Conductive Resin Composition - Metal Laminate

Abstract

Provided are a conductive resin composition-metal laminate and an organ model that can be used for medical procedure training that uses an energy device, and make it possible to affix, at a certain strength or greater, a counter electrode plate. A conductive resin composition-metal laminate and an organ model including the same, the conductive resin composition-metal laminate including: a substrate layer formed from a conductive resin composition containing a styrene-based thermoplastic elastomer; and a metal layer laminated on one surface of the substrate layer with an adhesive layer interposed therebetween.　

Description

Technical Field

[0001] The present invention relates to a conductive resin composition-metal laminate and an organ model using the same.

Background Art

[0002] In recent years, there has been an increasing expectation for minimally invasive surgeries that cause less burden on the human body and allow for early recovery, such as surgeries using endoscopes or laparoscopes, and the number of such cases has been increasing. For example, by removing a tumor formed in the lower layer of the inner mucosa of an organ under endoscopy (endoscopic submucosal dissection), surgery can be performed with a smaller wound compared to a normal laparotomy. Also, by stopping bleeding in the digestive tract under endoscopy (endoscopic hemostasis), shock due to bleeding can be prevented and emergency surgery can be avoided. Therefore, the physical burden on the patient is reduced, and early social rehabilitation is expected with a short hospital stay.

[0003] Therefore, the demand for a skill practice model for doctors and medical students that can handle surgeries using endoscopes or laparoscopes has been increasing, and proposals for medical skill training models have been made so far for the purpose of improving technology and the quality of medical practices (Patent Documents 1, 2, and 3). Also, as for the instruments used, the number of cases where a surgical energy device is used has been increasing.

[0004]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

[0005] When attaching the counter electrode plate to the skin, for example, a sticky gel in which an electrolyte is dispersed in polyacrylic acid or the like is used. However, with respect to conventional medical procedure training models, the counter electrode plate cannot be connected with sufficient strength, and when instruments such as energy devices and endoscopes touch the medical procedure training model, the counter electrode plate may be easily peeled off. Therefore, there is a need for an organ model that can be used for medical procedure training using an energy device and can attach the counter electrode plate with a strength equal to or greater than a certain level.

[0006] An object of the present invention is to provide a conductive resin composition-metal laminate and an organ model that can be used for medical procedure training using an energy device and can attach a counter electrode plate with a strength equal to or greater than a certain level.

[0007] As a result of examining various means, the present inventor has found that by laminating a metal layer via an adhesive layer on a base material layer formed of a conductive resin composition containing a styrene-based thermoplastic elastomer, the counter electrode plate can be attached with a strength equal to or greater than a certain level and conduction can be achieved, enabling it to be used for medical procedure training using an energy device, and thus the present invention has been completed.

[0008] The present invention relates to the following. (1) A conductive resin composition-metal laminate including a base material layer formed of a conductive resin composition containing a styrene-based thermoplastic elastomer and a metal layer laminated on one surface of the base material layer via an adhesive layer. (2) The volume resistivity is 1.0×10 2 ~1.0×10 7 Ω·cm, and the conductive resin composition-metal laminate according to (1). (3) The conductive resin composition-metal laminate according to (1) or (2), wherein the adhesive layer contains one or more adhesives selected from the group consisting of epoxy-based adhesives, olefin-based adhesives, cyanoacrylate-based adhesives, urethane-based adhesives, and silicone-based adhesives. (4) The conductive resin composition-metal laminate according to any one of (1) to (3) connected to a counter electrode plate. (5)An organ model for medical procedure training, comprising the conductive resin composition-metal laminate according to any one of (1) to (4). (6)The organ model according to (5), wherein the medical procedure training is medical procedure training using an energy device. (7)The organ model according to (5) or (6), wherein the energy device is any one selected from the group consisting of a high-frequency hemostatic forceps, an electric scalpel, an ultrasonic scalpel, and a high-frequency radio wave scalpel. (8)The organ model according to any one of (5) to (7), comprising a simulated blood vessel connected to a device capable of supplying simulated blood. (9)The organ model according to any one of (5) to (8), wherein the medical procedure training is training for endoscopic hemostasis. (10)The organ model according to (9), wherein the training for endoscopic hemostasis is training for hemostasis by a thermal coagulation method using an energy device.

[0009] According to the present invention, it is possible to provide a conductive resin composition-metal laminate and an organ model that can be used for medical procedure training such as hemostasis using an energy device and can attach a counter electrode plate with a strength of a certain level or more.

Brief Description of Drawings

[0010]

Figure 1

Figure 2

Figure 3

Mode for Carrying Out the Invention

[0011] Hereinafter, an embodiment of the present invention will be described in detail. The present invention is not limited to the following embodiments, and can be implemented with appropriate modifications within a range that does not inhibit the effects of the present invention.

[0012] [First Embodiment] The conductive resin composition - metal laminate according to the first embodiment of the present invention includes a base material layer formed of a conductive resin composition containing a styrene - based thermoplastic elastomer, and a metal layer laminated on one surface of the base material layer via an adhesive layer. FIG. 1 is a view showing the conductive resin composition - metal laminate 1 of the present embodiment, which includes a base material layer 2, an adhesive layer 3, and a metal layer 4 in this order. The volume resistivity of the conductive resin composition - metal laminate is preferably 1.0×10 2 ~1.0×10 7 Ω·cm, and more preferably 1.0×10 2 ~5.0×10 5 Ω·cm. The volume resistivity can be determined, for example, in accordance with JIS C2139. After adjusting a test piece of any shape for 24 hours or more in an environment of temperature 23 ± 2°C and relative humidity 50 ± 5%, using a commercially available machine (such as resistivity meter Loresta - GP (model number: MCP - T610) manufactured by Mitsubishi Chemical Analytech Co., Ltd., etc.), measure the volume resistivity 20 seconds after charging at a voltage of 10V using a PSP probe. By setting the volume resistivity to 1.0×10 7 Ω·cm or less, incision by an energy device becomes possible.

[0013] 〔Base material layer〕 As shown in FIG. 1, the base material layer in the present embodiment is one layer constituting the conductive resin composition - metal laminate, and is a structure formed of a conductive resin composition containing a styrene - based thermoplastic elastomer. The shape of the base material layer is not particularly limited and can be set according to its use. Also, the molding method of the base material layer can be appropriately selected from extrusion molding, casting molding, injection molding, compression molding, etc. according to the shape to be molded. In one embodiment of the present invention, the thickness of the base material layer can be 0.1 to 30 mm or 1 to 20 mm.

[0014] (Conductive resin composition) In one embodiment of the present invention, the conductive resin composition is a conductive resin composition containing a styrene - based thermoplastic elastomer, and its volume resistivity is preferably 1.0×10 2~1.0×10 7 Ω·cm, more preferably 1.0×10 2 ~1.0×10 6 Ω·cm. The volume resistivity of the conductive resin composition is measured by the same method as the method for measuring the volume resistivity of the above conductive resin composition - metal laminate.

[0015] (Styrene-based thermoplastic elastomer) The conductive resin composition of this embodiment contains a styrene-based thermoplastic elastomer. The styrene-based thermoplastic elastomer in one embodiment of the present invention is an aromatic vinyl-conjugated diene block copolymer composed of a block polymerization unit (X) derived from an aromatic vinyl and a block polymerization unit (Y) derived from a conjugated diene, or a hydrogenated product thereof.

[0016] The form of the aromatic vinyl-conjugated diene block copolymer having such a structure is, for example, X(YX) n or (XY) n 〔n is an integer of 1 or more〕. Among these, those in the form of X(YX) n in particular, those in the form of X-Y-X are preferred. As those in the form of X-Y-X, one or more copolymers selected from the group consisting of polystyrene-polybutadiene-polystyrene block copolymer, polystyrene-polyisoprene-polystyrene block copolymer, and polystyrene-polyisoprene-butadiene-polystyrene block copolymer are preferred.

[0017] In such an aromatic vinyl-conjugated diene block copolymer, the aromatic vinyl block unit (X) which is a hard segment exists as a crosslinking point of the conjugated diene rubber block unit (Y) to form a pseudo crosslinking (domain). The conjugated diene rubber block unit (Y) existing between these aromatic vinyl block units (X) is a soft segment and has rubber elasticity.

[0018] Examples of the aromatic vinyl for forming the block polymerization unit (X) include styrene, α-methylstyrene, 3-methylstyrene, p-methylstyrene, 4-propylstyrene, 4-dodecylstyrene, 4-cyclohexylstyrene, 2-ethyl-4-benzylstyrene, 4-(phenylbutyl)styrene, 1-vinylnaphthalene, 2-vinylnaphthalene, and the like. Among these, styrene is preferred.

[0019] Examples of the conjugated diene for forming the block polymerization unit (Y) include butadiene, isoprene, pentadiene, 2,3-dimethylbutadiene, and combinations thereof. Among these, one or more conjugated dienes selected from the group consisting of butadiene, isoprene, and a combination of butadiene and isoprene (copolymerization of butadiene and isoprene) are preferred. One or more of these conjugated dienes can also be used in combination. The conjugated diene block polymerization unit (Y) composed of a butadiene·isoprene copolymer unit may be any of a random copolymer unit of butadiene and isoprene, a block copolymer unit, and a tapered copolymer unit.

[0020] In the aromatic vinyl·conjugated diene block copolymer as described above, the content of the aromatic vinyl block polymerization unit (X) is preferably 5% by mass or more and 50% by mass or less, more preferably 20% by mass or more and 40% by mass or less. The content of this aromatic vinyl unit can be measured by conventional methods such as infrared spectroscopy and NMR spectroscopy.

[0021] In one embodiment of the present invention, the melt flow rate (MFR) (temperature 230 ° C, load 2.16 kg) of the styrene-based thermoplastic elastomer is 1 g / 10 min or less, preferably 0.1 g / 10 min or less. MFR (temperature 230 ° C, load 2.16 kg) refers to the MFR measured under the conditions of temperature 230 ° C and load 2.16 kg in accordance with JIS K7210. By setting the MFR to a certain value or less, it is possible to suppress the tendency of bleeding out when oil is added and the decrease in mechanical strength.

[0022] The aromatic vinyl-conjugated diene block copolymer as described above can be produced by various methods. Examples of the production methods include: (1) a method in which an aromatic vinyl and then a conjugated diene are sequentially polymerized using an alkyllithium compound such as n-butyllithium as an initiator; (2) a method in which an aromatic vinyl and then a conjugated diene are polymerized using an alkyllithium compound as an initiator, and then this is coupled with a coupling agent; (3) a method in which a conjugated diene and then an aromatic vinyl are sequentially polymerized using a lithium compound as an initiator, and the like.

[0023] In one embodiment of the present invention, a hydrogenated product of the aromatic vinyl-conjugated diene block copolymer as described above by a known method can be preferably used. A preferable hydrogenation rate is 90 mol% or more. This hydrogenation rate is a value when the total amount of carbon-carbon double bonds in the conjugated diene block polymerization unit (Y) is taken as 100 mol%. Examples of such hydrogenated styrenic thermoplastic elastomers include polystyrene-poly(ethylene / propylene) block (SEP), polystyrene-poly(ethylene / propylene) block-polystyrene (SEPS), polystyrene-poly(ethylene / butylene) block-polystyrene (SEBS), polystyrene-poly(ethylene-ethylene / propylene) block-polystyrene (SEEPS), and the like. More specifically, SEPTON (manufactured by Kuraray Co., Ltd.), Kraton (manufactured by Shell Chemical Co., Ltd.), Kraton G (manufactured by Shell Chemical Co., Ltd.), Taftec (manufactured by Asahi Kasei Corporation) (the above are trade names), and the like can be mentioned.

[0024] The hydrogenation rate is measured by a known method such as nuclear magnetic resonance spectrum analysis (NMR).

[0025] In the present invention, SEEPS is preferable as the styrenic thermoplastic elastomer. From the viewpoint of the oil absorption operation before kneading, the shape of the styrenic thermoplastic elastomer is preferably powder or amorphous (crumb) form.

[0026] (Oil) In one embodiment of the present invention, the conductive resin composition contains oil. The oil is not particularly limited, and examples include mineral oil-based oils such as paraffinic process oil, naphthenic process oil, aromatic process oil, and liquid paraffin, silicone oil, castor oil, linseed oil, olefin wax, and mineral wax. Among these, paraffinic and / or naphthenic process oils are preferred. Examples of process oils include Diana Process Oil series (manufactured by Idemitsu Kosan Co., Ltd.) and JOMO Process P (manufactured by Japan Energy Corporation). The oil is used, for example, to soften the resin composition and adjust the elastic modulus and hardness of the organ model. One or more of the above oils can be used in combination. It is preferable from the viewpoint of workability to previously absorb the oil into the hydrogenated styrene-based thermoplastic elastomer.

[0027] The content of the oil is preferably 100 to 1000 parts by mass, more preferably 100 to 700 parts by mass, still more preferably 100 to 600 parts by mass, and most preferably 200 to 500 parts by mass with respect to 100 parts by mass of the styrene-based thermoplastic elastomer. The content of the oil is adjusted according to the actual organ part to be modeled within the above range. By setting the content of the oil to 100 parts by mass or more with respect to 100 parts by mass of the styrene-based thermoplastic elastomer, it is possible to suppress insufficient softness, and by setting it to 1000 parts by mass or less, it is possible to suppress the inability to form a compound because the hydrogenated styrene-based thermoplastic elastomer cannot absorb the oil completely.

[0028] (Conductivity imparting agent) In one embodiment of the present invention, the conductive resin composition further contains a conductivity imparting agent. As the conductivity imparting agent, a polymer antistatic agent, an ionic liquid, or the like can be used.

[0029] ·Polymer antistatic agent Examples of the polymer antistatic agent include copolymers of a hydrophobic polymer and a hydrophilic polymer, carbon nanomaterials, and conductive polymers. ···Copolymer of a hydrophobic polymer and a hydrophilic polymer In one embodiment, the polymer antistatic agent is not particularly limited, but is preferably a copolymer of a hydrophobic polymer and a hydrophilic polymer, more preferably a copolymer having one or more hydrophobic polymer blocks and one or more hydrophilic polymer blocks. Hydrophilic means having a functional group or polarity that forms a hydrogen bond between molecules, and hydrophobic means non-hydrophilic. Here, the bonding mode of each block may be a block copolymer in which a hydrophobic polymer block and a hydrophilic polymer block are linearly connected, or a graft copolymer in which a graft chain is connected as a branch to one of the polymer chains, but a block copolymer is more preferred. For example, the antistatic agents described in JP-A No. 2001-278985, JP-A No. 2013-213195, JP-A No. 2015-096595, JP-A No. 2016-166332, JP-A No. 2017-101217, and International Publication No. 2016 / 084954 can be used as the polymer antistatic agent in one embodiment of the present invention.

[0030] More specifically, polyethers having a hydrophilic group and block copolymerized (nonionic types such as polyether ester amides, ethylene oxide-epichlorohydrins, polyether esters, anionic types such as polystyrene sulfonic acids, cationic types such as quaternary ammonium-containing poly(meth)acrylates, etc.) can be mentioned. Among them, a diblock copolymer having a structure in which a polyethylene glycol block and a polypropylene glycol block, or a polyether block and a polyolefin block are bonded via at least one bond selected from an ester bond, an amide bond, an ether bond, a urethane bond, and an imide bond, or a block copolymer having a structure in which they are repeatedly and alternately bonded can be used. As an example, a block copolymer having a structure in which a polyether block having a hydrophilic block with a volume resistivity of 10 5 ~10 11 Ω·cm and a polyolefin block are repeatedly and alternately bonded can be mentioned. The number average molecular weight (Mn) of the block copolymer is preferably 2000 to 60000.

[0031] In addition, examples of commercially available copolymers include products named "Pelestat (registered trademark)" (such as "Pelestat 300", "Pelestat 230", "Pelestat NC6321", "Pelestat NC6322", "Pelestat NC7350", "Pelestat HC250", etc.) manufactured by Sanyo Chemical Industries, Ltd., "Perektron (registered trademark)" (such as "Perektron PVH", "Perektron PVL", "Perektron HS", "Perektron LMP-FS", etc.), products named "Sunconol (registered trademark)" (such as "Sunconol TBX-65", etc.) manufactured by Sanko Chemical Industries Co., Ltd., products named "Entira (registered trademark) AS" manufactured by Mitsui DuPont, products named "Pebax (registered trademark)" manufactured by Arkema, products named "Statlite (registered trademark)" manufactured by Lubrizol, "IonPhasE (registered trademark) IPE (registered trademark) U2" manufactured by IonPhasE, products named "Pluronic (registered trademark) L-31", "Pluronic (registered trademark) L-41" manufactured by ADEKA Corporation, products named "Alcox (registered trademark) EP1010N", "Alcox (registered trademark) CP-A1H", etc. manufactured by Meisei Chemical Industry Co., Ltd. These may be used alone or in combination.

[0032] In addition, a block polymer in which a block of polyolefin, a block of polyisobutylene, and a block of a hydrophilic polymer having a volume resistivity of 1×10 5 ~1×10 11 Ω·cm are bonded via at least one bond selected from the group consisting of an ester bond, an amide bond, an ether bond, an imide bond, and a urethane bond can be used as the copolymer of this embodiment.

[0033] In addition, a block polymer having a block of a hydrophobic polymer without polyether, a block of a hydrophilic polymer, and a block of a hydrophobic polyether containing an aromatic ring as constituent units, a block of polyolefin, and a volume resistivity of 10 5 ~10 11A block polymer characterized by having a structure in which blocks of a hydrophilic polymer of Ω·cm are repeatedly and alternately bonded, or a block polymer having, as constituent units, a block of at least one hydrophobic polymer selected from the group consisting of polyamide, polyolefin, and polyamideimide, a block of a hydrophilic polymer, and a block of an aromatic ring-containing hydrophobic polyether can also be used.

[0034] In the present invention, the number-average molecular weight (Mn) and weight-average molecular weight (hereinafter abbreviated as Mw) of the copolymer can be measured under the following conditions using gel permeation chromatography (GPC). Apparatus (example): HLC-8321GPC / HT [manufactured by Tosoh Corporation], PL-GPC220 [manufactured by Agilent Technologies, Inc.], SSSC-7100 [manufactured by Senshu Science Co., Ltd.] Column (example): Two "TSK GEL GMH HR-H(20)HT" [manufactured by Tosoh Corporation] Measurement temperature: 140 °C Sample solution: 0.3 wt% orthodichlorobenzene solution Solution injection volume: 100 μl Detector: FT-IR detector Reference substance: Twelve standard polystyrenes (TSKstandard POLYSTYRENE) (molecular weights: 500, 1,050, 2,800, 5,970, 9,100, 18,100, 37,900, 96,400, 190,000, 355,000, 1,090,000, 2,890,000) [manufactured by Tosoh Corporation]

[0035] ··Carbon nanomaterials As the carbon nanomaterial, carbon nanotubes, carbon nanofibers, etc. can be used. The content of the carbon nano material is preferably 10 to 1000 parts by mass, more preferably 100 to 800 parts by mass, and even more preferably 200 to 800 parts by mass with respect to 100 parts by mass of the styrenic thermoplastic elastomer. By setting the content of the carbon nano material to 10 parts by mass or more with respect to 100 parts by mass of the styrenic thermoplastic elastomer, the volume resistivity becomes constant or less, and by setting it to 1000 parts by mass or less, a decrease in flexibility is suppressed.

[0036] ··Conductive polymer As the conductive polymer, a water-soluble polymer hydrogel, a polythiophene-based conductive polymer, or the like can be used. The content of the conductive polymer is preferably 50 to 1000 parts by mass, more preferably 100 to 800 parts by mass, and even more preferably 200 to 800 parts by mass with respect to 100 parts by mass of the styrenic thermoplastic elastomer. By setting the content of the conductive polymer to 50 parts by mass or more with respect to 100 parts by mass of the styrenic thermoplastic elastomer, the volume resistivity becomes constant or less, and by setting it to 1000 parts by mass or less, a decrease in mechanical strength can be suppressed.

[0037] The content of the polymer antistatic agent is preferably 10 to 200 parts by mass, more preferably 100 to 150 parts by mass with respect to 100 parts by mass of the styrenic thermoplastic elastomer. By setting the content of the polymer antistatic agent to 10 parts by mass or more with respect to 100 parts by mass of the styrenic thermoplastic elastomer, an increase in volume resistivity can be suppressed, and by setting it to 200 parts by mass or less, an increase in the hardness of the material can be suppressed.

[0038] -Ionic liquid- The ionic liquid is not particularly limited, but examples include those composed of a cation and an anion. The ionic liquid in one embodiment of the present invention does not contain a solvent such as water or ethylene glycol.

[0039] As the cation, an amidinium cation, a pyridinium cation, a pyrazolium cation, a guanidinium cation, or the like can be used.

[0040] As the anion, an anion obtained by removing a proton from an acid such as carboxylic acid, sulfonic acid, inorganic acid, inorganic acid substituted with a halogen atom-containing alkyl group, halogen atom-containing sulfonylimide, halogen atom-containing sulfonylmethide, halogen atom-containing carboxylic acid amide, nitrile group-containing imide, nitrile-containing methide, halogen atom-containing alkylamine, or cyanic acid can be used. The anion may be a mixture of two or more kinds.

[0041] Moreover, commercially available ionic liquids can also be used. Examples of commercially available ionic liquids include CIL312 (N-butyl-3-methylpyridinium bis(trifluoromethanesulfonyl)imide, manufactured by Nippon Carlit Co., Ltd.), Aminoion AS100 (manufactured by Nippon Emulsion Co., Ltd.), Aminoion AS300 (manufactured by Nippon Emulsion Co., Ltd.), FC-4400 (tri-n-butylmethylammonium bis(trifluoromethanesulfonate), manufactured by 3M), and Hisicolin (dodecyltributylphosphonium chloride, manufactured by Nippon Chemical Industry Co., Ltd.).

[0042] The method for synthesizing the ionic liquid is not particularly limited as long as the target ionic liquid can be obtained. Examples include the halide method, hydroxide method, acid ester method, complex formation method, and neutralization method described in "Ionic Liquids - The Frontiers and Future of Development -" [Hiroyuki Ohno, published in 2003, CMC Publishing].

[0043] The content of the ionic liquid is preferably 50 to 250 parts by mass, more preferably 50 to 240 parts by mass, and even more preferably 70 to 210 parts by mass with respect to 100 parts by mass of the styrenic thermoplastic elastomer. By setting the content of the ionic liquid to 50 parts by mass or more with respect to 100 parts by mass of the styrenic thermoplastic elastomer, it contributes to suppressing the increase in volume resistivity and imparting softness, and by setting it to 250 parts by mass or less, it is possible to suppress the bleeding out of the ionic liquid from the material.

[0044] (Other Additives) In the conductive resin composition of the present invention, if necessary, the above-mentioned other resins, elastomers, rubbers, plasticizers, fillers, stabilizers, anti-aging agents, light resistance improvers, ultraviolet absorbers, softeners, lubricants, processing aids, colorants, anti-fogging agents, anti-blocking agents, crystal nucleating agents, foaming agents, etc. can be blended and used. In particular, when using the conductive resin composition of the present embodiment as an organ model, within a range that does not inhibit the purpose, for example, colorants such as pigments and dyes are used, and it is preferable to color the organ model to a color approximated to that of a living organ.

[0045] In one embodiment of the present invention, the conductive resin composition contains a styrene-based thermoplastic elastomer, a polymer antistatic agent, an ionic liquid, and oil.

[0046] To produce the conductive resin composition of the present embodiment, a known appropriate blending method can be used. For example, melt mixing can be performed using a single-screw or twin-screw extruder, a Banbury mixer, a plast mill, a kneader, a heating roll, etc. Before performing the melt mixing, it is also advisable to uniformly mix each raw material using a Henschel mixer, a ribbon blender, a super mixer, a tumbler, etc. The melt mixing temperature is not particularly limited, but 100 to 300 °C, preferably 150 to 250 °C is common.

[0047] 〔Adhesive layer〕 The adhesive layer in the present embodiment is a layer formed of an adhesive, and as shown in FIG. 1, it is one of the layers constituting the conductive resin composition-metal laminate and is directly laminated on the base material layer. In one embodiment of the present invention, the average thickness of the adhesive layer is 500 μm or less, preferably 350 μm or less, more preferably 200 μm or less, and even more preferably 50 μm or less. The lower limit of the average thickness of the adhesive layer is not particularly limited within the feasible range, but it can be 5 μm or more, 10 μm or more, or 20 μm or more. By setting the thickness of the adhesive layer to 500 μm or less, the volume resistivity can be suppressed, and the conductive resin composition-metal laminate can be made flexible, enhancing its followability to curved surfaces. Also, by setting the thickness of the adhesive layer to 5 μm or more, the adhesive strength between the conductive resin composition molded article and the metal layer can be made a certain level or more. As described later, the adhesive layer is usually formed by coating. When formed by the coating method, the thickness referred to here is the thickness after drying. The measurement of the layer thickness is performed using a laser microscope (KEYENCE: VK-8510) after cutting out 20 mm square sections at five equally spaced positions in the width direction of the laminate and smoothing the end faces so that the layer structure can be determined. The average thickness of the adhesive layer is measured at five positions, and the arithmetic mean value is taken as the average thickness.

[0048] (Adhesive) As the adhesive for forming the adhesive layer, one or more adhesives selected from the group consisting of epoxy adhesives, olefin adhesives, cyanoacrylate adhesives, urethane adhesives, and silicone adhesives can be preferably used. Epoxy adhesives generally refer to adhesives of the type in which a compound having two or more reactive epoxy groups is cured with various curing agents such as amine compounds, polyamide compounds, dicyandiamide, and imidazole compounds. Specific examples of epoxy adhesives include adhesives combined with a main agent selected from liquid modified epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, and novolac type epoxy resin, and amine curing agents such as linear aliphatic amines, cycloaliphatic amines, and aromatic amines, and amide amine curing agents. Examples of the olefin-based adhesive include homopolymers of each olefin such as ethylene, propylene, butene, and hexene, copolymers of these monomers with each other, or copolymers of these monomers and non-olefin-based monomers. Specific examples of the olefin-based adhesive include ethylene-based resins such as low-density polyethylene, linear polyethylene (ethylene-α-olefin copolymer), and high-density polyethylene, propylene-based resins such as polypropylene and ethylene-propylene copolymer, poly(4-methylpentene-1), poly(butene-1), ethylene-vinyl acetate copolymer, and acid-modified polyolefin-based resins obtained by subjecting these to maleic anhydride modification (treatment). These may be used alone or in combination of two or more kinds. The cyanoacrylate-based adhesive refers to a composition containing 2-cyanoacrylate as a main polymerization component. Examples of 2-cyanoacrylate include alkyl 2-cyanoacrylate, cycloalkyl 2-cyanoacrylate, alkoxyalkyl 2-cyanoacrylate, alkenyl 2-cyanoacrylate, alkynyl 2-cyanoacrylate, fluoroalkyl 2-cyanoacrylate, and silicon-containing 2-cyanoacrylate. Specific examples of alkyl 2-cyanoacrylate include methyl 2-cyanoacrylate, ethyl 2-cyanoacrylate, various propyl 2-cyanoacrylates, various butyl 2-cyanoacrylates, various pentyl 2-cyanoacrylates, various hexyl 2-cyanoacrylates, and various octyl 2-cyanoacrylates. Specific examples of alkoxyalkyl 2-cyanoacrylate include ethoxyethyl 2-cyanoacrylate, methoxyethyl 2-cyanoacrylate, and methoxyisopropyl 2-cyanoacrylate. The urethane-based adhesive is preferably composed of at least one polyol component having at least two or more hydroxyl groups in the molecule, at least one polyisocyanate component having at least two or more isocyanate groups in the molecule, and / or a diisocyanate. The polyol component can be appropriately selected from polyester polyols, polyether polyols, acrylic polyols, polyolefin polyols, etc. Polyester polyols are particularly preferred because they have a high function of suppressing the deterioration of adhesiveness with the ink layer over time. Examples of diisocyanates include aromatic diisocyanates such as 4,4’-, 2,4’- and 2,2’-diisocyanatediphenylmethane, 1,5-diisocyanatenaphthalene, 4,4’-diisocyanatedicyclohexylmethane, 1,4-diisocyanatobenzene, and / or 2,4- or 2,6-diisocyanatetoluene, and aliphatic and alicyclic diisocyanates such as 1,6-diisocyanatohexane, 1,10-diisocyanatodecane, 1,3-diisocyanatocyclopentane, 1,4-diisocyanatocyclohexane, 1-isocyanate-3,3,5-trimethyl-3 or -5-isocyanatemethylcyclohexane. The polyisocyanate component can be produced from these diisocyanate monomers. Specifically, products such as "Ultra Multi-Purpose SU Premium Soft" manufactured by Konishi Co., Ltd. can be mentioned. The silicone-based adhesive means an adhesive mainly composed of a modified silicone polymer having a hydrolyzable silicon group as a reactive group and a polyoxyalkylene skeleton as the main chain, and examples include those composed of a polymer having hydrolyzable silyl groups at both ends of the polyoxypropylene in the main chain. For example, commercially available silicone-based adhesives include Super X Clear (manufactured by Cemedine Co., Ltd.).

[0049] In one embodiment of the present invention, the adhesive layer may contain metal particles such as copper, silver, gold, tin, nickel, titanium, platinum, etc., and the above-mentioned additives. The content is preferably 10 to 70% by mass, more preferably 15 to 60% by mass, and still more preferably 20 to 50% by mass in the composition constituting the adhesive layer. When adding metal particles, a volume resistivity of a certain level or less can be achieved by setting it to 10% by mass or more, and a decrease in adhesive strength can be suppressed by setting it to 70% by mass or less. In one embodiment of the present invention, the average particle diameter of the metal particles is preferably 0.01 to 50 μm, more preferably 0.03 to 30 μm, and still more preferably 0.03 to 10 μm. Here, the average particle diameter is the average primary particle diameter, which is a value measured by the laser diffraction / scattering particle size distribution measurement method and is the particle diameter at the integrated value of 50% in the volume-based particle size distribution. Two or more types of metal particles having different average particle diameters may be used, and the metal particles may be particles coated with a metal.

[0050] 〔Metal layer〕 The metal layer is a layer formed of a metal and is one layer constituting one surface of the conductive resin composition-metal laminate as shown in FIG. 1. As the metal layer, for example, metal foils or metal thin films such as aluminum, nickel, stainless steel, iron, copper, and titanium can be used. In one embodiment of the present invention, the average thickness of the metal layer is preferably 5 to 500 μm, more preferably 5 to 200 μm, and still more preferably 10 to 100 μm. By setting the thickness of the metal layer to 5 μm or more, the handleability can be improved. Also, by setting the thickness of the metal layer to 500 μm or less, the followability to the curved surface of the conductive resin composition-metal laminate can be improved. The measurement of the layer thickness is performed using a laser microscope (manufactured by KEYENCE: VK-8510) after cutting out 20 mm square sections from 5 locations at equal intervals in the width direction of the laminate and smoothing the end faces so that the layer structure can be determined. The average thickness of the adhesive layer is measured at 5 locations, and the arithmetic mean value thereof is taken as the average thickness.

[0051] [Second Embodiment] The organ model according to the second embodiment of the present invention is an organ model for medical procedure training, which includes the conductive resin composition-metal laminate of the first embodiment. FIG. 2 is a diagram showing a cross section of the organ model of this embodiment. The organ model can have an arbitrary shape selected from a circular shape, an elliptical shape, a polygonal shape, or an irregular shape.

[0052] The maximum width in a direction perpendicular to the thickness direction of the organ model can be, for example, in a range corresponding to the spread of a general ulcer, and may be, for example, in the range of 10 to 150 mm. The thickness of the organ model is not particularly limited, but may be about 1 to 30 mm, or about 2 to 20 mm.

[0053] The organ model of this embodiment can be attached to organ models such as the stomach, esophagus, duodenum, small intestine, large intestine, liver, spleen, biliary tract, pancreas, lung, and heart, and can be used for medical procedure training such as endoscopic hemostasis. In one embodiment of the present invention, the organ model may be fitted into a model mounting portion provided on the organ model for use, or the organ model may be attached to the inner wall of the organ model for use. The model mounting portion of the organ model may be a frame or a recess formed by partially removing the wall, or a jig for model mounting may be attached to the inner wall of the digestive organ model. The organ model can be attached to the inner wall using an adhesive, an adhesive agent, a double-sided tape, or the like.

[0054] The organ model of this embodiment can be formed by a known molding method. For example, when using an inner mold (core) and an outer mold and casting and molding in the space therebetween, when removing the inner mold, a cut may be made in the resin molded body and the inner mold may be removed from there. In that case, the cut can be adhered to complete the organ model. Also, a plurality of organ parts can be separately molded by injection molding or the like, and then adhered to complete the organ model.

[0055] Medical procedure training is training for improving the skills of doctors and medical students and the quality of medical practices. For example, there is medical procedure training performed under endoscopic observation and medical procedure training performed under ultrasonic observation. In one embodiment of the present invention, the organ model for medical procedure training is used for medical procedure training using an energy device. Examples of the energy device include a high-frequency hemostatic forceps, an electric scalpel, an ultrasonic scalpel, a high-frequency radio wave scalpel, a heat probe, a microwave scalpel, a laser scalpel, and the like. Specific examples of medical procedures include endoscopic mucosal resection, endoscopic submucosal dissection, endoscopic hemostasis, and the like.

[0056] The organ model in one embodiment of the present invention includes a simulated blood vessel connected to a device capable of supplying simulated blood. FIG. 3 is a diagram showing a cross section of the organ model of this embodiment. The simulated blood vessel is a path for supplying simulated blood to the surface on the base material layer side of the organ model during hemostasis practice and penetrates the organ model. As an arbitrary device capable of supplying simulated blood, for example, a tubular pump or a syringe can be used.

[0057] In one embodiment of the present invention, the simulated blood vessel has a tubular base material layer and a conductive layer disposed on the outer surface of the base material layer, and is a tubular structure that can be energized by an energy device. The simulated blood vessel in one embodiment of the present invention has a surface resistivity of 1.0×10 0 Ω / □ or more and 1.0×10 6 Ω / □ or less at the location where the conductive layer is disposed. In this embodiment, the surface resistance value is measured under the condition of 23±1°C using a high resistance meter UXMCP-HT800 and a Loresta-GP (MCP-T610) manufactured by Mitsubishi Chemical Analytech Co., Ltd. in accordance with JIS C2139. During the measurement, the thermoplastic resin composition is press-molded at 160 to 200°C and processed into a resin sheet having a size of 2.5 cm×2.5 cm and a thickness of 1.0 mm, and evaluated using a specimen having a conductive layer formed on the surface.

[0058] The organ model in one embodiment of the present invention can be used for training of endoscopic hemostasis. Examples of endoscopic hemostasis include so-called mechanical methods such as grasping with a hemostatic forceps or a clip at the bleeding site, and thermal coagulation methods such as thermal coagulation methods using an energy device.

Example

[0059] Examples are shown below to explain the present invention more specifically, but the interpretation of the present invention is not limited by these examples.

[0060] The various raw materials and manufacturing methods used in the examples etc. are as follows. (A) Substrate layer · Hydrogenated styrene-based thermoplastic elastomer: SEEPS (SEPTON 4055, manufactured by Kuraray Co., Ltd.) (MFR (temperature 230 °C, load 2.16 kg) 0.0 g / 10 min (0.0 g / 10 min means not flowing), styrene content 30 mass%, hydrogenation rate 90 mol% or more) · Oil: Paraffin oil (DIANA PROCESS OIL PW90, manufactured by Idemitsu Kosan Co., Ltd.) · Polymer antistatic agent: Polyolefin / polyether copolymer (Pelektron PVL, manufactured by Sanyo Chemical Industries, Ltd.) (MFR (measured at 190 °C, load 2.16 kg) 8 - 15 g / 10 min) · Ionic liquid as conductivity-imparting agent: CIL-312 (manufactured by Nippon Carlit Co., Ltd.) (B) Adhesive layer · Adhesive 1: Epoxy-based adhesive, Arlembond 556 (manufactured by Arlem Products, silver content 20 - 40 mass%, two-component mixing reaction type) · Adhesive 2: Olefin-based adhesive, TK Paste CN-7120 (manufactured by Kaken Tech Co., silver content 50 mass%) · Adhesive 3: Cyanoacrylate-based adhesive, PPX (manufactured by Cemedine Co., Ltd.) · Adhesive 4: Urethane-based adhesive, Ultra Multi-Purpose SU Premium Soft (manufactured by Konishi Co., Ltd.) · Adhesive 5: Silicone-based adhesive, Super X Clear (manufactured by Cemedine Co., Ltd.) (C) Metal layer · Aluminum foil, foil (manufactured by Mitsubishi Aluminum Co., Ltd., 12 μm thick) (D) Adhesive gel · Polyacrylic acid·polyvinyl alcohol (PVA) gel (manufactured by Sekisui Chemical Co., Ltd., TG-3)

[0061] (Manufacture and Evaluation of Conductive Resin Composition-Metal Laminate) [Examples 1-10] First, a conductive resin composition containing 100 parts by mass of a hydrogenated styrene-based thermoplastic elastomer, 500 parts by mass of oil, 40 parts by mass of a polymer antistatic agent, and 130 parts by mass of an ionic liquid was prepared. As Examples 1-10, an adhesive layer was formed at the thickness shown in Table 1 between the base material layer and the metal layer using Adhesives 1-5, and the 180° peel strength between the base material layer and the adhesive layer, the tensile shear adhesive strength between the base material layer and the adhesive layer, and the volume resistivity of the conductive resin composition-metal laminate were measured by the following methods.

[0062] ·180° Peel Strength A conductive resin composition molded product (base material layer) prepared to a width of 10 mm, a length of 70 mm, and a thickness of 1 mm was bonded with an adhesive (Cemedine Co., Ltd., PPX) from a position 30 mm above the bottom of an acrylic plate with a width of 25 mm, a length of 100 mm, and a thickness of 2 mm to prepare Test Piece 1. Next, an OPP tape (manufactured by Nitoms Co., Ltd., product name: Transparent Packaging Tape No. 3303) was bonded to an aluminum foil (metal layer) so that air did not enter the gap, and Test Piece 2 cut to a width of 10 mm and a length of 150 mm was prepared. Adhesives 1-5 were uniformly applied to the aluminum foil surface of Test Piece 2 using a baker applicator (manufactured by Yoshimitsu Seiki Co., Ltd., model number: YBA type). Immediately after applying Adhesives 1-3, and after leaving Adhesives 4 and 5 for 10 minutes, the surface of the base material layer of Test Piece 1 was bonded with an adhesive area (width 10 mm, length 70 mm), and the adhesive was cured by curing in an environment of 23 ± 2°C and a relative humidity of 50% ± 5% for 24 hours to form an adhesive layer, and Test Piece 3 was prepared. According to JIS K6854-2, at 23 ± 2°C, using a tensile testing machine (model number: AUTOGRAPH AG-X plus) manufactured by Shimadzu Corporation, the ends of the aluminum foil and acrylic plate of the obtained Test Piece 3 were respectively chucked, and the maximum force and minimum force at 180° peel were measured over a peel length of at least 50 mm excluding the first 10 mm with a distance between chucks of 80 mm and a tensile speed of 50 mm / min, and the arithmetic mean value of the maximum force and the minimum force was calculated.

[0063] · Tensile shear adhesion strength A conductive resin composition molded product (base material layer) prepared to a width of 10 mm, a length of 70 mm, and a thickness of 1 mm was joined with a cyanoacrylate-based adhesive (manufactured by Cemedine Co., Ltd., PPX) from a position 30 mm above the bottom of an acrylic plate with a width of 25 mm, a length of 100 mm, and a thickness of 2 mm to produce Test Specimen 1. Next, an OPP tape (manufactured by Nitoms Co., Ltd., product name: Transparent Packaging Tape No. 3303) was laminated on an aluminum foil (metal layer) so that air did not enter the gap, and Test Specimen 2 cut to a width of 10 mm and a length of 100 mm was produced. Adhesives 1-5 were uniformly applied to the aluminum foil surface of Test Specimen 2 using a baker applicator (manufactured by Yoshimitsu Seiki Co., Ltd., model number: YBA type). Immediately after application of Adhesives 1-3, and after leaving Adhesives 4 and 5 for 10 minutes, the surface of the base material layer of Test Specimen 1 was joined with an adhesive area (width 10 mm, length 10 mm), and the adhesive was cured by curing in an environment at a temperature of 23 ± 2°C and a relative humidity of 50% ± 5% for 24 hours to form an adhesive layer, and Test Specimen 3 was produced. Using a tensile testing machine (model number: AUTOGRAPH AG-X plus) manufactured by Shimadzu Corporation at 23 ± 2°C, the ends of the aluminum foil and acrylic plate of the obtained Test Specimen 3 were respectively chucked, the maximum value of the breaking force was measured at a distance of 80 mm between the chucks and a tensile speed of 50 mm / min, and it was obtained by dividing by the adhesive area (width 10 mm, length 10 mm).

[0064] · Volume resistivity Using a baker applicator (manufactured by Yoshimitsu Seiki Co., Ltd., model number: YBA type), adhesives 1-5 were uniformly applied to an aluminum foil (metal layer). Immediately after the application of adhesives 1-3, and after leaving adhesives 4 and 5 standing for 10 minutes, a conductive resin composition molded product (substrate layer) adjusted to a width of 25 mm, a length of 25 mm, and a thickness of 1 mm was joined with an adhesive area (width 25 mm, length 25 mm), and the adhesive was cured by curing for 24 hours in an environment of a temperature of 23 ± 2°C and a relative humidity of 50% ± 5% to form an adhesive layer, and a test piece (conductive resin composition - metal laminate) was produced. After adjusting the test piece for 24 hours or more in an environment of a temperature of 23 ± 2°C and a relative humidity of 50 ± 5%, the volume resistivity 20 seconds after the application of a voltage of 10 V was measured using a resistivity meter Loresta-GP (model number: MCP-T610) and a PSP probe manufactured by Mitsubishi Chemical Analytech Co., Ltd. with respect to the surface on the substrate layer side of the test piece.

[0065] The results are shown in Table 1.

Table 1

[0066] As can be seen from Table 1, it was shown that a conductive resin composition - metal laminate can be manufactured using adhesives 1-5. In particular, the cyanoacrylate-based adhesive of adhesive 3 has a 180° peel strength of 3.5 N / 10 mm or more and a tensile shear adhesive strength of 0.1 N / mm 2 or more, and no significant increase in volume resistivity was observed, indicating that it is preferably used.

[0067] In addition, in order to evaluate the adhesiveness between the conductive resin composition - metal laminate and the counter electrode plate, when the 180° peel strength and the tensile shear adhesive strength between the metal layer side of the conductive resin composition - metal laminate of Example 3 and the counter electrode plate (Erbe Co., thickness 1.0 mm) were measured, the 180° peel strength was 1.6 N / 10 mm and the tensile shear adhesive strength was 0.06 N / mm 2 It was as follows. From the above, it was confirmed that the counter electrode plate can be attached to the surface on the metal layer side of the conductive resin composition - metal laminate of Example 3 with a certain adhesive force or more, and it can be used for medical procedure training using an energy device.

[0068] [Comparative Example 1] As Comparative Example 1, an adhesive gel used when attaching the counter electrode plate to the skin was used instead of the adhesive, and the 180° peel strength between the structure made of the conductive resin composition and the adhesive gel and the tensile shear adhesive strength between the structure made of the conductive resin composition and the adhesive gel were measured in the same manner as in Example 1. The results are shown in Table 2.

Table 2

[0069] As can be seen from Table 2, it was shown that the adhesive gel did not adhere to the structure of the comparative example having no adhesive layer and metal layer with an adhesive force above a certain level, and it was confirmed that the counter electrode plate could not be attached with sufficient strength.

Industrial Applicability

[0070] The conductive resin composition-metal laminate of the present invention can be used for medical procedure training using energy devices.

Explanation of Signs

[0071] 1 Conductive resin composition-metal laminate 2 Base material layer 3 Adhesive layer 4 Metal layer 5 Simulated blood vessel

Claims

1. A conductive resin composition-metal laminate for medical procedure training organ models, comprising a base material layer formed of a conductive resin composition containing a styrene-based thermoplastic elastomer and a metal layer laminated on one surface of the base material layer via an adhesive layer, wherein the medical procedure is a medical procedure using an energy device, the volume resistivity of the conductive resin composition-metal laminate is 1.0×10² to 1.0×10⁷ Ω·cm, the adhesive layer contains one or more adhesives selected from the group consisting of epoxy adhesives, olefin adhesives, cyanoacrylate adhesives, urethane adhesives, and silicone adhesives, and the thickness of the adhesive layer is 5 μm or more and 500 μm or less.

2. The organ model according to claim 1, connected to a counter electrode plate.

3. The organ model according to claim 1 or 2, wherein the energy device is any one selected from the group consisting of high-frequency hemostatic forceps, electric scalpels, ultrasonic scalpels, and high-frequency radio scalpels.

4. The organ model according to claim 1 or 2, comprising a simulated blood vessel connected to a device capable of supplying simulated blood.

5. The organ model according to claim 1 or 2, wherein the medical procedure training is training in endoscopic hemostasis.

6. The organ model according to claim 5, wherein the training in endoscopic hemostasis is training in hemostasis by thermocoagulation using an energy device.

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