Container

Abstract

To provide a container which is excellent in recyclability and gas barrier property.SOLUTION: A container includes a base material layer, and a barrier layer, wherein the base material layer includes at least one kind selected from the group consisting of polyolefin, cyclic polyolefin, cyclic olefin copolymer, polycarbonate and polyester, the barrier layer contains a carboxy group-containing resin and a polyvinyl alcohol-based resin, and thickness of the barrier layer is 0.1 μm or more and 200.0 μm or less.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present disclosure relates to a container.

Background Art

[0002] Thermoplastic resins such as polyester are widely used in the manufacture of containers and the like because they are excellent in mechanical properties, chemical stability, heat resistance, gas barrier properties, transparency, and the like, and are inexpensive. In particular, in order to continuously maintain the quality of the contents, the development of containers having higher gas barrier properties is required.

[0003] Conventionally, various gas barrier materials that prevent the permeation of oxygen and the like are known, and containers provided with layers containing these have been proposed. As the gas barrier material, for example, gas barrier materials such as nylon resin, polyvinyl alcohol, ethylene-vinyl acetate copolymer, and polyacrylonitrile-based resin are known.

[0004] Furthermore, containers having improved gas barrier properties by providing a vapor deposition film of an inorganic oxide such as silicon oxide or aluminum oxide, or a vapor deposition film of an inorganic substance such as aluminum have been proposed. For example, Patent Documents 1 and 2 propose plastic bottles provided with a vapor deposition film of an inorganic oxide in order to improve gas barrier properties.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0006] In recent years, attempts have been made to recycle used containers for the purpose of reducing environmental impact. However, since it is difficult to separate the layer containing the gas barrier material as described above from the container, the container having such a layer is not excellent in recyclability and improvement is required.

[0007] Therefore, an object of the present disclosure is to provide a container excellent in recyclability and gas barrier properties.

Means for Solving the Problems

[0008] The present disclosure is solved by the following embodiments. <1> A container including a base material layer and a barrier layer, wherein the base material layer includes at least one selected from the group consisting of polyolefin, cyclic polyolefin, cyclic olefin copolymer, polycarbonate, and polyester, the barrier layer includes a carboxyl group-containing resin and a polyvinyl alcohol-based resin, and the thickness of the barrier layer is 0.1 μm or more and 200.0 μm or less. <2> The container according to <1>, wherein the carboxyl group-containing resin is polyacrylic acid. <3> The container according to <1> or <2>, wherein the content of the carboxyl group-containing resin is 1% by mass or more and 80% by mass or less based on all components contained in the barrier layer. <4> The container according to any one of <1> to <3>, wherein the mass ratio of the carboxyl group-containing resin to the polyvinyl alcohol-based resin is 1 / 20 or more and 10 / 1 or less. <5> The container according to any one of <1> to <4>, wherein the barrier layer is a dry coating film. <6> The oxygen permeability is 4.5454 cc / day·m 2 ·0.21 atm or less. <7> A vial having a mouth portion, a neck portion, a body portion, and a bottom portion, the container according to any one of <1> to <6>. <8> A syringe having a barrel tip, an outer barrel, a gasket, a plunger, and a flange, the container according to any one of <1> to <6>.

Advantages of the Invention

[0009] According to the present disclosure, a container excellent in recyclability and gas barrier properties can be provided.

Brief Description of the Drawings

[0010]

Figure 1

Figure 2

Modes for Carrying Out the Invention

[0011] <Container> The container of the present disclosure includes a base material layer and a barrier layer. Further, the container of the present disclosure may further include a protective layer. In addition, in this specification, "container" means a molded body for containing an article. Examples of the container include molded bodies such as compression molded bodies, injection molded bodies, blow molded bodies, and thermoformed bodies. Specific examples of the container include bottles, vials, cups, syringes such as prefilled syringes, trays, and packs. A vial is a container in which a rubber stopper is pressed into the mouth portion for sealing, and is mainly used as a container for medical reagents. A prefilled syringe is a syringe configured such that a chemical solution is stored in a sealed state in a syringe container in advance, and at the time of use, a sealing cap is removed and connected to an instrument such as an injection needle or a vascular catheter so that the chemical solution can be administered to a patient.

[0012] Hereinafter, the base material layer, barrier layer, and protective layer of the container will be described.

[0013] (Base material layer) In the container of the present disclosure, the base material layer can maintain the form of the container and contains a thermoplastic resin. The thermoplastic resin contained in the base material layer is at least one selected from the group consisting of polyolefins such as polyethylene and polypropylene, cyclic polyolefins such as polymers obtained by polymerizing and hydrogenating ring-opening polymerizable cycloolefin-based monomers (such as norbornenes or cyclotetradecenes), cyclic olefin copolymers such as copolymers made from ring-opening polymerizable cycloolefin-based monomers and olefins (such as ethylene or α-olefins), polycarbonate, and polyesters such as polyethylene terephthalate. Among these, from the viewpoint of moldability, polyester or polyolefin is preferable. When the base material layer contains polyester, from the viewpoint of the recyclability of the container, the content of polyester in the base material layer is preferably 90% by mass or more, and more preferably 97% by mass or more.

[0014] When the container is a bottle, the thermoplastic resin constituting the base material layer is preferably polyester. Also, when the container is a vial, the thermoplastic resin constituting the base material layer is preferably a cyclic polyolefin. Also, when the container is a syringe, the thermoplastic resin constituting the base material layer is preferably polyolefin, cyclic polyolefin, or cyclic olefin copolymer.

[0015] In the present disclosure, "polyester" means a polymer polymerized by an ester bond. Such a polyester is usually obtained by polycondensing a dicarboxylic acid compound and a diol compound. Examples of the dicarboxylic acid compound include malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, dodecanedioic acid, eicosanedioic acid, pimelic acid, azelaic acid, methylmalonic acid, ethylmalonic acid, adamantanedicarboxylic acid, norbornenedicarboxylic acid, cyclohexanedicarboxylic acid, decahydronaphthalenedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid, 5-sodium sulfoisophthalic acid, phenylenedendicarboxylic acid, anthracenedicarboxylic acid, phenanthrenedicarboxylic acid, 9,9'-bis(4-carboxyphenyl)fluorene acid, and ester derivatives thereof, etc. Examples of the diol compound include ethylene glycol, 1,2-propanediol, 1,3-propanediol, butanediol, 2-methyl-1,3-propanediol, hexanediol, neopentyl glycol, cyclohexanedimethanol, cyclohexanediethanol, decahydronaphthalenedimethanol, decahydronaphthalenediethanol, norbornanedimethanol, norbornanedietanol, tricyclodecanedimethanol, tricyclodecaneethanol, tetracyclododecanedimethanol, tetracyclododecanediethanol, decahydronaphthalenedimethanol, decahydronaphthalenediethanol, 5-methylol-5-ethyl-2-(1,1-dimethyl-2-hydroxyethyl)-1,3-dioxane, cyclohexanediol, bicyclohexyl-4,4'-diol, 2,2-bis(4-hydroxycyclohexyl)propane, 2,2-bis(4-(2-hydroxyethoxy)cyclohexyl)propane, cyclopentanediol, 3-methyl-1,2-cyclopentadiene diol, 4-cyclopentene-1,3-diol, adamantadiol, paraxylene glycol, bisphenol A, bisphenol S, styrene glycol, trimethylolpropane, pentaerythritol, and bis-β-hydroxyethyl terephthalate (BHET), etc. The polyester is preferably polyethylene terephthalate or modified polyethylene terephthalate obtained by polymerizing a raw material monomer of polyethylene terephthalate and a copolymer monomer.

[0016] The base material layer may contain additives as long as the characteristics of the present disclosure are not impaired. Examples of the additives include an oxygen absorber, a plasticizer, an ultraviolet stabilizer, an antioxidant, an anti-coloring agent, a matting agent, a deodorant, a flame retardant, a weather resistance agent, an antistatic agent, a yarn friction reducer, a slip agent, a release agent, an antioxidant, an ion exchange agent, and a coloring agent. These additives can be used alone or in combination of two or more.

[0017] The base material layer may have a single-layer structure or a multilayer structure of two or more layers. When the base material layer has a multilayer structure, each layer may have the same composition or different compositions.

[0018] The thickness of the base material layer is preferably 0.1 mm or more and 5.0 mm or less, more preferably 0.5 mm or more and 3.0 mm or less, still more preferably 0.5 mm or more and 2.0 mm or less, and even more preferably 1.0 mm or more and 1.5 mm or less. The thickness of the base material layer can be measured at the body portion or the outer cylinder of the container, and means the thickness of the cross section at the location where the thickness of the cross section of the base material layer is the smallest. When the base material layer is multilayered, the thickness of the base material layer is the sum of the thicknesses of all the layers.

[0019] The base material layer is preferably subjected to a surface treatment. Examples of the surface treatment include a corona treatment, a low-temperature plasma treatment, a flame treatment, and a coating treatment. By performing such a surface treatment, the wettability of the surface of the base material layer can be improved, and the adhesion between the base material layer and the layer in contact with the base material layer can be improved.

[0020] (Barrier layer) In the container of the present disclosure, the barrier layer contains a carboxyl group-containing resin and a polyvinyl alcohol-based resin. Polyvinyl alcohol-based resins have a high cohesive force and thus a high effect of blocking oxygen and water vapor (gas barrier property). Therefore, by including a polyvinyl alcohol-based resin in the barrier layer, a container with excellent gas barrier properties can be obtained. By including a carboxyl group-containing resin in the barrier layer, it has high solubility in acids or alkalis and can be easily separated and recovered by recycling, pulverizing, and washing the container. Therefore, a container having such a barrier layer has excellent recyclability. In addition, when the solvent of the coating liquid used for forming the barrier layer is water and / or a solvent having a hydroxy group, the carboxyl groups of the carboxyl group-containing resin form hydrogen bonds with these “-OH” groups, which can improve the viscosity of the coating liquid. As a result, depending on the coating method, the thickness of the barrier layer can be ensured with a small number of coating times, so that the productivity of the container can be improved. Furthermore, in conventional containers, in order to impart gas barrier properties, it was necessary to make the wall thickness of the container a certain thickness or more. However, in the container of the present disclosure, the wall thickness of the container can be made thinner, and the container can be lightened.

[0021] In the barrier layer, the mass ratio of the carboxyl group-containing resin to the polyvinyl alcohol-based resin is preferably 1 / 20 or more and 10 / 1 or less, more preferably 1 / 15 or more and 5 / 1 or less, and even more preferably 1 / 10 or more and 2 / 1 or less. By setting the above mass ratio to 1 / 20 or more, the recyclability of the container can be further improved. By setting the above mass ratio to 10 / 1 or less, the gas barrier property after blow molding can be further improved. Note that the above mass ratio is a solid content ratio.

[0022] As the carboxy group-containing resin contained in the barrier layer, existing carboxy group-containing resins can be used. The existing carboxy group-containing resins are a general term for resins containing carboxy groups in the polymer structure. The carboxy group-containing resins include homopolymers of carboxy group-containing unsaturated monomers, copolymers of carboxy group-containing unsaturated monomers, copolymers of carboxy group-containing unsaturated monomers and other polymerizable monomers, and polysaccharides containing carboxy groups in the molecule (also referred to as "acidic polysaccharides"). These carboxy group-containing resins can be used alone or in combination of two or more. Note that the carboxy group includes not only free carboxy groups but also acid anhydride groups (specifically, dicarboxylic acid anhydride groups). The acid anhydride group may be partially ring-opened to form a carboxy group. Further, in the carboxy group-containing resin, a part of the carboxy groups may be neutralized with an alkali.

[0023] As the carboxy group-containing unsaturated monomer, α,β-monoethylenically unsaturated carboxylic acids are preferred. Accordingly, the carboxy group-containing resins include homopolymers of α,β-monoethylenically unsaturated carboxylic acids, copolymers of two or more α,β-monoethylenically unsaturated carboxylic acids, and copolymers of α,β-monoethylenically unsaturated carboxylic acids and other polymerizable monomers. Examples of the other polymerizable monomers include ethylenically unsaturated monomers.

[0024] Examples of the α,β-monoethylenically unsaturated carboxylic acids include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; unsaturated dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid; and unsaturated dicarboxylic acid anhydrides such as maleic anhydride and itaconic anhydride. These acids can be used alone or in combination of two or more.

[0025] Other polymerizable monomers copolymerizable with α,β-monoethylenically unsaturated carboxylic acids, particularly ethylenically unsaturated monomers, include, for example, ethylene; α-olefins such as propylene, 1-butene, 1-pentene, 1-hexene, 1-octene; vinyl esters of saturated carboxylic acids such as vinyl acetate; alkyl acrylates such as methyl acrylate, ethyl acrylate; alkyl methacrylates such as methyl methacrylate, ethyl methacrylate; chlorine-containing vinyl monomers such as vinyl chloride, vinylidene chloride; fluorine-containing vinyl monomers such as vinyl fluoride, vinylidene fluoride; unsaturated nitriles such as acrylonitrile, methacrylonitrile; aromatic vinyl monomers such as styrene, α-methylstyrene; alkyl itaconates; and the like. These monomers can be used alone or in combination of two or more.

[0026] Examples of the carboxy group-containing polysaccharides include acidic polysaccharides having a carboxy group in the molecule, such as alginic acid, carboxymethyl cellulose, pectin, and the like. These acidic polysaccharides can be used alone or in combination of two or more. Further, the acidic polysaccharides can also be used in combination with a (co)polymer of α,β-monoethylenically unsaturated carboxylic acid.

[0027] When the carboxy group-containing resin used in the present disclosure is a copolymer of an α,β-monoethylenically unsaturated carboxylic acid and other ethylenically unsaturated monomers, from the viewpoints of recyclability and gas barrier properties, the composition of the copolymerization preferably has a composition of the α,β-monoethylenically unsaturated carboxylic acid monomer of 60 mol% or more, more preferably 80 mol% or more, and particularly preferably 90 mol% or more.

[0028] The carboxy group-containing resin is preferably selected from one or more of polyacrylic acid, polymethacrylic acid, and maleic acid polymers. The carboxy group-containing resin is relatively easy to obtain, and from the viewpoints of recyclability, barrier properties, and productivity of the container, polyacrylic acid is more preferable.

[0029] From the viewpoint of the moldability of the container, the number average molecular weight of the carboxyl group-containing resin is preferably in the range of 2,000 or more and 10,000,000 or less, more preferably in the range of 5,000 or more and 1,000,000 or less, and still more preferably in the range of 10,000 or more and 500,000 or less. The number average molecular weight can be measured by gel permeation chromatography (GPC). In GPC measurement, generally, the number average molecular weight of the polymer is measured in terms of standard polystyrene.

[0030] The content of the carboxyl group-containing resin is preferably 1% by mass or more and 80% by mass or less, more preferably 2% by mass or more and 70% by mass or less, and still more preferably 5% by mass or more and 60% by mass or less with respect to all components contained in the barrier layer. By setting the content of the carboxyl group-containing resin to 1% by mass or more, the recyclability of the container can be further improved. By setting the content of the carboxyl group-containing resin to 80% by mass or less, the gas barrier property of the container can be further improved.

[0031] The polyvinyl alcohol-based resin (also referred to as "PVA-based resin") contained in the barrier layer is a resin containing alcoholic hydroxy groups in the polymer structure. The PVA-based resin is usually obtained by saponifying a vinyl ester-based polymer.

[0032] The vinyl ester-based polymer is usually obtained by polymerizing a vinyl ester monomer as a polymerization component. Examples of the vinyl ester monomer include fatty acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caprylate, vinyl versatate, and vinyl monochloroacetate, and aromatic carboxylic acid vinyl esters such as vinyl benzoate (for example, C7-12 aromatic carboxylic acid-vinyl ester). These monomers can be used alone or in combination of two or more.

[0033] The vinyl ester polymer may have units derived from other polymerizable monomers (monomers copolymerizable with vinyl esters). Examples of other polymerizable monomers include ethylene; α-olefins such as propylene, 1-butene, 1-pentene, 1-hexene, 1-octene; alkyl methacrylates such as methyl methacrylate and ethyl methacrylate; chlorine-containing vinyl monomers such as vinyl chloride and vinylidene chloride; fluorine-containing vinyl monomers such as vinyl fluoride and vinylidene fluoride; unsaturated nitriles such as acrylonitrile and methacrylonitrile; aromatic vinyl monomers such as styrene and α-methylstyrene; alkyl itaconates; and the like. These monomers can be used alone or in combination of two or more.

[0034] The PVA-based resin may be one in which a part of the vinyl alcohol units is modified by reactions such as acetalization, etherification, acetoacetylation, and cationization.

[0035] The degree of polymerization of the PVA-based resin is preferably 1000 or more and 4000 or less, more preferably 1500 or more and 3500 or less, and even more preferably 2000 or more and 3000 or less. The average degree of polymerization of the PVA-based resin can be measured in accordance with JIS K 6726:1994.

[0036] From the viewpoints such as excellent solubility in a solvent and storage stability of the composition, the saponification degree of the PVA-based resin is preferably 70 mol% or more and 99.9 mol% or less, more preferably 90 mol% or more and 99.5 mol% or less, and even more preferably 95 mol% or more and 99.5 mol% or less. The saponification degree of the PVA-based resin can be measured in accordance with JIS K 6726:1994.

[0037] The PVA-based resins can be used alone or in combination of two or more.

[0038] The content of the PVA-based resin is preferably 20% by mass or more and 99% by mass or less, more preferably 30% by mass or more and 98% by mass or less, and still more preferably 40% by mass or more and 95% by mass or less, based on all components contained in the barrier layer. By setting the content of the PVA-based resin to 20% by mass or more, the gas barrier property can be further improved. By setting the content of the PVA-based resin to 99% by mass or less, the recyclability of the container can be further improved.

[0039] The barrier layer may contain additives as long as the characteristics of the present disclosure are not impaired. Examples of the additives include an oxygen absorber, a plasticizer, an ultraviolet stabilizer, an antioxidant, an anti-coloring agent, a matting agent, a deodorant, a flame retardant, a weathering agent, an antistatic agent, a yarn friction reducer, a slip agent, a release agent, an antioxidant, an ion exchanger, and a coloring agent. These additives can be used alone or in combination of two or more.

[0040] The barrier layer may be a single layer or a multilayer of two or more layers. When the barrier layer is a multilayer, each layer may have the same composition or different compositions.

[0041] The thickness of the barrier layer is 0.1 μm or more and 200.0 μm or less, preferably 5.0 μm or more and 50.0 μm or less. Thereby, the gas barrier property of the container can be improved. Note that the thickness of the barrier layer can be measured, for example, in the body or outer cylinder of the container, and means the thickness of the cross-section at the location where the thickness of the cross-section of the barrier layer is the smallest. When the barrier layer is a multilayer, the thickness of the barrier layer is the sum of the thicknesses of all layers.

[0042] (Protective layer) In the container of the present disclosure, the protective layer is for protecting the barrier layer and preferably contains a thermoplastic resin. By having the protective layer in the container, it is possible to prevent deterioration of the barrier function due to physical factors such as breakage or peeling of the barrier layer, or chemical factors such as moisture absorption or dissolution during the manufacture and use of the container. Examples of the thermoplastic resin include polyolefins (such as polyethylene, polypropylene, and polymethylpentene), polyvinyl chloride, polystyrene, polyvinyl acetate, acrylic resins, polyacetals, polyesters, polyurethanes, and polyvinyl acetals. These thermoplastic resins can be used alone or in combination of two or more. The protective layer preferably contains polyvinyl acetal.

[0043] The polyvinyl acetal contained in the protective layer is particularly preferably polyvinyl butyral. Polyvinyl butyral is a polymer having a structural unit having a vinyl butyral group in the molecule. Among them, it is preferably a polymer having at least a structural unit having a vinyl butyral group and a structural unit having a hydroxy group, represented by the following chemical formula (I).

[0044]

Chemical formula

[0045] Polyvinyl butyral is obtained by reacting polyvinyl alcohol (also referred to as "PVA") with butyraldehyde for acetalization. When acetalizing PVA, it is difficult to completely acetalize PVA, and hydroxy groups inevitably remain partially. Therefore, polyvinyl butyral resin contains hydroxy groups. Also, PVA is usually produced by saponifying polyvinyl acetate. However, since a small amount of acetyl groups often remain during the saponification in the production process of polyvinyl alcohol, it is common for acetyl groups and hydroxy groups to inevitably remain partially in polyvinyl butyral. Therefore, polyvinyl butyral usually contains acetyl groups, and a polymer having a structural unit with a vinyl butyral group, a structural unit with an acetyl group, and a structural unit with a hydroxy group is preferably used.

[0046] From the perspective of the durability of the protective layer, the degree of butyralization of polyvinyl butyral is preferably 50 mol% or more and 90 mol% or less, more preferably 60 mol% or more and 85 mol% or less, and still more preferably 65 mol% or more and 75 mol% or less. Here, the degree of butyralization is the molar fraction obtained by dividing the amount of ethylene groups to which butyral groups are bonded by the total amount of ethylene groups in the main chain, and corresponds to the mol% (l) of the structural unit having a vinyl butyral group in the formula (I).

[0047] From the perspective of the durability of the protective layer, the structural unit having a hydroxy group, that is, the structural unit (m) derived from vinyl alcohol in polyvinyl butyral is preferably 10.0 mol% or more and 40.0 mol% or less, more preferably 14.9 mol% or more and 34.0 mol% or less, and still more preferably 24.5 mol% or more and 31.0 mol% or less.

[0048] Polyvinyl butyral preferably has a structural unit having an acetyl group, that is, a structural unit (n) derived from vinyl acetate, of 10.0 mol% or less, more preferably 0.1 mol% or more and 6.0 mol% or less, and even more preferably 0.5 mol% or more and 4.0 mol% or less.

[0049] Polyvinyl butyral may further have a structural unit obtained by reacting vinyl alcohol with an aldehyde different from butyraldehyde for acetalization. Such a structural unit is preferably 10 mol% or less. In Chemical Formula (I), it is preferable that the sum of l, m, and n is 100 mol%.

[0050] From the viewpoints of the moldability of the container and the durability of the protective layer, the number average molecular weight of polyvinyl butyral is preferably 15,000 to 90,000, more preferably 20,000 to 70,000, and even more preferably 25,000 to 65,000.

[0051] From the viewpoint of the durability of the protective layer, the glass transition temperature (Tg) of polyvinyl butyral is preferably 50°C or higher and 100°C or lower, and more preferably 60°C or higher and 80°C or lower. The glass transition temperature (Tg) can be obtained by measuring the heat quantity change by DSC (differential scanning calorimetry) (DSC method).

[0052] The protective layer may contain additives within a range that does not impair the characteristics of the present disclosure. Examples of the additives include an oxygen absorber, a plasticizer, an ultraviolet stabilizer, an antioxidant, an anti-coloring agent, a matting agent, a deodorant, a flame retardant, a weathering agent, an antistatic agent, a yarn friction reducer, a slip agent, a release agent, an antioxidant, an ion exchanger, and a coloring agent. These additives can be used alone or in combination of two or more.

[0053] The protective layer may be a single layer or a multilayer of two or more layers. Further, when the barrier layer is a multilayer, each layer may have the same composition or different compositions.

[0054] The thickness of the protective layer is preferably 0.01 μm or more and 200.00 μm or less, more preferably 0.10 μm or more and 70.00 μm or less, still more preferably 0.50 μm or more and 50.00 μm or less, and even more preferably 0.70 μm or more and 30.00 μm or less. Thereby, the deterioration resistance of the barrier layer can be further improved. Note that the thickness of the protective layer can be measured, for example, on the body or outer cylinder of the container, and means the thickness of the cross-section at the location where the thickness of the cross-section of the protective layer is the smallest. Further, when the protective layer is multilayered, the thickness of the protective layer is the sum of the thicknesses of all the layers.

[0055] (Vapor deposition layer) In order to further improve the gas barrier property, the container of the present disclosure may have a vapor deposition film.

[0056] Examples of the vapor deposition film include vapor deposition films composed of metals such as aluminum, inorganic oxides such as aluminum oxide, silicon oxide, magnesium oxide, calcium oxide, zirconium oxide, titanium oxide, boron oxide, hafnium oxide, and barium oxide, organosilicon compounds such as hexamethyldisiloxane, and hard carbon films such as DLC (Diamond Like Carbon) films. Note that the hard carbon film made of a DLC film is also called an i-carbon film or a hydrogenated amorphous carbon film (a-C:H), and is an amorphous carbon film mainly composed of SP 3 bonding.

[0057] Also, the thickness of the vapor deposition film is not particularly limited, and can be, for example, 1 nm or more and 150 nm or less. Note that the thickness of the vapor deposition layer can be measured, for example, on the body or outer cylinder of the container, and means the thickness of the cross-section at the location where the thickness of the cross-section of the vapor deposition film is the smallest.

[0058] The vapor deposition film can be formed by using a conventionally known method, for example, physical vapor deposition methods such as vacuum vapor deposition method, sputtering method, and ion plating method (Physical Vapor Deposition method, PVD method), and chemical vapor deposition methods such as plasma chemical vapor deposition method, thermal chemical vapor deposition method, and photo chemical vapor deposition method (Chemical Vapor Deposition method, CVD method), etc. can be mentioned.

[0059] In the container of the present disclosure, the oxygen permeability is preferably 4.5454 cc / day·m 2 ·0.21 atm or less, more preferably 1.8181 cc / day·m 2 ·0.21 atm or less, still more preferably 0.1820 cc / day·m 2 ·0.21 atm or less, and even more preferably 0.1140 cc / day·m 2 ·0.21 atm or less is even more preferable. The above oxygen permeability is a value measured under the conditions of 23°C and a humidity of 40% RH by using an oxygen permeability measuring device (for example, manufactured by MOCON, trade name: OX-TRAN 2 / 61) in accordance with JIS K 7126-2:2006. It is measured for the entire container with the opening blocked by a jig, and is a value obtained by dividing by the surface area of the entire container excluding the opening.

[0060] The thickness of the container of the present disclosure is preferably 0.1 mm or more and 5.0 mm or less, more preferably 0.1 mm or more and 3.0 mm or less, still more preferably 0.5 mm or more and 2.5 mm or less, and even more preferably 0.5 mm or more and 1.7 mm or less. The thickness of the container can be measured, for example, at least in the body or outer cylinder of the container having a base material layer, a barrier layer, and a protective layer. The thickness of the container means the thickness of the cross section at the location where the thickness of the cross section of the container is the smallest.

[0061] The container of the present disclosure preferably has a volume / weight of 5 mL / g or more and 50 mL / g or less, and more preferably 8 mL / g or more and 45 mL / g or less. By setting the volume / weight of the container to 5 mL / g or more, the weight of the container can be reduced. Also, by setting the volume / weight of the container to 50 mL / g or less, the strength of the container can be improved.

[0062] The container of the present disclosure may have a volume of, for example, 2000 mL or less. The volume of the container is preferably 50 mL or less. Also, the volume of the container of the present disclosure is preferably 1 mL or more, and more preferably 2 mL or more.

[0063] The container of the present disclosure may be printed. The image formed by the printing is not particularly limited, and examples include patterns and characters. From the viewpoint of not being affected by the color tone of the container, the printing is preferably applied to the outer surface of the container. The printing can be performed by a known method. Examples of the printing method include an inkjet method, a gravure printing method, an offset printing method, a flexographic printing method, a thermal transfer method, a silk screen method, a pad method, a hot stamping method, a cold stamping method, and the like.

[0064] Hereinafter, a vial and a syringe will be exemplified, and an embodiment of the structure of the container according to the present disclosure will be described with reference to the drawings. Note that each figure is shown schematically. Therefore, the size and shape of each part are exaggerated as appropriate for easy understanding. Also, it can be implemented with appropriate changes without departing from the technical idea. Also, the numerical values and material names of the dimensions of each member described in this specification are examples as an embodiment, and are not limited thereto, and can be appropriately selected and used. In this specification, terms specifying shapes and geometric conditions, such as terms like parallel, orthogonal, and perpendicular, are interpreted to include not only the strictly meant state but also substantially the same state.

[0065] FIG. 1 is a schematic semi-sectional view showing a vial, which is an embodiment of the container of the present disclosure. As shown in FIG. 1, the vial 50 includes a cylindrical body 53 for accommodating articles such as chemicals, a bottom 54 closing the lower end of the body 53, a cylindrical neck 52 provided above the body 53 and having an outer diameter smaller than that of the body 53, and a cylindrical mouth 51 provided above the neck 52 and having an outer diameter larger than that of the neck 52.

[0066] Although the body 53 in FIG. 1 has a cylindrical shape with a generally uniform diameter as a whole, it is not limited thereto, and the body 53 may have a polygonal cylindrical shape such as a quadrangular cylindrical shape or an octagonal cylindrical shape. Alternatively, the body 53 may have a cylindrical shape with a non-uniform horizontal cross-section from top to bottom. Also, although the body 53 in FIG. 1 has no unevenness and has a substantially flat surface, it is not limited to this. For example, unevenness such as panels or grooves may be formed on the body 53.

[0067] As shown in FIG. 1, in the vial 50, the mouth 51 is composed of a base material layer 55, and the neck 52, the body 53, and the bottom 54 are composed of the base material layer 55, a barrier layer 56, and a protective layer 57. As shown in FIG. 1, in the neck 52, the body 53, and the bottom 54, the barrier layer 56 and the protective layer 57 are provided over the entire outer area of the base material layer 55 so as to surround the base material layer 55. In one embodiment, the barrier layer 56 and the protective layer 57 may be provided in all or part of one or more selected from the mouth 51, the neck 52, the body 53, and the bottom 54.

[0068] The barrier layer 56 and the protective layer 57 may be provided inside the vial 50 (not shown). The vial 50 may be provided with a vapor deposition film on at least one selected from the group including the inside and the outside of the vial (not shown).

[0069] When using the vial 50 for storing chemicals or the like, after accommodating the chemicals or the like in its body 53, a rubber stopper (not shown) having gas barrier properties is fitted into the mouth portion 51. Further, a cap (not shown) made of a relatively soft metal such as aluminum is caulked (wound and tightened) from above, thereby sealing the vial 50. As a result, a vial 50 having gas barrier properties can be obtained.

[0070] FIG. 2 is a schematic semi-sectional view showing a syringe which is an embodiment of the container of the present disclosure. As shown in FIG. 2, the syringe 60 includes a cylindrical outer cylinder 61 having a substantially uniform diameter as a whole, a cylinder tip 62 formed at the upper end of the outer cylinder 61 for injecting or discharging a chemical solution, a gasket 63 housed in the outer cylinder 61 and capable of sliding in the outer cylinder 61 in a liquid-tight manner, a plunger 64 attached to the gasket 63 for sliding the gasket 63 up and down in the outer cylinder 61, and a flange 65 for hanging a finger when pushing out and moving the plunger 64 upward.

[0071] As shown in FIG. 2, in the syringe 60, the cylinder tip 62 and the flange 65 are constituted by a base material layer 66, and the outer cylinder 61 is constituted by the base material layer 66, a barrier layer 67, and a protective layer 68. As shown in FIG. 2, in the outer cylinder 61, the barrier layer 67 and the protective layer 68 are provided over the entire outer region of the base material layer 66 so as to surround the base material layer 66. In one embodiment, the barrier layer 67 and the protective layer 68 may be provided in all or a part of one or more selected from the outer cylinder 61, the cylinder tip 62, and the flange 65.

[0072] The barrier layer 67 and the protective layer 68 may be provided on the inner side of one or more selected from the outer cylinder 61, the cylinder tip 62, and the flange 65 (not shown). The syringe 60 may be provided with a vapor deposition film on at least one selected from the group including the inner side and the outer side of one or more selected from the outer cylinder 61, the cylinder tip 62, and the flange 65 (not shown).

[0073] The tip 62 is sealed with a sealing cap (not shown). Thereby, the syringe 60 having gas barrier properties can be obtained. The sealing cap may be a cap-shaped one made of an elastic material such as rubber or elastomer and covering the tip 62 so as to wrap it. Alternatively, a cap-shaped molded product is produced from a synthetic polymer resin composition, and a cap-shaped one in which an elastic material such as rubber or elastomer is disposed so as to close the tip 62 may be used to cover the tip 62. Or, a cap-shaped molded product having a through hole provided in the top surface is produced from a synthetic polymer resin composition, and a cap-shaped sealing cap in which a resealing material such as rubber or elastomer is disposed so as to close the through hole may be used to cover the tip 62. Note that, as the synthetic polymer resin composition, a composition containing polypropylene or cyclic polyolefin as a constituent component is suitable.

[0074] <Method for manufacturing a container> Hereinafter, a method for manufacturing a container according to an embodiment of the present disclosure will be described while exemplifying a vial.

[0075] In one embodiment, the vial 50 shown in FIG. 1 can be manufactured by the following procedure. First, a base material layer 55 having a mouth portion 51, a neck portion 52, a body portion 53, and a bottom portion 54 is produced by injection molding a material constituting the base material layer 55 using a conventionally known apparatus. Next, a coating liquid for a barrier layer containing a carboxyl group-containing resin, a polyvinyl alcohol-based resin, and a solvent is prepared. Next, the coating liquid for a barrier layer is applied to the neck portion 52, the body portion 53, and the bottom portion 54 of the base material layer 55 to form a coating film. Next, the coating film is dried to remove the solvent, thereby forming a barrier layer 56 which is a dried coating film. Next, a coating liquid for a protective layer containing a material constituting the protective layer 57 and a solvent is prepared. Next, the coating liquid for a protective layer is applied to the surface of the barrier layer 56 to form a coating film. Next, by drying the coating film to remove the solvent, a protective layer 57, which is a dried coating film, can be formed, and the vial 50 described in FIG. 1 can be manufactured. Note that the syringe 60 described in FIG. 2 can be manufactured by appropriately selecting the shape of the base material layer 66 and the coating locations of the coating liquid for the barrier layer and the coating liquid for the protective layer. Moreover, by omitting the formation of the protective layer, a container having a base material layer and a barrier layer and not having a protective layer can be manufactured.

[0076] The solvent used in the coating liquid for the barrier layer is not particularly limited as long as it can dissolve the carboxy group-containing resin and the polyvinyl alcohol-based resin. Examples of the solvent include water; alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, n-propyl alcohol, n-butyl alcohol, and n-pentyl alcohol; and polar organic solvents such as dimethyl sulfoxide, N,N-dimethylformamide, and N,N-dimethylacetamide. These solvents can be used alone or in combination of two or more. As the solvent, it is preferable to use water, alcohols, or a mixture thereof, and it is more preferable to use a mixed solvent of water and isopropyl alcohol. Thereby, the viscosity of the coating liquid is improved, and the number of coating times can be reduced, so that the productivity of the container can be improved.

[0077] In the coating liquid for the barrier layer, the total concentration of the solid content of the carboxy group-containing resin and the polyvinyl alcohol-based resin is preferably 2% by mass or more and 15% by mass or less, and more preferably 3% by mass or more and 10% by mass or less. Thereby, a barrier layer with a uniform thickness can be formed.

[0078] The viscosity of the coating liquid for the barrier layer is preferably 25 mPa·s or more and 300 mPa·s or less, and more preferably 30 mPa·s or more and 270 mPa·s or less. Thereby, the productivity of the container can be further improved. The viscosity of the coating liquid can be measured using a rotational viscometer at a temperature of 20°C in accordance with JIS Z 8803:2011.

[0079] Coating of the coating liquid for the barrier layer can be performed by a conventionally known method. Examples thereof include a method of coating with a brush or the like, a method of immersing a container in the coating liquid for the barrier layer, and a method of spraying the coating liquid for the barrier layer on the surface of the container.

[0080] The drying temperature of the coating film formed from the coating liquid for the barrier layer is not particularly limited as long as it can remove the solvent, but is preferably 20°C or higher and 80°C or lower, and more preferably 50°C or higher and 70°C or lower.

[0081] The solvent used in the coating liquid for the protective layer is not particularly limited as long as it can dissolve and emulsify and disperse the material for forming the protective layer. For example, water, acetone, ethyl methyl ketone, methyl isobutyl ketone, ethyl acetate, methanol, ethanol, isopropanol, etc. can be used.

[0082] Coating of the coating liquid for the protective layer can be performed by a conventionally known method. Examples of the coating method include a method of coating with a brush or the like, a method of immersing a container in the coating liquid for the protective layer, and a method of spraying the coating liquid for the protective layer on the surface of the container.

[0083] The drying temperature of the coating film formed from the coating liquid for the protective layer is not particularly limited as long as it can remove the solvent, but is preferably 20°C or higher and 80°C or lower, and more preferably 40°C or higher and 70°C or lower.

[0084] The manufacturing method of the container according to one embodiment may include a step of printing an image such as a pattern and characters on the surface of the container. Printing can be performed by known methods. Examples of printing methods include, for example, inkjet method, gravure printing method, offset printing method, flexographic printing method, thermal transfer method, silk screen method, pad method, hot stamping method, cold stamping method and the like. For example, when using the inkjet method, a UV-curable ink can be applied to a container, irradiated with UV, and cured to form a printing layer. Also, printing may be performed using a thermal transfer sheet.

Examples

[0085] Next, examples will be given to explain the present disclosure in more detail, but the present disclosure is not limited to these examples.

[0086] [Example 1] As a base material layer, a syringe body (trade name: ClearJect (registered trademark), manufactured by Daisheng Chemical Co., Ltd.) made of cyclic polyolefin, with a cross-sectional thickness of the outer cylinder of 1.5 mm and a capacity of 2.5 mL was prepared. Next, 18.75 g of PVA (manufactured by Kuraray Co., Ltd., trade name: 60-98, degree of polymerization: 2400, degree of saponification: 98.0 to 99.0%) was added to 462.5 g of water, and then 18.75 g of polyacrylic acid (manufactured by Nippon Shokubai Co., Ltd., trade name: AS-58, number average molecular weight: 106,000) was added and stirred to prepare a coating liquid for the barrier layer with a solid content concentration of 7.5 mass% (viscosity: 1933 mPa·s (20 °C)). This coating liquid for the barrier layer was applied to the outer cylinder of the above syringe body with a cap attached to the tip of the cylinder to form a coating film. The coating film was dried at 50 °C for 10 minutes to form a barrier layer with a thickness of 12 μm. The solid content mass ratio of polyacrylic acid to PVA is 1 / 1. Next, a copolymerized polyester containing ethylene glycol and neopentyl glycol as the diol copolymerization component and terephthalic acid and isophthalic acid as the dicarboxylic acid copolymerization component was prepared. The TG of the copolymerized polyester was 67°C, and the Mw of the copolymerized polyester was 17,000. The copolymerized polyester was dissolved in a mixed solvent of ethyl acetate and methyl ethyl ketone (1:1 mixed solution) so that the content of the copolymerized polyester was 25% by mass, and a coating liquid for the protective layer was prepared. This coating liquid for the protective layer was applied to the barrier layer with a cap attached to the tip of the cylinder of the syringe body to form a coated film. By drying the coated film at 50°C for 10 minutes, a protective layer with a thickness of 30 μm was formed, and the syringe of Example 1 was produced. The syringe of Example 1 had a structure as shown in Figure 2 except that it did not include a gasket and a plunger.

[0087] [Example 2] A syringe body (product name: Syringe DS2.5mL Lock, manufactured by Nipro Corporation) made of polypropylene with a cross-sectional thickness of the outer cylinder of 1.5 mm and a capacity of 2.5 mL was used as the base material layer, and the syringe of Example 2 was produced in the same manner as in Example 1 except for this.

[0088] [Comparative Example 1] A syringe of Comparative Example 1 was produced in the same manner as in Example 1 except that the barrier layer and the protective layer were not formed.

[0089] [Comparative Example 2] A syringe of Comparative Example 2 was produced in the same manner as in Example 2 except that the barrier layer and the protective layer were not formed.

[0090] <<Gas Barrier Property Evaluation>> The oxygen permeability of the syringes obtained in the above Examples and Comparative Examples was measured to evaluate the gas barrier properties of the syringes. The measurement of the oxygen permeability was carried out under the conditions of 23 °C and 40% RH using an oxygen gas permeability measuring device (manufactured by MOCON, product name: OX-TRAN2 / 61) in accordance with JIS K 7126-2:2006. The numerical value of the oxygen permeability was the value measured for the entire syringe with the opening blocked by a jig (unit: cc / day·pkg·0.21 atm), and the value obtained by dividing this measured value by the surface area of the entire syringe excluding the opening (unit: cc / day·m 2 ·0.21 atm). The measurement results are shown in Table 1.

[0091]

Table 1

[0092] As is clear from Table 1, the syringes of Examples 1 and 2 have low oxygen permeability and excellent gas barrier properties.

Explanation of Signs

[0093] 50: Vial 51: Mouth 52: Neck 53: Barrel 54: Bottom 55: Base layer 56: Barrier layer 57: Protective layer 60: Syringe 61: Outer cylinder 62: Tip of cylinder 63: Gasket 64: Plunger 65: Flange 66: Base layer 67: Barrier layer 68: Protective layer

Claims

1. A container comprising a base material layer and a barrier layer, wherein the base material layer contains at least one selected from the group consisting of polyolefin, cyclic polyolefin, cyclic olefin copolymer, polycarbonate, and polyester, the barrier layer contains a carboxyl group-containing resin and a polyvinyl alcohol-based resin, and the thickness of the barrier layer is 0.1 μm or more and 200.0 μm or less.

2. The container according to Claim 1, wherein the carboxyl group-containing resin is polyacrylic acid.

3. The container according to Claim 1 or 2, wherein the content of the carboxyl group-containing resin is 1% by mass or more and 80% by mass or less based on all components contained in the barrier layer.

4. The container according to Claim 1 or 2, wherein the mass ratio of the carboxyl group-containing resin to the polyvinyl alcohol-based resin is 1 / 20 or more and 10 / 1 or less.

5. The container according to Claim 1 or 2, wherein the barrier layer is a dry coating film.

6. The oxygen permeability is 4.5454 cc / day·m ２ ·0.21 atm or less, the container according to claim 1 or 2.

7. The container according to Claim 1 or 2, which is a vial having a mouth portion, a neck portion, a body portion, and a bottom portion.

8. The container according to Claim 1 or 2, which is a syringe having a barrel tip, an outer barrel, a gasket, a plunger, and a flange.

Images