JP2007084644A - Antibacterial resin molding, and liquid sending hose comprising the antibacterial resin molding and for food and drink - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide antibacterial resin moldings having better antibacterial property than silver ion, capable of keeping transparency when used as a transparent material, containing eluate as little as possible and usable for food applications. <P>SOLUTION: The antibacterial resin molding comprises a resin having recurring units represented by chemical formula (1) [X is O, S or Se; and (a) is an integer of 0-10] and a resin having recurring units of alkylene imine. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a resin molded article having excellent antibacterial properties, and more particularly to an antibacterial resin molded article that can be used for both transparent resins and opaque resins, and is suitably used as a tubular material. It is.

  Conventionally, products that can prevent the occurrence of mold and bacteria in parts that require a sanitary environment such as indoor water circulation and hot and humid places have been demanded.

  Other technologies that specifically control the growth of harmful microorganisms by incorporating antibacterial substances into various polymer materials such as food packaging, construction, clothing, sanitary goods, kitchenware, and water treatment equipment Pre-existing.

  In particular, in the case of food packaging materials and water treatment devices, it has been common to use silver ion-substituted zeolite, which is an inorganic compound, as the main antibacterial substance for safety to humans. Among metal ions, silver ions have the strongest antibacterial properties, and silver nitrate solutions have a history of being used as disinfectants for medical and military purposes. However, silver-containing antibacterial agents are excellent in antibacterial activity among inorganic compounds, but have problems such as discoloration due to high temperature or light irradiation, and loss of transparency, and the antibacterial performance deteriorates with time. As antibacterial substances, not only inorganic compounds but also natural products are attracting attention from the viewpoint of safety, but natural products have problems such as low antibacterial performance.

  On the other hand, organic compounds generally have better antibacterial performance than natural products and inorganic compounds, but are easily dissolved in water, organic solvents, etc., and are also easily volatilized and separated. Also, because of its toxicity, it tends to be avoided. Therefore, it is not suitable for applications that require antibacterial performance for a long period of time, such as clothes, daily necessities, furniture, or building materials.

  Under such circumstances, recently, an insoluble, non-toxic immobilized antibacterial material in which an organic antibacterial agent is ionically or covalently bonded to a polymer material has been developed.

Specifically, an antibacterial material mainly composed of a polymer substance containing an antibacterial component having a quaternary ammonium base ion-bonded with an acidic group such as a carboxyl group or a sulfonic acid group has been proposed (see Patent Document 1). In addition, as inventions in which phosphonium salts are immobilized on a polymer substance and attempted to expand the application, a proposal for an antibacterial agent of a phosphonium salt vinyl polymer (see Patent Document 2), an antibacterial property of a vinylbenzylphosphonium salt vinyl polymer Proposals for agents (see Patent Document 3) and other proposals for antibacterial resin compositions containing a polymeric antibacterial agent and a hydrophilic vinyl polymer (see Patent Document 4) have been made.
JP 54-86584 A JP-A-4-814365 JP-A-5-310820 JP 2001-055518 A

  However, in the kneading of the silver-substituted zeolite into the plastic sheet, the silver ions used are only a small amount of the silver-substituted zeolite exposed on the surface, which means that the utilization efficiency of expensive silver is very high. It is low. Furthermore, when the antibacterial sheet is used in the presence of a nutrient source, the antibacterial property is determined by the competitive relationship between the ability of silver ions to prevent the growth of microorganisms and the growth rate of microorganisms. Need to increase. However, in the conventional kneading method, due to continuous productivity and a decrease in barrier properties due to pinholes, the upper limit of the zeolite content is 5% by weight, and the silver ion concentration on the surface is in a very limited range. There was a problem that could only be changed. In addition, it becomes cloudy by kneading silver ions even with transparent resins, and problems such as changes in contents cannot be visually observed in food packaging applications and water treatment equipment applications, and there are limits to the useful life There is also.

  In addition, for antibacterial resin compositions containing a high molecular weight antibacterial agent and a hydrophilic vinyl polymer, for example, for use in food, the hydrophilic vinyl polymer is eluted in food or has an antibacterial effect. Problems such as long-lasting will occur.

  Accordingly, an object of the present invention is to solve the above-mentioned problems, have antibacterial properties better than silver ions, can maintain transparency even when used in transparent materials, and can be used for food applications. It is in providing a conductive resin molding.

  In order to solve the above-mentioned problems, the antibacterial resin molded body of the present invention has the following configuration. That is, the antibacterial resin molding of the present invention has the following chemical structural formula (1)

(Wherein X represents oxygen, sulfur or selenium, and a is an integer of 0 to 10), and the following chemical structural formula (2)

(Wherein x, y and z are each an integer of 1 to 10, the ratio of m to n is 0.1: 99.9 to 99.9: 0.1, and A and B are each independently hydrogen An antibacterial resin molded product comprising a resin having a repeating unit represented by the following formula:

  In a preferred embodiment of the antibacterial resin molded article of the present invention, the resin having a repeating unit represented by the chemical structural formula (1) is polyvinyl pyrrolidone or a copolymer thereof, and the chemical structural formula (2 ) Is a polyethyleneimine or a copolymer thereof.

  In a preferred embodiment of the antibacterial resin molded article of the present invention, the antibacterial resin molded article of the present invention contains a resin comprising repeating units of polysulfone and / or polyethersulfone.

  In a preferred embodiment of the antibacterial resin molded body of the present invention, the antibacterial resin molded body of the present invention contains a resin composed of repeating units of ethylene vinyl alcohol.

  In a preferred embodiment of the antibacterial resin molded body of the present invention, the antibacterial resin molded body of the present invention contains a polyalkylene glycol having an alkyl group with 1 to 10 carbon atoms.

  In a preferred embodiment of the antibacterial resin molded body of the present invention, the amount of elution of the antibacterial resin molded body of the present invention in water is 500 ppm or less.

  In a preferred embodiment of the antibacterial resin molded body of the present invention, the shape of the antibacterial resin molded body of the present invention is tubular, and this tubular antibacterial resin molded body is suitable for a liquid feeding hose for beverages, etc. The liquid feeding hose for beverages is suitably used for a water purifier or the like.

  In a preferred embodiment of the antibacterial resin molded body of the present invention, the antibacterial resin molded body is formed by irradiation with radiation after the molding step, and the radiation is preferably an electron beam or γ-ray.

  According to the present invention, a transparent antibacterial molded article having excellent antibacterial properties and originally using a transparent polymer compound material can be obtained, and even when a hydrophilic polymer is contained, the amount of elution in water is extremely small An antibacterial resin molding is obtained. Moreover, since the antibacterial resin molding of the present invention contains a hydrophilic polymer and has improved slipperiness, it has the effect of being less likely to have deposits such as scale.

  The antibacterial resin molding of the present invention has the following chemical structural formula (1)

(Wherein X represents oxygen, sulfur or selenium, and a and b are integers of 0 to 1), and the following chemical structural formula (2)

(Wherein x, y and z are each an integer of 1 to 10, the ratio of m to n is 0.1: 99.9 to 99.9: 0.1, and A and B are each independently hydrogen An antibacterial resin molded product comprising a resin having a repeating unit represented by the following formula: A and B are each independently selected from a hydrogen atom and a bond: A and B are linear polymers such as primary amines composed of hydrogen atoms, one of A or B is a hydrogen atom, the other Represents a branched polymer such as a secondary amine in which is a bond to a carbon atom, or a tertiary amine in which A and B are a bond to a carbon atom.

  In the present invention, various monomer repeating units can be used in the polymer material depending on the function to be imparted. In order to impart hydrophilicity, biocompatibility and antistatic properties, in the above chemical structural formula (1), X can be selected from oxygen, sulfur or selenium, and a is an integer in the range of 0-10. You can choose. Moreover, in said chemical structural formula (2), x, y, and z can also be selected in the integer range of 0-10, respectively.

  As a typical example of a resin having a repeating unit represented by each structural formula above, for the chemical structural formula (1), polyvinyl pyrrolidone, polyallyl pyrrolidone, or a copolymer thereof may be used, and irradiation with radiation may be performed. In consideration of the graft activity at the time, in particular, when X is oxygen, a = 1 and b = 0, the following chemical structural formula (3)

The polyvinylpyrrolidone represented by these or its copolymer is suitable.

  Regarding chemical structural formula (2), for example, polyethyleneimine, polytrimethyleneimine, polytetramethyleneimine, polypentamethyleneimine, polyhexamethyleneimine, polypolyheptamethyleneimine, polyoctamethyleneimine, polynonamethyleneimine , Polydecanmethyleneimine and 1-propanimine or copolymers thereof, and other synthetic polymer compounds such as polyvinylamine and polyallylamine, and polyamino acids such as polyornithine and polylysine are also used. it can. Among these, polyethyleneimine or a copolymer thereof in which x, y, and z are all 2 and the ratio of m to n is 1: 1 is preferable in consideration of the graft activity during irradiation.

  For the resin having a repeating unit represented by the chemical structural formula (1) used in the present invention, a hydrophilic polymer is preferably used. The polymer is preferable to the monomer because the polymer is generally less likely to elute into various aqueous solutions than the monomer when it comes into contact with various aqueous solutions as an antibacterial material after resin molding.

  The weight average molecular weight of the polyvinylpyrrolidone used suitably by this invention becomes like this. Preferably it is 2000-2 million, More preferably, it is 10000-15500. From the viewpoint of easy availability, commercially available polyvinyl pyrrolidone having a weight average molecular weight of 1.1 million, 45,000, 29,000, 9000 and 2900 is preferably used. The weight average molecular weight of polyvinylpyrrolidone described here is the molecular weight at the raw material stage. When means such as radiation crosslinking is used in the subsequent process, the molecular weight of polyvinylpyrrolidone is larger than the molecular weight in the raw material stage.

  Examples of polyvinyl pyrrolidone products include “Kollidon” (registered trademark) 12 PF, 17 PF, 25, 30, and 90 (manufactured by BASF), “Lubicol” (registered trademark) K17, K 30, K80, K90 (manufactured by BASF), and "Prasdon" (registered trademark) K-29 / 32, K-25, K-90, K-90D, K90-M (manufactured by ISP) And the like.

  The polyvinyl pyrrolidone used in the present invention is preferably a homopolymer, but may be copolymerized with other monomers as long as the effects of the present invention are not hindered. Examples of the monomer to be copolymerized include vinyl alcohol, alkylene glycol, and cationic monomer (vinyl imidazolium methochloride). The amount of the copolymerization monomer is not particularly limited, but is preferably 80% by weight or less.

  Examples of polyvinyl pyrrolidone copolymer products include “Kollidon” (registered trademark) VA 64 (manufactured by BASF), “Rubicol” (registered trademark) VA 64 (manufactured by BASF), and “Rubitec” (registered trademark). Examples include polyvinyl pyrrolidone copolymers such as VPI55K18P, VPI55K72W, Quat 73W, VPMA 91W, VPC55 K65W (manufactured by BASF), and “Prasdon” (registered trademark) S-630 (manufactured by ISP). .

  In the present invention, it is preferable to use polyvinyl pyrrolidone in combination with other resin materials in order to stably hold polyvinyl pyrrolidone as a material form and prevent it from eluting, deforming, or collapsing in large quantities. The constitution and the composite method of the polyvinyl pyrrolidone and the other resin material are not particularly limited, and the other resin material and the polyvinyl pyrrolidone may be laminated, but are preferably mixed or compatible. .

  The amount of polyvinyl pyrrolidone contained in the antibacterial resin molded product of the present invention is preferably 0.1% by weight or more and 70% by weight or less because in many cases the antibacterial resin molded product requires a certain level of strength. More preferably, it is 0.5 wt% or more and 50 wt% or less, and most preferably 1 wt% or more and 30 wt% or less.

  The amount of polyethyleneimine contained in the antibacterial resin molded product of the present invention is preferably 0.01% by weight or more and 40% by weight or less, and more preferably, because the antibacterial resin molded product requires a certain degree of strength. It is 0.01 weight% or more and 20 weight% or less, Most preferably, it is 0.01 weight% or more and 10 weight% or less. Considering the transparency of the antibacterial resin molding, the amount of polyethyleneimine is preferably less than the amount of polyvinylpyrrolidone, more preferably the blending ratio of polyvinylpyrrolidone: polyethyleneimine is 3: 1 or less, Most preferably, it is 5: 1 or less.

  The polyvinyl pyrrolidone content can be confirmed by a single method or a combination of known methods such as elemental analysis and NMR (nuclear magnetic resonance analysis).

  In the present invention, in addition to the resin having the repeating unit represented by the chemical structural formula (1), the resin having the repeating unit represented by the chemical structural formula (2) is used in combination in the antibacterial resin molding. To do. By using a combination of polymers having amino groups as described above, the antibacterial effect can be further enhanced. Among the resins having a repeating unit represented by the chemical structural formula (2), polyethyleneimine and its copolymer are most preferably used as described above.

  The number average molecular weight of the polyethyleneimine used in the present invention is preferably 200 to 100,000, more preferably 250 to 70,000. From the viewpoint of easy availability, commercially available polyethyleneimines having number average molecular weights of 250, 300, 600, 1000, 1200, 1800, 10000 and 70000 are suitable. The number-average molecular weight of polyvinylpyrrolidone described here is the molecular weight at the raw material stage. When means such as radiation crosslinking is used in the subsequent process, the molecular weight of polyethyleneimine is larger than the molecular weight in the raw material stage.

  Examples of polyethyleneimine products include "Epomin" (registered trademark) SP-003, SP-006, SP-012, SP-018, SP-200, SP-200, SP-103, Examples include polyethyleneimine such as SP-110 and P-1000 (manufactured by Nippon Shokubai Co., Ltd.).

  The number average molecular weight of the polyethyleneimine copolymer used in the present invention is preferably 300 to 1500,000, and is a branched one containing not only a linear polymer that is a primary amine but also a secondary or tertiary amine. Are preferably used, and primary, secondary, and tertiary amines can be used alone or in combination of two or more. Examples of copolymerization include alkylene glycol, vinyl alcohol, ethylene oxide, and vinyl pyrrolidone.

  A resin such as polyethyleneimine having a repeating unit represented by the chemical structural formula (2) is used in combination with a resin having a repeating unit represented by the chemical structural formula (1). The total amount of the resin having the repeating unit represented by the chemical structural formula (1) and the resin having the repeating unit represented by the chemical structural formula (2) contained in the antibacterial resin molded article of the present invention is preferably It is 0.1 to 70% by weight, more preferably 0.5 to 50% by weight, and most preferably 1 to 30% by weight.

  In the present invention, a resin having a repeating unit represented by the chemical structural formula (1), a chemical structure, in order to stably hold as a material form and prevent elution, deformation, or collapse in a large amount A resin having a repeating unit represented by the formula (2) is preferably used in combination with another resin material.

  Examples of other resin materials used in the antibacterial resin molding of the present invention include thermoplastic resins and thermosetting resins, and other general-purpose resins and rubbers can also be used. Of these, hydrophobic polymer compounds are preferably used as other resin materials.

  Specific examples of such other resin materials include polyolefin, polystyrene, polyvinyl, polyacryl, polyhaloolefin, polydiene, polyether, polyester, polyamide, polyurethane, polyurea, polyimide, polyanhydride, polycarbonate, Polyimine, polysiloxane, polyphosphazene, polyketone, polysulfone, polyethersulfone, polyphenylene, phenol resin, urea resin, melamine resin, diallyl phthalate resin, silicon resin, vinyl chloride, vinylidene chloride, vinyl acetate, polyvinyl alcohol, polyvinyl acetal, polystyrene AS resin (copolymer of styrene and acrylonitrile), ABS resin, ACS resin (chlorinated polyethylene graft polymerized with acrylonitrile and styrene) , Methacrylic resin, polyethylene (low density and / or high density), EVA resin (ethylene and vinyl acetate copolymer), EVOH resin (ethylene vinyl alcohol), polypropylene resin, polybutene resin, polybutylene resin, methylpentene resin, Polybutadiene resin, fluororesin (polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, Tetrafluoroethylene-ethylene copolymer), polyamide, polyacetal, saturated polyester, polyphenylene ether, polyphenylene sulfide, polyarylate, polyether ether Teruketon, liquid crystal plastic, cellulosic polymer, thermoplastic elastomer, artificial rubber and natural rubber.

  Other resin materials particularly preferably used in the present invention are polyethylene, polypropylene, polystyrene, polymethylpentene, polysulfone, polyethersulfone, polyacrylate, polyacrylamide, polyvinyl chloride, polyacrylonitrile, polyvinyl acetate, polyvinyl alcohol, and polyvinylpyrrolidone. In the case of radiation-disintegrating polymers such as polyisobutylene and polyvinylidene chloride, it is necessary to react with a very reduced amount of radiation, even if the same vinyl-type monomer is used. Since these distinctions are affected by the conditions at the time of radiation irradiation, such as temperature and atmosphere, depending on the conditions, not only polyolefin resin but also nylon or polydimethylsiloxane can be used.

  When irradiating with radiation, polytetrafluoroethylene or the like is likely to deteriorate over time when irradiated with extremely strong radiation, and may cause deterioration of physical properties. In addition, although polyvinyl chloride is a cross-linked polymer, it undergoes a dehydrochlorination reaction and is colored by radiation. The degree of coloring varies depending on the radiation dose, and the color becomes dark blue at a low dose and turns brown at a high dose, but the degree and color of the coloring also change depending on the additive. Therefore, when irradiating other resin materials that are these polymer materials with radiation, the radiation dose is adjusted by paying attention to changes in physical properties.

  In the present invention, a polysulfone polymer is most preferably used as another resin material. In particular, those having an aromatic ring, a sulfonyl group and an ether group in the main chain, for example, polysulfone and polyethersulfone are preferably used. The number average molecular weight of these polymers (resins) is preferably 5,000 to 100,000, more preferably 10,000 to 50,000.

  Examples of polysulfone products include “Udel” (registered trademark) P-1700, P-3500 (manufactured by Teijin Amoco), “Ultra Zone” (registered trademark) S3010, S6010 (manufactured by BASF), “Victorolx”. "(Registered trademark) (Sumitomo Chemical)," Radel "A-200A, A-300," Radel "(registered trademark) R-5000, R-5800 (manufactured by Teijin Amoco)," Ultra Zone "(registered) Trademarks) Polysulfone such as E (manufactured by BASF), “Sumika Excel” (manufactured by Sumitomo Chemical Co., Ltd.)

  The polysulfone-based polymer used in the present invention may be copolymerized with other monomers within a range that does not interfere with the antibacterial effect, or may be a blend with other polymers. The addition amount of the other copolymerization monomer or blend polymer is not particularly limited, but the use ratio is preferably 30% by weight or less.

  In the present invention, ethylene vinyl alcohol polymer (EVOH polymer) is most preferably used as the other resin material. The preferred number average molecular weight of this polymer is 100 to 10000000. Further, the ethylene content is preferably 10 to 90%, most preferably 15 to 50%.

  Examples of commercial products of the ethylene vinyl alcohol polymer include “EVAL” (registered trademark) L101, F101, H101, E101, G101 (manufactured by Kuraray Eval Company), and “Soarnol” (registered trademark) V2603, D2908, AT4403, Examples thereof include ethylene vinyl alcohol polymers such as A4412, H4815 (manufactured by Nippon Synthetic Chemical).

  The ethylene vinyl alcohol polymer used in the present invention may be copolymerized with other monomers as long as the antibacterial effect is not hindered, or may be a blend with other polymers. The addition amount of the other copolymerization monomer or blend polymer is not particularly limited, but the use ratio is preferably 30% by weight or less.

  The antibacterial resin molded body of the present invention includes other resin materials that are the main components of the antibacterial resin molded body, a resin having a repeating unit represented by the chemical structural formula (1), and a chemical structural formula (2). In addition to the resin having a repeating unit, other polymers, additives, and the like may be mixed within a range not impeding the effects of the present invention.

  Specifically, it is also possible to use a photosensitizer in the antibacterial resin molding of the present invention. When a photosensitizer is used, photons are absorbed and excited, hydrogen is extracted from the material constituting the antibacterial resin molding, and radical active sites can be formed in the antibacterial resin molding. Examples of such photosensitizers include benzophenone, 3,3 ′, 4,4′-benzophenone tetracarboxylic anhydride, 4,4′-dimethoxybenzophenone, 4-chlorobenzophenone, 2 , 4-dichlorobenzophenone, 4,4′-dichlorobenzophenone, 4-fluorobenzophenone, 4-trifluoromethylbenzophenone, 4-methoxybenzophenone, 4-methylbenzophenone, 4, Benzophenone photosensitizers such as 4′-dimethylbenzophenone, 4-cyanobenzophenone and o-benzoylbenzophenone, benzyl photosensitizers such as benzyl and dibenzylketone, 2-methylthioxanthone, 2 -Thioxanthone photosensitizers such as ethylthioxanthone, thioxanthone, 2-isopropylthioxanthone, anthraquinone, 2-ethyl Anthraquinone photosensitizers such as tilanthraquinone, 2-chloroanthraquinone and 2-t-butylanthraquinone; benzaldehyde photosensitizers such as benzaldehyde, 4-methoxybenzaldehyde, 4-methylbenzaldehyde and 1-naphthaldehyde; Dione photosensitizers such as 3-butanedione and 2,3-pentanedione, dibenzosuberone, methyl-o-benzoylbenzoate, 9-fluorenone, 3,4-benzofluorene, 1-acetylnaphthalene, benzanthrone, 9 , 10-phenanthrenequinone, 2-benzoylnaphthalene, 3,5-dimethylacetophenone and 4-bromoacetophenone. The blending amount of the photosensitizer in the present invention is preferably used in the range of 0.0001 to 5% by weight.

  In the antibacterial resin molded article of the present invention, polyethylene glycol and polyvinyl alcohol can be further mixed and used. The compounding ratio is the other resin material which is the main component of the antibacterial resin molding, the resin having the repeating unit represented by the chemical structural formula (1), and the resin having the repeating unit represented by the chemical structural formula (2). Can be used as long as there is no problem with compatibility.

  The preferred number average molecular weight of polyethylene glycol is 100 to 30,000, more preferably 100 to 20,000. The blending ratio can also be 0.1 to 50% by weight, preferably 0.5 to 30% by weight, more preferably 1 to 20% by weight. By mixing polyethylene glycol, the molding temperature of the resin can be lowered, the fluidity during molding can be improved, and molding distortion, coloring, and a decrease in the antibacterial effect can be prevented.

  The form of the antibacterial resin molded product of the present invention is not particularly limited, and various shapes can be obtained by using stretch molding, injection molding, extrusion molding, cast film forming method, wet coagulation method and the like. it can. The antibacterial resin molded body is used in the form of, for example, a tubular body such as a tube, a bead, a knitted fabric, a nonwoven fabric, a cut fiber, a flat membrane, a hollow fiber membrane, a film and a sheet.

  Further, the solvent for various resins used in the present invention is not particularly limited as long as the resin to be used is basically dissolved. For example, N, N-dimethylacetamide, dimethylsulfoxide, dimethylformamide, N-methylpyrrolidone, dioxane, dichloromethane and dichloroethane are preferably used as the solvent for the polysulfone polymer, and dimethylacetamide is the most preferable from the viewpoint of safety and toxicity. preferable.

  In this case, the solution concentration of the polysulfone polymer is preferably 10 to 35% by weight, more preferably 15 to 30% by weight. Examples of the poor solvent for insoluble or swelling the polysulfone-based polymer include water, methanol, ethanol, isopropanol, hexanol, and 1,4-butanediol, and water is particularly preferably used in view of production cost. Here, when water is used, since the polysulfone-based polymer has high coagulability, the amount of water added is preferably 7% by weight or less, and particularly preferably 1 to 5% by weight. When an additive having a low coagulation property is used, the amount added may be increased, and a suitable amount can be appropriately selected.

  If this resin solution is formed by a known cast film forming method, an antibacterial film can be obtained. If a known wet coagulation method is used, a hollow fiber membrane can be obtained, and a known extrusion molding method can be used. If used, a hollow tube can be obtained.

  In addition, in order to obtain a molded product, a molded product can be produced by evaporating the solvent after producing a high-concentration resin solution, but by subjecting this to stretch molding, injection molding, and extrusion molding, Various shaped bodies can be formed. For example, a tubular tube can be formed by extruding from a circular die. The tube-shaped antibacterial resin molded body of the present invention can be used as a 1-layer to 10-layer tube when it is used in multiple layers depending on the intended use or demands for internal pressure or external pressure. Moreover, the tube-shaped antibacterial resin molded body of the present invention is most preferably used for the innermost layer or the outermost layer of the 1-layer to 10-layer tube in order to make the best use of the antibacterial action.

  As described above, the antibacterial resin molded body of the present invention may have any shape such as a plate, rod, sheet, tube, film, fiber, bead, powder, hollow fiber, and other molded products. It may be in a shape, and those that can be irradiated with radiation are particularly preferable.

  When irradiating the antibacterial resin molded body of the present invention with radiation, a resin having a repeating unit represented by the chemical structural formula (1) as a main component of the antibacterial resin molded body and a repeating represented by the chemical structural formula (2) It is preferable that the resin having the unit and the other resin material are in a compatible state. However, since both of them may be separated into a sea-island state, radiation is applied to the antibacterial resin molded body of such a mixture. Irradiation is possible.

  The timing of irradiating the antibacterial resin molded body of the present invention with radiation is not particularly limited, but the pellet-shaped or powder-shaped molded body before being formed into a resin molded body is irradiated with radiation, and then a known molding method is used. There is a method of forming a tubular tube, hollow fiber, film or other molded body, or a method of irradiating radiation after forming a tubular tube, hollow fiber, film or the like by a known molding method in advance, Either method may be used as long as it is after the molding step.

  When other resin materials contain a resin having a repeating unit represented by the chemical structural formula (1) and a resin having a repeating unit represented by the chemical structural formula (2), irradiation with radiation, ultraviolet rays, etc. In a method such as plasma treatment by arc, direct current glow, high frequency, microwave and corona discharge, or UV-ozone treatment, a radical polymerizable monomer is allowed to act on the generated radical as a starting point, A method of forming a graft polymerization layer on the surface is also widely used. For example, A.I. Henglein, Angew. Chem. , 70,461 (1955), graft polymerization using radiation has been proposed. Ogiwara, et. al. , Poym. Sci. , Polym Letter Ed. , 19, 457 (1981) proposes a method of graft polymerization of methyl methacrylate or acrylic acid using an aqueous polyvinyl acetate solution on a polypropylene surface or a polyethylene surface. In the present invention, radiation (α The graft layer is preferably formed by irradiation with ultraviolet rays, β-rays, γ-rays, electron beams, X-rays, etc., and irradiation with any one of γ-rays, electron beams, and ultraviolet rays is also preferably used. Most preferred are γ rays and electron beams.

  In the present invention, the hydrophilic polymer such as polyvinylpyrrolidone and polyethyleneimine contained in the antibacterial resin molded article is heated or irradiated with radiation to crosslink the hydrophilic polymer so that the hydrophilic polymer does not elute as much as possible. You can get a body. The radiation described here is particularly preferably an electron beam and a γ-ray, and particularly as an electron beam characteristic, an acceleration voltage is at least 10 Kv or more from the viewpoint of transmission power and activation efficiency. As an electron beam accelerator, for example, An electro curtain system, a scanning type, a double scanning type, a bandegraph, a cold cathode, or the like may be used. The dose of radiation such as γ rays is preferably 10 kGy or more, more preferably 20 kGy or more, and most preferably 25 kGy or more. The reason is that when the radiation dose is small, the antibacterial resin molded article is not sufficiently crosslinked, and the effect of reducing the effluent is not sufficient. On the other hand, if the radiation dose is too large, there are problems of deterioration in physical properties, aging deterioration and coloring of the obtained molded product.

  During irradiation, replacement with an inert gas such as nitrogen or helium is performed because high concentrations of oxygen can cause deactivation of graft active species (mainly free radicals) or collapse of the polymer due to oxidation reactions. It is preferable to reduce the oxygen concentration. However, this is not the case when a peroxide is used as the graft active species. The grafting reaction can be achieved by reacting with a monomer directly or using a solvent after irradiation or reacting with a vaporized monomer. In general, a monomer alone often has a slow reaction rate, and thus a reaction in a solution system using a solvent is advantageous. In order to prevent homopolymerization of the monomer alone, a radical polymerization inhibitor such as a mole salt, a redox additive such as metallic copper or cuprous chloride, or a polymerization inhibitor such as hydroquinone monomethyl ether may be used in combination. Good.

  The grafting reaction by irradiation with radiation has an advantage that the reaction is fast because it has a high dose rate, it can be performed at a low temperature, and the amount of grafting is large. In addition, other resin materials can be pre-sterilized by irradiation. In addition, when starting the reaction, grafting is possible without using a polymerization initiator that leaves a harmful and offensive odor decomposition product in the graft layer even after the end of the reaction. It is. In the grafting reaction by radiation irradiation, it is efficient to simultaneously irradiate with other resin materials and the polymer to be grafted (simultaneous irradiation method), but avoid the polymerization of the polymer to be grafted alone. Therefore, it is effective only when the homopolymer does not interfere with its action (antibacterial properties and mechanical properties).

When the antibacterial resin molding is irradiated with radiation, it is not particularly limited in a dry (wet) state or a wet (wet) state, but radiation in a wet state is preferably used.
The antibacterial resin molded article of the present invention is preferably transparent. The term “transparent” as used in the present invention means that the film having a thickness of 70 μm of the antibacterial resin molded product has a light transmittance of 40% or more, preferably 60% or more, and more preferably 80% or more. The most preferable is 88% or more.

  In order to obtain a transparent antibacterial resin molding, it is important that other resin materials and polyvinylpyrrolidone and / or polyethyleneimine are uniformly compatible. The compatibility method is not particularly limited regardless of whether it is made compatible with a solution or melted.

  About the amount of elution in water in the present invention, it can be mentioned in the Food Sanitation Law (Ministry of Health, Labor and Welfare) Notification No. 370 (in the third instrument and container packaging, B. Potassium acid consumption test method) Test method is used. The operation method and the method for preparing the leaching solution during the dissolution test are described below.

(Operation method)
Place 100 ml of water, 5 ml of sulfuric acid and 5 ml of 0.002 mol / l potassium permanganate solution in an Erlenmeyer flask, boil for 5 minutes, discard the liquid and wash with water. Take 100 ml of the test solution in this Erlenmeyer flask, add 5 ml of sulfuric acid, add 10 ml of 0.002 mol / l potassium permanganate solution, and boil for 5 minutes. Next, stop heating and immediately add 10 ml of 0.01 mol / l sodium oxalate solution to remove the color, then titrate with 0.002 mol / l potassium permanganate solution until the slight red color remains without disappearing. Separately, a blank test is carried out in the same manner, and the consumption of potassium permanganate is determined by equation (1).

Potassium permanganate consumption (ppm) = {(ab) × 0.316 × 1000} / 100 (1)
However, a is the titration (ml) of 0.002 mol / l potassium permanganate solution in this test, and b is the titration (ml) of 0.002 mol / l potassium permanganate solution in the blank test.

(Leaching solution preparation method)
Wash the sample thoroughly with water and use 2 ml of pure water per 1 cm ² of surface area of the sample. As the leaching condition, the sample was immersed for 30 minutes while keeping pure water at 60 ° C. to obtain a leaching solution.

  In the antibacterial resin molded article of the present invention, the amount of the eluate in water is preferably 500 ppm or less, more preferably 150 ppm or less, further preferably 60 ppm or less, and most preferably the amount eluted in water is 30 ppm or less. . More preferably, it is 10 ppm or less. In addition, since there is an effect on the human body in drinking water and food applications, the amount of the eluate in water is preferably 5 ppm or less, more preferably 1000 ppb or less, further preferably 500 ppb or less, and most preferably. The elution amount in water is 100 ppb or less.

  To reduce the amount of eluate in water, change the insoluble matter by cross-linking with γ-rays, that is, adjust the degree of cross-linking, for example, remove the excess eluate not cross-linked by washing. Can be adopted.

  The tubular antibacterial resin molded body obtained by the present invention is transparent and can be easily observed inside. Further, since it suppresses various germs, it is preferably used for a liquid feeding hose for foods and beverages. For example, it is very useful for a liquid supply hose for soy sauce or sauce, a soft drink server used in a restaurant, a liquid supply hose such as a beer server in a food manufacturing factory or the like.

  In addition, it can be used effectively for household water purifiers. In the undersink type water purifier in which the cartridge for the water purifier is installed under the kitchen, a polyethylene tube, a stainless steel tube or the like is conventionally used in the section between the card ridge under the kitchen and the faucet outlet on the kitchen. These tubes are filled with purified water dechlorinated by the cartridge. In such a state, if left untreated, bacterial growth was severe in clean water, and in severe cases, metabolites (white lumps) produced by bacterial growth were generated. With conventional polyethylene tubes and stainless steel tubes, the inside of the tube could not be observed, so it was not possible to notice any abnormalities until water was removed.

  By using the liquid feeding hose for beverages of the present invention, bacterial growth can be suppressed and the inside can be observed, which is very effective.

The present invention will be described based on examples.
(Antimicrobial test method)
The antibacterial test is conducted according to JIS Z2801-2004.

(1) Pre-culture of test bacteria Test bacteria (E. coli, Staphylococcus aureus) are cultured on a normal agar medium at a temperature of 35 ° C. for 18 to 24 hours, and further subcultured, and then cultured on a normal agar medium at a temperature of 35 ° C. for 18 to Incubate for 20 hours.

(2) Preparation of test bacterial solution The bacterial cells of the test bacteria after culturing are uniformly dispersed in 1/500 ordinary bouillon cold region (ordinary bouillon medium diluted 500 times with purified water). Adjust to 5-10 × 10 ² / ml.

(3) Inoculation of test bacterial solution After 0.4 ml of bacterial solution is dropped onto the test bacteria of a test piece (5 cm x 5 cm film), polyethylene (4 cm x 4 cm film) is placed over the bacterial solution, and the bacterial solution is applied to the test piece. Adhere to.

(4) Viable count of test piece immediately after inoculation Measure the viable count of unprocessed test piece.

(5) Culture The test piece inoculated with the bacterial solution is cultured at a temperature of 35 ° C. and a relative humidity of 90 or more for 24 hours.

(6) Viable count of the test piece after culture The viable count of the test piece (non-processed and antibacterial processed) is measured. The measurement of said (1)-(6) was performed 3 samples per 1 sample and 1 microbial species.
(Measurement of elution amount in water)
It was confirmed by gas chromatography (GC) that there was no detection peak of the organic solvent (dimethylacetamide) in the molded product.

Detection peak of dimethylacetamide: 4.5 to 4.8 min
Gas Chromatography-Measurement Conditions Equipment Used: Gas Chromatography (GC-14B, Shimadzu Corporation)
Column: TC-1 (manufactured by GL Sciences, 100% Dimethyl polysiloxane, length 60 m, inner diameter: 0.25 mm, film thickness: 0.25 microns)
Measurement temperature conditions: 100 ° C. (10 minutes hold), temperature rise (4 ° C./min), 250 ° C. (10 minutes hold)
_{Detector: FID 250 ℃, H 2:} 60Kpa, air: 50Kpa,
Make-up gas: N ₂ (40 ml / min)
Carrier gas: He, inlet pressure: 250 Kpa, total flow rate: 77 ml / min
Column flow rate: 1.45 ml / min, INJ purge: 3 ml / min,
Linear velocity: 29.2 cm / s
Analog signal: Linear, Range: * 1
Sample injection method: Split method, Split ratio: 50: 1
Sample preparation: Dissolve in methylene chloride so that the polymer concentration is 7 wt%.

GC injection volume: 1.0 μl
A molded body (1 cm × 1 cm film) was immersed in 4 ml of pure water kept at 60 ° C. for 30 minutes to obtain a leachate.

The leaching solution obtained above was subjected to a potassium permanganate consumption test method, which is a general test method for equipment or containers and packaging listed in the Food Sanitation Law (Ministry of Health, Labor and Welfare Notification) Notification No. 370.
(Transmittance measurement)
The measurement was performed using an SM color computer SM-7-CH manufactured by Suga Test Instruments. The measurement was performed on a molded body having a thickness of 70 μm in a room adjusted to a temperature of 25 ° C.

Example 1
Polysulfone (Udel-P3500 manufactured by Solvay) 80% by weight, polyvinylpyrrolidone (polyvinylpyrrolidone K90 manufactured by Wako Pure Chemical Industries, Ltd. 19.99% by weight) and polyethyleneimine (polyethyleneimine manufactured by Wako Pure Chemical Industries, An average molecular weight of 10,000) 0.01% by weight was dissolved in dimethylacetamide and stirred for 20 hours to obtain a resin solution having a concentration of 25% by weight. This resin solution was cast on a glass plate (200 mm × 200 mm) with a knife clearance of 320 μm. The glass plate cast with this resin solution was placed in a constant temperature dryer at a temperature of 90 ° C., dried for 30 minutes, and then heat-treated in a constant temperature dryer at a temperature of 120 ° C. After drying, the glass plate was taken out and immersed in a water bath to peel off the film to obtain a transparent film having a thickness of 70 μm. This transparent film was put in a polyethylene (PE) bag filled with water, and irradiated with γ rays with a cobalt-60 radiation source to obtain a radiation-treated film. The absorbed gamma ray dose was 25 kGy. About the obtained radiation processing film, the measurement of the light transmittance and the elution amount in water, and the antibacterial test were done. As the measurement result, an average value of three measurement values was used. The results are shown in Table 1.

(Example 2)
75% by weight of polysulfone (Solvay Udel-P3500), polyvinyl pyrrolidone (Wako Pure Chemical Industries, polyvinyl pyrrolidone K90, weight average molecular weight 360,000) 20% by weight and polyethylene imine (Wako Pure Chemical Industries, polyethylene imine, average molecular weight 10,000) 5% by weight was dissolved in dimethylacetamide and stirred for 20 hours to obtain a resin solution having a concentration of 25% by weight. Thereafter, a film was formed in the same manner as in Example 1, and after the radiation treatment, the obtained radiation-treated film was subjected to a light transmittance and an antibacterial test. As the measurement result, an average value of three measurement values was used. The results are shown in Table 1.

(Example 3)
Polysulfone (Udel-P3500 manufactured by Solvay) 80% by weight, polyvinylpyrrolidone (polyvinylpyrrolidone K90 manufactured by Wako Pure Chemical Industries, Ltd. 15% by weight) and polyethyleneimine (polyethyleneimine manufactured by Wako Pure Chemical Industries, average molecular weight 10,000) 5% by weight was dissolved in dimethylacetamide and stirred for 20 hours to obtain a resin solution having a concentration of 25% by weight. Thereafter, the film was formed and evaluated in the same manner as in Example 2. The results are shown in Table 1.

Example 4
Polyethersulfone (Sumitomo Chemical "Sumika Excel" (registered trademark) 3600P) 80 wt%, polyvinylpyrrolidone (Wako Pure Chemical Industries polyvinylpyrrolidone K90 weight average molecular weight 360,000) 19.99 wt% and polyethyleneimine ( 0.01% by weight of polyethyleneimine (average molecular weight 10,000) manufactured by Wako Pure Chemical Industries, Ltd. was dissolved in dimethylacetamide and stirred for 20 hours to obtain a solution having a concentration of 25% by weight. Thereafter, the film was formed and evaluated in the same manner as in Example 1. The results are shown in Table 2.

(Example 5)
75% by weight of polyethersulfone (Sumitomo Chemical Co., Ltd. “Sumika Excel” (registered trademark) 3600P), 20% by weight of polyvinylpyrrolidone (polyvinylpyrrolidone K90 with a weight average molecular weight of 360,000 manufactured by Wako Pure Chemical Industries, Ltd.) and polyethyleneimine (Wako Pure) 5% by weight of polyethyleneimine (average molecular weight 10,000) manufactured by Yakuhin Kogyo Co. was dissolved in dimethylacetamide and stirred for 20 hours to obtain a resin solution having a concentration of 25% by weight. Thereafter, the film was formed and evaluated in the same manner as in Example 2. The results are shown in Table 1.

(Example 6)
70% by weight of polysulfone (Solvay Udel-P3500), polyvinyl pyrrolidone (Wako Pure Chemical Industries, polyvinyl pyrrolidone K90, weight average molecular weight 360,000) 20% by weight, polyethylene imine (Wako Pure Chemical Industries, polyethylene imine, average molecular weight 10,000) 5% by weight and 5% by weight of polyethylene glycol (polyethylene glycol 200 manufactured by Wako Pure Chemical Industries, Ltd.) were dissolved in dimethylacetamide and stirred for 20 hours to obtain a resin solution having a concentration of 25% by weight. Thereafter, the film was formed and evaluated in the same manner as in Example 2. The results are shown in Table 1.

(Example 7)
Polyethersulfone (Sumitomo Chemical Co., Ltd. Sumika Excel 3600P) 75 wt%, Polyvinylpyrrolidone (Wako Pure Chemical Industries, Ltd. Polyvinylpyrrolidone K90 Weight average molecular weight 360,000) 20 wt%, Polyethyleneimine (Wako Pure Chemical Industries, Ltd. Polyethyleneimine 5% by weight of an average molecular weight of 10,000) and 5% by weight of polyethylene glycol (polyethylene glycol 400 manufactured by Wako Pure Chemical Industries, Ltd.) were dissolved in dimethylacetamide and stirred for 20 hours to obtain a resin solution having a concentration of 25% by weight. Thereafter, a film was formed in the same manner as in Example 2, and the film was allowed to stand at 180 ° C. for 24 hours, followed by heat treatment, and evaluated in the same manner as in Example 2. The results are shown in Table 1.

(Example 8)
98% ethylene vinyl alcohol polymer (Soarnol D2908 manufactured by Nippon Synthetic Chemical Co., Ltd.), 1% polyvinyl pyrrolidone (polyvinylpyrrolidone K90 manufactured by Wako Pure Chemical Industries, Ltd.), polyethyleneimine (polyethyleneimine manufactured by Wako Pure Chemical Industries, Ltd.) , 1% by weight of average molecular weight 10000) was extruded at 220 ° C. with a 15 mm single screw extruder (manufactured by Tanabe Plastic Co., Ltd.), and press-molded as it was to form a film. The film was left to stand at 150 ° C. for 24 hours for heat treatment. Thereafter, radiation treatment and evaluation were performed in the same manner as in Example 2. The results are shown in Table 1.

Example 9
The melt-extruded machine (15 mm type extruder: Tanabe) equipped with an orifice type double cylindrical die (12 mm outer diameter, 9 mm inner diameter) was pulverized and dried with a household juice mixer obtained in Example 1 A transparent tube (outer diameter 10 mm, inner diameter 8 mm, wall thickness 1 mm) was obtained from Plastic. The antibacterial test uses the test fungus solution described in (2) of the above-mentioned antibacterial biotest, seals (caps) one side of a 10 cm long tube, fills the test fungus solution, and seals the mouth (cap) The test bacterial solution was not leaked. The tube was cultured at 35 ° C. and a relative humidity of 90 or more for 24 hours, and then sealed and the number of viable bacteria in the test bacterial solution was measured. The results are shown in Table 1.

(Example 10)
The resin tube between the cartridge and the faucet outlet of the undersink type water purifier (“Trevino” (registered trademark) SK55, manufactured by Toray Industries, Inc.) was replaced with the tube obtained in Example 9. This undersink type water purifier was connected to a water supply in a temperature control room having a temperature of 35 ° C., and tap water was passed through. Then the water supply was stopped and left for 30 days. After 30 days, 800 cc of water was passed through a 1 L container, and the occurrence of metabolites produced by bacterial growth was observed. The results are shown in Table 1.

(Comparative Example 1)
Polysulfone (Udel-P3500 manufactured by Solvay) was dissolved in dimethylacetamide and stirred for 20 hours to obtain a resin solution having a concentration of 25% by weight. This resin solution was cast on a glass plate with a knife clearance of 320 μm. The glass plate cast with this resin solution was placed in a constant temperature dryer at a temperature of 90 ° C. and dried for 30 minutes. After drying, the glass plate was taken out and immersed in a water bath to peel off the film to obtain a transparent film having a thickness of 70 μm. This transparent film was irradiated with γ rays with a cobalt-60 radiation source to obtain a radiation-treated film. The absorbed gamma ray dose was 25 kGy. About the obtained radiation processing film, the measurement of the light transmittance and the elution amount in water, and the antibacterial test were done. As the measurement result, an average value of three measurement values was used. The results are shown in Table 1.

(Comparative Example 2)
Polyethersulfone (Sumitomo Chemical Co., Ltd. Sumika Excel 3600P) was dissolved in dimethylacetamide and stirred for 20 hours to obtain a resin solution having a concentration of 25% by weight. Thereafter, the film was formed and evaluated in the same manner as in Comparative Example 1. The results are shown in Table 1.

(Comparative Example 3)
The radiation irradiated film obtained in Comparative Example 1 was pulverized with a household juice mixer, and a melt extruder (15 mm type extruder: Tanabe Plastic Co., Ltd.) equipped with an orifice type double cylindrical die (12 mm outside diameter, 9 mm inside diameter) A transparent tube was obtained. The antibacterial test uses the test fungus solution described in (2) of the above-mentioned antibacterial biotest, seals (caps) one side of a 10 cm long tube, fills the test fungus solution, and seals the mouth (cap) The test bacterial solution was not leaked. The tube was cultured at 35 ° C. and a relative humidity of 90 or more for 24 hours, and then sealed and the number of viable bacteria in the test bacterial solution was measured. The results are shown in Table 1.

(Comparative Example 4)
The resin tube between the cartridge and the faucet outlet of the undersink type water purifier (“Trevino” (registered trademark) SK55, manufactured by Toray Industries, Inc.) was replaced with the tube obtained in Comparative Example 3. This under-sink type water purifier was connected to a water supply in a temperature control room at 35 ° C., and tap water was passed through. Then the water supply was stopped and left for 30 days. After 30 days, 800 cc of water was passed through a 1 L container, and the occurrence of metabolites produced by bacterial growth was observed. The results are shown in Table 1.

  Comparing various items in Table 1 for Examples 1 to 10 and Comparative Examples 1 to 4, Examples 1 to 10 of the present invention are transparent from a high transmittance and have a low amount of elution in water. In the antibacterial test, it can be seen that Examples 1 to 10 of the present invention drastically reduce the viable counts of Staphylococcus aureus and Escherichia coli compared to Comparative Examples 1 to 4. Moreover, when the tubular molded body of the present invention was used by replacing the resin hose of the undersink type water purifier as described in Example 9, metabolites due to bacterial growth that occurred in the comparative example were generated. There wasn't. From the above, according to the present invention, it is possible to obtain an antibacterial molded article that is transparent and has a low amount of elution in water.

Since the antibacterial resin molded article of the present invention solves the above-mentioned problems and is transparent and excellent in antibacterial properties, it can be used for any application. In particular, it can be used effectively for beverages and food applications that are transparent and have antibacterial properties and require as little elution as possible, especially for liquid feeding tubes and packaging containers for foods and beverages.

Claims (12)

The following chemical structural formula (1)

(Wherein X represents oxygen, sulfur or selenium, and a is an integer of 0 to 10) and a repeating unit represented by the following chemical structural formula (2) An antibacterial resin molded product comprising a resin.

(Wherein x, y and z are each an integer of 1 to 10, the ratio of m to n is 0.1: 99.9 to 99.9: 0.1, and A and B are each independently hydrogen An antibacterial resin molded product comprising a resin having a repeating unit represented by the following formula: The antibacterial resin molded article according to claim 1, wherein the resin having a repeating unit represented by the chemical structural formula (1) is polyvinylpyrrolidone or a copolymer thereof. The antibacterial resin molded article according to claim 1 or 2, wherein the resin having a repeating unit represented by the chemical structural formula (2) is polyethyleneimine or a copolymer thereof. The antibacterial resin molded article according to claim 1, comprising polysulfone and / or polyethersulfone. The antibacterial resin molded article according to any one of claims 1 to 3, comprising a resin composed of repeating units of ethylene vinyl alcohol. 6. The antibacterial resin molded article according to claim 1, comprising a polyalkylene glycol having 1 to 10 carbon atoms in the alkyl group. The antibacterial resin molded article according to any one of claims 1 to 6, wherein an elution amount in water is 500 ppm or less. It is tubular, The antibacterial resin molded product according to any one of claims 1 to 7. The antibacterial resin molded article according to any one of claims 1 to 8, which is irradiated with radiation after the molding step. The antibacterial resin molded article according to claim 9, wherein the radiation is an electron beam and / or a gamma ray. A liquid feeding hose for food and beverage, comprising the antibacterial resin molded article according to claim 8. A water purifier comprising the food and beverage feeding hose according to claim 11.