nickel oxide, nickel hydroxide, nickel chloride, nickel sulfamate, nickel sulfate, etc. The source of lithium ions is lithium salts such as lithium carbonate, lithium chloride, lithium oxide, lithium hydroxide, and lithium citrate, and the cobalt ions are cobalt silicate, cobalt oxide, and cobalt chloride. The source is zinc salts such as cobalt aluminate and zinc sulfate. A chelate complex is obtained by ionic bonding a metal salt of these ion sources and a ligand via an appropriate solvent, and a dry-isolated one is used in the present invention.

The ligands are amino acids, ethylenediamine, diethylenetriamine, triethylenetetramine, pipyridine, acetylacetonate, ethylenediaminetetraacetic acid, hydroxyethylethylenediaminetriacetic acid, dihydroxyethylethylenediaminediacetic acid, 1,3-propanediaminetetraacetic acid, diethyltriaminepentaacetic acid. , Triethylenetetramine hexaacetic acid, pyrithione, phenanthroline, porphyrin, and crown ether. As the amino acid, one or more amino acids specifically selected from glycine, histidine, and methionine are preferable. In particular, crown ether is a cyclic polyether represented by [(9 + 3n) -crown- (3 + n)] formula: n is an integer of 1 or more, the first number is the total number of atoms, and the last number is oxygen. Represents the number of atoms. Further, as a benzo crown ether, at least one benzene ring was bonded to these [(9 + 3n) -crown- (3 + n)] crown ethers in common with two carbon atoms of the crown ether. A cyclohexyl in which at least one cyclohexane ring is shared and bonded to a benzo crown ether or a crown ether of these [(9 + 3n) -crown- (3 + n)] formulas with two carbon atoms of the crown ether. Sano crown ethers, aza crown ethers in which some or all of the oxygen atoms of the crown ether group are replaced with nitrogen atoms (NH), benzo aza crown ethers, cyclohexano aza crown ethers, and some of the oxygen atoms of the crown ether group. Alternatively, a thia crown ether in which all of them are replaced with sulfur atoms (S), a benzothia crown ether, a cyclohexanothia crown ether, and a part or all of oxygen atoms in the above crown ether group are nitrogen atoms (NH) and sulfur atoms (S). Examples thereof include azathia crown ethers substituted with, benzoazathia crown ethers, and cyclohexanoazathia crown ethers, in which functional groups and / or substituents are introduced into these crown ethers, and these crown ethers are used as repeating units. It may be a polymer having. Specific examples thereof include histidine silver, glycine copper, pyrithione zinc, pyrithione copper, triethylenetetramine copper, dibenzo24-crown-8 silver, and dibenzo24-crown-8 copper. These chelate complexes exhibit antibacterial and antifungal properties. The antibacterial property has an effect of suppressing the growth of Staphylococcus aureus, Escherichia coli, Pseudomonas aeruginosa, Pseudomonas aeruginosa, methicillin-resistant Staphylococcus aureus, enterohemorrhagic Escherichia coli and the like.

When the antistatic resin layer is composed of a soft vinyl chloride resin composition, 10 to 60% by mass with respect to the mass of the antistatic resin layer (1 to 10 mass% in the case of a thermoplastic resin other than the soft vinyl chloride resin). %), And the occupancy of the conductive plasticizer [Chemical formula 1] and / or [Chemical formula 2] with respect to the amount of the plasticizer is preferably 50 to 100% by mass. The combined mass ratio of the ester compounds described in paragraphs [0020] to [0022] and the chelate complexes described in paragraphs [0023] to [0024] is 100: 1 to 5: 1, particularly 50: 1 to 10: 1. Is preferable. Due to the presence of the ester compound and the chelate complex, an antistatic sheet having more excellent antistatic properties and antibacterial / antifungal properties can be obtained. In addition, antibacterial and antifungal properties may be insufficient, and if the content of the chelate complex exceeds 5: 1, the transparency of the antistatic resin layer may be insufficient.

Further, in the antistatic resin layer, stabilizers such as calcium-zinc composite system, barium-zinc composite system, organic tin laurate, organic tin mercaptite, and epoxy system can be used alone or in combination of two or more to prevent the charge of the present invention. It suppresses thermal deterioration and discoloration during the manufacture of sex antibacterial film materials, and further improves weather resistance. Further, the antistatic antibacterial film material of the present invention can be freely colored with a pigment, and in particular, coloring such as white or pastel makes the contrast of inkjet printing or marking film character insertion clear. In addition, various known additives for thermoplastic resins can be blended in various arbitrary amounts, and if necessary, flame retardant (phosphorus-containing compound, nitrogen-containing compound, inorganic compound, halogen-substituted organic compound), light-resistant stabilizer. (HALS), UV absorbers (benzotriazole-based, benzophenone-based, etc.), antioxidants (phenol-based), fluorescent whitening agents, antistatic agents, curing agents (isocyanate-based, etc.), insect repellents (pyresloid-based, etc.), Deodorants (silicon oxide / metal oxide composites, etc.), heat shield fillers (hollow particles, coarse-grained titanium oxide, etc.), fragrances, phosphorescent pigments (strontium aluminate, etc.), aluminum flake pigments, pearl pigments, inorganics It can contain fillers (calcium carbonate, barium sulfate, etc.) and the like.

In particular, the antistatic resin layer preferably contains a mold-proof organic compound, and examples of the mold-proof organic compound include molds, bacteria (gram-positive, gram-negative), cell walls of fungi, cell membranes, cytoplasm, and cell nuclei. On the other hand, it is an organic compound that exerts actions such as oxidative phosphorylation inhibition, electron transfer system inhibition, -SH group inhibition, DNA synthesis inhibition, cell epidermis function inhibition, lipid metabolism inhibition, chelate formation, etc., and specifically, an imidazole compound. , 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 Bisphenoxyalcin, 2- (4-thiazolyl) -benzimidazole is particularly preferred. These antifungal organic compounds include mesoporous silica, (synthetic) zeolite, titanium zeolite, zirconium phosphate, calcium phosphate, calcium zinc phosphate, hydrotalcite, hydroxyapatite, silica alumina, calcium silicate, magnesium silicate, magnesium silicate. It is preferably supported on one or more kinds of inorganic porous particles selected from calcium silicate soil and these treated products of a silane coupling agent. The content of these antifungal organic compounds or inorganic porous particle carriers contained in the antistatic resin layer (particularly the soft vinyl chloride resin composition) is 0.01 to 5% by mass with respect to the antistatic resin layer. , Preferably 0.1 to 1% by mass.

The antistatic effect can be further enhanced by forming the coating film layer on the entire surface or in a network on at least one surface of the flexible laminate. This coating film layer is 1). It contains at least one selected from carbon nanotubes, fullerenes and π-electron conjugated conductive polymers, and it is particularly preferable to contain a binder resin from the viewpoint of wear durability. The content of carbon nanotubes and / or fullerene is 0.1 to 6% by mass, preferably 0.3 to 3% by mass with respect to the coating layer, and the π-electron-conjugated conductive polymer is a single or acrylic type. It can be used in combination with a resin, a urethane resin, a fluorine-based copolymer resin, or the like at an arbitrary concentration, and these single resins or a combined resin can be used as a binder resin in combination with carbon nanotubes and / or fullerene. The binder resin contained in the coating layer is 94 to 99.9% by mass with respect to the coating layer, and the binder may be any of an organic compound, an inorganic compound, and a mixture of the organic compound and the inorganic compound, and the organic compound. Examples include (meth) acrylic resin, (meth) acrylic copolymer resin, (meth) acrylate radical polymer (ultraviolet curable resin), urethane resin, acrylic-modified urethane resin, silicon-modified urethane resin, and polyester-based resin. Examples thereof include vinyl acetate resin, vinyl chloride resin, vinyl chloride-vinyl vinegar copolymer resin, and fluorine-containing copolymer resin. Examples of the inorganic compound include metal oxide gels and / or metal hydroxide gels such as silica sol, alumina sol, zirconia sol, and niobium oxide, and sol-gel thin films mainly composed of silicon compounds such as polysiloxane, colloidal silica, and silica. .. 2). Further, on the coating layer of 1), one or more nanoparticles selected from silica, titanium oxide, zinc oxide, tin oxide, zirconium oxide, cerium oxide, and alumina, and a silane compound (methyltrimethoxysilane, Methyltriethoxysilane, etc.) is contained in a mixing ratio of nanoparticles and a silane compound or a hydrolysis product thereof, in a mass% ratio of 9: 1 to 4: 6, and 0.1 to 5 with respect to the coating layer. By forming a mass% nanoparticle network, the antistatic effect can be further enhanced.

Each of the coating film layers is a continuous having an area occupancy of 20 to 100%, preferably 35 to 70%, per one surface of the flexible laminate (relative to the area of the target surface on which the coating film layer is provided). ^{By attaching a conductive network of a conductive coating film of 0.05 to 20} g / m 2, preferably 0.5 to 10 g / m ² , on one side or both sides of the flexible laminate, the body is more charged. The prevention effect can be enhanced. Such a continuum (network) is a regular continuum such as a square grid, a triangular grid, a honeycomb, a round hole punching, a mesh, or an irregular continuum, as well as a single stroke character or pattern. An example is a honeycomb shape. Such a coating film layer (conductive network) is formed by a printing means using a gravure roll or a printing means using a rotary screen.

The carbon nanotubes have 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. By type, 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, carbon oxide nanotubes, and functionalization. One or more selected from carbon nanotubes (terminal modification and / or side wall modification) and metal (deposited or sputtered) carbon nanotubes, and the hexagonal arrangement (chiral index) constituting the carbon nanotubes is (n, n). It may be any of an armchair type, a (n, 0) zigzag type, and a (n, m) helical type. These carbon nanotubes can be further improved in conductivity when used in combination with oxides of transition metals such as Ru, Ir, W, Mo, Mn, Ni, and Co. In particular, a π-electron conjugated conductive polymer (described in paragraph [0032]) can also be used as a binder. In particular, metal (deposited or sputtered) carbon nanotubes are carbon nanotubes whose surface is metallized by vapor deposition or sputtering of Au, Ag, Cu, Al, Zn, Ti, etc., and have a two-layer structure in which the anchor is a Ti layer. Au / Ti, Ag / Ti, and Cu / Ti are effectively improved in conductivity.

As the fullerene, C ₆₀ fullerene, C ₇₀ fullerene, organically modified fullerene, inorganic modified fullerene, non-metal atom-encapsulating fullerene, metal atom-encapsulating fullerene, and the like can be used. C ₆₀ fullerenes are soccer ball-shaped cages composed of 20 faces of 6-membered rings and 32 faces of 12 faces of 5-membered rings, and organically modified fullerenes are one or more on the surface of _{C 60} or C _{70 fullerenes.} A polymer having a substituent and / or one or more functional groups, or a polymer in which a functional group-substituted fullerene is grafted on the side chain of the polymer. The metal-encapsulated fullerene can be added to any of the above fullerenes by Li, Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Ba, Ra, Sc, Y, Ti, Zr, lanthanoid, actinide atom, or It is the one in which metal ions are incorporated. Non-metal endohedral fullerenes include any of the above fullerenes, hydrogenated fullerenes containing H, carbonized fullerenes containing C, nitrogenized fullerenes containing N, oxygenated fullerenes containing O, sulfurized fullerenes containing S, and the like. be.

Specific examples of the π-electron-conjugated conductive polymer include 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 the side chain, the presence or absence of a substituent, the side chain, and the type of the substituent are not particularly limited, but polypyrrole, polythiophene, poly (N-methylpyrrole), and poly (3-methylthiophene). ), Poly (3-methoxythiophene), poly (3,4-ethylenedioxythiophene), etc., polypyrrole and polythiophene are particularly preferable, and poly (N-methylpyrrole), poly (3-methylthiophene), etc. Alkyl-substituted compounds are preferable because they have excellent solubility in organic solvents. In addition, a polymer carboxylate (polyacrylic acid, polymethacrylic acid, polymaleic acid, etc.) is doped into a π-electron-conjugated conductive polymer, or a polymer sulfonic acid (polyvinyl sulfonic acid, polystyrene sulfonic acid, polyisoprene sulfone, etc.) is doped. Doping acid, ethyl sulfonic acid polyacrylate, butyl sulfonic acid poly acrylate, poly (2-acrylamide-2-methyl-1-propane sulfonic acid), etc., or polymerized carboxylate and polymerized sulfone The conductivity can be further improved by combined doping with an acid at 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. The ratio of the ~ 1: 1, π-electron-conjugated conductive polymer to the polymer carboxylate and the polymer sulfonic acid is preferably 5: 1 to 1: 1, and the polymer carboxylate or the polymer. The carboxylate and the polymeric sulfonic acid coexist with the monomer of the π-electron-conjugated conductive polymer during the synthesis of the π-electron-conjugated conductive polymer, and the π-electron-conjugated system during the oxidative polymerization of the π-electron-conjugated conductive polymer synthesis. It is preferably doped in a conductive polymer.

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., the antistatic antibacterial film material of the present invention is bonded to each other (aligned on the same surface). (End overlap bonding) can be joined by high frequency vibration using a high frequency welder machine. Specifically, a film material is placed between two electrodes (one electrode is a weld bar), and a potential difference oscillating at a high frequency (1 to 200 MHz) is applied while pressurizing with the weld bar to prevent the film material from being charged. The sex resin layer is fused by being melted and softened by molecular frictional heat, and then cooled and solidified in that state to obtain a bonded body. Further, an ultrasonic fusion method in which the amplitude of ultrasonic energy (16 to 30 KHz) generated from an ultrasonic vibrator is amplified and fusion is performed by utilizing the frictional heat generated at the interface of the film material, or the electric heater. A hot air fusion method in which hot air set steplessly at 100 to 700 ° C. is blown between the membrane materials through a nozzle to melt and soften the surface of the membrane material, and the membrane material is crimped and fused immediately after passing through the nozzle. Bonding is possible by a hot plate fusion method or the like in which the adherend is crimped and fused using a mold (iron) that has a built-in heater and is heated above the melting temperature of the antistatic resin layer. In the above bonding method, when the area occupancy of the coating film layer is 90 to 100%, the compatibility between the binder resin of the coating film layer and the antistatic resin layer is poor, or the temperature difference of the softening temperature is large. Since the bonding adhesive force between the obtained film materials becomes insufficient, the area occupancy of the coating film layer is set to 35 to 70%, and the region other than the coating film layer, that is, the antistatic resin layer whose surface is exposed is already used. It is desirable to provide a state in which the antistatic resin layers on the back surface of one of the film materials are at least thermally melted and can be firmly adhered to each other.

Next, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited to the scope of these examples. In the following examples and comparative examples, the effect of the antistatic antibacterial film material was evaluated by the surface resistivity.
(1) Surface resistivity measurement (JIS K7194 compliant)
After allowing the film material piece to stand at 23 ° C. and a relative humidity of 50% RH for 24 hours, the surface resistivity was measured three times using the following resistivity meter (JIS K7194 compliant), and the average value was taken as the surface resistivity. However, since the quality of the surface resistivity depends on the blending amount of the conductive material, the quality of the antistatic property was judged on the premise of having the "low colorability" which is the subject of the present invention. ..
The antistatic properties used as examples were those having a surface resistivity of 10 ⁵ Ω / □ to 10 ⁹ Ω / □ and a surface resistivity of 10 ¹⁰ Ω / □ or less as comparative examples.
1) High resistance / resistivity meter "High Resta UP MCP-HT800 (range 10 ³ to 10 ¹⁴ Ω)" manufactured by Mitsubishi Chemical Analytech Co., Ltd.
2) Low resistivity / resistivity meter "Loresta GX MCP-T700 (range 10 ^-4 to 10 ⁷ Ω)" manufactured by Mitsubishi Chemical Analytech Co., Ltd.
(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 cells were cultured in an environment of 35 ° C. ± 1 ° C. and a relative humidity of 90% or more for 24 hours ± 1 hour. After that, the test piece sheet was washed away, ^{the viable cell count per 1 cm 2 of} the test piece sheet was measured, and the antibacterial activity value (value obtained by subtracting the bacterial count logarithmic value in the sheet produced in the example from the bacterial count logarithmic value in the target group). Was calculated. The target group was a sheet to which no cyclic polyether ion complex was added. A 1/200 NB medium was used as the bacterial solution adjusting solution. The bacterial species used are shown below. The numerical value in the table is the ^{number of viable bacteria per 1 cm 2} of the test piece, and "ND" is defined as "Not Detected".
Staphylococcus aureus subsp. Aures 12732
Escherichia coli NBRC 3972
(3) Mold resistance (JIS Z2911 culture test)
A test piece sheet having a width of 3 cm and a length of 3 cm was inoculated with the following test mold spores, placed on a potato dextrose agar medium, and observed in a petri dish at 28 ° C. for 7 days. It was evaluated by the judgment criteria.
1: No hyphal growth is observed in the inoculated part of the test piece 2: The area of the hyphal growth part observed in the inoculated part of the test piece does not exceed 1/3 of the total area 3: Admitted in the inoculated part of the test piece <Test mold> (A) + (B) + (C) mixed mold where the area of the growing part of the hyphae exceeds 1/3 of the total area
(A) Aspergillus niger NBRC 105649 (black mold)
(B) Penicillium citrinum NBRC 6352 (Penicillium)
(C) Cladosporium cladosporioides NBRC 6348 (Kurokawa mold)

[Example 1]
Polyester fiber plain woven base fabric (warp 1111dtex multifilament yarn: yarn density 22 / 2.54 cm × weft 1111dtex multifilament yarn: yarn density 24 / 2.54 cm: void ratio 21%: mass 165 g / m ² ) As a base material, a 0.2 mm thick calendar molded film made of the following soft vinyl chloride resin composition (1) is used as an antistatic resin layer on both sides thereof, and a bridge melt laminate is performed by thermal pressure bonding to obtain a "antistatic resin layer /. A tarpaulin (1) having a thickness of 0.75 mm and a mass of 785 g / m ^{2 composed of a "base cloth / antistatic resin layer" was obtained.}
<Soft vinyl chloride resin composition (1)>
Vinyl chloride resin (degree of polymerization 1300) 100 parts by mass Conductive plasticizer (1) 30 parts by mass * Adipic acid diester by reaction between alcohol with ethylene oxide added to n-octanol and adipic acid: (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 Tricredil phosphate (flameproof plasticizer) 10 parts by mass Eoxidized soybean oil (stabilizer and plasticizer) 5 parts by mass Barium / zinc composite stabilizer 2 parts by mass Antimon trioxide (flame retardant) 10 parts by mass Rutyl type Titanium oxide (white pigment) 5 parts by mass Bentriazole skeleton compound (ultraviolet absorber) 0.3 parts by mass Histidine silver (chelate complex 1) 1 part by mass * The combined mass ratio of conductive plastic agent (1) and chelate complex 1 is 30: 1

[Example 2]
In the tarpaulin (1) of Example 1, 30 parts by mass of the conductive plasticizer (1) of the soft vinyl chloride resin composition (1) was added to n-octanol with ethylene oxide added to phthalic acid by the reaction of alcohol and phthalic anhydride. Diester: Conductive plasticizer (2): (corresponding to ester compound [Chemical Formula 1] having two ether bonds), thickness 0.75 mm, mass 785 g in the same manner as in Example 1 except that it was replaced with 30 parts by mass. A tarpaulin (2) of / m ^{2 was obtained.}

[Example 3]
In the tarpaulin (1) of Example 1, 30 parts by mass of the conductive plasticizer (1) of the soft vinyl chloride resin composition (1) is sebacic acid obtained by reacting sebacic acid with an alcohol obtained by adding propylene oxide to n-octanol. Diester: Conductive plasticizer (3): (corresponding to ester compound [Chemical formula 1] having two ether bonds), thickness 0.75 mm, mass 785 g in the same manner as in Example 1 except that it was replaced with 30 parts by mass. A tarpaulin (3) of / m ^{2 was obtained.}

[Example 4]
In the tarpaulin (1) of Example 1, 30 parts by mass of the conductive plasticizer (1) of the soft vinyl chloride resin composition (1) was added to the octyl acid ester of tetraethylene glycol: the conductive plasticizer (4) :( ether. A tarpaulin (4) having ^{a thickness of 0.75 mm and a mass of 785 g / m 2} was obtained in the same manner as in Example 1 except that the ester compound [Chemical formula 2] having three bonds was replaced with 30 parts by mass.

[Example 5]
In the tarpaulin (1) of Example 1, 1 part by mass of histidine silver (chelate complex 1) of the soft vinyl chloride resin composition (1) was replaced with 1 part by mass of copper ethylenediaminetetraacetic acid (chelate complex 2). A tarpaulin (5) having a thickness of 0.75 mm and a mass of 785 g / m ^{2 was obtained in the same manner as in Example 1.}

[Example 6]
In Example 1 except that 1 part by mass of histidine silver (chelate complex 1) of the soft vinyl chloride resin composition (1) was replaced with 1 part by mass of glycine copper (chelate complex 3) in the tarpaulin (1) of Example 1. In the same manner as above, a tarpaulin (6) having a thickness of 0.75 mm and a mass of 785 g / m ^{2 was obtained.}

[Example 7]
In the tarpaulin (1) of Example 1, 1 part by mass of histidine silver (chelate complex 1) of the soft vinyl chloride resin composition (1) was replaced with 1 part by mass of silver ethylenediaminetetraacetic acid (chelate complex 4). A tarpaulin (7) having a thickness of 0.75 mm and a mass of 785 g / m ^{2 was obtained in the same manner as in Example 1.}

[Example 8]
In the tarpaulin (1) of Example 1, 1 part by mass of histidine silver (chelate complex 1) of the soft vinyl chloride resin composition (1) was replaced with 1 part by mass of dibenzo18-crown-6 silver (chelate complex 5). A tarpaulin (8) having a thickness of 0.75 mm and a mass of 785 g / m ^{2 was obtained in the same manner as in Example 1 except for the above.}
* Chelate complex 5: -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-) Supports silver ions

[Example 9]
On the antistatic resin layer on the surface side of the tarpaulin (1) of Example 1, a coating liquid (solid content concentration 16.9% by mass) for the following coating film layer (1) was used, and a 120-mesh square lattice was used. By the pattern gravure roll coating, a coating film layer (1) of a grid-like continuum (lattice width 5 mm, square pores 10 mm × 10 mm) having an area occupancy of 55.5% was formed, and a mass of 787 g / m ² was formed. A tarpaulin (9) was obtained.
<Solution for coating film layer (1)>
Methyl methacrylate resin (acrylic resin) 100 parts by mass Single-walled carbon nanotube (1.5 to 2.5 nm in diameter) 0.5 parts by mass Benzotriazole skeleton compound (ultraviolet absorber) 0.3 parts by mass Methyl ethyl ketone (diluting solvent) 250 Parts by mass Toluene (diluting solvent) 250 parts by mass

[Example 10]
0.5 parts by mass of the single-walled carbon nanotubes of the solution for the coating layer (1) of Example 9 _{was changed to 0.5 parts by mass of fullerene C 60} (diameter 1.01 nm), and this solution was changed to the coating layer (2). A tarpaulin (10) having ^{a thickness of 0.75 mm and a mass of 787 g / m 2} was obtained in the same manner as in Example 9 except that the coating layer (2) was formed by using the solution as a solution.

[Example 11]
The tarpaulin (11) ^{having a thickness of 0.75 mm and a mass of 787 g / m 2} is the same as that of Example 9 except that the solution for the coating film layer (1) of Example 9 is changed to the solution for the coating film layer (3) below. Got
<Solution for coating film layer (3)>
Poly (3,4-ethylenedioxythiophene) * 70 parts by mass of polythiophene Methyl methacrylate resin (acrylic resin) 30 parts by mass Benzotriazole skeleton compound (ultraviolet absorber) 0.3 parts by mass Methyl ethyl ketone (diluting solvent) 250 parts by mass Toluene (Diluting solvent) 250 parts by mass

[Example 12]
A tarpaulin (12) ^{having a thickness of 0.75 mm and a mass of 787 g / m 2 was} the same as in Example 9 except that the solution for the coating film layer (1) of Example 9 was changed to the solution for the coating film layer (4) below. Got
<Solution for coating film layer (4)>
Poly (3,4-ethylenedioxythiophene) * 70 parts by mass of polythiophene Methyl methacrylate resin (acrylic resin) 30 parts by mass Organosilica sol (silica nanoparticles) 40 parts by mass * Particle size 10 to 15 nm: Solid content 30% by mass : Methyl ethyl ketone solvent Methyl triethoxysilane (silane compound) 8 parts by mass * A nanoparticle network with a mass ratio of silica sol and methyl triethoxysilane of 3: 2 is formed in the coating layer. Parts by mass Methyl ethyl ketone (diluting solvent) 250 parts by mass Toluene (diluting solvent) 250 parts by mass

[Effects of Examples 1 to 8]
Ester compounds having one or more ether bonds in the molecule, and tarpaulin (1) comprising an antistatic resin layer containing a chelate complex to (8) are each a surface resistivity of 10 ⁹ Ω / □ or degree , It had better antistatic properties, and also had antibacterial and anti-mold properties. Especially on tarpaulin (1) of Example 1, the coating layer of the grid-shaped continuum (1) tarpaulins added to (4) (9) to (12) are all surface resistivity 10 ⁶ Ω~10 ^It had excellent antistatic properties of 8 Ω / □, and also had antibacterial and antifungal properties.

[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. Substituted with 30 parts by mass, the plasticizer in the soft vinyl chloride resin composition was 50 parts by mass of 4-cyclohexene-1,2-dicarboxylate bis (2-ethylhexyl), and the plasticizer having an ether bond in the molecule was contained. A tarpaulin (13) having a ^{mass of 785 g / m 2} was obtained in the same manner as in Example 1 except that it was not used. ^{The antistatic property of the obtained tarpaulin was 8.5 × 10 11} Ω / □, which was inferior to that of the tarpaulin (1) of Example 1, but the antibacterial and antifungal properties were good.

[Comparative Example 2]
In the laminated film material (1) of Example 1, a tarpaulin ^{having a mass of 785 g / m 2} is the same as that of Example 1 except that the chelate complex (1) of the soft vinyl chloride resin composition (1) and 1 part by mass are omitted. 14) was obtained. The antistatic property of the obtained tarpaulin was 4.8 × 10 ¹² Ω / □, which was inferior to that of the tarpaulin (1) of Example 1, and the antibacterial and antifungal properties were also inferior.

As is clear from the above Examples and Comparative Examples, according to the present invention, antibacterial and antistatic properties having more excellent antistatic properties are used without using an antistatic agent such as a surfactant or carbon black. Since the antistatic sheet can be obtained, it can be widely used for industrial material sheets such as sheet shutters, partitions, floor sheets, equipment covers, and aprons.

Claims (6)

A flexible laminate having a woven fabric as a base material and having at least one antistatic resin layer provided on the base material, and the antistatic resin layer has one or more ether bonds in the molecule. The chelate complex contains a liquid ester compound having a silver ligand, a copper ligand, a zinc ligand, an aluminum ligand, a nickel ligand, a lithium ligand, and a cobalt. An antistatic antibacterial film material, which is one or more selected from ligands. The antistatic antibacterial film material according to claim 1, wherein the liquid ester compound is at least one selected from [Chemical formula 1] and [Chemical formula 2].

[Chemical 1]
R (AO) _n OOC-X-COO (AO) _m R
(In the formula, 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 to ₁₅ linear or branched alkyl group (R). Are the same or different from each other), A is: _{an alkylene group of C 2-4} , m and n are integers of 1 to 10 (compounds represented by the same or different from each other)

[Chemical 2]
R ₁ CO (OCH ₂ CH-R ₂ ) _n COOR ₃
(In the formula, R ₁ and R ₃ are: C _{3 to 15} linear or branched alkyl or alkenyl groups, R ₂ is: H, CH ₃ , C ₂ H ₅ , n is an integer of 3 to 20. Compound represented by) The ligands of the chelate complex are amino acids, ethylenediamine, diethylenetriamine, triethylenetetramine, pipyridine, acetylacetonate, ethylenediaminetetraacetic acid, hydroxyethylethylenediaminetriacetic acid, dihydroxyethylethylenediaminediacetic acid, 1,3-propanediaminetetraacetic acid, The antistatic antibacterial film material according to claim 1 or 2, which is one or more selected from diethyltriamine pentaacetic acid, triethylenetetramine hexaacetic acid, pyrithione, phenanthroline, porphyrin and crown ether. The antistatic antibacterial film material according to any one of claims 1 to 3, wherein the combined mass ratio of the liquid ester compound and the chelate complex is 100: 1 to 5: 1. A coating film layer is entirely formed or reticulated on at least one surface of the flexible laminate, and the coating film layer is one selected from carbon nanotubes, fullerenes, and π-electron conjugated conductive polymers. The antistatic antibacterial film material according to any one of claims 1 to 4, which includes the above. The antistatic antibacterial film material according to claim 5 , wherein the coating film layer is a continuous body having an area occupancy of at least 20% with respect to one surface of the flexible laminate.