JPH07148882A - Conductive structure - Google Patents

Abstract

PURPOSE:To develop a conductive structure keeping almost permanently suitable conductive performance, which is equipped with an electric conductivity on a surface and free from generation of fuzz of conductive fiber or its omission therefrom. CONSTITUTION:A composition for curing [principal component: polyester acrylate prepolymer containing 50wt.% of zinc oxide powder] is applied to a PP film, and cured by irradiating it with electron beams to make a thermoplastic film C with a crosslinked cured film (c1) on one side surface. Separately, a conductive unwoven fabric (B; weight per unit area 50g/m<2>) is prepared of 30wt.% of pitch based carbon fiber and 70wt.% of PP based composite fiber. Then, the B is superimposed on one side surface of a base material PP sheet A (1mm thickness). Further, the C is superimposed so that its resin side comes in contact with the B. A laminated material of the A, B, and C is integrated by fusion weld by passing it through a heating roll and a cooling roll to obtain a conductive structure. In that case the (c1) comes in contact with the heating roll. Thereby, injury-receiving resistance becomes about three times, and ommission of the conductive fiber comes to be all gone.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a conductive structure having a conductive surface. More specifically, the present invention relates to a conductive structure that does not cause fluffing of conductive fibers from the structure, has almost permanent suitable conductive performance, and has excellent wear resistance.

[0002]

2. Description of the Related Art As a measure for semi-permanently imparting conductivity to the surface of an electrical insulator (hereinafter sometimes simply referred to as "insulator"), the surface of a substrate is randomly entangled with conductive fibers. A conductive structure having a structure in which a heat-meltable fiber and a heat-meltable fiber are fixed to each other in a mesh shape by heat melting is already known (Japanese Patent Publication No.
(See Japanese Patent No. 12175). However, in the conductive structure, fluffing of the conductive fibers still clearly occurs, and deficiencies in scratch resistance (scratch resistance) and abrasion resistance remain.

As another measure, a nonwoven fabric is formed on at least one surface of the thermoplastic resin film, and the heat-fusible fibers and the conductive fibers are irregularly entangled and fused and integrated, and then the surface of the nonwoven fabric is treated. There is also known a conductive thermoplastic resin sheet obtained by applying a curing composition containing an unsaturated resin and a reactive diluent as its main components to the treated surface and then curing the applied composition (Japanese Patent Publication No. 5-20270). reference). Although this conductive thermoplastic resin sheet shows an improvement in scratch resistance and abrasion resistance, fluffing of conductive fibers is still observed on the surface of the sheet when observed with an electron microscope, so that electronic parts are transported. As a material for the tray or the box, a floor material or a wall material for a clean room or the like still needs improvement.

Further, even if the conventional conductive thermoplastic resin sheet is used for applications such as a bag, a tray, a box, a partition plate or a desk mat for handling an IC, an LSI or a printed circuit board which are not sensitive to static electricity, I met when it couldn't be used. In particular, when the conductive fibers in the sheet are carbon fibers or corrosion-resistant steel (stainless steel), the circuit may be damaged as a result of a sudden electrostatic charge outflow from the charged IC or LSI. The cause lies in the too high conductivity of the conductive fibers.

As a measure for solving the above-mentioned problems of the conventional conductive non-woven fabric, there is also known a conductive polypropylene-based sheet having a structure in which a non-conductive non-woven fabric is laminated on the outer side of the conductive non-woven fabric ( (See Japanese Patent Laid-Open No. 64-26435). However, with this configuration, the following problems occurred: -The desired conductivity cannot be obtained when processed at a temperature that is too low. The cause is that the conductive fiber does not appear in the surface layer. ・ Highly rigid conductive fiber such as carbon fiber and corrosion resistant steel fiber easily protrudes into the surface layer. ・ Conductive fiber when processed at too high temperature. It is impossible to adjust (control) to an appropriate conductivity in addition to always falling off.-Due to insufficient scratch resistance, it is a bag, tray, box or partition plate that is used repeatedly, or dragging under constant load, etc. It is difficult to use for desk mats or floor materials exposed to.

[0006]

DISCLOSURE OF THE INVENTION The present invention fundamentally solves the problems associated with the conventional conductive sheet as described above, and is a conductive sheet which is worn even when worn due to use. It is an object of the present invention to provide a conductive structure that does not fall off, is excellent in scratch resistance and wear resistance, and can maintain appropriate conductive performance substantially permanently, easily and economically.

[0007]

The conductive structure of the present invention has the constitutions described in the following "basic constitution" and "improved constitution 1" to "improved constitution 5": [basic constitution] substrate ( Conductive fiber on at least one side of A)
(b1) a conductive cloth material (B) is overlaid, and a thermoplastic resin film having a cross-linked cured film (c1) on one surface thereof
(C) the base material (A) of the multilayer body laminated so that its thermoplastic resin surface is in contact with the cloth-like material (B), the cloth-like material (B) and the thermoplastic resin film (C ) A conductive structure having a structure in which the respective layers are fused and integrated.

[Improved Structure 1] The conductive structure according to "Basic Structure", in which the tensile modulus of the conductive fiber (b1) is 2,000 kgf / mm ² or more.

[Improved Structure 2] The conductive structure according to "Basic Structure" and "Improved Structure 1", in which the crosslinked cured film (c1) exhibits conductivity.

[Improved Structure 3] The crosslinked cured film (c1) has a surface resistivity of 10 ⁴ to 10 ⁸ Ω / □ and is described in "Basic Structure", "Improved Structure 1" and "Improved Structure 2". Conductive structure.

[Improved Structure 4] The "basic structure" and "improved structure 1" to "improved structure 3" in which the crosslinked cured film (c1) is a cured film containing an acrylate prepolymer / monomer as a main component.
The conductive structure according to.

[Improved Structure 5] The crosslinked cured film (c1) is a cured film obtained by electron beam irradiation with an electron beam acceleration voltage of 125 kv to 300 kv and a dose of 1 Mrad to 20 Mrad, "basic structure" and "improved structure 1" to "improved structure". 4] The conductive structure according to item 4.

[Specific Structure of the Invention] The base material (A) used for preparing the conductive structure of the present invention is a plate-like material, and is not limited to a single plate but a composite plate (laminated plate). Specifically, sheets, films, woven fabrics, non-woven fabrics, papers, synthetic papers, chipboards (particle boards) and plates [metal plates, glass plates, mica (mica), etc.], etc., and composite plates thereof ( Hereinafter, may be collectively referred to as "sheet-like material"), the material is synthetic resin, synthetic fibers, natural fibers (wood fibers, animal fibers, mineral fibers, etc.), metal fibers, glass fibers, Examples include rock wool (rock wool) and whiskers (whiskers).

Among these plate-like materials, the preferred one as the base material (A) is one having a synthetic resin sheet, especially a thermoplastic resin sheet or film mounted on the surface thereof. The reason is that the conductive cloth (B) to be laminated on the surface of the substrate (A) and the thermoplastic resin film (C) exhibit favorable adhesive strength to both non-crosslinked cured side surfaces of the thermoplastic resin film (C). .

[Conductive Cloth (B)] As the conductive cloth (B), a conductive non-woven fabric, a conductive woven fabric and a conductive knitted fabric containing at least a part of the conductive fiber (b1) are used. Can be mentioned. These conductive cloth materials (B) are conductive fibers (b1)
In addition to, the following various fibers (c2) are also included: -Low temperature side meltable fiber (c2) [also includes low temperature side meltable composite fiber (c2)] constitutes a thermoplastic resin film (C) Those that melt below the melting point (Tm) of the thermoplastic resin High temperature side meltable fiber (c2) [including high temperature side meltable composite fiber (c2)] Thermoplastic resin that constitutes the thermoplastic resin film (C) Those that melt above the melting point (Tm) ・ Non-melting fiber (c2).

For the above-mentioned various fibers (c2), the purpose is selected from additives such as heat resistance stabilizers, weather resistance stabilizers, antistatic agents, pigments, dyes, antibacterial agents or antifungal agents (antifungal agents). Appropriate ones are blended according to.

The basis weight of the conductive cloth material (B) is not particularly limited, but is usually selected in the range of 10 to 100 g / m ² , preferably 20 to 100 g / m ² . When it is much lower than this lower limit, it is difficult to manufacture. On the contrary, when it is much higher than the upper limit, no performance problem occurs, but it is economically disadvantageous.

The content of the electrically conductive fibers (b1) in the electrically conductive cloth (B) is not particularly limited, but is usually in the range of 3 to 70% by weight. Within this range, the conductive cloth material (B) is easy to manufacture and economically disadvantageous.

The conductive fibers (b1) may include the following: -A composite fiber comprising a metal fiber and a synthetic fiber or a metal compound fiber and a synthetic fiber-A metal-coated synthetic fiber or a metal compound-coated synthetic fiber- Metal-coated glass fiber or metal compound-coated glass fiber-Metal coated carbon fiber or metal compound-coated carbon fiber-Carbon fiber or carbon composite fiber-Carbon fiber-composite fiber composed of synthetic fiber-Carbon-coated synthetic fiber or carbon-coated composite synthetic fiber- Metal fiber or metal compound fiber-A conductive composite fiber which is a combination of conductive fibers selected from two or more of the above-mentioned various conductive fibers (b1) group.

The present inventors have examined each of the above-mentioned various conductive fibers (b1) and found that the tensile elastic modulus is 2,000 kgf.
When using a conductive fiber having a high elasticity of / mm ² or more,
It has been found that the following effects are exhibited: -Preferable conductive fibers are carbon fibers and corrosion-resistant steel fibers-Crosslinked cured film that penetrates the thermoplastic resin film (C) during heat fusion and is located on the back side thereof ( It can easily come into contact with c1), and this contact improves the conductivity of the crosslinked cured film in the conductive structure formed by heat fusion rather than the conductivity of the crosslinked cured film before heat fusion.

The thermoplastic resin which is the material of the thermoplastic resin film (C) constituting the conductive structure of the present invention includes the following: ・ Polyolefin resin: polyethylene, polypropylene, ethylene-acetic acid Vinyl copolymer, etc .; Styrene resin: acrylonitrile-butadiene-styrene copolymer (ABS), acrylonitrile-styrene copolymer resin, etc .; Acrylic resin: polymethylmethacrylate (PMM)
A), ethylene-ethyl acrylate (EEA), etc.;-Polyamide resin: 6-nylon, 7-nylon, 12-nylon, 66-nylon (6,6-nylon), 610-nylon (6,10-
Nylon), 612-Nylon (6,12-Nylon), etc. ・ Polyester resin: polyethylene terephthalate (PET), polyethylene terephthalate isophthalate (PEIT), polybutylene terephthalate (PB)
T) etc.;-Polyhalogen-containing vinyl resin: polyvinyl chloride resin (PVC), polyvinylidene chloride resin (PVDC), etc.-Polycarbonate resin (PC): bisphenol F
Type, bisphenol A type, bisphenol AD type (using bisphenol obtained from acetaldehyde as a raw material), bisphenol AP type (using bisphenol obtained from acetophenone as a raw material) and bisphenol BP type (using bisphenol obtained from benzophenone as a raw material) -Ionomer resin: ethylene-sodium methacrylate copolymer, ethylene-zinc methacrylate copolymer, etc.-Polyurethane resin (PU): ethylene glycol (E
G) -Tolylene diisocyanate (TDI) co-condensate, etc .; Two or more combinations of one or more resins selected from the above groups (mixed resin; resin composition).

Among the above-mentioned groups, preferable thermoplastic resins include those which are easily softened by heating and have a low melt viscosity upon heating and include the following: -Polyolefin resins such as polyethylene and polypropylene. -Halogen-containing vinyl resin such as (poly) vinyl chloride resin and (poly) vinylidene chloride resin.

As additives to the above-mentioned thermoplastic resins, oxidation resistance stabilizers, heat resistance stabilizers, weather resistance stabilizers, light resistance stabilizers, plasticizers, lubricants, nucleating agents (nucleating agents, nucleating agents), antistatic agents. In addition to a flame retardant, an antibacterial agent, an antifungal agent, a pigment, a dye, an inorganic filler, and an organic filler, a charge transfer type polymer, a conductive filler and the like can be appropriately blended according to the purpose of use.

[Thermoplastic Resin Film (C)] The thermoplastic resin film (C) may be stretched. The thickness is usually 10 to 1000 μm (1 mm), preferably 15 to 500
Select to μm (0.5 mm). It is generally difficult to produce ultrathin films well below the above lower limits. On the other hand, an extremely thick film (sheet) that greatly exceeds the above upper limit causes difficulty in heat fusion, and the conductive fibers (b1) protruding from the conductive cloth (B) are difficult to contact with the crosslinked cured film. Often comes the difficulty of becoming.

The above-mentioned thermoplastic resin film (C) may be subjected to a surface treatment to improve its adhesiveness to the crosslinked cured film (c1). This type of surface treatment includes chemical treatment (oxidation treatment, partial elution treatment, etc.), coupling treatment,
Examples thereof include primer treatment, plasma treatment, corona discharge treatment and the like.

[Crosslinked cured film (c1)] The main component (trunk polymer) of the crosslinkable resin material (prepolymer) forming the crosslinked cured film (c1) laminated on one surface of the thermoplastic resin film of the present invention The following can be mentioned as examples: -Epoxy resin-Polyester resin-Polyurethane resin-Polyamide resin-Melamine resin-Polyether resin-Polyol resin-Ester formation that can remain at the terminal or side chain of the trunk molecule in the above resins Prepolymers in which an acryloyl group is introduced into the above groups, for example, the following are preferable in that they exhibit high radiation activity, and among them, polyester acrylate is preferable: -Polyepoxy acrylate-Polyester acrylate-Polyurethane acrylate-Polyether acrylate Required for various prepolymers Flip can be added a reactive diluent. Examples of the reactive diluent include the following: Monofunctional monomers: vinylpyrrolidone, 2-hydroxyethyl (meth) acrylate, butoxyethyl acrylate, ethyldiethylene glycol acrylate,
2-Ethylhexyl acrylate, etc .; Polyfunctional monomer: trimethylolpropane triacrylate, pentaerythritol acrylate, ethylene glycol diacrylate, triacryloxyethyl phosphate; ... One or more selected from any of the above groups Or a combination of one or more monofunctional monomers and polyfunctional monomers each selected from both groups.

In the present invention, various additives are added to the curable composition in order to impart conductivity to the crosslinked cured film (c1). The additive is an antistatic filler, a charge transfer complex type polymer or the like, but it is capable of reacting with a curable composition as an antistatic agent and an electrically conductive filler in order to permanently exhibit electrically conductive performance. Is preferably used.

The above-mentioned antistatic agents may include the following: -nonionic surfactants-cationic surfactants-anionic surfactants-amphoteric surfactants.

No particular difference is found in the performance of any of the above-mentioned surfactants, but in order to enhance the durability of the antistatic performance and reduce the performance deterioration due to washing with water, etc., It is preferable to use the above-mentioned antistatic agent capable of reacting with the acrylate prepolymer or the acrylate reactive monomer. Examples of such antistatic monomers or antistatic polymers include the following: (meth) acryloyloxyethyltrimethylammonium chloride, (meth) acryloyloxyethyltrimethylammonium bromide, (meth) acryloyloxy. Ethyl trimethyl ammonium methosulfate, polyethylene glycol mono (meth) acrylate, acrylic acid adduct of polyethylene glycol mono (meth) acrylate / glycidyl (meth) acrylate copolymer, polyethylene glycol mono (meth) acrylate-glycidyl (meth) acrylate Glycidyl acrylate adduct of polymer, 3-chloro-2-hydroxypropyl (meth) acrylate, 3-bromo-2-hydroxypropyl (meth) acrylate DOO, methyl oleate -
Sodium taurate phosphate, trialkyl alkyl ether ammonium salt, trialkyl alkyl ether ammonium sulfate, alkylbenzene sulfonic acid triethanol (methanol) amine and the like.

Among the above-mentioned antistatic agents, the quaternary ammonium salt-containing material can exhibit the desired conductive performance at 1 to 30% by weight (composition basis). The reason is that this antistatic agent is excellent in antistatic effect, so that it can exhibit sufficient performance even with a smaller compounding amount than other antistatic agents, and in addition, in the conductive cloth (B) It is interpreted that the synergistic contribution with the conductive fiber (b1) contained in is added.

The above-mentioned conductive filler is not particularly limited as long as it does not significantly impair the coating suitability of the composition for forming a cured film on its surface, and carbon black,
Powdered metal, metal oxide, metal-coated titanium oxide or the like or fibrous material, for example, ultrafine short fibers such as vapor grown carbon fiber, metal-coated or metal oxide-coated potassium titanate whiskers (whiskers) Etc. can be mentioned.

The content of these conductive fillers is 10 to 50% by weight in the granular filler and 5 to 20% by weight in the fibrous filler, as in the case of the antistatic agent described above, the conductive cloth material (B) is used. The desired conductive performance is obtained by a synergistic action with the conductive fiber (b1) inside.

The crosslinkable and curable composition of the present invention is a thermoplastic resin film constituting the conductive structure of the present invention.
It is a raw material for the crosslinked cured film (c1) in (C), and may further contain various additives, if necessary. Examples of the additive include synthetic polymer substances, natural polymer substances, antibacterial agents, antifriction agents, pigments, dyes, matting agents, plasticizers, viscosity modifiers, solvents and various other auxiliaries listed below. Can be mentioned.

The antibacterial agents added to the conductive cloth (B) of the present invention include organic antibacterial agents and inorganic antibacterial agents, and applicable bacteria thereof include Escherichia coli, Salmonella, Pseudomonas aeruginosa, Staphylococcus aureus and the like. Not only bacteria, black koji mold, flavus koji mold,
It is also effective against fungi such as blue mold, Fusarium mold, pill mold, and Aureobasidium mold.

Examples of organic antibacterial agents include the following: pentachlorophenol, 4-chloro-3,5-dimethylphenol, 4-chloro-3-methylphenol, p-chlorophenoxy- (3-iodo -2-Propargyl) oxymethane-benzyl bromoacetate, 2- (4-thiazolyl) -benzimidazole, methyl-benzimidazolyl-2-carbamate, etc.

Examples of the inorganic antibacterial agents include the following: cuprous oxide, copper rhodanide (copper thiocyanate), metal ion-containing zeolite, zirconium phosphate, soluble glass and silica gel.

Among the above antibacterial agents, preferred are heavy metal ions, especially zeolites containing silver ions and / or copper ions, zirconium phosphate, soluble glass and silica gel. These are selected from the viewpoints of durability of antibacterial performance and nontoxicity to human body.

<Antifriction Material> The antifriction material in the above additives can be added to the crosslinkable composition which is a raw material of the crosslinked cured film constituting the conductive structure of the present invention. The functions can be broadly classified into, for example, the following two types: -When aiming at the function of improving the hardness of the crosslinked cured film (c1) itself-Reducing the friction coefficient of the surface to prevent scratching (improving scratch resistance) When aiming for a function.

The following may be mentioned as measures for improving the hardness of the crosslinked cured film (c1) itself: Alumina, silicon carbide (carborundum), silicon oxide (silica), as an inorganic antifriction material Measures to use iron oxide (ferrite) powder, granules, etc. alone or in combination.

As a measure for reducing the friction coefficient of the surface of the crosslinked cured film (c1), the following can be mentioned: ・ Fluorine-based polymer, silicone-based polymer (oil or grease, etc.) in the curable composition ) Or an organic antifriction material such as a silicon monomer containing an unsaturated double bond or a fatty acid amide containing an unsaturated double bond.

<Pigment> Examples of the above-mentioned pigments include the following: Extension pigments: barite (barium hydroxide) powder, barium sulfate, barium carbonate, calcium carbonate, gypsum, clay (clay), silica powder, Talc, alumina white, etc .; ・
Inorganic pigments: zinc white, lead white, yellow lead, ultramarine blue, titanium oxide (titanium white), zinc chromate, red iron oxide, carbon black; Organic pigments: permanent red, benzidine yellow, lake red, phthalocyanine blue, etc.

<Matting Agent> When a matting agent is blended, an organic matting agent and an inorganic matting agent are mainly used. As the former example, polyacrylonitrile powder is used, and as the latter example, powdered silica or Its modified form and the like.

<Plasticizer> When a plasticizer is used,
Examples thereof include dibutyl phthalate (DBP), dioctyl phthalate (DOP) and chlorinated paraffin.

When a viscosity modifier is used, examples thereof include bentonite, silica gel and aluminum octoate. <Solvent> When a solvent is used, for example, the following are usually used: Hydrocarbons: Aliphatic hydrocarbons, alicyclic hydrocarbons and aromatic hydrocarbons; Ketones, alcohols, esters , Ether type.

When other auxiliaries are used, known defoaming agents, leveling agents, surfactants, ultraviolet absorbers, flame retardants and the like can be mentioned. [Crosslinking Curing Method] <Electron Beam Curing> Electron beam curing is the most effective curing method for producing the conductive structure of the present invention and has many advantages as follows: -Excellent productivity That is, it can be cured with a small amount of energy.-It is hardly affected by the conductive filler or various fillers.-It is possible to cure a relatively thick coating film.

For electron beam curing, an electron beam accelerator is selected as an irradiation device from the following various beam methods, and subsequent curing of the coating film is performed in a nitrogen gas atmosphere (oxygen concentration of 400 ppm or less) under an electron beam accelerating voltage of 125 to 300 kV and a dose of 1 It can be performed at about 20 Mrad: ・ Scanning beam method ・ Curtain beam method <Thermal curing> When the heat supply means is something like a heating furnace, infrared irradiation, microwave irradiation, etc., a radical initiator is used. Combined. Examples of the radical initiator include ketone peroxide, saturated or unsaturated alkyl hydroperoxide, saturated or unsaturated cycloalkyl hydroperoxide, aryl hydroperoxide, dialkyl peroxide, dicycloalkyl peroxide, diaryl peroxide, diacyl peroxide. Select at least one of oxide and diaryloyl peroxide.

<Normal Temperature Curing> In the case of curing at a relatively low temperature such as a room temperature curing reaction, it is preferable to use ketone peroxide, diacyl peroxide, a combination of hydroperoxide and a reducing amine as an accelerator. .

<UV Curing> When the crosslinking curing means is UV irradiation, for example, a photoinitiator is used: benzoin compound: benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin butyl ether, benzoin octyl ether; -Carbonyl compound: benzyl, diacetyl, methylanthraquinone, acetophenone, benzophenone, etc.-Sulfur compound: diphenylsulfide, dithiocarbamate; -Naphthalene compound: α-chloromethylnaphthalene; -Anthracene compound; -Iron chloride.

[Crosslinked cured film and formation thereof] Crosslinked cured film (c
The thickness of 1) is not particularly limited, and usually selected to be 1 to 50 μm is sufficient for exhibiting the conductivity and wear resistance of the conductive structure of the present invention. From an economic point of view, it is preferable to make it thin.

When forming a crosslinkable film, it is preferable to apply an uncured film material as a solid coating. This coating method is preferable from the economical viewpoint as well so as to prevent the conductive fiber (b1) from protruding outward from the surface on the opposite side of the film. In addition, when a regular shape such as a mesh, a halftone dot, a stripe (stripe) or another amorphous shape is applied to the crosslinked cured film surface of the conductive structure of the present invention, a heating roll or a heating roller is used at the time of heat fusion. It is practical to use a press plate or the like that is decorated to perform shaping.

Examples of the apparatus for applying the curable composition for forming the crosslinked cured film (c1) include a blade coater, a knife coater, a roll coater, a direct coater, an offset coater and a gravure coater.

In the conductive structure of the present invention, the thermoplastic resin film (C) having the cross-linked cured film (c1) formed as described above laminated on the surface is integrally formed on at least one surface of the substrate (A). Are joined together. A fusion method is generally suitable as the joining means.
Specific operations for the integral joining include the following: <Joining operation-1>: The conductive cloth material (B) is overlaid on at least one surface of the base material (A), and the (B) A thermoplastic resin film on top of which a crosslinked cured film (c1) is laminated on one side
The surface on the non-crosslinking cured side of (C) is brought into contact with each other and passed between a pair of heating rolls or between a pair of rolls composed of a heating roll and a cooling roll. <Joining operation-2>: In order to form a film as the base material (A), a thermoplastic resin is extruded from an extruder, and a conductive cloth material (B) is laid on at least one surface of the thermoplastic resin, and at the same time, A thermoplastic resin film with a cross-linked cured film (c1) laminated on one side of it (C). Wear together. <Joining operation-3>: In order to form a film as a base material (A), a thermoplastic resin is extruded from an extruder, and a conductive cloth material (B) is laid on at least one surface of the thermoplastic resin, and at the same time, Thermoplastic resin film with a cross-linked cured film (c1) laminated on one side of it (C) The non-cross-linked cured side of the laminated multi-layered product so that it contacts the press die of the heating and cooling press It is mounted in between and sandwiched by a mold to fuse and integrate the layers. <Joining operation-4>: In order to form a film to be the base material (A), a thermoplastic resin is extruded from an extruder to form (A), and a conductive cloth material (B) is laid on at least one surface thereof, At the same time, a thermoplastic resin film on top of (B) with a cross-linked cured film (c1) laminated on one side of it (C) is injection-molded into a layered product with the non-cross-linked cured side in contact It is mounted in a mold, and a thermoplastic resin which is a material of the base material (A) is injected into the mold to form the base material (A) on the surface of the conductive cloth-like material (B) of the multi-layered product. By doing so, they are fused and integrated.

The conductive structure obtained by the above-mentioned four kinds of bonding operations is further subjected to secondary molding such as vacuum molding, pressure molding, deep drawing molding, bending, bag making, etc. to obtain various desired shapes. It is also possible to obtain a shaped conductive structure that is shaped into. The shaped conductive structure obtained by the above secondary molding can be suitably used for various applications exemplified in the "effect of the invention" described later.

[0054]

EXAMPLES The conductive structure of the present invention will be specifically described below with reference to Examples and, if necessary, Comparative Examples.
The present invention is not limited to these. The performance of the conductive structure of the present invention was evaluated by observing its surface electrical resistivity, electrostatic charge decay rate, scratch resistance and conductive fiber dropout degree. (1) Surface electrical resistivity ・ Measuring device: Product name "Hiresta" (manufactured by Mitsubishi Yuka) ・ Operation: Conductive paint [Product name: DOTITE D-550 (manufactured by Fujikura Kasei)] on the contact surface of the sample electrode After coating and drying, it is used for measurement. (2) Electrostatic charge decay rate ・ Measuring device: Product name `` STATIC DECAY METER (Electro-tech
System Inc.) "・ Measurement conditions: applied voltage 5000 V, relative humidity (RH) 50% ・ Operation: voltage is applied to the sample, and the charging potential is 5 after grounding
The time to decay to 00V is measured. (3) Scratch resistance ・ Measuring device: Product name "Rotary Ablation Tester" (manufactured by Toyo Seiki Seisakusho) and wear ring: Product name "CS1"
0 "(manufactured by Taber Co., Ltd.)-Operation: The sample is abraded by the above device and the weight loss after 500 tests is measured. (4) Detachment degree of the conductive fiber ・ Operation: The sample (length 30 cm) is reciprocally abraded with the flannel cloth 10 times, and it is observed with an optical microscope whether or not the conductive fiber adheres to the surface of the flannel cloth. .

[0055]

Example 1 A composition for crosslinking and curing having the following composition was applied to the surface of a polypropylene film (thickness: 15 μm) and then irradiated with an electron beam (electron beam accelerating voltage 160 kv; dose 6 Mra).
A thermoplastic resin film (C) having a cross-linked cured film (c1; coating thickness 5 μm) on one side was prepared by d) and curing: Main component: polyester acrylate prepolymer [viscosity η = 500- (Measured at 1,100 cps / 25 ° C); Trade name: M8030 (manufactured by Toagosei Co., Ltd.); contains the following conductive filler] ・ ・ Conductive filler: zinc oxide powder (average particle size 0.2μ
m) 50% by weight (composition basis).

Separately, a conductive non-woven fabric (B; basis weight 50 g / m ² ) was prepared using the following two fibers: Pitch-based carbon fiber (diameter 13 μm; tensile elastic modulus 3,50)
0 kgf / mm ² ) 30% by weight and 70% by weight of polypropylene-based composite fiber (thickness 3 denier).

Next, a conductive structure of the present invention was obtained by performing the following operations: The above-mentioned conductive nonwoven fabric (B) was laminated on one side of a base polypropylene sheet (A; thickness 1 mm), Further, the thermoplastic resin film (C) is laminated so that its thermoplastic resin side faces the surface of the conductive nonwoven fabric (B), and then these (A), (B) and (C) are laminated. The body is passed between a pair of heating rolls and cooling rolls to fuse and integrate the layers. When this fusion is integrated,
The crosslinked cured film (c1) is a heating roll (surface temperature 200 ° C)
It was arranged to come into contact with. The performance evaluation results of the obtained conductive structure are shown in Table 1.

[0058]

Example 2 The composition for curing used in Example 1 was applied to the surface of a polypropylene film (thickness: 15 μm) and then cured by electron beam irradiation under the same conditions as in Example 1 to crosslink and cure. A thermoplastic resin film (C) having the film (c1) on one surface was prepared.

Separately, PAN (polyacrylonitrile)
Carbon fiber (average diameter 8μm; tensile modulus 2,000kgf / m
A conductive woven fabric (B; basis weight: 200 g / m ² ) was obtained by plain weaving with 5000 wefts as m ² ) and 1000 polypropylene-based composite fibers (thickness 3 denier) as warps.

Next, the conductive woven fabric (B) is laminated on one surface of the base polypropylene sheet (A; thickness 1 mm), and the thermoplastic resin film (C) is conductive on the thermoplastic resin side. After being laminated so as to face the surface of the non-woven fabric (B), the laminated body of these (A), (B) and (C) is passed between a pair of heating rolls and cooling rolls to form an interlayer. The conductive structure of the present invention was obtained by fusing and integrating. The cross-linked cured film (c1) was placed in contact with a heating roll (surface temperature of 200 ° C.) during this fusion and integration. The performance evaluation results of the obtained conductive structure are shown in Table 1.

[0061]

Example 3 A curing composition having the following composition was used as polyvinyl chloride.
After applying on the surface of (PVC) film (thickness 50 μm),
Then, a thermoplastic resin film (C) having a crosslinked cured film (c1; coating thickness 10 μm) on one side was prepared by irradiating and curing with electron beam under the same conditions as in Example 1: Main component: Polyester acrylate prepolymer [viscosity η = 7,000 to 13,000 cps / measured at 25 ° C); trade name: M860 (manufactured by Toagosei Co., Ltd.); contains both components below] Alkylbenzenesulfonic acid triethanolamine 3% by weight (composition basis) and 30% by weight of alumina powder (average particle size 3 μm) (composition basis).

Separately, a conductive woven fabric (B;
A basis weight of 50 g / m ² ) was obtained: Corrosion resistant steel fiber (average diameter 8 μm; tensile modulus 19 000 k)
gf / mm ² ) 40% by weight and polyvinyl chloride fiber (thickness 3 denier) 60% by weight.

Next, the conductive woven fabric (B) is laminated on one surface of the base material polyvinyl chloride sheet (A; thickness 2 mm), and the thermoplastic resin film (C) is attached to the thermoplastic resin. After stacking so that the side faces the surface of the conductive woven fabric (B), insert these stacked bodies of (A), (B), and (C) between the hot plates of the heating press to separate the layers. The conductive structure of the present invention was obtained by fusing and unifying (heating temperature 180 ° C.). The performance evaluation results of the obtained conductive structure are shown in Table 1.

[0064]

Comparative Example 1 Pitch-based carbon fiber (diameter 13 μm; tensile elastic modulus 3,500 kgf / mm ² ) 30% by weight and polypropylene-based composite fiber (thickness 3 denier) 70% by weight were used to make a conductive non-woven fabric (B; A basis weight of 50 g / m ² ) was prepared.

Next, a polypropylene sheet as a base material
(A) (thickness: 1 mm) on one side, the conductive non-woven fabric (B) is overlaid, and further, the conductive non-woven fabric (B) is overlaid with a polyester film (C; thickness 12 μm).
(A), a conductive non-woven fabric (B) and a polyester film (C), a multilayer body composed of three members, while the polyester film (C) is in contact with a heating roll at 200 ° C., and a pair of heating roll and cooling roll. To obtain a conductive structure of the present invention by fusing the layers to fuse and integrate them.
Next, a corona discharge treatment is applied to the non-woven fabric fused surface of the conductive structure to improve the wetting tension of the surface to 50 dyne / cm, and then the polyester acrylate prepolymer [viscosity of 7,000 to 13,000cps / 25
[° C.] to form a coating film (thickness 3 μm). Then, the coating film surface is irradiated with an electron beam (electron beam accelerating voltage 160 kv,
At a dose of 6 Mrad), a conductive structure having a crosslinked cured film was obtained. Table 1 shows the performance evaluation results of the conductive structure having the obtained crosslinked cured film.

[0066]

[Comparative Example 2] Conductive non-woven fabric (B; basis weight) using 30% by weight of pitch-based carbon fiber (diameter 13 μm; tensile elasticity of 35,000 kgf / mm ² ) and 70% by weight of polypropylene-based composite fiber (thickness 3 denier) A weight of 50 g / m ² ) was prepared.

Separately, an insulating (non-conductive) woven fabric (B '; basis weight 20 g / m ² ) was obtained from 100% by weight of polypropylene-based composite fiber (thickness 3 denier). Next, the conductive non-woven fabric (B) is overlaid on one side of the base polypropylene sheet (A; thickness 1 mm), and the insulating non-woven fabric is placed on it.
After stacking (B '), these (A), (B) and (B') laminated bodies are inserted between the hot plates of a heating press to fuse and integrate the layers (heating temperature 200 ° C. By doing so, a conductive structure was obtained. Table 1 shows the performance evaluation results of the obtained conductive structures.
Shown in.

[0068]

Comparative Example 3 A composition for curing having the following composition was applied to the surface of a polypropylene film (thickness: 15 μm) and then cured by irradiation with an electron beam under the same conditions as in Example 1 to obtain a crosslinked cured film (c1). A thermoplastic resin film (C) having one side) was prepared. • Polyester acrylate prepolymer (Example 1
The same as in the above, but containing the following zinc oxide):-Zinc oxide powder (average particle size 0.2 μm) 50% by weight (composition basis).

Next, the above-mentioned thermoplastic resin film (C) is laminated on one surface of the base polypropylene sheet (A; thickness 1 mm) so that the thermoplastic resin side faces the surface of the conductive nonwoven fabric (B). After that, these (A) and (C) superposed bodies are inserted between the hot plates of the hot press to fuse and integrate the layers (heating temperature 200 ° C.) to obtain the conductive structure of the present invention. Obtained. The performance evaluation results of the obtained conductive structure are shown in Table 1.

[0070]

[Comparative Example 4] A curing composition having the following composition was made into polyvinyl chloride.
After applying on the surface of (PVC) film (thickness 50 μm),
An electron beam was applied and cured under the same conditions as in Example 1 to prepare a thermoplastic resin film (C) having a crosslinked cured film (c1; coating thickness 10 μm) on one side. Main component: polyester Acrylate-based prepolymer (containing both components below):-Alkylbenzenesulfonic acid triethanolamine 3% by weight and-Alumina powder (average particle size 3 µm) 30% by weight.

Next, the above-mentioned thermoplastic resin film was formed on one surface of the base material polyvinyl chloride (PVC) sheet (A; thickness 2 mm).
(C) is laminated so that its thermoplastic resin side faces the surface of the conductive woven fabric (B), and then the laminated body of these (A) and (C) is placed between the hot plates of the heating and cooling press. The conductive structure of the present invention was obtained by inserting and fusing the layers together (heating temperature 180 ° C.). The performance evaluation results of the obtained conductive structure are shown in Table 1.

[0072]

[Table 1]

[0073]

EFFECTS OF THE INVENTION According to the conductive structure of the present invention, the following effects can be exhibited: -Exhibits excellent wear resistance. That is, there is no loss of conductive fibers due to surface abrasion-Exhibits even more excellent conductive performance that complements the conductive performance of the crosslinked cured film-Provides stable conductive performance-Wide range of applications Suitable for the following applications Can be used: -Precision electronic parts such as bags, trays, boxes, partition boards for handling IC, LSI, printed circuit boards, etc.-Interior items such as desk mats, floor materials or wall materials-For food handling Cases, separate sheets, sheet pallets, etc.

[Brief description of drawings]

FIG. 1 is a schematic cross-sectional view of a conductive structure of the present invention.

[Explanation of symbols]

 A base material B conductive cloth C thermoplastic resin film b1 conductive fiber c1 crosslinked cured film

Claims (6)

[Claims] 1. A thermoplastic resin in which a conductive cloth (B) containing conductive fibers (b1) is superposed on at least one surface of a base material (A), and a crosslinked cured film (c1) is further formed on one surface thereof. the film
(C) the base material (A) of the multilayer body laminated so that its thermoplastic resin surface is in contact with the cloth-like material (B), the cloth-like material (B) and the thermoplastic resin film (C ) A conductive structure having a structure in which the respective layers are fused and integrated. 2. The tensile modulus of the conductive fiber (b1) is 2,000.
The electrically conductive structure according to claim 1, having a weight of 0 kgf / mm ² or more. 3. The crosslinked cured film (c1) exhibits conductivity.
Or the conductive structure according to 2. 4. The crosslinked cured film (c1) has a surface resistivity of 10 ⁴ -1.
0 ⁸ Ω / □ conductive structure according to any one of claims 1 to 3 illustrating a conductive. 5. The crosslinked cured film (c1) is a cured film containing an acrylate prepolymer / monomer as a main component.
The electroconductive structure according to any one of to 4. 6. The crosslinked cured film (c1) has an electron beam acceleration voltage of 125.
The conductive structure according to any one of claims 1 to 5, which is a cured film formed by electron beam irradiation with kv to 300 kv and a dose of 1 Mrad to 20 Mrad.