Container

Abstract

To provide a container which is excellent in recyclability and has gas barrier property.SOLUTION: A container includes a base material layer, a protective layer provided on one surface of the base material layer, and a barrier layer provided between the base material layer and the protective layer, and has capacity of 2,000 mL or less, wherein the base material layer contains a thermoplastic resin, and the barrier layer contains a resin having water solubility or alkali solubility.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present disclosure relates to a container.

Background Art

[0002] In recent years, for the purpose of reducing environmental loads such as carbon dioxide emissions, recycling of used plastic containers has been carried out. Since recycling needs to be performed with the same kind of material, for example, when recycling a used bottle, the collected bottle needs to be separated into a label, a cap, and a bottle body. Further, when the bottle body has a multilayer structure, for example, when it includes a base material layer and a coating layer provided on the surface of the base material layer, it is necessary to separate the base material layer and the coating layer.

[0003] Patent Document 1 discloses a plastic bottle having a polyvinyl alcohol coating as a barrier layer on the outer surface of a base material layer and a polyvinyl butyral coating as a protective layer on the polyvinyl alcohol coating. Since polyvinyl alcohol has water solubility, the plastic bottle disclosed in Patent Document 1 can dissolve the barrier layer between the base material layer and the protective layer during recycling, and as a result, the base material layer, the barrier layer, and the protective layer can be separated.

[0004] Also, from the viewpoint of reducing environmental loads, lightweight bottle containers with a reduced amount of material (for example, a thermoplastic resin such as polyester) used to form the container have come to be used.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0006] However, since the lightweight container as described above is thin-walled, it has higher gas permeability than a normal container and is not suitable as a container having gas barrier properties.

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

Means for Solving the Problems

[0008] The inventors of the present invention have found that by providing a protective layer on a base material layer via a barrier layer, a container having gas barrier properties can be realized while improving recyclability and reducing the amount of materials used. The present disclosure has been completed through further studies based on such findings.

[0009] The present disclosure is solved by the following embodiments. <1> A container comprising a base material layer, a protective layer provided on one surface of the base material layer, and a barrier layer provided between the base material layer and the protective layer, the container having a capacity of 2000 mL or less, wherein the base material layer contains a thermoplastic resin, and the barrier layer contains a water-soluble or alkali-soluble resin. <2> The container according to <1>, wherein the water-soluble or alkali-soluble resin contains at least one of a carboxyl group-containing resin and a polyvinyl alcohol-based resin. <3> The container according to <1> or <2>, wherein the thickness of the base material layer is 0.1 mm or more and 5.0 mm or less. <4> The container according to any one of <1> to <3>, wherein the thickness of the barrier layer is 0.1 μm or more and 200 μm or less. <5> The container according to any one of <1> to <4>, wherein the thickness of the protective layer is 0.01 μm or more and 200.00 μm or less. <6> The container according to any one of <1> to <5>, wherein the container is an ampoule bottle having a mouth portion, a neck portion, a body portion, and a bottom portion. <7> The container according to any one of <1> to <5>, wherein the container is a syringe having a barrel tip, an outer barrel, a gasket, a plunger, and a flange. <8> The container according to any one of <1> to <7>, wherein the protective layer is made of at least one resin selected from the group consisting of polyolefin, polyvinyl chloride, polystyrene, polyvinyl acetate, acrylic resin, polyacetal, polyester, polyurethane, and polyvinyl acetal.

Advantages of the Invention

[0010] According to the present disclosure, a container excellent in recyclability and having a gas barrier property can be provided.

Brief Description of the Drawings

[0011]

Figure 1

Figure 2

Modes for Carrying Out the Invention

[0012] <Container> The container of the present disclosure includes a base material layer, a protective layer provided on at least one surface side of the base material layer, and a barrier layer provided between the base material layer and the protective layer. In the present specification, the "container" means a molded body for housing 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, ampoule bottles, cups, syringes such as prefilled syringes, trays, and packs. An ampoule bottle 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 to store a medicinal solution in a sealed state in a syringe container in advance, remove a sealing cap during use, connect it to an instrument such as an injection needle or a blood vessel catheter, and administer the medicinal solution to a patient.

[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. Examples of the thermoplastic resin contained in the base material layer include polyolefins such as polyethylene and polypropylene, cyclic polyolefins such as polymers obtained by polymerizing and hydrogenating ring-opening polymerizable cycloolefin monomers (such as norbornenes or cyclotetradecenes), cyclic olefin copolymers such as copolymers made from ring-opening polymerizable cycloolefin monomers and olefins (such as ethylene or α-olefins), polycarbonate, polyvinyl chloride, polyesters such as polyethylene terephthalate, polyamides such as nylon 6 and nylon 6,6, and mixtures thereof. Among these, from the viewpoint of moldability, polyester or polyolefin is preferred. When the container is a vial, the thermoplastic resin constituting the base material layer is preferably a cyclic polyolefin. When the container is a syringe, the thermoplastic resin constituting the base material layer is preferably polyolefin, cyclic polyolefin or cyclic olefin copolymer.

[0014] In this specification, "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, phenylendadicarboxylic 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.

[0015] The polyester is preferably polyethylene terephthalate or a modified polyethylene terephthalate obtained by polymerizing a raw material monomer of polyethylene terephthalate and a copolymer monomer. The copolymer monomer can be appropriately selected from the above-described dicarboxylic acid components and diol components.

[0016] Within the range that does not impair the characteristics of the present disclosure, the polyester may contain monomers other than the dicarboxylic acid compound and the diol compound, but the content thereof is preferably 10 mol% or less, more preferably 5 mol% or less, and still more preferably 3 mol% or less based on all the constituent units.

[0017] The polyester may be polymerized using a polymerization catalyst. Examples of the polymerization catalyst include a manganese (Mn) catalyst, a titanium (Ti) catalyst, an aluminum (Al) catalyst, a lithium (Li) catalyst, a germanium (Ge) catalyst, and an antimony (Sb) catalyst.

[0018] The above-described polyester may be not only virgin polyester but also recycled polyester from the viewpoint of reducing environmental load. In the present specification, "virgin polyester" means polyester that has not been recycled, and "recycled polyester" means polyester recycled by collecting products such as used containers shipped on the market. In addition, as recycled polyester, there are polyester obtained by decomposing the collected used polyester containers to the monomer level and then repolymerizing them (hereinafter referred to as "chemical recycled polyester"), and polyester obtained by sorting, pulverizing, and washing the collected used products to remove contaminants and foreign substances, obtaining flakes, and further treating the flakes under high temperature and reduced pressure for a certain period of time to remove the contaminants inside the resin (hereinafter referred to as "mechanical recycled polyester"). The mechanical recycled polyester may contain two or more kinds of catalysts. In this case, the mechanical recycled polyester may contain two or more of, for example, Sb catalyst polyester, Mn catalyst polyester, Ti catalyst polyester, Al catalyst polyester, Li catalyst polyester, and Ge catalyst polyester.

[0019] In mechanical recycled polyester, it is known that the content ratios of antimony (Sb) element, sodium (Na) element, calcium (Ca) element, and / or magnesium (Mg) element are different from those of virgin polyester and chemical recycled polyester. Specifically, it is known that mechanical recycled polyester contains Sb element at a ratio of 20 mg / L or more and 54 mg / L or less, Na element at a ratio of 12 mg / L or more, Ca element at a ratio of 4 mg / L or more, and / or Mg element at a ratio of 2.5 mg / L or more. Therefore, mechanical recycled polyester can be distinguished from virgin polyester and chemical recycled polyester by whether the polyester satisfies one or more of these content ratios. In addition, in mechanical recycled polyester, the content ratio of Sb element is preferably 25 mg / L or more and 50 mg / L or less, the content ratio of Na element is preferably 14 mg / L or more, the content ratio of Ca element is preferably 4.5 mg / L or more, and the content ratio of Mg element is preferably 3 mg / L or more.

[0020] When the container of the present disclosure contains mechanically recycled polyester, the content of the mechanically recycled polyester is preferably 20 parts by mass or more and 100 parts by mass or less, more preferably 60 parts by mass or more and 90 parts by mass or less, based on 100 parts by mass of the total amount of the resin material contained in the container.

[0021] From the viewpoint of recyclability, the content of one type of thermoplastic resin in the base material layer is preferably 85% by mass or more, more preferably 97% by mass or more.

[0022] The base material 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, a matting agent, a deodorant, a flame retardant, a weathering agent, an antistatic agent, a friction reducer, a slip agent, a mold release agent, an antioxidant, and an ion exchanger. These additives can be used alone or in combination of two or more.

[0023] The base material layer may have a single-layer structure or a multilayer structure of two or more layers. Further, when the base material layer has a multilayer structure, each layer may have the same composition or different compositions within a range that does not impair the characteristics of the present disclosure.

[0024] 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.

[0025] 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. Incidentally, the thickness of the base material layer can be measured in 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. Further, when the base material layer is multilayered, the thickness of the base material layer is the sum of the thicknesses of all the layers.

[0026] (Protective layer) In the container of the present disclosure, the protective layer is for protecting the barrier layer. By the container having the protective layer, deterioration of the barrier function can be suppressed due to physical factors such as breakage or peeling of the barrier layer, or chemical factors such as moisture absorption or dissolution during the production and use of the container.

[0027] In one embodiment, the protective layer contains a thermoplastic resin. Examples of the thermoplastic resin contained in the protective layer include polyolefin, polyvinyl chloride, polystyrene, polyvinyl acetate, acrylic resin, polyacetal, polyester, polyurethane, and polyvinyl acetal. These thermoplastic resins can be used alone or in combination of two or more.

[0028] In one embodiment, the thermoplastic resin contained in the protective layer is preferably polyvinyl acetal from the viewpoint of adhesion to the barrier layer. Polyvinyl acetal is particularly preferably polyvinyl butyral. Polyvinyl butyral is a polymer having a structural unit having a vinyl butyral group in the molecule. Among them, preferably, it is 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).

[0029] [Chemical formula] (In Chemical formula (I), "l" is the mol% of the structural unit having a vinyl butyral group, and is represented by the total mol% of the structural units derived from butyralized vinyl alcohol. "m" represents the mol% of the structural unit derived from vinyl alcohol, and "n" represents the mol% of the structural unit derived from vinyl acetate. Both l and m are numbers greater than 0, and n may be 0.)

[0030] 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, but 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.

[0031] From the viewpoint of the durability of the protective layer, polyvinyl butyral preferably has a butyralization degree of 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 butyralization degree 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 Chemical Formula (I).

[0032] From the viewpoint of the durability of the protective layer, polyvinyl butyral preferably has a structural unit having a hydroxy group, that is, a structural unit (m) derived from vinyl alcohol, of 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.

[0033] Polyvinyl butyral has a structural unit having an acetyl group, that is, a structural unit (n) derived from vinyl acetate, which is preferably 10.0 mol% or less, more preferably 0.1 mol% or more and 6.0 mol% or less, and still more preferably 0.5 mol% or more and 4.0 mol% or less.

[0034] Polyvinyl butyral may further have a structural unit obtained by acetalizing vinyl alcohol with an aldehyde different from butyraldehyde. Such a structural unit is preferably 10 mol% or less. In Chemical Formula (I), the sum of l, m, and n is preferably 100 mol%.

[0035] From the viewpoint of 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 still more preferably 25,000 to 65,000.

[0036] 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, 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).

[0037] In another embodiment, the thermoplastic resin contained in the protective layer is preferably polyurethane from the viewpoints of heat resistance and water resistance. Polyurethane can be obtained by a known method, and the production method is not limited. Polyurethane is, for example, a reaction product formed by the reaction (urethane-forming reaction) of an organic polyol and an organic polyisocyanate.

[0038] Examples of the organic polyol include a compound having 2 to 6, preferably 2 to 4 functional groups in one molecule and having a number average molecular weight of 500 to 100,000, preferably 1,000 to 30,000. More specifically, polyester polyol, polyether polyol, polyether ester polyol, polyester amide polyol, acrylic polyol, polycarbonate polyol, polyhydroxyl alkane, polyurethane polyol, castor oil, or a mixture thereof (hereinafter, these may be referred to as organic polyol (1)). Among these, the organic polyol is preferably a polyurethane polyol. In the present specification, the number average molecular weight can be measured by gel permeation chromatography (GPC). In GPC measurement, generally, the number average molecular weight of a polymer is measured in terms of standard polystyrene.

[0039] Examples of the polyester polyol include a polyester polyol obtained by reacting a dibasic acid such as terephthalic acid, isophthalic acid, adipic acid, azelaic acid, sebacic acid or a dialkyl ester thereof or a mixture thereof with a glycol such as ethylene glycol, propylene glycol, diethylene glycol, butylene glycol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 3,3'-dimethylolheptane, polyoxyethylene glycol, polyoxypropylene glycol, polytetramethylene ether glycol or a mixture thereof. Further, examples of the polyester polyol include a polyester polyol obtained by ring-opening polymerization of lactones such as polycaprolactone, polyvalerolactone, poly(β-methyl-γ-valerolactone).

[0040] Examples of polyether polyols include polyether polyols obtained by polymerizing oxirane compounds such as ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran using low molecular weight polyols such as water, ethylene glycol, propylene glycol, trimethylolpropane, and glycerin as initiators.

[0041] Examples of polyether ester polyols include polyether ester polyols obtained by reacting dibasic acids such as terephthalic acid, isophthalic acid, adipic acid, azelaic acid, and sebacic acid, or their dialkyl esters or mixtures thereof, with the above polyether polyols.

[0042] Examples of polyester amide polyols include polyester amide polyols obtained by mixing aliphatic diamines having amino groups such as ethylenediamine, propylenediamine, and hexamethylenediamine as raw materials during the above esterification reaction.

[0043] Examples of acrylic polyols include acrylic polyols obtained by copolymerizing hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, etc., each containing one or more hydroxy groups in one molecule, or their corresponding methacrylic acid derivatives, with, for example, acrylic acid, methacrylic acid, or their esters.

[0044] Examples of the polycarbonate polyol include a polycarbonate polyol obtained by reacting one or more glycols selected from ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,9-nonanediol, 1,8-nonanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, bisphenol A, and hydrogenated bisphenol A with dimethyl carbonate, diphenyl carbonate, ethylene carbonate, phosgene, or the like.

[0045] Examples of the polyhydroxyalkane include butadiene or a liquid rubber obtained by copolymerizing butadiene with acrylamide or the like.

[0046] The polyurethane polyol is a polyol having a urethane bond in one molecule. Examples thereof include a polyurethane polyol obtained by reacting a polyol such as a polyether polyol, a polyester polyol, or a polyether ester polyol having a number average molecular weight of 200 or more and 20,000 or less with an organic polyisocyanate so that the ratio (NCO / OH) of the isocyanate group to the hydroxy group is less than 1, preferably 0.9 or less. In the polyurethane polyol, the polyol preferably used is a polyester polyol having a number average molecular weight of 200 or more and 20,000 or less. Such a polyurethane polyol may also be referred to as a polyester polyurethane polyol.

[0047] As the organic polyol, those having a carboxy group in their molecules (inside the molecule or at the molecular end) (hereinafter referred to as organic polyol (2)) can be used. The organic polyol (2) is preferably obtained by reacting the above-mentioned organic polyol (1) with a polybasic acid or its anhydride. As the organic polyol (1) used at this time, those containing two or more hydroxy groups at the molecular end and having a number average molecular weight of preferably 1,000 or more and 100,000 or less, more preferably 3,000 or more and 15,000 or less can be mentioned.

[0048] Examples of the polybasic acid or its anhydride include aromatic polybasic acids such as phthalic acid, trimellitic acid, and pyromellitic acid and their anhydrides, and among them, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, etc., which are their anhydrides, are particularly suitable. Furthermore, ethylene glycol bisanhydrotrimellitate, glycerol trisanhydrotrimellitate, ethylene glycol bisanhydropyromellitate, glycerol trisanhydropyromellitate, derived from these anhydrides, abietic acid of rosin component, derivatives obtained by addition reaction of maleic anhydride to C10H16 diene compounds and their mixtures, etc. can be used.

[0049] The synthesis of the organic polyol (2) is carried out by adding a polybasic acid or its anhydride, preferably a polybasic acid anhydride, under heating after the synthesis of the organic polyol (1). However, it is possible to obtain a compound containing a carboxy group inside or at the molecular end in one step from a polyvalent carboxylic acid and a polyvalent alcohol during the synthesis of the organic polyol.

[0050] Organic polyisocyanates have two or more isocyanate groups in one molecule. Examples of organic polyisocyanates include linear alkylene diisocyanates such as trimethylene diisocyanate, tetramethylene diisocyanate, and hexamethylene diisocyanate; branched alkylene diisocyanates such as 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, and 2,2,4-trimethylhexamethylene diisocyanate, etc., aliphatic diisocyanates; alicyclic diisocyanates such as 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate, 4,4'-methylenebis(cyclohexyl isocyanate), methyl 2,4-cyclohexane diisocyanate, methyl 2,6-cyclohexane diisocyanate, 1,4-bis(isocyanatomethyl)cyclohexane, 1,3-bis(isocyanatomethyl)cyclohexane, etc.; aromatic diisocyanates such as m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4- or 2,6-tolylene diisocyanate or a mixture thereof, 4,4'-toluidine diisocyanate, dianisidine diisocyanate, 4,4'-diphenyl ether diisocyanate, etc.; aromatic aliphatic diisocyanates such as 1,3- or 1,4-xylylene diisocyanate or a mixture thereof, ω,ω'-diisocyanate-1,4-diethylbenzene, 1,3- or 1,4-bis(1-isocyanato-1-methylethyl)benzene or a mixture thereof, etc.; organic polyisocyanate monomers such as organic triisocyanates such as triphenylmethane-4,4',4''-triisocyanate, 1,3,5-triisocyanate benzene, 2,4,6-triisocyanate toluene, etc., and organic tetraisocyanates such as 4,4'-diphenyldimethylmethane-2,2'-5,5'-tetraisocyanate, etc. In addition to the above monomers, examples of the organic polyisocyanate include dimers, trimers, biurets, and allophanates derived from the above polyisocyanate monomers; polyisocyanates having a 2,4,6-oxadiazinetrione ring obtained from carbon dioxide gas and the above polyisocyanate monomers; low molecular weight polyols having a molecular weight of less than 200 such as ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 3,3'-dimethylolpropane, cyclohexanedimethanol, diethylene glycol, triethylene glycol, dipropylene glycol, glycerol, trimethylolpropane, pentaerythritol, sorbitol, etc. and adducts of these with the above polyisocyanate monomers; polyester polyols, polyether ester polyols, polyester amide polyols, polycaprolactone polyols, polyvalerolactone polyols, acrylic polyols, polycarbonate polyols, polyhydroxyalkanes, castor oil, polyurethane polyols, etc. having a molecular weight of 200 or more and 20,000 or less and adducts of these with the above polyisocyanate monomers, and the like. The organic polyisocyanate may be used alone or as a mixture of two or more of the above-mentioned ones. In one embodiment, the organic polyisocyanate is preferably the above adduct, more preferably an adduct of a polyisocyanate monomer and a polyurethane polyol.

[0051] For the urethanization reaction, at least one selected from the group consisting of a silane coupling agent, an oxyacid of phosphorus, and a derivative of an oxyacid of phosphorus may be further used.

[0052] As the silane coupling agent, for example, those represented by the following chemical formula (II) or (III) can be used. R-Si≡(X) 3 ·····(II) R-Si≡(R’)(X) 2 ·····(III) In formulas (II) and (III), R represents an organic group having a vinyl group, an epoxy group, an amino group, an imino group or a mercapto group, R' represents a lower alkyl group, and X represents a methoxy group, an ethoxy group or a chlorine atom. Examples of the silane coupling agent include chlorosilanes such as vinyltrichlorosilane, aminosilanes such as N-(dimethoxymethylsilylpropyl)ethylenediamine and N-(triethoxysilylpropyl)ethylenediamine; epoxysilanes such as γ-glycidoxypropyltrimethoxysilane and γ-glycidoxypropyltriethoxysilane; vinylsilanes such as vinyltriethoxysilane and the like. The addition amount of the silane coupling agent is preferably 0.1% by mass or more and 5.0% by mass or less based on the polyurethane obtained.

[0053] Among the oxygen acids of phosphorus or their derivatives, as the oxygen acids of phosphorus, any one having at least one free oxygen acid may be used. For example, phosphoric acids such as hypophosphorous acid, phosphorous acid, orthophosphoric acid, and metaphosphoric acid; condensed phosphoric acids such as metaphosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, polyphosphoric acid, and ultraphosphoric acid can be mentioned. Examples of the derivatives of the oxygen acids of phosphorus include those partially esterified with alcohols in a state where at least one free oxygen acid of the above oxygen acids of phosphorus remains. Examples of these alcohols include aliphatic alcohols such as methanol, ethanol, ethylene glycol, and glycerin; aromatic alcohols such as phenol, xylenol, hydroquinone, catechol, and phloroglucinol. One or more of the oxygen acids of phosphorus or their derivatives may be used. The addition amount of the oxygen acid of phosphorus or its derivative is preferably 0.01% by mass or more and 10.00% by mass or less, more preferably 0.05% by mass or more and 5.00% by mass or less, still more preferably 0.10% by mass or more and 1.00% by mass or less based on the polyurethane obtained.

[0054] In one embodiment, the polyurethane is a polyurethane polyol, preferably a reaction product of a polyurethane polyol having a carboxy group in the molecule and an organic polyisocyanate. The organic polyisocyanate is preferably an adduct of a polyisocyanate monomer and a polyurethane polyol. By using such a reaction product as the polyurethane, the heat resistance of the container can be further improved.

[0055] In one embodiment, the polyurethane may be a reaction product of a polyester polyol and two or more organic polyisocyanates. At least one of the two or more organic polyisocyanates may be a linear alkylene diisocyanate. The linear alkylene diisocyanate may be hexamethylene diisocyanate.

[0056] The protective 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 mold release agent, an antioxidant, an ion exchanger, and a coloring agent. These additives can be used alone or in combination of two or more.

[0057] The protective 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.

[0058] The protective layer may be colored in colors such as red, blue, yellow, green, brown, dark brown, orange, black, and white, and may be further transparent or opaque. When the protective layer is colored, it can absorb light entering the container from the outside such as sunlight, similar to the case of coloring the barrier layer, and can suppress the deterioration of the contents of the container. Since it can effectively absorb visible light with a wavelength of 400 nm or more and 500 nm or less, the protective layer is preferably colored in dark brown or orange. The coloring of the protective layer can be achieved, for example, by using a coloring agent.

[0059] 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 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. Also, when the protective layer is multilayered, the thickness of the protective layer is the sum of the thicknesses of all the layers.

[0060] (Barrier layer) The barrier layer is a layer having gas barrier properties. A container provided with such a barrier layer can suppress the permeation of gases such as oxygen, and thus can suppress the deterioration of the contents.

[0061] In the container of the present disclosure, the barrier layer contains a resin having water solubility or alkali solubility. Thereby, a container excellent in recyclability can be obtained. The reason is as follows. In the recycling of used containers, first, the containers are pulverized into flakes, and then washed using a liquid such as water and an alkali solution. When a barrier layer having water solubility or alkali solubility exists between the base material layer and the protective layer, in this washing step, the barrier layer dissolves, the protective layer can be peeled off from the base material layer, and the base material layer can be separated. Therefore, such containers are excellent in recyclability. Note that the barrier layer may be a layer having both water solubility and alkali solubility. In this specification, "water-soluble" means that the barrier layer dissolves in distilled water at 20 °C in an amount of 3% by mass or more, preferably 10% by mass or more, and more preferably 20% by mass or more. In this specification, "alkali-soluble" means that the barrier layer dissolves in a 1.5% by mass aqueous sodium hydroxide solution at 90 °C in an amount of 3% by mass or more, preferably 10% by mass or more, and more preferably 20% by mass or more.

[0062] The barrier layer is preferably a layer having light-shielding properties, gloss, color, gas barrier properties, etc., depending on the use of the container. The barrier layer is particularly preferably a barrier layer having gas barrier properties.

[0063] In one embodiment, the water-soluble or alkali-soluble resin includes a polyvinyl alcohol-based resin. Since the polyvinyl alcohol-based resin has high cohesive force, it has a high effect of blocking oxygen and carbon dioxide gas (gas barrier property). By including the polyvinyl alcohol-based resin in the barrier layer, a barrier layer having water solubility or alkali solubility can be obtained, and the gas barrier property of the container can be improved.

[0064] In one embodiment, the water-soluble or alkali-soluble resin includes at least one of a carboxyl group-containing resin and a polyvinyl alcohol-based resin. As described above, by including the polyvinyl alcohol-based resin in the barrier layer, a barrier layer having water solubility or alkali solubility can be obtained, and the gas barrier property of the container can be improved. In addition, by including the carboxyl group-containing resin in the barrier layer, the water solubility or alkali solubility of the barrier layer is improved, and the recyclability of the container can be improved. Furthermore, the carboxyl group of the carboxyl group-containing resin forms a hydrogen bond with the "-OH" of the polyvinyl alcohol-based resin or the solvent of the coating liquid used for forming the barrier layer (for example, water and an organic solvent having a hydroxy group), increasing the viscosity of the coating liquid. As a result, depending on the coating method, the thickness of the barrier layer can be increased with fewer coating times, improving the productivity of the container.

[0065] Hereinafter, the polyvinyl alcohol-based resin and the carboxyl group-containing resin will be described.

[0066] The polyvinyl alcohol-based resin (also referred to as "PVA-based resin") 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.

[0067] Vinyl ester polymers are usually obtained by polymerizing vinyl ester monomers as polymerization components. Examples of vinyl ester monomers 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 arene carboxylic acid - vinyl ester). These monomers can be used alone or in combination of two or more.

[0068] Vinyl ester polymers 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, and 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; and alkyl itaconates. These monomers can be used alone or in combination of two or more.

[0069] 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.

[0070] 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 still more preferably 2000 or more and 3000 or less. The average degree of polymerization of the PVA resin can be measured in accordance with JIS K 6726:1994.

[0071] The saponification degree of the PVA-based resin is preferably 70.0 mol% or more and 99.9 mol% or less, more preferably 90.0 mol% or more and 99.5 mol% or less, and still more preferably 95.0 mol% or more and 99.5 mol% or less, from the viewpoints of excellent solubility in a solvent and storage stability of the composition. The saponification degree of the PVA-based resin can be measured in accordance with JIS K 6726:1994.

[0072] One or more PVA-based resins can be used in combination.

[0073] As the carboxy group-containing resin, existing carboxy group-containing resins can be used. The existing carboxy group-containing resins are a general term for resins containing a carboxy group 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 a carboxy group 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. In the carboxy group-containing resin, a part of the carboxy group may be neutralized with an alkali.

[0074] The carboxy group-containing unsaturated monomer is preferably an α,β-monoethylenically unsaturated carboxylic acid. Therefore, the carboxy group-containing resin includes 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 other polymerizable monomers include ethylenically unsaturated monomers.

[0075] Examples of 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. The α,β-monoethylenically unsaturated carboxylic acid is preferably selected from one or more of acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, and itaconic acid, and more preferably selected from one or more of acrylic acid, methacrylic acid, and maleic acid.

[0076] Examples of other polymerizable monomers copolymerizable with α,β-monoethylenically unsaturated carboxylic acids, particularly ethylenically unsaturated monomers, include ethylene; α-olefins such as propylene, 1-butene, 1-pentene, 1-hexene, and 1-octene; vinyl esters of saturated carboxylic acids such as vinyl acetate; alkyl acrylates such as methyl acrylate and ethyl acrylate; 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; and alkyl itaconates. These monomers can be used alone or in combination of two or more.

[0077] Examples of carboxy group-containing polysaccharides include acidic polysaccharides having a carboxy group in the molecule, such as alginic acid, carboxymethyl cellulose, and pectin. These acidic polysaccharides can be used alone or in combination of two or more. The acidic polysaccharides can be used in combination with a (co)polymer of α,β-monoethylenically unsaturated carboxylic acid.

[0078] 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, the composition of the copolymer is such that the composition of the α,β-monoethylenically unsaturated carboxylic acid monomer is preferably 60 mol% or more, more preferably 80 mol% or more, and still more preferably 90 mol% or more.

[0079] The carboxy group-containing resin is preferably a homopolymer or copolymer obtained by polymerization of only an α,β-monoethylenically unsaturated carboxylic acid. When the polycarboxylic acid polymer is a (co)polymer consisting of only an α,β-monoethylenically unsaturated carboxylic acid, the carboxy group-containing resin is preferably a homopolymer, copolymer, or a mixture of two or more thereof obtained from a carboxylic acid selected from one or more of acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, and itaconic acid, and more preferably a homopolymer, copolymer, or a mixture of two or more thereof obtained from a carboxylic acid selected from one or more of acrylic acid, methacrylic acid, and maleic acid.

[0080] 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 is preferably polyacrylic acid from the viewpoints of recyclability and gas barrier properties.

[0081] The number average molecular weight of the carboxy 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.

[0082] When the barrier layer contains a carboxyl group-containing resin and a vinyl alcohol-based resin, the mass ratio of the carboxyl group-containing resin to the vinyl alcohol-based resin (carboxyl group-containing resin / vinyl 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 still 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 of the container can be further improved. Note that the above mass ratio is a solid content ratio.

[0083] When the barrier layer contains a carboxyl group-containing resin and a vinyl alcohol-based resin, 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.

[0084] When the barrier layer contains a carboxyl group-containing resin and a polyvinyl alcohol-based resin, the content of the polyvinyl alcohol-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 with respect to all components contained in the barrier layer. By setting the content of the polyvinyl alcohol-based resin to 20% by mass or more, the gas barrier property of the container can be further improved. By setting the content of the polyvinyl alcohol-based resin to 99% by mass or less, the recyclability of the container can be further improved.

[0085] In another embodiment, the barrier layer contains a reaction product of a carboxyl group-containing resin and a polyvalent metal compound. Even with such a configuration of the barrier layer, a barrier layer having water solubility or alkali solubility can be obtained, and a container with improved gas barrier properties can be obtained.

[0086] Hereinafter, the polyvalent metal compound will be described. Note that the carboxyl group-containing resin described above can be used.

[0087] The polyvalent metal compound is a simple polyvalent metal atom having a valence of 2 or more for metal ions and its compound.

[0088] Examples of the polyvalent metal include beryllium, magnesium, calcium, barium, titanium, zirconium, chromium, manganese, iron, cobalt, nickel, copper, zinc, aluminum, etc. These polyvalent metals can be used alone or in combination of two or more. The polyvalent metal is preferably selected from one or more of magnesium, calcium, and zinc. By selecting the polyvalent metal from one or more of these, the barrier layer can be made transparent, so that various designs can be imparted to the container, and a container rich in design can be obtained. The polyvalent metal is particularly preferably magnesium.

[0089] Examples of the polyvalent metal compound include oxides, hydroxides, organic acid salts, inorganic acid salts of polyvalent metals, and furthermore, ammonium complexes of polyvalent metals, secondary to quaternary amine complexes of polyvalent metals, and organic acid salts and inorganic acid salts of these complexes. Examples of the organic acid salt include acetate, oxalate, citrate, lactate, stearate, and monoethylenically unsaturated carboxylate. Examples of the inorganic acid salt include chloride, nitrate, carbonate, sulfate, phosphate, phosphite, and hypophosphite. In addition, alkyl alkoxides of polyvalent metals and the like can be mentioned. These compounds can be used alone or in combination of two or more. The polyvalent metal compound is preferably selected from one or more of chloride, nitrate, sulfate, phosphate, phosphite, and hypophosphite, and more preferably chloride, nitrate, or a mixture thereof.

[0090] When the barrier layer contains a reaction product of a carboxy group-containing resin and a polyvalent metal compound, the amount of the polyvalent metal compound is preferably 0.05 chemical equivalent or more and 5.00 chemical equivalents or less, more preferably 0.10 chemical equivalent or more and 3.00 chemical equivalents or less, still more preferably 0.20 chemical equivalent or more and 2.00 chemical equivalents or less, and even more preferably 0.30 chemical equivalent or more and 1.50 chemical equivalents or less, relative to all carboxy groups of the carboxy group-containing resin. Note that the term "all carboxy groups" is used to mean including carboxy groups of the carboxy group-containing resin that did not participate in the reaction and carboxy groups that become polyvalent metal salts of polycarboxylic acids in the reaction product obtained by the reaction of the carboxy group-containing resin and the polyvalent metal compound. The chemical equivalent can be determined, for example, as follows. Taking the case where the carboxy group-containing resin is acrylic acid and the polyvalent metal compound is magnesium chloride as an example. The molecular weight of the monomer unit of polyacrylic acid is 72, and since each molecule of the monomer has one carboxy group, when the mass of polyacrylic acid is 100 g, the amount of carboxy groups in 100 g of polyacrylic acid is 1.39 mol. At this time, 1 equivalent with respect to 100 g of polyacrylic acid is the amount of base that neutralizes 1.39 mol. Therefore, when 0.2 equivalents of magnesium chloride are mixed with 100 g of polyacrylic acid, magnesium chloride sufficient to neutralize 0.278 mol of carboxy groups may be added. Since the valence of magnesium is divalent and the formula weight of magnesium chloride is 95, 0.2 equivalents of magnesium chloride with respect to 100 g of polyacrylic acid is 13.2 g (0.139 mol).

[0091] When the barrier layer contains a reaction product of a carboxy group-containing resin and a polyvalent metal compound, the barrier layer may contain components other than this reaction product. Examples of such components include unreacted carboxy group-containing resin, unreacted polyvalent metal compound, by-products generated by the reaction of the carboxy group-containing resin and the polyvalent metal compound, and other resin components.

[0092] The barrier layer may contain an additive as long as the characteristics of the present disclosure are not impaired. Examples of the additive include an oxygen absorber, a plasticizer, an ultraviolet stabilizer, an antioxidant, 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, and an ion exchanger. These additives can be used alone or in combination of two or more.

[0093] The barrier 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.

[0094] The barrier layer may be colored in colors such as red, blue, yellow, green, brown, dark brown, orange, black, and white, and may be further transparent or opaque. By coloring the barrier layer, light entering the container from the outside such as sunlight can be absorbed, and deterioration of the contents of the container can be suppressed. Since it can effectively absorb visible light with a wavelength of 400 nm or more and 500 nm or less, the barrier layer is preferably colored in brown or orange. For coloring the barrier layer, for example, a coloring agent can be used.

[0095] The thickness of the barrier layer is preferably 0.1 μm or more and 200.0 μm or less, more preferably 0.5 μm or more and 100.0 μm or less, still more preferably 0.7 μm or more and 50.0 μm or less, and even more preferably 5.0 μm or more and 30.0 μm or less. Note that the thickness of the barrier 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 barrier layer is the smallest. Also, when the barrier layer is multilayer, the thickness of the barrier layer is the sum of the thicknesses of all the layers.

[0096] (Vapor deposition film) The container of the present disclosure may have a vapor deposition film in order to further improve the gas barrier property.

[0097] 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 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.

[0098] 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.

[0099] The formation of the vapor deposition film can be carried out by a conventionally known method. For example, physical vapor deposition methods (Physical Vapor Deposition method, PVD method) such as vacuum evaporation method, sputtering method, and ion plating method, and chemical vapor deposition methods (Chemical Vapor Deposition method, CVD method) such as plasma chemical vapor deposition method, thermal chemical vapor deposition method, and photo chemical vapor deposition method can be mentioned.

[0100] Hereinafter, taking a vial and a syringe as examples, 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 schematically shown. Therefore, the size and shape of each part are exaggerated as appropriate for easy understanding. Also, it can be appropriately changed and implemented 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 embodiments 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 to be interpreted to include not only the strictly meant state but also a substantially same state.

[0101] 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 portion 53 for accommodating articles such as chemicals, a bottom portion 54 closing the lower end of the body portion 53, a cylindrical neck portion 52 provided above the body portion 53 and having an outer diameter smaller than that of the body portion 53, and a cylindrical mouth portion 51 provided above the neck portion 52 and having an outer diameter larger than that of the neck portion 52.

[0102] Although the body portion 53 in FIG. 1 has a cylindrical shape with a generally uniform diameter as a whole, it is not limited to this, and the body portion 53 may have a polygonal cylindrical shape such as a square cylindrical shape or an octagonal cylindrical shape. Alternatively, the body portion 53 may have a cylindrical shape with a non-uniform horizontal cross-section from top to bottom. Also, although the body portion 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 portion 53.

[0103] As shown in FIG. 1, in the vial 50, the mouth portion 51 is composed of a base material layer 55, and the neck portion 52, the body portion 53, and the bottom portion 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 portion 52, the body portion 53, and the bottom portion 54, the barrier layer 56 and the protective layer 57 are provided over the entire outer region 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 regions selected from the mouth portion 51, the neck portion 52, the body portion 53, and the bottom portion 54.

[0104] 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).

[0105] When the vial 50 is used for storing chemicals or the like, after storing the chemicals or the like in its body portion 53, a rubber stopper (not shown) having gas barrier properties is fitted into the mouth portion 51. Further, by caulking (winding and tightening) a cap (not shown) made of a relatively soft metal such as aluminum thereon, the vial 50 is sealed. Thereby, a vial 50 having gas barrier properties can be obtained.

[0106] Figure 2 is a schematic semi-cross-sectional view showing a syringe which is an embodiment of the container of the present disclosure. As shown in Figure 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.

[0107] As shown in Figure 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 Figure 2, in the outer cylinder 61, the barrier layer 67 and the protective layer 68 are provided over the entire outer area 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 over all or a partial area of one or more selected from the outer cylinder 61, the cylinder tip 62, and the flange 65.

[0108] The barrier layer 67 and the protective layer 68 may be provided inside 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 inside and the outside of one or more selected from the outer cylinder 61, the cylinder tip 62, and the flange 65 (not shown).

[0109] The cylinder 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 cylinder tip 62. Alternatively, a cap-shaped molded article may be made of 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 cylinder tip 62 may be covered on the cylinder tip 62. Or, a cap-shaped molded article having a through hole provided on the top surface may be made of 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 covered on the cylinder tip 62. Note that as the synthetic polymer resin composition, a composition containing polypropylene or cyclic polyolefin as a constituent component is preferable.

[0110] 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 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 portion blocked by a jig, and is a value obtained by dividing by the surface area of the entire container excluding the opening portion.

[0111] The container of the present disclosure preferably has a mass of 50 g or less, more preferably 10 g or more and 40 g or less, and still more preferably 10 g or more and 25 g or less. By setting the mass of the container to 50 g or less, the weight of the container can be reduced. Also, by setting the mass of the container to 10 g or more, the strength of the container can be improved.

[0112] The container of the present disclosure has a volume / mass of 4 mL / g or more and 200 mL / g or less, preferably 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 / mass of the container to 4 mL / g or more, the weight of the container can be reduced. Also, by setting the volume / mass of the container to 200 mL / g or less, the strength of the container can be improved.

[0113] The container of the present disclosure is a container with a volume of 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.

[0114] In the container of the present disclosure, the transmittance of visible light with a wavelength of 400 nm or more and 500 nm or less is preferably 20% or less. The transmittance is more preferably 15% or less, still more preferably 5% or less, and even more preferably 1% or less. Such transmittance can be adjusted by appropriately coloring at least one layer selected from the group including a protective layer and a barrier layer. The transmittance of visible light with a wavelength of 400 nm or more and 500 nm or less can be obtained by measuring the light transmittance of visible light wavelengths at intervals of 0.5 nm using a spectrophotometer. As the spectrophotometer, an ultraviolet-visible spectrophotometer manufactured by Shimadzu Corporation can be used. Note that the transmittance of the container is measured, for example, at least in the body or outer cylinder of the container having at least a base material layer, a barrier layer, and a protective layer.

[0115] The container of the present disclosure may be printed on its surface. The image formed by 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 performed on the outer surface of the container. Printing can be carried out 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, etc.

[0116] <Method for manufacturing a container> Hereinafter, while exemplifying a vial, a method for manufacturing a container according to an embodiment of the present disclosure will be described.

[0117] In one embodiment, the vial 50 shown in FIG. 1 can be manufactured by the following procedure. First, by injection molding the material constituting the base material layer 55 using a conventionally known apparatus, 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. Next, a coating liquid for the barrier layer containing the material constituting the barrier layer 56 and a solvent is prepared. Next, the coating liquid for the 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 the barrier layer 56. Next, a coating liquid for the protective layer containing the material constituting the protective layer 57 and a solvent is prepared. Next, the coating liquid for the protective layer is applied to the surface of the barrier layer 56 to form a coating film. Next, the coating film is dried to remove the solvent, thereby forming the protective layer 57, and the vial 50 shown in FIG. 1 can be manufactured. Note that the syringe 60 shown 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.

[0118] The solvent used in the coating liquid for the barrier layer is one that can dissolve or emulsify and disperse the materials constituting the barrier layer. 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 organic solvents such as dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, and methyl ethyl ketone. These solvents can be used alone or in combination of two or more. Preferably, water, alcohols, or a mixture thereof is used as the solvent, and more preferably, a mixed solvent of water and isopropyl alcohol is used.

[0119] In the coating liquid for the barrier layer, the total concentration of the solid components of the materials constituting the barrier layer 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 uniform thickness can be formed.

[0120] 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.

[0121] The coating of the coating liquid for the barrier 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 dipping the 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 base material layer.

[0122] The drying temperature of the coating film formed from the coating liquid for the barrier layer is a temperature at which the solvent can be removed. The drying temperature is preferably 20°C or more and 180°C or less, more preferably 40°C or more and 150°C or less, and still more preferably 50°C or more and 120°C or less.

[0123] 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, methyl ethyl ketone, ethyl acetate, n-propyl acetate, methanol, ethanol, isopropanol, hexane, heptane, cyclohexane, methylcyclohexane, etc. can be used. Among these, since the polymer component can be well dissolved or emulsified and dispersed, the solvent used in the coating liquid for the protective layer is preferably ethyl acetate, methyl ethyl ketone, or a mixed solvent of ethyl acetate and methyl ethyl ketone.

[0124] 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 dipping a container into the coating liquid for the protective layer, a method of spraying the coating liquid for the protective layer onto the surface of the container, etc. By applying these methods, a protective layer (coating layer) can be formed.

[0125] The drying temperature of the coating film formed from the coating liquid for the protective layer is a temperature at which the solvent can be removed. The drying temperature is preferably 40°C or higher and 180°C or lower, more preferably 50°C or higher and 150°C or lower.

[0126] 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 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, and a cold stamping method. For example, when performing printing by the inkjet method, a UV-curable ink is applied to the container, and UV irradiation is performed thereon to cure it, thereby performing printing. Also, printing may be performed using a thermal transfer sheet.

Examples

[0127] Next, examples are given to explain the present disclosure in more detail, but the present disclosure is not limited to these examples.

[0128] [Example 1] As the 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. Separately, 7.5 parts by mass of polyacrylic acid (trade name: AS-58, number average molecular weight: 106,000) manufactured by Nippon Shokubai Co., Ltd. was added to 92.5 parts by mass of water while stirring, and then completely dissolved by heating to 80 °C to obtain a 7.5 mass% aqueous polyacrylic acid solution. Separately, 7.5 parts by mass of polyvinyl alcohol (trade name: 60-98, degree of polymerization: 2400, saponification degree: 98.0% or more and 99.0% or less) manufactured by Kuraray Co., Ltd. was added to 92.5 parts by mass of water while stirring, and then completely dissolved by heating to 90 °C to obtain a 7.5 mass% PVA aqueous solution. These two solutions were mixed at room temperature so that the mass ratio was 1:1 to prepare a coating liquid for the barrier layer (viscosity: 230 mPa·s (20 °C)). This coating liquid for the barrier layer was applied to the outer cylinder of the 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. Next, 42.1 parts by mass of the main agent of a urethane-based coating material (trade name: EL-540) manufactured by Toyo Morton Co., Ltd., 7.9 parts by mass of the curing agent, and 50 parts by mass of ethyl acetate were mixed to prepare a coating liquid for the protective layer. This coating liquid for the protective layer was applied to the outer cylinder of the 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 protective layer with a thickness of 30 μm, and the syringe of Example 1 was manufactured. The syringe of Example 1 had a structure as shown in Figure 2, except that it did not have a gasket and a plunger.

[0129] [Example 2] Polyvinyl butyral A (Mowital (registered trademark) B30H, manufactured by Kuraray Co., Ltd., Mn: 28,000 or more and 38,000 or less) and ethyl acetate were mixed to prepare a coating solution for the protective layer with a polyvinyl butyral A content of 11% by mass. A syringe of Example 2 was produced in the same manner as in Example 1, except that the protective layer was formed using this coating solution for the protective layer.

[0130] [Example 3] A syringe of Example 3 was produced in the same manner as in Example 1, except that Unistal (registered trademark) A-200PM, manufactured by Mitsui Chemicals, Inc., an olefin / acrylic-based material, was used as the coating solution for the protective layer.

[0131] [Example 4] A syringe of Example 4 was produced in the same manner as in Example 1, except that 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.

[0132] [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.

[0133] [Comparative Example 2] A syringe of Comparative Example 2 was produced in the same manner as in Example 1, except that the barrier layer and the protective layer were not formed.

[0134] [[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 a humidity of 40% RH using an oxygen gas permeability measuring device (manufactured by MOCON, trade 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.

[0135]

Table 1

[0136] As is clear from Table 1, the syringes of Examples 1 to 4 have low oxygen permeability and excellent gas barrier properties.

Explanation of Reference Signs

[0137] 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 having a base layer, a protective layer provided on one surface of the base layer, and a barrier layer provided between the base layer and the protective layer, the container having a capacity of 2000 mL or less, wherein the base layer contains a thermoplastic resin, and the barrier layer contains a water-soluble or alkali-soluble resin.

2. The container according to claim 1, wherein the water-soluble or alkali-soluble resin contains at least one of a carboxyl group-containing resin and a polyvinyl alcohol-based resin.

3. The container according to claim 1 or 2, wherein the thickness of the base layer is 0.1 mm or more and 5.0 mm or less.

4. The container according to claim 1 or 2, wherein the thickness of the barrier layer is 0.1 μm or more and 200 μm or less.

5. The container according to claim 1 or 2, wherein the thickness of the protective layer is 0.01 μm or more and 200.00 μm or less.

6. The container according to claim 1 or 2, wherein the container is a vial having a mouth portion, a neck portion, a body portion, and a bottom portion.

7. The container according to claim 1 or 2, wherein the container is a syringe having a barrel tip, an outer barrel, a gasket, a plunger, and a flange.

8. The container according to claim 1 or 2, wherein the protective layer is made of at least one resin selected from the group consisting of polyolefin, polyvinyl chloride, polystyrene, polyvinyl acetate, acrylic resin, polyacetal, polyester, polyurethane, and polyvinyl acetal.

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