JP3830489B2 - Elastomer molded body for endoscope - Google Patents

Description

  The present invention relates to an elastomer molded body, and more particularly to an elastomer molded body for an endoscope.

  In an endoscope, an elastomer molded body made of a fluorine-based elastomer having excellent chemical resistance is used as an outer skin of the curved tube. For example, as an example of such an elastomer molding, a terpolymer of vinylidene fluoride / hexafluoropropylene / tetrafluoroethylene, a liquid fluorine-based elastomer, perhexa 2,5B, triallyl isocyanate, hydrous silica, and reinforcement There is a rubber tube for a curved portion obtained by blending and kneading a functional carbon and crosslinking-mixing the mixed kneaded product (for example, see Patent Document 1).

  By the way, medical endoscopes are required to be completely disinfected and sterilized. Under these demands, in recent years, disinfection and sterilization methods using chemicals such as hydrogen peroxide plasma and peracetic acid and acid water that are non-polluting and environmentally friendly with the characteristics of becoming water or harmless substances after treatment, In addition, high-temperature and high-pressure autoclave methods are beginning to be used.

However, these disinfection and sterilization methods are harsh environments with a very strong oxidizing power, and thus have disadvantages such as corrosion of endoscope parts. For example, it is known that even a fluorine-based elastomer having excellent chemical resistance causes defects such as cracking and swelling when exposed to these environments for a long period of time using conventional compounding techniques. Further, when trying to avoid the above-mentioned problems, problems such as generation of outgas and loss of elasticity peculiar to the elastomer occur and it cannot be used for an endoscope.
JP-A-5-300938

  The present invention has been made in view of the above problems, and an object of the present invention is to provide an elastomer molded body that can be used for an endoscope excellent in resistance under severe disinfection and sterilization environments.

  The present invention solves the above-mentioned problems, and as a result of studies conducted by the present inventors to improve resistance under severe disinfection and sterilization environments, two or more kinds of fluorine having a crosslinking reactive group have been obtained. The present inventors have found that it is effective to blend and apply an elastomer based on the present invention, and have reached the present invention.

The present invention provides an elastomer molded article for an endoscope, comprising two or more kinds of fluorine-based elastomers having a crosslinkable reactive group .

  According to a preferred aspect of the present invention, a thermoplastic elastomer can be used as the fluoroelastomer in the elastomer molded body used for the endoscope.

  According to a preferred aspect of the present invention, the elastomer molded body used for the endoscope may further contain a low molecular weight fluorine-based elastomer having no cross-linking reactive group as a plasticizer.

  Moreover, according to the preferable aspect of this invention, the elastomer molded object used for this endoscope can further contain reinforcing carbon as a coloring agent.

  Moreover, according to the preferable aspect of this invention, the elastomer molded object used for this endoscope can further contain a silica as a reinforcing agent.

  Moreover, according to the preferable aspect of this invention, the elastomer molded object used for this endoscope can be shape | molded as a curved-part outer skin of an endoscope.

  Moreover, according to the preferable aspect of this invention, the elastomer molded object used for this endoscope can be shape | molded as a bending prevention member of an endoscope.

  Moreover, according to the preferable aspect of this invention, the elastomer molded object used for this endoscope can be shape | molded as the outer cover which covers the switch button or switch button of an endoscope.

  Moreover, according to the preferable aspect of this invention, the elastomer molded object used for this endoscope can be shape | molded as an O-ring used for the inside of an endoscope.

  ADVANTAGE OF THE INVENTION According to this invention, the fluorine-type elastomer molded object for endoscopes excellent in the tolerance in a severe disinfection and sterilization environment is obtained.

  The elastomer molded body for an endoscope of the present invention contains two or more types of crosslinkable fluorine-based elastomers.

  Two or more kinds of fluorine-based elastomers used in the present invention are different from each other in, for example, the number of cross-linking reactive groups per molecule or the average molecular weight.

  Here, the term “crosslinking reactive group” means a functional group capable of causing a crosslinking reaction.

  The elastomer molded body for an endoscope of the present invention can be molded using a molding raw material containing a fluorine-based elastomer and various compounding agents.

  When the cross-linking reactive groups of the elastomer are not close to each other at the time of molding, the cross-linking reactive groups do not cause cross-linking and remain in a pendant shape. Thus, if a cross-linking reactive group that does not cause cross-linking exists in the molded body, the unreacted portion is likely to cause deterioration in a harsh environment. Although it is conceivable to increase the blending amount of the crosslinking agent in order to cause the crosslinking reaction sufficiently, there are problems such as an increase in volatile content from the molded article, so-called outgas, and it cannot be applied as a molding raw material for endoscopes. .

  On the other hand, according to the present invention, a molding raw material suitable for an endoscope can be obtained by blending two or more different fluorine-based elastomers, and a molded body using such a molding raw material is harsh. Resistance to disinfection and sterilization is significantly improved. This is because when two or more different types of fluoroelastomers are blended, the cross-linking reactive groups are more likely to be close due to the difference in the molecular weight of the elastomer, resulting in more cross-linking. This is thought to be due to a decrease in resistance to sterilization and chemicals.

  The elastomer molded body for an endoscope of the present invention is used, for example, in a curved portion outer skin of an endoscope, a bending prevention member of the endoscope, an outer skin covering the switch button or the switch button of the endoscope, and the inside of the endoscope. Can be molded as an O-ring.

  Hereinafter, the present invention will be described in more detail with reference to the drawings. In each figure, the same or similar components are denoted by the same reference numerals, and redundant description will be omitted.

  FIG. 1 is a schematic side view of an endoscope according to an embodiment of the present invention. FIG. 2 is an enlarged side view of a part of the endoscope shown in FIG. In FIG. 2, the curved portion is partially cut away.

  The endoscope shown in FIG. 1 includes an operation unit main body 1, a flexible unit 2 that extends from the operation unit main unit 1 and bends when an external force is applied, and has one end supported at the tip of the flexible unit 2, and the operation unit It has a bending portion 3 that bends to an arbitrary angle by a predetermined operation on the main body 1, a tip portion 4 provided at the other end of the bending portion 3, and the like. The distal end portion 4, the bending portion 3, and the flexible portion 2 constitute an insertion portion that is inserted into a hole or the like when the endoscope is used.

  The operation unit main body 1 is provided with an eyepiece 5, an operation knob 6, an air / water button 7, a suction button 8, a treatment instrument insertion port 9, a light guide snake tube 10, and the like. The eyepiece part 5 enables observation of an object located in front of the tip part 4 through the objective lens provided at the tip part 4 and the optical fiber built in the bending part 3 and the flexible part 2. Is. The operation knob 6 adjusts the degree of bending of the bending portion 3, thereby enabling the tip portion 4 to be oriented in a desired direction. The air / water supply button 7 is provided to control the air / water supply from the air / water supply port provided at the distal end portion 4, and the suction button 8 is sucked from the suction port provided at the distal end portion 4. Provided to control. The treatment instrument insertion port 9 allows a treatment instrument such as forceps to be used by protruding from a channel provided in the distal end portion 4. The light guiding flexible tube 10 includes an optical fiber for guiding light from an external light source and irradiating an object located in front of the distal end portion 4.

  The flexible portion 2 includes optical fibers for observation and illumination, and includes a flexible tube 11 and a bend preventing member 12. The bend preventing member 12 is provided to prevent the flexible tube 11 from being bent at the connection position with the operation unit main body 4 and is made of an elastic body containing an elastomer.

  The bending portion 3 includes a plurality of bending pieces 13 in which an optical fiber or the like is housed, a tight pipe 14 that covers the bending pieces 13, an outer skin 15 that covers the tight pipe 14, and the like. Each of the bending pieces 13 has a substantially cylindrical shape, and adjacent ones are rotatably connected with a connecting pin 16 as a rotation axis. Further, a wire (not shown) is connected to the bending pieces 13. With such a structure, the bending tube portion 3 can be bent at a desired angle. The steel pipe 14 that covers the curved piece 13 is made of, for example, a fine metal wire, and prevents the outer skin 15 from being damaged as the curved piece 13 rotates. The outer skin 15 is made of an elastic body containing an elastomer, and prevents the bending portion 3 from damaging the inner wall when, for example, inserting / removing the insertion portion into / from the hole and performing a bending operation in the hole.

  As described above, the distal end portion 4 is provided with an objective lens, an air / water supply port, a suction port, a channel, and the like. The objective lens is used for observing an object positioned in front of the front end portion 4 and irradiating the object with illumination light. The air / water supply port is formed, for example, as a nozzle that sprays fluid onto the surface of the objective lens. In this case, the suction port is used to remove liquid remaining on the surface of the objective lens.

  In the endoscope described above, in order to prevent leakage of liquid or gas accompanying air supply / water supply or suction operation, an O-ring (see FIG. Not shown) is used. In the endoscope described above, the air / water button 7 and the suction button 8 are made of an elastic skin (not shown) for the purpose of preventing the components from corroding during sterilization and sterilization. It may be covered with

  Now, in the endoscope according to the present embodiment, the outer skin 15 of the bending portion 3, the anti-bending member 12, the O-ring, the air / water supply button 7, the suction button 8, or these buttons 7, 8, etc. At least one of the covering skins is substantially composed of a fluoroelastomer molded body formed by cross-linking reaction of a molding raw material in which two or more types of fluoroelastomers having cross-linking reactive groups are blended. Such a fluoroelastomer molded body hardly cracks or swells even when exposed to a chemical solution with strong oxidizing power for a long time. Therefore, an elastomer molded body molded from the molding raw material at least on the outer skin 15 of the curved portion 3. By using this, an endoscope excellent in chemical resistance can be realized. In addition, in order to realize better chemical resistance, the above-mentioned is also applied to the anti-bending member 12, the O-ring, the air / water supply button 7, the suction button 8, or the outer skin covering these buttons 7, 8 and the like. It is preferable to use an elastomer molded body molded from a molding raw material.

  The fluorine-based elastomer molded product of the present invention can be produced by various conventional methods. Prepare at least two kinds of fluorine-based elastomers used in the present invention as main components, knead with a kneader such as a biaxial roll, kneader, Banbury mixer, etc., and add cross-links with various additive components such as cross-linking agents. In such a case, a molding raw material can be prepared by adding a crosslinking aid, a filler and the like while kneading, and finally adding a crosslinking agent. The molding step can be performed using a known rubber molding method such as injection molding or extrusion molding using the molding raw material. For example, this molding raw material can be filled in a mold having a desired shape, heated and pressed, and then irradiated with, for example, radiation. If desired, secondary crosslinking can be performed in a hot air stream. Note that the shape of the molded body is not limited, and is appropriately selected depending on the application, for example, a sheet shape, a rod shape, a ring shape, various complicated block shapes, and the like.

  As a fluorine-type elastomer used for this invention, a well-known thing can be used widely. For example, vinylidene fluoride / hexafluoropropylene copolymer (for example, Daiel G-801 made by Daikin Industries, Florel FC-2260 made by DAINION), vinylidene fluoride / hexafluoropropylene / tetrafluoroethylene copolymer (for example, Dupont) Viton GF, Daikin Kogyo Daiel G-902, Daikin Kogyo Daiel G-912, Dainion Florel FLS-2650, Audimont Technoflon P959), vinylidene fluoride / perfluoromethyl vinyl ether / tetrafluoroethylene copolymer (For example, Viton GLT manufactured by DuPont), tetrafluoroethylene / propylene copolymer (for example, Aphras manufactured by Asahi Glass), ethylene / tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer ( DuPont Viton ETP), and the like if example. Of these, tetrafluoroethylene / propylene copolymers, vinylidene fluoride / hexafluoropropylene / tetrafluoroethylene copolymers, and ethylene / tetrafluoroethylene / perfluoroalkyl vinyl ether copolymers are particularly preferable.

  A thermoplastic elastomer is mentioned as a fluorine-type elastomer preferably used for this invention.

  Such a fluorinated thermoplastic elastomer comprises at least one elastomeric polymer chain segment and at least one non-elastomeric polymer chain segment, at least one of which is a fluorinated polymer chain segment. The ratio of the elastomeric polymer chain segment to the non-elastomeric polymer chain segment is preferably 40 to 95:60 to 5 by weight.

  The specific structure of the fluorine-based thermoplastic elastomer is present in the above-described chain composed of the elastomeric polymer chain segment and the non-elastomeric polymer chain segment, the iodine atom present at one end of the chain, and the other end of the chain. It consists of a residue obtained by removing at least one iodine atom from an iodide compound.

  The elastomeric polymer chain segment is preferably (1) a copolymer of vinylidene fluoride / hexafluoropropylene / tetrafluoroethylene (molar ratio 40 to 90: 5 to 50: 0 to 35), or (2) perfluoro It is a copolymer of alkyl vinyl ether / tetrafluoroethylene / vinylidene fluoride (molar ratio 15 to 75: 0 to 85: 0 to 85), and has a molecular weight of 30,000 to 1,200,000. The non-elastomeric polymer chain segment is preferably (3) a copolymer of vinylidene fluoride / tetrafluoroethylene (molar ratio 0 to 100: 0 to 100), or (4) ethylene / tetrafluoroethylene / hexa. Fluoropropylene, 3,3,3-trifluoropropylene-1,2-trifluoromethyl-3,3,3-trifluoropropylene-1 or perfluoroalkyl vinyl ether (molar ratio 40-60: 60-40: 0 30) a copolymer having a molecular weight of 3,000 to 400,000. As an example of such a fluorinated thermoplastic elastomer, for example, “Dai-L Thermoplastic” manufactured by Daikin Industries, Ltd. may be mentioned.

  The blend ratio of the fluorine-based elastomer can be mixed at an arbitrary weight ratio in the case of blending the two kinds, but is preferably 8: 2 to 5: 5. In the case of blending three or more kinds, a mixing ratio is arbitrarily set in accordance with desired characteristics.

  In addition, as a preferable combination of fluorine-based elastomers, for example, when two types of fluorine-based elastomers are used, there is a combination of Daikin Industries, Ltd. Daiel G902 and Daikin Industries, Ltd. Daiel G912. Is 30/70 to 70/30.

  Moreover, when using 3 types of fluorine-type elastomers, the combination of Daikin Industries, Ltd. Daiel G901, Daikin Industries, Ltd. Daiel G902, and Daikin Industries, Ltd. Daiel G912 is mentioned. A preferred weight mixing ratio in this case is 15 to 70:15 to 70:15 to 70.

  When the above-mentioned preferable combination is used, an elastomer molded article superior in resistance under a severe disinfection / sterilization environment can be obtained.

  Moreover, the additional component added to the fluorine-type elastomer molded object of this invention is as follows.

  As the crosslinking agent used in the elastomer molded body of the present invention, a known peroxide having good chemical resistance can be used. For example, dicumyl peroxide (for example, Park Mill D manufactured by NOF Corporation), -T-butylperoxydiisopropylbenzene (for example, perbutyl P manufactured by NOF Corporation), 2,5-dimethyl-2,5-di (t-butylperoxy) hexane (for example, PERHEXA 25B manufactured by NOF Corporation) and the like. Of these, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane is particularly preferable.

  The addition amount of the peroxide crosslinking agent is preferably 0.5 to 5 parts by weight, more preferably 1 to 3 parts by weight with respect to 100 parts by weight of the fluorine-based elastomer mixture.

  Examples of the co-crosslinking agent include triallyl isocyanurate (for example, TAIC manufactured by Nippon Kasei Chemical Co., Ltd.), triallyl cyanurate (for example, TAC manufactured by Musashino Chemical Laboratory), triallyl trimellilate (for example, TRIAM-705 manufactured by Wako Pure Chemical Industries), N, N'-m-phenylene dimaleimide (for example, Balnock PM-P manufactured by Ouchi Shinsei Chemical), trimethylolpropane trimethacrylate (for example, High Cross M manufactured by Seiko Chemical Co., Ltd.), and other acrylate and methacrylate monomers Can also be used. Of these, triallyl isocyanurate is particularly preferable.

  The addition amount of the co-crosslinking agent is preferably 1 to 10 parts by weight, more preferably 3 to 8 parts by weight with respect to 100 parts by weight of the fluorine-based elastomer mixture.

  When the blending amount of the peroxide crosslinking agent and the co-crosslinking agent is lower than the above value, crosslinking is insufficient, and mechanical properties such as hardness and tensile strength of the molded product tend to be insufficient. On the other hand, when the blending amount exceeds the above range, problems such as outgas generation, a phenomenon in which an alignment component oozes out on the bloom or the surface, or so-called bleeding, tends to occur.

  Moreover, the elastomer molded body for an endoscope of the present invention may further contain a low molecular weight fluorine-based elastomer having no crosslinking reactive group as a plasticizer.

  An example of such a low molecular weight fluorine elastomer is Daiel G101 manufactured by Daikin Industries.

  The addition amount of the low molecular weight fluorine-based elastomer is preferably 1 to 50 parts by weight, more preferably 1 to 15 parts by weight with respect to 100 parts by weight of the fluorine-based elastomer mixture. If it is less than 1 part by weight, the function as a plasticizer cannot be expressed and the moldability during molding tends to deteriorate, and if it exceeds 50 parts by weight, it tends to cause stickiness on the surface of bloom or the like. is there.

  In addition, the elastomer molded body for an endoscope of the present invention may further contain reinforcing carbon as a colorant. When reinforcing carbon is used, for example, in addition to the coloring effect, desired hardness can be obtained depending on the blending amount, and the effect of improving heat resistance can be obtained.

  The amount of reinforcing carbon added is preferably 0.05 to 50 parts by weight, more preferably 0.5 to 15 parts by weight, with respect to 100 parts by weight of the fluorine-based elastomer mixture. If the amount is less than 0.5 part by weight, the coloring effect tends to be small, and if it exceeds 50 parts by weight, the endoscope tends to be too hard.

  Moreover, the elastomer molded body for an endoscope of the present invention may further contain silica as a reinforcing agent. When silica is used, the same effect as the reinforcing carbon can be obtained.

  Moreover, a filler can also be mix | blended as needed. Specific examples include inorganic fillers such as carbon black, silica, barium sulfate, titanium oxide, aluminum oxide, calcium carbonate, calcium silicate, magnesium silicate, and aluminum silicate. Examples of the organic filler include, but are not limited to, polytetrafluoroethylene resin, polyethylene resin, polypropylene resin, phenol resin, polyimide resin, melamine resin, and silicone resin. It is also possible to use a plurality of fillers in combination.

  Furthermore, a fiber etc. can be mix | blended if desired. For example, asbestos, glass fiber, alumina fiber, inorganic fiber such as rock wool, cotton, wool, silk, hemp, nylon fiber, aramid fiber, vinylon fiber, polyester fiber, rayon fiber, acetate fiber, phenol-formaldehyde fiber, polyphenylene sulfide Examples thereof include, but are not limited to, organic fibers such as fibers, acrylic fibers, polyvinyl chloride fibers, polyvinylidene chloride fibers, polyurethane fibers, and tetrafluoroethylene fibers. It is also possible to use a plurality of fibers in combination.

  EXAMPLES Hereinafter, an Example is shown and this invention is demonstrated more concretely.

  The present invention is not limited to the following examples.

Example 1
A material having the following composition was prepared.

Fluorine-based elastomer (DuPont Paiton GLT) 50 parts by weight Fluorine-based elastomer (Augimont Technoflon P959) 50 parts by weight Peroxide-based cross-linking agent (NIPPON YOSHI PERHEX 25B) 2 parts by weight Co-cross-linking agent (Nippon Kasei TAIC) 4 parts by weight Filler (US Silica Mini Seal # 5) 10 parts by weight Colorant (Printtech 140) 0.7 parts by weight Plasticizer (Daikin Kogyo Co., Ltd. Daiel G101) 5 parts by weight A compound as a forming raw material was obtained by kneading with an open roll.

  The compound was filled in a mold and subjected to crosslinking molding at 170 ° C. for 10 minutes, and then subjected to secondary crosslinking in an oven at 200 ° C. for 4 hours to obtain a tube-shaped molded product.

  About the obtained tube-shaped molded article, the durometer hardness was measured by the method according to JIS K6252.

  Further, the molded product was subjected to a tensile test according to JIS K6251 and a tear test according to JIS K6252.

  In addition, as a crack generation test, the degree of crack generation was observed when a needle having a diameter of 1 mm with a weight of 40 g was dropped vertically on the obtained tubular molded product.

  The degree of occurrence of cracks was evaluated as “◎: None”, “◯: Almost absent”, “△: Somewhat present”, and “×: Many”.

  In addition, as a chemical solution immersion accelerated deterioration test, the molded product was immersed in a 3.7% peracetic acid aqueous solution at 53 ° C. for 30 days, and the occurrence of deterioration was observed. The degree of deterioration was evaluated in the same manner as the degree of cracking.

  Furthermore, a volatile matter test was performed on the molded body when heated at 200 ° C. for 10 hours. Here, the case where the volatile content was 1000 ppm or less was evaluated as ◯, and the case where the volatile content exceeded 1000 ppm was evaluated as x.

  The composition of the molding material is shown in Table 1 below, and the results of hardness, tensile test, tear test, crack generation test, chemical immersion accelerated deterioration test, and molded product volatile content test are shown in Table 2 below.

  The obtained molded product was treated with steam at 135 ° C. at 202.925 kPa (2.2 atm) for 100 hours in an autoclave apparatus. The crack generation test was similarly conducted on the molded product after the autoclave treatment. The degree of occurrence of cracks after treatment is also shown in Table 2 below.

Example 2
A material having the following composition was prepared.

Fluorine elastomer (Daikin Kogyo Co., Ltd., Daiel G902) 50 parts by weight Fluorine elastomer (Daikin Kogyo Co., Ltd., Daiel G912) 50 parts by weight Peroxide-based cross-linking agent (Nippon Yushi Fatty Perb 25B) 2 parts by weight Co-crosslinking Agent (Nippon Kasei TAIC) 4 parts by weight Filler (US Silica Mini-Seal # 5) 10 parts by weight Colorant (Printtech 140) 0.7 parts by weight Got the compound as. The compound was filled in a mold and subjected to crosslinking molding at 170 ° C. for 10 minutes, and then subjected to secondary crosslinking in an oven at 200 ° C. for 4 hours to obtain a tube-shaped molded product.

  The composition of the molding material is shown in Table 1 below.

  The obtained molded product was subjected to hardness, tensile test, tear test, crack generation test, chemical immersion accelerated deterioration test, and molded product volatile content test in the same manner as in Example 1. Further, the obtained molded product was subjected to the same autoclave treatment as in Example 1, and a crack generation test was performed on the molded product after the treatment. The results are shown in Table 2 below.

Example 3
A material having the following composition was prepared.

Fluorine-based elastomer (Audimont Technoflon P959) 33 parts by weight Fluorine-based elastomer (Daikin Industries, Ltd., Daiel G902) 33 parts by weight Fluorine-based elastomers (Daikin Industries, Ltd., Daiel G912) 33 parts by weight Peroxide-based crosslinking 2 parts by weight of co-crosslinking agent (TAIC made by Nippon Kasei) 4 parts by weight Filler (USSeal Mini-Seal # 5) 10 parts by weight Colorant (Printtech 140) 0.7 Part by weight Plasticizer (Daiel Industries, Ltd., Daiel G101) 5 parts by weight The above materials were kneaded with an open roll to obtain a compound as a forming raw material. The compound was filled in a mold and subjected to cross-linking molding at 170 ° C. for 10 minutes, and then subjected to secondary cross-linking at 200 ° C. for 4 hours in an oven to obtain a tubular molded product.

  The composition of the molding material is shown in Table 1 below.

  The obtained molded product was subjected to hardness, tensile test, tear test, crack generation test, chemical immersion accelerated deterioration test, and molded product volatile content test in the same manner as in Example 1. Further, the obtained molded product was subjected to the same autoclave treatment as in Example 1, and a crack generation test was performed on the molded product after the treatment. The results are shown in Table 2 below.

Example 4
A material having the following composition was prepared.

Fluorine-based elastomer (Daikin Kogyo Co., Ltd. Daiel G902) 70 parts by weight Fluorine-based elastomer (Daikin Kogyo Co., Ltd. Daiel G912) 30 parts by weight Peroxide-based cross-linking agent (Nippon Oil & Fats Park Mill D) 2 parts by weight Co-crosslinking Agent (Nippon Kasei TAIC) 4 parts by weight Filler (US Silica Mini Seal # 5) 10 parts by weight Colorant (Printtech 140) 0.7 parts by weight Plasticizer (Daikin Kogyo Co., Ltd. Daiel G101) ) 5 parts by weight The above materials were kneaded with an open roll to obtain a compound as a forming raw material. The compound was filled in a mold and subjected to cross-linking molding at 170 ° C. for 10 minutes, and then subjected to secondary cross-linking at 200 ° C. for 4 hours in an oven to obtain a tubular molded product.

  The composition of the molding material is shown in Table 1 below.

  The obtained molded product was subjected to hardness, tensile test, tear test, crack generation test, chemical immersion accelerated deterioration test, and molded product volatile content test in the same manner as in Example 1. Further, the obtained molded product was subjected to the same autoclave treatment as in Example 1, and a crack generation test was performed on the molded product after the treatment. The results are shown in Table 2 below.

Example 5
A material having the following composition was prepared.

Fluorine-based elastomer (Aflas 100H manufactured by Asahi Glass Co., Ltd.) 70 parts by weight Fluorine-based elastomer (Aflas 150P manufactured by Asahi Glass Co., Ltd.) 30 parts by weight Peroxide-based cross-linking agent (Perhexa 25B manufactured by NOF Corporation) Nippon Kasei TAIC) 4 parts by weight Filler (US Silica Mini Seal # 5) 10 parts by weight Colorant (Printtech 140) 0.7 parts by weight Plasticizer (Daikin Industries, Ltd. Daiel G101) 5 Part by weight The above materials were kneaded with an open roll to obtain a compound as a forming raw material. This compound was filled in a mold and subjected to cross-linking molding at 170 ° C. for 10 minutes, and then subjected to secondary cross-linking at 200 ° C. for 4 hours in an oven to obtain a tubular molded product.

  The composition of the molding material is shown in Table 1 below.

  The obtained molded product was subjected to hardness, tensile test, tear test, crack generation test, chemical immersion accelerated deterioration test, and molded product volatile content test in the same manner as in Example 1. Further, the obtained molded product was subjected to the same autoclave treatment as in Example 1, and a crack generation test was performed on the molded product after the treatment. The results are shown in Table 2 below.

Example 6
A material having the following composition was prepared.

Fluorine-based elastomer (Daikin Industries, Ltd. Daiel G912) 50 parts by weight Fluorine-based elastomer (Daikin Industries, Ltd. Daiel Thermoplastic T530) 50 parts by weight Co-crosslinking agent (Nippon Kasei TAIC) 4 parts by weight Filler ( Aerosil 200, manufactured by Nippon Aerosil Co., Ltd. 10 parts by weight Colorant (Printtech 140) 0.7 parts by weight Plasticizer (Daiel Industries, Ltd., Daiel G101) 5 parts by weight The above materials are kneaded in a kneader heated to 240 ° C. and molded. A compound as a raw material was obtained. The compound was filled in a mold and molded at 170 ° C. for 10 minutes, and then the mold was cooled to room temperature. After cooling the mold, an electron beam having an acceleration voltage of 3 MeV and a dose of 80 KGy was irradiated to obtain a tube-shaped molded product.

  The composition of the molding material is shown in Table 1 below.

  The obtained molded product was subjected to hardness, tensile test, tear test, crack generation test, chemical immersion accelerated deterioration test, and molded product volatile content test in the same manner as in Example 1. Further, the obtained molded product was subjected to the same autoclave treatment as in Example 1, and a crack generation test was performed on the molded product after the treatment. The results are shown in Table 2 below.

Comparative Example 1
A material having the following composition was prepared.

Fluoroelastomer (Augmont's Technoflon P959) 100 parts by weight Peroxide-based cross-linking agent (Nippon Oil & Fats Perhexa 25B) 2 parts by weight Co-crosslinking agent (Nippon Kasei TAIC) 4 parts by weight Filler (made by US Silica) Mini-seal # 5) 10 parts by weight Colorant (Printtech 140) 0.7 parts by weight Plasticizer (Daikin Kogyo Co., Ltd., Daiel G101) 5 parts by weight The above materials are kneaded with an open roll and compounded as a molding raw material. Obtained. The compound was filled in a mold and subjected to cross-linking molding at 170 ° C. for 10 minutes, followed by secondary cross-linking in an oven at 200 ° C. for 4 hours to obtain a tube-shaped molded product.

  The composition of the molding material is shown in Table 1 below.

  The obtained molded product was subjected to hardness, tensile test, tear test, crack generation test, chemical immersion accelerated deterioration test, and molded product volatile content test in the same manner as in Example 1. Further, the obtained molded product was subjected to the same autoclave treatment as in Example 1, and a crack generation test was performed on the molded product after the treatment. The results are shown in Table 2 below.

Comparative Example 2
A material having the following composition was prepared.

Fluorine-based elastomer (Daiel Kogyo Co., Ltd., Daiel G902) 100 parts by weight Peroxide-based cross-linking agent (Nippon Oil & Fats Perhexa 25B) 2 parts by weight Co-crosslinking agent (Nippon Kasei TAIC) 4 parts by weight Filler (US Silica Mini-Seal # 5) 10 parts by weight Colorant (Printtech 140) 0.7 parts by weight Plasticizer (Daikin Kogyo Co., Ltd., Daiel G101) 5 parts by weight Got the compound. This compound was filled in a mold and subjected to cross-linking molding at 170 ° C. for 10 minutes, and then subjected to secondary cross-linking at 200 ° C. for 4 hours in an oven to obtain a tubular molded product.

  The composition of the molding material is shown in Table 1 below.

  The obtained molded product was subjected to hardness, tensile test, tear test, crack generation test, chemical immersion accelerated deterioration test, and molded product volatile content test in the same manner as in Example 1. Further, the obtained molded product was subjected to the same autoclave treatment as in Example 1, and a crack generation test was performed on the molded product after the treatment. The results are shown in Table 2 below.

Comparative Example 3
A material having the following composition was prepared.

Fluorine-based elastomer (Daiel Industries, Ltd., Daiel G912) 100 parts by weight Peroxide-based cross-linking agent (Nippon Oil & Fats Perhexa 25B) 2 parts by weight Co-crosslinking agent (Nippon Kasei TAIC) 8 parts by weight Filler (US Silica mini seal # 5) 10 parts by weight Colorant (Printtech 140) 0.7 parts by weight Plasticizer (Daikin Kogyo Co., Ltd. Daiel G101) 5 parts by weight Got the compound. The compound was filled in a mold and subjected to cross-linking molding at 170 ° C. for 10 minutes, and then subjected to secondary cross-linking at 200 ° C. for 4 hours in an oven to obtain a tubular molded product.

  The composition of the molding material is shown in Table 1 below.

  The obtained molded product was subjected to hardness, tensile test, tear test, crack generation test, chemical immersion accelerated deterioration test, and molded product volatile content test in the same manner as in Example 1. Further, the obtained molded product was subjected to the same autoclave treatment as in Example 1, and a crack generation test was performed on the molded product after the treatment. The results are shown in Table 2 below.

Comparative Example 4
A material having the following composition was prepared.

Fluorine elastomer (Daikin Industries, Ltd. Daiel Thermoplastic T530) 100 parts by weight Co-crosslinking agent (TAIC manufactured by Nippon Kasei) 4 parts by weight Filler (Aerosil 200 manufactured by Nippon Aerosil) 10 parts by weight Colorant (Printtech 140) 0.7 parts by weight The above material was kneaded with a kneader heated to 240 ° C. to obtain a compound as a molding material. The compound was filled in a mold and molded at 170 ° C. for 10 minutes, and then the mold was cooled to room temperature. After cooling the mold, an electron beam having an acceleration voltage of 3 MeV and a dose of 80 KGy was irradiated to obtain a tube-shaped molded product.

  The composition of the molding material is shown in Table 1 below.

The obtained molded product was subjected to hardness, tensile test, tear test, crack generation test, chemical immersion accelerated deterioration test, and molded product volatile content test in the same manner as in Example 1. Further, the obtained molded product was subjected to the same autoclave treatment as in Example 1, and the molded product after the treatment was subjected to a crack generation test. The results are shown in Table 2 below.

  As can be seen from Table 2, in Examples 1 to 6, the results of the tensile test, the tear test, the crack generation test, the chemical immersion accelerated deterioration test, and the volatile content test of the molded body are good, and the crack generation after the autoclave treatment There were no problems with the test.

  Compared with Examples 1 to 6, Comparative Example 1 is good in hardness and tensile strength, but is slightly inferior in tear strength, cracks are generated after autoclaving, and deterioration occurs due to chemical immersion. Occurred. In Comparative Example 2, the hardness and tensile strength were good, but the tear strength was somewhat inferior, and some cracks were seen after autoclaving. In Comparative Example 3, although the hardness was somewhat large, the tensile test, the tear test, the crack generation test, and the chemical immersion accelerated deterioration test were sufficient, but the molded article had a large amount of volatile matter, and thus the unreacted co-polymer It was found that a crosslinking agent was generated and was not practical. In Comparative Example 4, although the hardness and tensile strength were good, the tear strength was somewhat inferior, and some cracks were generated after autoclaving, and deterioration was caused by chemical immersion.

  As is clear from these test results, Examples 1 to 6 have better mechanical properties, better chemical resistance, and almost no deterioration in a sterilized environment as compared with Comparative Examples 1 to 4. I found that there was no. Thus, it has been found that when the present invention is used, it is possible to obtain an elastomer molded article for an endoscope which has a remarkably excellent resistance under a severe disinfection / sterilization environment.

  The present invention is not limited to the above embodiments, and various modifications can be made without departing from the spirit of the present invention.

(Appendix)
Appendix 1. An elastomer molded article for an endoscope, comprising two or more types of cross-linkable fluoroelastomers.

  Appendix 2. 2. The elastomer molded article for an endoscope according to claim 1, wherein the fluorine elastomer is a fluorine thermoplastic elastomer.

  Appendix 3. The elastomer molded article for an endoscope according to claim 1 or 2, further comprising a low molecular weight fluorine-based elastomer having no crosslinking reactive group as a plasticizer.

  Appendix 4. The elastomer molded body for an endoscope according to any one of claims 1 to 3, further comprising silica as a reinforcing agent.

  Appendix 5. The elastomer molded body for an endoscope according to any one of claims 1 to 4, further comprising reinforcing carbon as a colorant.

  Appendix 6. The elastomer molded body for an endoscope according to any one of claims 1 to 5, wherein the elastomer molded body for an endoscope is molded as an outer skin of a curved portion of an endoscope.

  Appendix 7. The elastomer molded body for an endoscope according to any one of claims 1 to 6, wherein the elastomer molded body for an endoscope is molded as a bending prevention member of an endoscope.

  Appendix 8. The elastomer molded body for an endoscope according to any one of claims 1 to 7, wherein the elastomer molded body for an endoscope is formed as a switch button of an endoscope or an outer skin covering the switch button.

  Appendix 9. The elastomer molded body for an endoscope according to any one of claims 1 to 8, characterized in that it is molded as an O-ring used inside an endoscope.

1 is a schematic side view of an endoscope according to an embodiment of the present invention. The side view which expanded a part of endoscope shown in FIG.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Operation part main body, 2 ... Flexible part, 3 ... Bending part, 4 ... Tip part, 5 ... Eyepiece part, 6 ... Operation knob, 7 ... Air supply / water supply button, 8 ... Suction button, 9 ... Treatment Tool insertion port, 10 ... Light guiding tube, 11 ... Flexible tube, 12 ... Anti-bending member, 13 ... Curved piece, 14 ... Steel tube, 15 ... Outer skin, 16 ... Connecting pin

Claims (9)

An elastomer molded article for an endoscope, comprising two or more kinds of fluorine-based elastomers having a crosslinkable reactive group .   The endoscope elastomer molded body according to claim 1, wherein the fluorine-based elastomer is a fluorine-based thermoplastic elastomer.   The elastomer molded article for an endoscope according to claim 1 or 2, further comprising a low molecular weight fluorine-based elastomer having no crosslinking reactive group as a plasticizer.   The elastomer molded body for an endoscope according to any one of claims 1 to 3, further comprising silica as a reinforcing agent.   The elastomer molded body for an endoscope according to any one of claims 1 to 4, further comprising reinforcing carbon as a colorant.   The elastomer molded body for an endoscope according to any one of claims 1 to 5, wherein the elastomer molded body for an endoscope is molded as an outer skin of a curved portion of an endoscope.   The elastomer molded body for an endoscope according to any one of claims 1 to 6, wherein the elastomer molded body for an endoscope is molded as a bending prevention member of an endoscope.   The elastomer molded body for an endoscope according to any one of claims 1 to 7, wherein the elastomer molded body for an endoscope is formed as a switch button of an endoscope or an outer skin covering the switch button.   The elastomer molded body for an endoscope according to any one of claims 1 to 8, characterized in that it is molded as an O-ring used inside an endoscope.

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