JP2006341375A - Resin container - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin container capable of hermetically sealing a substance to be filled such as medicines, seasonings, etc. , capable of being easily opened for the purpose of using the substance to be filled without causing twist cutting and fold-cutting, deforming the container at the time of opening and causing the occurrence of cut refuse such as a resin powder or the like and having a smooth separation surface. <P>SOLUTION: The resin container is constituted by joining at least two members mutually after subjecting at least one of them to plasma treatment or optical ozone treatment and subsequently pressing the other member to the member subjected to plasma treatment or optical ozone treatment to form them into a container shape. In this resin container, the joined part can be separated. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to medical uses such as ampoules, needleless syringes, prefilled syringes, vials, test cells (microplates, etc.); bio-related uses such as microfluidic devices, DNA chips, seasoning containers, beverage containers, etc. Regarding resin containers suitable for food applications, in particular, when fillings such as pharmaceuticals and seasonings can be sealed, and when using the fillings, when the seal is opened by twisting or breaking In addition, the present invention relates to a resin container that can be easily opened without deformation of the container and without generating chips such as resin powder, and has a smooth separation surface.

  In general, ampoules are known as pharmaceutical containers. This ampoule is used as a single-dose container, and is filled with an object to be filled and the opening is sealed, and is opened by folding the minimum diameter portion, that is, the portion called the constricted portion. (Patent Document 1). Further, a prefilled syringe is known as a pharmaceutical container. This prefilled syringe is used as a single-dose container as well as the ampoule, and at the same time as a syringe. For example, two kinds of filling materials (medicine etc.) are shielded and enclosed in a syringe by a separation wall, When an injection is to be performed, it is possible to perform a treatment such as destroying the separation wall by mixing a piston, etc., mixing two kinds of objects to be filled, and injecting the medicine into the living body as it is. In addition, some prefilled syringes are needleless types that can inject a chemical solution into a living body without using a needle.

  The resin container such as ampoule or prefilled syringe is opened by folding or twisting, and the parts are made thin by blow molding with the same material, or the same kind by two-color molding, co-injection molding, insert molding, etc. Alternatively, the dissimilar materials are joined by contact with each other at the opening portion, or another member is welded or fused by heat, laser, ultrasonic waves, ultraviolet rays, or the like, or bonded through an adhesive. However, since the container sealed by these joining methods has a sharply separated surface, the needleless prefilled syringe does not have a good touch at the pointed portion when brought into contact with the living body. Further, if an incorrect folding method is performed, chips may be generated.

  Moreover, as described in Patent Document 2, a weak seal is used in which the container walls are welded so as to be peeled from each other under conditions such as temperature and time at which the container walls are welded completely and integrally. A liquid container is known that seals a storage chamber or partitions a plurality of storage chambers so that they can communicate with each other. This weak seal is formed with a peel strength that is weak enough to be peeled by hand, but it needs to be formed with a peel strength that does not peel even if an unexpected force is applied during manufacturing or storage. This is different from the state in which the container walls are in close contact with each other. This container is intended to achieve a weak seal by forming a sea-island structure of polyethylene and polypropylene on the inner surface layer and joining them at a temperature at which polyethylene is welded. However, in order to realize a weak seal with uniform peel strength, polyethylene and polypropylene must be sufficiently mixed to form a very uniform mixture, which requires labor. In addition, since the mixture is incompatible with the sea island structure, the molded container wall has low strength, resulting in a thick container wall material and low transparency.

JP 2000-43128 A Japanese Patent Laid-Open No. 2003-20065

  An object of the present invention is to seal a filling material such as a pharmaceutical product or a seasoning, and in order to use the filling material, the container is not deformed when the seal is opened by twisting or breaking. Another object of the present invention is to provide a resin container that can be easily opened without generating chips such as resin powder and has a smooth separation surface.

  As a result of investigating a method of joining a portion opened by breaking such as folding or twisting, the present inventor exposed plasma to one member to activate the surface and remain in the activated state. By simply pressing another member against the surface, it has been found that both members can be adhered with such a strength that they do not peel off even if an unexpected force is applied, without using an adhesive or the like. It was found that even if the part was opened by breaking such as breaking, the sealing could be released without generating dust such as resin powder, and the separation surface was smooth. The present inventor has completed the present invention based on this finding.

  Thus, according to the present invention, two or more members are bonded to each other to form a container shape, and the bonding performs plasma treatment or photo-ozone treatment on at least one member, and then the plasma treatment or photo-ozone treatment. A resin container is provided in which another member is pressed against the formed member, and the joined portion is separable.

The resin container of the present invention has a peel strength that does not peel even if an unexpected force is applied at the time of manufacture or storage when the joint that sealed the container is opened, and when the joint is opened by destruction The container is not deformed, chips such as resin powder are not generated, and the separation surface is smooth. For example, even when the resin container of the present invention is applied to a needleless prefilled syringe, there are advantages such as good touch to the living body.
Since the resin container of the present invention has good characteristics as described above, it is suitable for medical uses such as ampoules, needleless syringes, prefilled syringes and vials, and food uses such as seasoning containers and beverage containers.

  In the resin container of the present invention, two or more members are bonded to each other to form a container shape, and the bonding is performed by plasma treatment or photo-ozone treatment of at least one member, and then the plasma treatment or photo-ozone treatment. The other member is pressed against the formed member, and the joined portion can be separated.

  The shape of the two or more members constituting the resin container is not particularly limited as long as it is a container shape that can accommodate an object to be filled when bonded. For example, the container which consists of the container 11 and the lid | cover 15 as shown in FIG. 3 is mentioned. Moreover, a bag-shaped container may be sufficient.

  Each member is formed of resin. The resin to be used is not particularly limited. For example, a resin having an alicyclic structure (hereinafter sometimes abbreviated as “alicyclic structure-containing resin”), a polyolefin resin such as poly-4-methylpentene, a polycarbonate resin, a polyester resin, a polysulfone resin, and a polyether polysulfone. Resin, polystyrene resin, polyvinyl alcohol resin, cellulose acetate resin, polyvinyl chloride resin, polyacrylate resin, polyamide resin, silicone resin such as polydimethylsiloxane, thermoplastic elastomer such as styrene elastomer and ester elastomer, crosslinked rubber, etc. Can be mentioned. These resins can be used alone or in combination of two or more. Of these, alicyclic structure-containing resins are preferred.

  This alicyclic structure-containing resin has an alicyclic structure in the main chain and / or side chain, and preferably contains an alicyclic structure in the main chain from the viewpoint of heat resistance, mechanical strength, and the like.

  Examples of the alicyclic structure include a cycloalkane structure and a cycloalkene structure, but a cycloalkane structure is preferable from the viewpoint of mechanical strength, heat resistance, and the like. The number of carbon atoms constituting the alicyclic structure is usually in the range of 4 to 30, preferably 5 to 20, and more preferably 5 to 15 from the viewpoints of mechanical strength, heat resistance, and moldability. The proportion of the repeating unit having an alicyclic structure is appropriately selected according to the purpose of use, but is usually 50% by weight or more, preferably 70% by weight or more, more preferably 90% by weight or more. It is preferable from the viewpoint of heat resistance and mechanical strength that the ratio of the repeating unit having an alicyclic structure is in this range.

  Specific examples of the alicyclic structure-containing resin include norbornene polymers, monocyclic olefin polymers, cyclic conjugated diene polymers, vinyl alicyclic hydrocarbon polymers, and hydrogenated products thereof. Can be mentioned. Among these, norbornene polymers, vinyl alicyclic hydrocarbon polymers, and hydrogenated products thereof are preferable, and norbornene polymers are more preferable from the viewpoint of heat resistance and mechanical strength.

  (1) The norbornene-based polymer is a known polymer disclosed in, for example, Japanese Patent Application Laid-Open No. 3-14882 and Japanese Patent Application Laid-Open No. 3-122137. Examples thereof include ring polymers and hydrogenated products thereof, addition polymers of norbornene monomers, and addition copolymers of norbornene monomers and vinyl compounds.

  Specific examples of the norbornene-based monomer used for the polymerization include bicyclo [2.2.1] hept-2-ene (common name: norbornene), 5-methyl-bicyclo [2.2.1] hept-2-ene, 5,5-dimethyl-bicyclo [2.2.1] hept-2-ene, 5-ethyl-bicyclo [2.2.1] hept-2-ene, 5-butyl-bicyclo [2.2.1] Hept-2-ene, 5-hexyl-bicyclo [2.2.1] hept-2-ene, 5-octyl-bicyclo [2.2.1] hept-2-ene, 5-octadecyl-bicyclo [2. 2.1] hept-2-ene, 5-ethylidene-bicyclo [2.2.1] hept-2-ene, 5-methylidene-bicyclo [2.2.1] hept-2-ene, 5-vinyl- Bicyclo [2.2.1] hept-2-ene, 5-propyl Propenyl - bicyclo [2.2.1] hept-2-ene,

  5-methoxy-carbonyl-bicyclo [2.2.1] hept-2-ene, 5-cyano-bicyclo [2.2.1] hept-2-ene, 5-methyl-5-methoxycarbonyl-bicyclo [2 2.1] hept-2-ene, 5-methoxycarbonyl-bicyclo [2.2.1] hept-2-ene, 5-ethoxycarbonyl-bicyclo [2.2.1] hept-2-ene, 5 -Methyl-5-ethoxycarbonyl-bicyclo [2.2.1] hept-2-ene, bicyclo [2.2.1] hept-5-enyl-2-methylpropionate, bicyclo [2.2.1 ] Hept-5-enyl-2-methyloctanoate, bicyclo [2.2.1] hept-2-ene-5,6-dicarboxylic anhydride, 5-hydroxymethyl-bicyclo [2.2.1] hept -2-ene, 5, -Di (hydroxymethyl) -bicyclo [2.2.1] hept-2-ene, 5-hydroxy-i-propyl-bicyclo [2.2.1] hept-2-ene, bicyclo [2.2.1 ] Hept-2-ene, 5,6-dicarboxy-bicyclo [2.2.1] hept-2-ene, bicyclo [2.2.1] hept-2-ene-5,6-dicarboxylic imide, 5-cyclopentyl-bicyclo [2.2.1] hept-2-ene, 5-cyclohexyl-bicyclo [2.2.1] hept-2-ene, 5-cyclohexenyl-bicyclo [2.2.1] hept 2-ene, 5-phenyl-bicyclo [2.2.1] hept-2-ene,

Tricyclo [4.3.1 ^2,5 . 0 ^1,6 ] deca-3,7-diene (common name dicyclopentadiene), tricyclo [4.3.1 ^2,5 . 0 ^1,6 ] dec-3-ene, tricyclo [4.4.1 ^2,5 . 0 ^1,6 ] undeca-3,7-diene or tricyclo [4.4.1 ^2,5 . 0 ^1,6 ] undeca-3,8-diene, tricyclo [4.4.1 ^2,5 . 0 ^1,6 ] undec-3-ene, tetracyclo [7.4.1 ^10,13 . 0 ^1,9 . 0 ^2,7 ] trideca-2,4,6,11-tetraene (also referred to as 1,4-methano-1,4,4a, 9a-tetrahydrofluorene), tetracyclo [8.4.1 ^11,14 . 0 ^1,10 . 0 ^3,8 ] tetradeca-3,5,7,12-tetraene (also referred to as 1,4-methano-1,4,4a, 5,10,10a-hexahydroanthracene) or the like norbornene type having no norbornane ring monomer;

Tetracyclo [4.4.1 ^2,5 . 1 ^7,10 . 0] dodec-3-ene (also simply referred to as tetracyclododecene), 8-methyl-tetracyclo [4.4.1 ^2,5 . 1 ^7,10 . 0] dodec-3-ene, 8-methyl-tetracyclo [4.4.1 ^2,5 . 1 ^7,10 . 0] dodec-3-ene, 8-ethyl-tetracyclo [4.4.1 ^2,5 . 1 ^7,10 . 0] dodec-3-ene, 8-methylidene-tetracyclo [4.4.1 ^2,5 . 1 ^7,10 . 0] dodec-3-ene, 8-ethylidene-tetracyclo [4.4.1 ^2,5 . 1 ^7,10 . 0] dodec-3-ene, 8-vinyl-tetracyclo [4.4.1 ^2,5 . 1 ^7,10 . 0] dodec-3-ene, 8-propenyl-tetracyclo [4.4.1 ^2,5 . 1 ^7,10 . 0] dodec-3-ene, 8-methoxycarbonyl-tetracyclo [4.4.1 ^2,5 . 1 ^7,10 . 0] dodec-3-ene, 8-methyl-8-methoxycarbonyl-tetracyclo [4.4.1 ^2,5 . 1 ^7,10 . 0] dodec-3-ene, 8-hydroxymethyl-tetracyclo [4.4.1 ^2,5 . 1 ^7,10 . 0] dodec-3-ene, 8-carboxy-tetracyclo [4.4.1 ^2,5 . 1 ^7,10 . 0] dodec-3-ene, 8-cyclopentyl-tetracyclo [4.4.1 ^2,5 . 1 ^7,10 . 0] dodec-3-ene, 8-cyclohexyl-tetracyclo [4.4.1 ^2,5 . 1 ^7,10 . 0] dodec-3-ene, 8-cyclohexenyl-tetracyclo [4.4.1 ^2,5 . 1 ^7,10 . 0] dodec-3-ene, 8-phenyl-tetracyclo [4.4.1 ^2,5 . 1 ^7,10 . 0] dodec-3-ene, pentacyclo [6.5.1, ^1,8 . 1 ^3,6 . 0 ^2,7 . 0 ^9,13] pentadeca-3,10-diene, pentacyclo ^{[7.4.1 3,6.} 1 ^10,13 . 0 ^1,9 . And norbornene-based monomers having a norbornane ring such as 0 ^2,7 ] pentadeca-4,11-diene.

Also, 5-methoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-methyl-5-methoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyanobicyclo [2.2 .1] hept-2-ene, 8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-ethoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-n-propoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-isopropoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-n-butoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-ethoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-n-propoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-isopropoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-n-butoxycarbonyltetracyclo [4.4.0.1 ^2,5 . And a norbornene-based monomer having a polar group such as ^{17, 10} ] dodec-3-ene.

  The above norbornene monomers can be used alone or in combination of two or more.

  In the present invention, in addition to the norbornene-based monomer, examples of addition copolymerizable monomers include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl- 1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4- 2 to 20 carbon atoms such as ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene Α-olefin having: cyclobutene, cyclopentene, cyclohexene, 3,4-dimethylcyclopentene, 3-methylcyclohexene, 2- (2- Cyclobutyl) -1-cyclohexene, cyclooctene, 3a, 5,6,7a-tetrahydro-4,7-methano-1H-indene and the like; 1,4-hexadiene, 4-methyl-1,4-hexadiene, Non-conjugated dienes such as 5-methyl-1,4-hexadiene and 1,7-octadiene; These copolymerizable monomers can be used alone or in combination of two or more.

The ring-opening polymer of the above monomer is a catalyst system comprising a metal halide such as ruthenium, rhodium, palladium, osmium, iridium, platinum, nitrate or acetylacetone compound and a reducing agent as a ring-opening polymerization catalyst, or titanium. Polymerization temperature of −50 ° C. to 100 ° C. in a solvent or in the absence of a solvent using a catalyst system comprising a metal halide such as vanadium, zirconium, tungsten, molybdenum, or an acetylacetone compound and an organoaluminum compound, It can be obtained by ring-opening polymerization at a polymerization pressure of 0 to 50 kg / cm ² . The hydrogenated norbornene-based polymer can be obtained by a method of hydrogenating a ring-opening polymer with hydrogen in the presence of a hydrogenation catalyst according to a conventional method.

An addition polymer of a norbornene monomer or an addition copolymer of a norbornene monomer and the above copolymerizable monomer is, for example, a monomer component in a solvent or without a solvent, and a titanium, zirconium, or vanadium compound and an organoaluminum compound. In the presence of a catalyst system consisting of the following, usually by a method of copolymerization at a polymerization temperature of −50 ° C. to 100 ° C. and a polymerization pressure of 0 to 50 kg / cm ² .

  (2) Examples of monocyclic olefin polymers include addition polymers of monocyclic olefin monomers such as cyclohexene, cycloheptene, and cyclooctene disclosed in JP-A No. 64-66216. Can be used.

  (3) As the cyclic conjugated diene polymer, for example, cyclic conjugated diene monomers such as cyclopentadiene and cyclohexadiene disclosed in JP-A-6-136057 and JP-A-7-258318 are used. , 2- or 1,4-addition polymerized polymer and hydrogenated product thereof can be used.

  (4) Examples of vinyl alicyclic hydrocarbon polymers include polymers of vinyl alicyclic hydrocarbon monomers such as vinyl cyclohexene and vinyl cyclohexane disclosed in JP-A-51-59989. And hydrogenated products thereof, aromatic rings of polymers of vinyl aromatic monomers such as styrene and α-methylstyrene disclosed in JP-A-63-43910 and JP-A-64-1706 Partial hydrogenation or the like can be used.

  Vinyl alicyclic hydrocarbon polymers include conjugated diene monomers such as butadiene and isoprene, chain olefin monomers such as ethylene and propylene, nitrile monomers such as acrylonitrile and methacrylonitrile, methyl (meth) acrylate, (meth) An acrylic monomer such as ethyl acrylate can also be copolymerized. Further, the steric configuration of these vinyl alicyclic hydrocarbon polymers may be any of atactic, isotactic, and syndiotactic. For example, any of 0 to 100% in syndiotacticity by dyad display. Can also be used.

  The alicyclic structure-containing polymer used in the present invention may have a polar group. Examples of the polar group include a hetero atom or an atomic group having a hetero atom, and examples of the hetero atom include an oxygen atom, a nitrogen atom, a silicon atom, and a halogen atom. Among these heteroatoms, an oxygen atom and a nitrogen atom are preferable from the viewpoint of dispersibility and compatibility with an inorganic compound. Specific examples include a carboxyl group, a carbonyloxycarbonyl group, an epoxy group, a hydroxy group, an oxy group, an ester group, a silanol group, a silyl group, an amino group, a nitrile group, and a sulfone group.

  The method for obtaining the alicyclic structure-containing polymer having a polar group is not particularly limited. For example, in the case of a norbornene polymer, (1) a polar group selected from various norbornene monomers. A method in which a compound having a polar group is reacted (modification reaction) with an unmodified polymer obtained by polymerizing a norbornene-based monomer having no polar group, and (2) a polarity selected from various norbornene-based monomers. A method in which a norbornene monomer having no group and a norbornene monomer having a polar group are copolymerized and further subjected to chemical changes such as hydrolysis, if necessary, (3) selected from various norbornene monomers A polymer obtained by polymerizing a norbornene-based monomer having no polar group, and the method (1) or (2) And a method such as mixing the norbornene-based polymer having more resulting polar group. The alicyclic structure-containing polymer other than the norbornene polymer is the same as that of the norbornene polymer.

  The molecular weight of the resin used in the present invention is appropriately selected depending on the purpose of use, but is converted to polyisoprene measured by gel permeation chromatography method of cyclohexane solution (toluene solution when the polymer does not dissolve). When the weight average molecular weight is in the range of 5,000 to 500,000, preferably 8,000 to 300,000, more preferably 10,000 to 200,000, the mechanical strength and moldability are high. And is suitable. Although the glass transition temperature (Tg) of resin used by this invention should just be suitably selected according to a use purpose, it is 50-300 degreeC normally, Preferably it is 60-200 degreeC, More preferably, it is 70-180 degreeC. is there.

  Coloring agents such as pigments and dyes, optical brighteners, dispersants, heat stabilizers, light stabilizers, UV absorbers, antistatic agents, antioxidants, lubricants, solvents, etc. are appropriately blended in the resin. Also good.

  Each member used in the present invention can be easily obtained by molding a resin by a known molding method. Examples of the molding method include injection molding, blow molding, extrusion molding, press molding, and insert molding.

  In the resin container of the present invention, the members are joined to each other to form a container shape. In joining the members, first, at least one member is subjected to plasma treatment or optical ozone treatment. Next, another member is pressed against the plasma-treated or photo-ozone-treated member. This joining method is similar to the method disclosed in Japanese Patent Application Laid-Open No. 2004-536168, Japanese Patent Application Laid-Open No. 2004-154898, or Japanese Patent Application Laid-Open No. 2005-11649, but the purpose of this publication is to increase the adhesive force. It ’s just that. The present inventor has conceived for the first time to apply for the purpose of providing an easily separable container that can be opened by a method such as folding, twisting, and scoring.

The plasma treatment is a known method as a surface modification treatment method. Examples of the plasma processing method include a method of irradiating the surface of a member with plasma generated in a plasma generation chamber through a nozzle (FIG. 1). An atmospheric pressure (normal pressure) plasma irradiation apparatus is generally commercially available from Arios Co., Ltd. under the trade name ATMP-600. The microwave power of this device can be adjusted within the range of 0-600 W, and the frequency of the microwave is within the range of 2.45 GHz ± 50 MHz. The plasma generating gas species is nitrogen, argon, helium or oxygen, and the gas flow rate is usually 20 L / min or less. The plasma generation chamber is made of, for example, quartz glass having a diameter of 10 mm. According to the atmospheric pressure (normal pressure) plasma irradiation apparatus, the member does not need to be sealed in a chamber, and plasma irradiation can be performed while maintaining the atmospheric pressure (normal pressure). By irradiating the plasma, the organic contaminant molecules adhering to the surface of the member are separated and removed in the state of carbon dioxide CO ₂ to clean the surface.

  According to the plasma processing, for example, in the case of a member having a length of about 100 mm, the passing time under the radiating nozzle is only a few seconds (for example, 5 seconds), and the member is continuously radiated by a conveying conveyor or the like. If it passes below, the surface to be bonded can be subjected to surface modification treatment very efficiently. In addition, since the member is always placed under atmospheric pressure, the operability is excellent, and there is an advantage that it is easy to automate conveyance between atmospheric pressure plasma radiation and the manufacturing process (for example, pressing process) before and after the atmospheric pressure plasma radiation.

In the present invention, the same effect as the plasma treatment can be achieved by the photo-ozone treatment.
In the photo-ozone treatment method, reactive groups or radicals are introduced to the surface of the member by ozone generated when oxygen is irradiated with ultraviolet rays. Examples of the irradiation apparatus used in the photo-ozone treatment method include an ultraviolet irradiation apparatus and an excimer UV irradiation apparatus. In the excimer UV irradiation apparatus, a dielectric barrier discharge lamp is used. In this dielectric barrier discharge lamp, a gas containing xenon as a main component is enclosed as a discharge gas in a discharge vessel, and this xenon atom is excited to enter an excimer state (Xe ₂ *). When dissociating into xenon atoms, light having a wavelength of about 172 nm is generated. When this light having a wavelength of 172 nm is irradiated to oxygen, ozone having a higher concentration than that obtained by irradiating oxygen with a light having a wavelength of 185 nm emitted from a conventional low-pressure mercury lamp can be obtained. Sexual decomposition products are also obtained.

  When excimer UV irradiation is used, the passing speed of the member under the dielectric barrier discharge lamp needs to be slower than that of the atmospheric pressure plasma irradiation. However, the irradiation width of the dielectric barrier discharge lamp is wide, a plurality of members can be processed in parallel at the same time, and the productivity is still higher than that of the conventional vacuum plasma. Since excimer UV irradiation can also be performed under atmospheric pressure, it is a great advantage in the same manner as the atmospheric pressure plasma irradiation described above. In addition, the excimer UV irradiation apparatus is less expensive than the atmospheric pressure plasma irradiation apparatus.

The members are joined by pressing another member against the plasma-treated or photo-ozone-treated member.
It is presumed that a chemical bond is formed when an active reactive group or radical introduced by performing plasma treatment or photo-ozone treatment is pressed against another member.
The pressure at the time of pressing is not particularly limited as long as the member is not broken. The pressure during pressurization is preferably 100 kg / cm ² or less, more preferably 10 kg / cm ² or less. Moreover, you may heat when pressing. The heating temperature is preferably lower than the melting temperature and / or glass transition temperature of the resin constituting the member, and is usually 100 ° C. or lower. When pressurizing, it may pressurize over the whole surface or may be local. Moreover, when heating, you may heat over the whole surface, and may be local in order to prevent quality changes, such as decomposition | disassembly and evaporation.

  The step of pressing the member is preferably performed in an inert atmosphere or a reduced pressure atmosphere so as not to deactivate the active reactive groups or radicals introduced by the plasma treatment or the photo-ozone treatment.

The resin container obtained by the above joining has such a peel strength that the joint does not peel even if an unexpected force is applied during transportation or storage. On the other hand, the joint is separable. That is, by separating the joint portion, the container can be opened and the filling material can be taken out. For example, when a stress is applied to the joint portion 22 in FIG. 3, the lid 15 can be removed as shown in FIG.
In the resin container of the present invention, when the joint portion is separated, the container is not deformed, chips such as resin powder are not generated, and the separation surface is smooth.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated further more concretely, this invention is not restrict | limited to the following Example. Parts and% are based on weight unless otherwise specified.

Examples 1-3
The following resin was injection molded under the conditions shown in Table 1 to obtain a cylindrical container A having an inner diameter of 30 mm, a height of 30 mm, and a wall thickness of 2.5 mm with an upper portion opened and a lower portion having a bottom. In addition, a cylindrical molded body B having an inner diameter of 30 mm, a height of 30 mm, and a wall thickness of 2.5 mm was obtained with the same resin under the same injection molding conditions. The opening edge of the cylindrical container A and one opening edge of the cylindrical molded body B were each mirror-finished with No. 2000 sandpaper.

ZEONEX: alicyclic structure polymer (ZEONEX 690R manufactured by Nippon Zeon Co., Ltd.) Glass transition temperature (Tg) = 137 ° C.
PC: Polycarbonate (PANLITE AD5503 made by Teijin Limited) Tg = 140 ° C.
PS: Polystyrene (GPPS HF77 manufactured by PS Japan) Tg = 94 ° C.

(A) Next, the distance (irradiation distance) from the tip of the plasma irradiation nozzle to the mirror-treated surface on the mirror-treated surface of the cylindrical container A and the cylindrical molded body B using an atmospheric pressure plasma treatment machine (manufactured by Matsushita Electric Works) Plasma treatment was performed under the conditions of 5 mm, a passing speed of 20 mm / second, and a high frequency power of 700 W (FIG. 5A). (B) Next, the cylindrical container A and the cylindrical molded body B are brought together at the plasma treatment surface, and are crimped at a temperature of 80 ° C. and a pressure of 1.5 kgf / cm ² , and have an inner diameter of 30 mm, a height of about 60 mm, and a wall thickness of 2.5 mm. A bottomed cylindrical container C was obtained (FIGS. 5B and 5C). The container C was evaluated by the following method. The results are shown in Table 2.

(Smoothness of the joint)
The joint part of the container C is visually observed, and “smooth” means that there are no burrs, resin residue, or adhesive residue, and burrs, resin residue, or adhesive residue has one or more. It was judged as “rough”.

(Sealing)
Ten containers C were prepared, water was added to the container capacity to 2/3, and the containers were wiped well with a dry cloth. Cobalt chloride paper was wound around the joint of the container C, the cobalt chloride paper was covered with a colorless waterproof seal, and the cobalt chloride paper was fixed to the container C. The container C was left in a room at normal temperature and pressure for 3 hours.
The number of containers in which the cobalt chloride paper was discolored was counted, and when the number of discolored containers was 2 to 10, it was judged as x, when it was 1, and when it was 0. Cobalt chloride paper changes color when contacted with water.

(Separability)
A hole with an inner diameter of 3 mm is drilled 15 mm from the upper and lower ends of the container C, and a round bar is passed through the hole, and attached to an autograph (manufactured by Shimadzu Corporation) as shown in FIG. 6, with a pulling speed of 300 mm / min. Pulled on both ends of the container. This test was performed on 10 containers and the separation surface was observed. A case where all 10 containers had no burr, resin residue, or adhesive residue was judged as “good”.

Example 4
A photo-ozone treatment was performed using an excimer UV irradiation device (made by USHIO INC.) Under conditions of an irradiation distance of 2 mm, an irradiation time of 80 seconds, a wavelength of 172 nm, and an irradiation output of 14.5 mW / cm ² instead of plasma processing. Obtained a container C in the same manner as in Example 1 and evaluated it. The results are shown in Table 2.

Comparative Example 1
A cylindrical container C was obtained in the same manner as in Example 1 except that a cyanoacrylate-based instantaneous adhesive was applied to the mirror-treated surface subjected to plasma treatment instead of the pressure bonding performed in Example 1, and evaluation was performed. It was. The results are shown in Table 2. In the manufacture of the container of Comparative Example 1, since the adhesive may protrude from the joint, it is necessary to remove it. In addition, the number of manufacturing processes increases, such as the need for an adhesive application process.

Comparative Example 2
The mirror-treated cylindrical container A obtained in Example 1 was set in a mold for obtaining a bottomed cylindrical container C having an inner diameter of 30 mm, a height of about 60 mm, and a wall thickness of 2.5 mm. A cylindrical container C was obtained by injection molding under the conditions shown in Table 1 so that a member corresponding to the cylindrical molded body B was joined to the mirror-finished surface of the container A. The container C was evaluated in the same manner as in Example 1. The results are shown in Table 2.

Comparative Example 3
A green colorant was applied to the mirror-treated surface of the container A obtained in Example 1 to color the mirror-treated surface. Next, using a laser welding apparatus (manufactured by Fine Device Co., Ltd.), the colored container A and the uncolored cylindrical molded body B are laser-welded at a passing speed of 10 mm / second and an irradiation output of 15 W, and the cylindrical container C Got. The container C was evaluated in the same manner as in Example 1. The results are shown in Table 2. In the container production of Comparative Example 3, it is necessary to color the container to be welded, and there is a limit in applications where colorless and transparent properties are required.

Comparative Example 4
The opening edges of the cylindrical container A and the cylindrical molded body B obtained by injection molding in Example 1 were cut so that the cross-section was a triangle having a height of 2 mm and a tip angle of 60 degrees. The cylindrical container A and the cylindrical molded body B that have been machined are brought together and ultrasonically welded using an ultrasonic welding apparatus (manufactured by BRANSON) under the conditions of a frequency of 20 kHz and a maximum applied pressure of 1.96 kN. Got. The container C was evaluated in the same manner as in Example 1. The results are shown in Table 2.

Example 5
Plasma treatment was performed on the mirror-treated surface of the cylindrical container A obtained in Example 1 in the same manner as in Example 1. Two plasma-treated cylindrical containers A were put together on the plasma-treated surface and pressure-bonded to obtain a container D sealed inside. The joint was smooth and had a good separation surface with no burrs or resin residue.

  From the above results, the resin container of the present invention has a strength that prevents the contents from leaking out. On the other hand, when pulled with a little strong force, the joint is separated and the separation surface is smooth. Therefore, even if it uses for the use which presses a separation surface to a biological body, there exists an effect of not giving a strange feeling to a biological body.

The figure which shows the place which is irradiating plasma to a container member. The figure which shows the place which is pressing the vessel member and the cover member. The figure which shows the resin container of this invention. The figure which shows the state which folded and opened this invention resin container. The figure which shows the manufacturing process of the container used by evaluation of a present Example. The figure which shows the attachment state in the tension test done by the present Example comparative example

Explanation of symbols

11: Container member 12: Object to be filled 13: Plasma 14: Opening 15: Lid member 20: Cylindrical container A
21: Edge of opening 22: Joint 23: Cylindrical molded body B

Claims (2)

Two or more members are joined together to form a container shape,
The joint is formed by plasma-treating or photo-ozone treatment of at least one member, and then pressing another member against the plasma-treated or photo-ozone treated member, and the joined portion is separable. Resin container. The resin container according to claim 1, which can enclose a medicine.

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