Coating liquid and container

Abstract

To provide a coating liquid capable of forming a protective layer of which heat resistance is improved such as to be applied to a container in which sterilization is performed with an autoclave.SOLUTION: The present disclosure relates to a coating solution containing a copolyester and an isocyanate compound, wherein the copolyester includes ethylene glycol and either neopentyl glycol or propylene glycol as a diol component, and includes terephthalic acid as a dicarboxylic acid component. A weight average molecular weight of the copolyester is greater than 1,000 and less than or equal to 20,000, and the isocyanate compound contains two or more isocyanate groups in its molecular structure, with the blending ratio of the isocyanate compound to the copolyester (isocyanate compound / copolyester) being 1 / 3,500 or more and 1 / 1 or less by mass.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present disclosure relates to a coating liquid and a container having a protective layer formed using the coating liquid. [Background technology]

[0002] Ampoules, vials, prefilled syringes, etc. are used as medical packaging containers for filling and storing medicinal liquids in a sealed state. Ampoules are containers whose mouths are heat-sealed, while vials are containers whose mouths are sealed by pushing a rubber stopper into them. Both ampoules and vials are mainly used as containers for medical reagents. A prefilled syringe is a syringe in which a medicinal liquid is previously contained in a syringe container in a sealed state, and when in use, the sealing cap is removed and the syringe is connected to an instrument such as an injection needle or a vascular catheter, so that the medicinal liquid can be administered to a patient.

[0003] Glass medical packaging containers have traditionally been used, but in recent years, plastics such as polycarbonate, polypropylene, and cycloolefin polymers have begun to be used for medical packaging containers instead of glass. Various improvements have been made to plastic medical packaging containers.

[0004] For example, Patent Document 1 describes a prefilled syringe made of plastic, with a label made of an inorganic compound vapor-deposited plastic film covering 70% or more of the outer surface of the barrel. This prefilled syringe can prevent deterioration due to oxidation of the medicinal solution for about three days after the prefilled syringe is removed from the barrier packaging bag.

[0005] Patent Document 2 describes a prefilled syringe in which the outer periphery of the shoulder of the syringe barrel is protruded and the outer surface of the syringe barrel together with the protruding part is covered with a barrier packaging material. According to this prefilled syringe, the part containing the medicinal liquid is completely covered with a barrier packaging material, so that deterioration of the medicinal liquid can be reliably prevented.

[0006] Furthermore, Patent Document 3 describes a medical multilayer container having at least three layers in this order: a first resin layer containing a thermoplastic resin (b), a resin layer containing a polyester compound (a) and a dibenzoylmethane compound, and a second resin layer containing a thermoplastic resin (b), and having excellent oxygen barrier properties, UV barrier properties, and low elution properties.

[0007] Patent Document 3 describes an injection molding method as a manufacturing method for the medical multi-layer container described therein. However, since the injection molding method is a method of manufacturing a container by preparing a mold for each shape of the container, there is a problem that the size and type of container that can be manufactured are limited by the mold. Therefore, instead of the injection molding method, it has been considered to form a protective layer by applying a coating liquid in which a resin is dissolved to the container body, thereby manufacturing a container with a protective layer. For example, Patent Document 4 describes a container with a protective layer using a specific copolymer polyester. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] JP 2004-267662 A [Patent Document 2] International Publication No. 2007 / 023736 [Patent Document 3] Patent Publication No. 2021-11305 [Patent Document 4] JP 2023-97400 A Summary of the Invention [Problem to be solved by the invention]

[0009] However, the copolymer polyester described in Patent Document 4 does not have sufficient heat resistance, and there is room for improvement. For example, medical multi-layer containers are generally sterilized by autoclave treatment, which is a heat sterilization treatment using high-temperature, high-pressure saturated steam, but when a container having a protective layer formed using the copolymer polyester described in Patent Document 4 is sterilized by autoclave treatment, the surface of the protective layer may become rough.

[0010] Therefore, an object of the present disclosure is to provide a coating liquid capable of forming a protective layer having improved heat resistance so that it can be applied to a container that is sterilized by autoclaving. Another object of the present disclosure is to provide a container having a protective layer formed by coating the coating liquid. [Means for solving the problem]

[0011] The inventors have discovered that when a protective layer is formed using a coating liquid in which a specified amount of a specified isocyanate compound is mixed into a solution in which a specified polyester resin is dissolved, the heat resistance of the protective layer is improved, and the function of the intermediate layer covered with the protective layer is less likely to be impaired even if a container having the protective layer is sterilized by autoclaving. The present disclosure was completed based on this knowledge and through further investigation.

[0012] The present disclosure is solved by the following embodiments. <1> A coating liquid containing a copolymer polyester and an isocyanate compound, The copolymer polyester contains, as a diol component, ethylene glycol and neopentyl glycol or propylene glycol, The copolymer polyester contains terephthalic acid as a dicarboxylic acid component, The weight average molecular weight of the copolymer polyester is more than 1,000 and not more than 20,000, The isocyanate compound has two or more isocyanato groups in the molecule, a mixing ratio of the isocyanate compound to the copolymer polyester (isocyanate compound / copolymer polyester) is 1 / 3500 or more and 1 / 1 or less in mass ratio in the coating liquid. <2> The copolymer polyester further contains isophthalic acid as a dicarboxylic acid component. <1> The coating solution according to claim 1. <3> The glass transition temperature of the copolymer polyester is 35° C. or higher and 100° C. or lower. <1> or <2> The coating solution according to claim 1. <4> The isocyanate compound is at least one selected from the group consisting of metaxylylene diisocyanate and isophorone diisocyanate. <1> ~ <3> 13. The coating solution according to claim 12 . <5> A container comprising a container body, a protective layer provided on at least a portion of a surface of the container body, and an intermediate layer provided between the container body and the protective layer, the protective layer contains a copolymer polyester and an isocyanate compound, The copolymer polyester contains, as a diol component, ethylene glycol and neopentyl glycol or propylene glycol, The copolymer polyester contains terephthalic acid as a dicarboxylic acid component, The weight average molecular weight of the copolymer polyester is more than 1,000 and not more than 20,000, The isocyanate compound has two or more isocyanato groups in the molecule, The container has a compounding ratio of the isocyanate compound to the copolymer polyester (isocyanate compound / copolymer polyester) of 1 / 3500 or more and 1 / 1 or less in mass ratio. <6> The copolymer polyester further contains isophthalic acid as a dicarboxylic acid component. <5> A container as described in claim 1. <7> The glass transition temperature of the copolymer polyester is 35° C. or higher and 100° C. or lower. <5> or <6> A container as described in claim 1. <8> The isocyanate compound is at least one selected from the group consisting of metaxylylene diisocyanate and isophorone diisocyanate. <5> ~ <7> 3. A container according to any one of the preceding claims. <9> The thickness of the protective layer is 0.1 μm or more and 100 μm or less. <5> ~ <8> 3. A container according to any one of the preceding claims. <10> The container body contains at least one selected from the group consisting of polyolefins, cyclic polyolefins, cyclic olefin copolymers, polycarbonates, and polyesters. <5> ~ <9> 3. A container according to any one of the preceding claims. <11> The intermediate layer is at least one layer selected from the group consisting of an ultraviolet shielding layer and a barrier layer. <5> ~ <10> 3. A container according to any one of the preceding claims. <12> It is a vial. <5> ~ <11> 3. A container according to any one of the preceding claims. <13> It is a syringe. <5> ~ <11> 3. A container according to any one of the preceding claims. Effect of the Invention

[0013] The present disclosure can provide a coating liquid capable of forming a protective layer having improved heat resistance such that it can be applied to containers that are sterilized by autoclaving. The present disclosure can also provide a container having a protective layer formed by applying the coating liquid. [Brief description of the drawings]

[0014] [Figure 1] FIG. 1 is a schematic half-sectional view showing one embodiment of a vial bottle, which is an example of a container according to the present disclosure. [Diagram 2] 1 is a partial half-sectional view showing a schematic diagram of an embodiment of a syringe, which is an example of a container according to the present disclosure. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0015] <Coating fluid> The coating liquid of the present disclosure contains a copolymerized polyester. In the present disclosure, the copolymerized polyester is a product of polycondensation of terephthalic acid as a main dicarboxylic acid component and ethylene glycol as a main diol component, and contains, as a copolymerization component, neopentyl glycol or propylene glycol as a diol component in addition to ethylene glycol. In this specification, "main" means that the total constituent units of each component are 100 mol %, and the content is more preferably 55 mol % or more, and even more preferably 60 mol % or more.

[0016] The copolymer polyester used in the coating solution of the present disclosure has a weight average molecular weight of more than 1,000 and 20,000 or less. In the present disclosure, a copolymer polyester containing neopentyl glycol or propylene glycol as a diol copolymerization component and having a weight average molecular weight in the above range is used as a constituent material of the protective layer. If the weight average molecular weight (hereinafter sometimes referred to as Mw) of the copolymer polyester is 1,000 or less, tack occurs in the protective layer, and the handleability of the container deteriorates. The preferred range of Mw of the copolymer polyester is 10,000 or more and 18,000 or less. The weight average molecular weight means a value calculated by gel permeation chromatography according to a standard method.

[0017] In one embodiment, the copolymerized polyester may contain a component other than neopentyl glycol or propylene glycol as a diol copolymerization component, as long as the effects of the present disclosure are not impaired. For example, the copolymerized polyester may contain an aliphatic diol such as diethylene glycol, triethylene glycol, 1,4-butanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,5-pentanediol, 2,2-diethyl-1,3-propanediol, 1,9-nonanediol, or 1,10-decanediol; an alicyclic diol such as 1,4-cyclohexanedimethanol or 1,4-cyclohexanediethanol; or an aliphatic polyhydric alcohol such as trimethylolpropane or pentaerythritol.

[0018] The copolymer polyester contains terephthalic acid as the main dicarboxylic acid component, but may contain aromatic dicarboxylic acids such as isophthalic acid, naphthalene-1,4- or -2,6-dicarboxylic acid, 5-sodium sulfoisophthalic acid, 4,4'-diphenyldicarboxylic acid, and diphenylsulfodicarboxylic acid as dicarboxylic acid copolymerization components; and aliphatic dicarboxylic acids such as glutaric acid, adipic acid, sebacic acid, azelaic acid, oxalic acid, and succinic acid. Among these, isophthalic acid is preferred from the viewpoint of the effects of the present disclosure.

[0019] The copolymer polyester preferably has a glass transition temperature of 35°C or higher and 100°C or lower. By containing the copolymerization components as described above, the glass transition temperature (hereinafter, sometimes referred to as Tg) is lower than that of polyethylene terephthalate, and the film quality of the protective layer is improved. On the other hand, if the glass transition temperature is too low, the heat resistance may be poor. The preferred glass transition temperature is 65°C or higher and 90°C or lower. The glass transition temperature means a value calculated from the inflection point of the endothermic peak associated with the glass transition using a differential scanning calorimeter according to a standard method.

[0020] The coating liquid of the present disclosure includes an isocyanate compound. The isocyanate compound has two or more isocyanato groups in the molecule. For example, known compounds such as diisocyanate compounds having two isocyanato groups and polyisocyanate compounds having three or more isocyanato groups can be used. The isocyanate compound may be either aromatic or aliphatic, and may be either a low molecular weight compound or a high molecular weight compound. The isocyanate compound may be a blocked isocyanate compound obtained by addition reaction using a known isocyanate blocking agent by a known and commonly used appropriate method.

[0021] When the isocyanate group in the isocyanate compound reacts with the hydroxy group present at the terminal or the like of the copolymerized polyester, the isocyanate compound crosslinks the copolymerized polyesters to form a higher molecular weight resin in the coating liquid, which is believed to improve the heat resistance of the protective layer formed by applying the coating liquid of the present disclosure.

[0022] Specific examples of the isocyanate compound include tetramethylene diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, meta-xylylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, or trimers of these isocyanate compounds, and adducts, biurets, allophanates, and the like obtained by reacting an excess amount of these isocyanate compounds with low molecular weight active hydrogen compounds such as ethylene glycol, propylene glycol, meta-xylylene alcohol, 1,3-bishydroxyethylbenzene, 1,4-bishydroxyethylbenzene, trimethylolpropane, glycerol, pentaerythritol, erythritol, sorbitol, ethylenediamine, monoethanolamine, diethanolamine, triethanolamine, and meta-xylylenediamine, and alkylene oxide adducts thereof, various polyester resins, polyether polyols, and polymeric active hydrogen compounds such as polyamides. Among them, the isocyanate compound is preferably at least one selected from the group consisting of metaxylylene diisocyanate and isophorone diisocyanate.

[0023] In the coating liquid of the present disclosure, the blending ratio of the isocyanate compound to the copolymer polyester (isocyanate compound / copolymer polyester) is, in mass ratio, 1 / 3500 or more, preferably 1 / 3000 or more, more preferably 1 / 2500 or more, even more preferably 1 / 2000 or more, and particularly preferably 1 / 1500 or more. By making the blending amount of the isocyanate compound a certain amount or more, the heat resistance of the protective layer formed by applying the coating liquid is improved. In the coating solution of the present disclosure, the blending ratio of the isocyanate compound to the copolymer polyester (isocyanate compound / copolymer polyester) is 1 / 1 or less by mass, preferably 1 / 5 or less, more preferably 1 / 100 or less, even more preferably 1 / 500 or less, and particularly preferably 1 / 700 or less. By keeping the blending amount of the isocyanate compound at a certain level or less, it is possible to prevent the protective layer prepared by applying the coating solution from becoming cloudy and losing transparency.

[0024] The coating liquid of the present disclosure may contain additives within the range that does not impair the characteristics of the present disclosure. Examples of additives include oxygen absorbers, plasticizers, ultraviolet absorbers, ultraviolet stabilizers, antioxidants, coloring inhibitors, matting agents, deodorants, flame retardants, weather resistance agents, antistatic agents, thread friction reducing agents, slip agents, release agents, antioxidants, ion exchange agents, and colorants. These additives can be used alone or in combination of two or more.

[0025] The solvent used in the coating solution of the present disclosure is not particularly limited as long as it can dissolve or emulsify and disperse the copolymerized polyester and the isocyanate compound, and examples of the solvent that can be used include water, acetone, methyl isobutyl ketone, methyl ethyl ketone, ethyl acetate, n-propyl acetate, methanol, ethanol, isopropanol, hexane, heptane, cyclohexane, methylcyclohexane, etc. Among these, the solvent used in the coating solution of the present disclosure is preferably ethyl acetate, methyl ethyl ketone, or a mixed solvent of ethyl acetate and methyl ethyl ketone, since it can satisfactorily dissolve or emulsify and disperse the copolymerized polyester.

[0026] <Container> The container of the present disclosure comprises a container body, a protective layer provided on at least a portion of the surface of the container body, and an intermediate layer provided between the container body and the protective layer. In this specification, the term "container" refers to a molded body that contains 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, and syringes such as prefilled syringes.

[0027] Each of the components that may be included in the container of the present disclosure will be described below.

[0028] (Container body) In the container of the present disclosure, the container body is capable of maintaining the shape of the container and is made of a thermoplastic resin. Examples of the thermoplastic resin constituting the container body include polyolefins such as polyethylene and polypropylene, cyclic polyolefins such as polymers obtained by polymerizing and hydrogenating ring-opening polymerizable cycloolefin monomers (norbornenes or cyclotetradodecenes, etc.), cyclic olefin copolymers such as copolymers made from ring-opening polymerizable cycloolefin monomers and olefins (ethylene or α-olefins, etc.), polyesters such as polycarbonate, polyvinyl chloride, polyethylene terephthalate, polyamides such as nylon 6 and nylon 6,6, and mixtures thereof. Among these, at least one selected from the group consisting of polyolefins, cyclic polyolefins, cyclic olefin copolymers, polycarbonates, and polyesters is preferred from the viewpoint of moldability. When the container is a vial, the thermoplastic resin constituting the container body is preferably a cyclic polyolefin. Furthermore, when the container is a syringe, the thermoplastic resin constituting the container body is preferably at least one selected from the group consisting of cyclic polyolefins and cyclic olefin copolymers.

[0029] The container body may contain additives within the range that does not impair the characteristics of the present disclosure. Examples of additives include oxygen absorbers, plasticizers, ultraviolet absorbers, ultraviolet stabilizers, antioxidants, matting agents, deodorants, flame retardants, weather resistance agents, antistatic agents, friction reducers, slip agents, mold release agents, antioxidants, and ion exchange agents. These additives can be used alone or in combination of two or more.

[0030] The container body may have a single layer structure or a multi-layer structure of two or more layers. When the container body has a multi-layer structure, each layer may have the same composition or different compositions as long as the characteristics of the present disclosure are not impaired.

[0031] The cross-sectional thickness of the container body varies depending on the application of the container, but is preferably 0.1 mm or more and 5 mm or less, and more preferably 0.5 mm or more and 3 mm or less. The cross-sectional thickness of the container body can be measured, for example, at the body of the container. The cross-sectional thickness of the container body means the point where the cross-sectional thickness is the thinnest. When the container body is multi-layered, the cross-sectional thickness of the container body is the sum of the thicknesses of all layers.

[0032] The container body is preferably surface-treated. Examples of surface treatments include corona treatment, low-temperature plasma treatment, and flame treatment. By carrying out such surface treatments, the wettability of the surface of the container body is improved, and the adhesion between the container body and an intermediate layer described below can be improved.

[0033] (Middle class) The intermediate layer located between the container body and the protective layer can be provided with various functions, such as blocking light such as ultraviolet light, oxygen barrier properties, water vapor barrier properties, etc.

[0034] In one embodiment, the intermediate layer is an ultraviolet shielding layer having an ultraviolet shielding function. A container having an intermediate layer that is an ultraviolet shielding layer can suppress the transmission of ultraviolet rays, and therefore can suppress the deterioration of contents that are easily altered by ultraviolet rays, such as medicines and quasi-drugs. Examples of the ultraviolet shielding layer include a layer containing an ultraviolet absorbing agent, such as a layer containing a UV-cut ink.

[0035] In one embodiment, the intermediate layer is a barrier layer having oxygen barrier properties. A container having an intermediate layer that is a barrier layer can suppress the permeation of gases such as oxygen, and therefore can suppress deterioration of the contents.

[0036] In one embodiment, the intermediate layer has both an ultraviolet shielding function and an oxygen barrier property. That is, the intermediate layer is an ultraviolet shielding layer and a barrier layer. A container having an intermediate layer that is an ultraviolet shielding layer and a barrier layer can suppress deterioration of the contents that are easily altered by ultraviolet rays and oxygen.

[0037] The barrier layer, which is an example of the intermediate layer, will be described below.

[0038] In one embodiment, the barrier layer contains a polyvinyl alcohol-based resin. Polyvinyl alcohol-based resins have a high cohesive force and therefore are highly effective in blocking oxygen and water vapor. By including the polyvinyl alcohol-based resin in the barrier layer, the gas barrier properties of the container can be improved.

[0039] In one embodiment, the barrier layer contains a carboxy-containing resin and a polyvinyl alcohol-based resin. As described above, when the barrier layer contains a polyvinyl alcohol-based resin, the gas barrier properties of the container can be improved.

[0040] In addition, by including a carboxyl group-containing resin in the barrier layer, the carboxyl group of the carboxyl group-containing resin forms hydrogen bonds with the polyvinyl alcohol resin or the "-OH" of the solvent of the coating liquid used to form the barrier layer (e.g., water and an organic solvent having a hydroxyl group, etc.), increasing the viscosity of the coating liquid. This allows the thickness of the barrier layer to be increased with fewer coating cycles, improving the productivity of containers.

[0041] The polyvinyl alcohol resin and the carboxyl group-containing resin will be described below.

[0042] Polyvinyl alcohol resins (also called "PVA resins") are resins that contain alcoholic hydroxyl groups in the polymer structure. PVA resins are usually obtained by saponifying vinyl ester polymers.

[0043] 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 arene carboxylates (e.g., C7-12 arene carboxylic acid vinyl esters) such as vinyl benzoate. These monomers can be used alone or in combination of two or more.

[0044] The vinyl ester polymer may have a unit derived from another polymerizable monomer (monomer copolymerizable with vinyl ester). Examples of other polymerizable monomers include ethylene; α-olefins such as propylene, 1-butene, 1-pentene, 1-hexene, and 1-octene; methacrylic acid alkyl esters 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 itaconic acid alkyl esters. These monomers can be used alone or in combination of two or more.

[0045] The PVA-based resin may be one in which a part of the vinyl alcohol units has been modified by a reaction such as acetalization, etherification, acetoacetylation, or cationization.

[0046] The degree of polymerization of the PVA-based resin is preferably 1,000 or more and 4,000 or less, more preferably 1,500 or more and 3,500 or less, and further preferably 2,000 or more and 3,000 or less. The average degree of polymerization of the PVA resin can be measured in accordance with JIS K 6726:1994.

[0047] From the viewpoints of excellent solubility in a solvent and excellent 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 degree of saponification of the PVA-based resin can be measured in accordance with JIS K 6726:1994.

[0048] The PVA resin has an aqueous solution viscosity of preferably 3 mPa·s or more and 70 mPa·s or less, more preferably 50 mPa·s or more and 68 mPa·s or less, and even more preferably 54 mPa·s or more and 66 mPa·s or less, when the PVA resin is dissolved in pure water to a concentration of 4 mass %. The viscosity of the coating solution can be measured at a temperature of 20°C in accordance with JIS Z 8803:2011.

[0049] The PVA-based resins can be used alone or in combination of two or more.

[0050] The carboxyl group-containing resin may be an existing carboxyl group-containing resin. The existing carboxyl group-containing resin is a general term for resins that contain a carboxyl group in the polymer structure. Examples of the carboxyl group-containing resin include homopolymers of carboxyl group-containing unsaturated monomers, copolymers of carboxyl group-containing unsaturated monomers, copolymers of carboxyl group-containing unsaturated monomers and other polymerizable monomers, and polysaccharides containing a carboxyl group in the molecule (also called "acidic polysaccharides"). These carboxyl group-containing resins may be used alone or in combination of two or more. The carboxy group includes not only a free carboxy group but also an acid anhydride group (specifically, a dicarboxylic acid anhydride group). The acid anhydride group may be partially opened to form a carboxy group. In the carboxy group-containing resin, a part of the carboxy group may be neutralized with an alkali.

[0051] The carboxyl group-containing unsaturated monomer is preferably an α,β-monoethylenically unsaturated carboxylic acid. Therefore, the carboxyl group-containing resin includes a homopolymer of an α,β-monoethylenically unsaturated carboxylic acid, a copolymer of two or more kinds of α,β-monoethylenically unsaturated carboxylic acids, and a copolymer of an α,β-monoethylenically unsaturated carboxylic acid and another polymerizable monomer. The other polymerizable monomer may be an ethylenically unsaturated monomer.

[0052] Examples of α,β-monoethylenically unsaturated carboxylic acids include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, etc., unsaturated dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid, etc., unsaturated dicarboxylic anhydrides such as maleic anhydride, itaconic anhydride, etc. These acids can be used alone or in combination of two or more.

[0053] 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.

[0054] 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; saturated carboxylic acid vinyl esters such as vinyl acetate; acrylic acid alkyl esters such as methyl acrylate and ethyl acrylate; methacrylic acid alkyl esters 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; itaconic acid alkyl esters, etc. These monomers can be used alone or in combination of two or more.

[0055] Examples of the carboxyl group-containing polysaccharides include acidic polysaccharides having a carboxyl group in the molecule, such as alginic acid, carboxymethylcellulose, 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 an α,β-monoethylenically unsaturated carboxylic acid.

[0056] In the container of the present disclosure, when the carboxy group-containing resin is a copolymer of α,β-monoethylenically unsaturated carboxylic acid and other ethylenically unsaturated monomer, the composition of the copolymer is such that the composition of α,β-monoethylenically unsaturated carboxylic acid monomer is preferably 60 mol % or more, more preferably 80 mol % or more, and even more preferably 90 mol % or more.

[0057] The carboxyl group-containing resin is preferably a homopolymer or copolymer obtained by polymerization of only α,β-monoethylenically unsaturated carboxylic acid. When the polycarboxylic acid polymer is a (co)polymer consisting of only α,β-monoethylenically unsaturated carboxylic acid, the carboxyl group-containing resin is preferably a homopolymer, copolymer, or 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 mixture of two or more thereof obtained from a carboxylic acid selected from one or more of acrylic acid, methacrylic acid, and maleic acid.

[0058] The carboxyl group-containing resin is preferably one or more selected from polyacrylic acid, polymethacrylic acid, and maleic acid polymers. The carboxyl group-containing resin is preferably polyacrylic acid, which is relatively easy to obtain and has good gas barrier properties.

[0059] The number average molecular weight of the carboxyl group-containing resin is preferably in the range of 2,000 to 10,000,000, more preferably in the range of 5,000 to 1,000,000, and even more preferably in the range of 10,000 to 500,000. The number average molecular weight refers to a value calculated by gel permeation chromatography according to a standard method.

[0060] In the barrier layer, 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 even more preferably 40% by mass or more and 95% by mass or less, based on the total components contained in the barrier layer, thereby further improving the gas barrier property of the container.

[0061] When the barrier layer contains a carboxyl group-containing resin and a polyvinyl alcohol 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 even more preferably 5% by mass or more and 60% by mass or less, based on the total components contained in the barrier layer, thereby further improving the gas barrier properties of the container.

[0062] When the barrier layer contains a carboxyl group-containing resin and a polyvinyl alcohol-based resin, the mass ratio of the carboxyl group-containing resin to the polyvinyl alcohol-based resin (carboxyl group-containing resin / 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. This can further improve the gas barrier properties of the container. The mass ratio is a solid content ratio.

[0063] The intermediate layer may contain additives within the range that does not impair the characteristics of the present disclosure. Examples of additives include oxygen absorbers, plasticizers, ultraviolet stabilizers, antioxidants, matting agents, deodorants, flame retardants, weather resistance agents, antistatic agents, thread friction reducing agents, slip agents, mold release agents, antioxidants, and ion exchange agents. These additives can be used alone or in combination of two or more.

[0064] The intermediate layer may be a single layer or a multi-layer structure having two or more layers. When the intermediate layer is a multi-layer structure, each layer may have the same composition or different compositions.

[0065] The thickness of the intermediate layer is preferably 0.01 μm or more and 50 μm or less, and more preferably 0.1 μm or more and 30 μm or less. The thickness of the intermediate layer can be measured, for example, at the body of the container. The thickness of the barrier layer means the part where the thickness is the thinnest. When the intermediate layer is a multi-layered layer, the thickness of the barrier layer is the sum of the thicknesses of all the layers.

[0066] (protective layer) The protective layer is for protecting the intermediate layer. By providing the protective layer to the container, deterioration of the intermediate layer due to physical factors such as breakage or peeling of the intermediate layer or chemical factors such as moisture absorption or dissolution can be suppressed during the manufacture and use of the container.

[0067] In the container according to one embodiment of the present disclosure, the protective layer contains a copolymer polyester and an isocyanate compound. The protective layer may also contain an additive. In particular, when the intermediate layer does not have a function as an ultraviolet shielding layer, the protective layer preferably contains an ultraviolet absorber as an additive. This allows the container of the present disclosure to have an ultraviolet shielding function even if the intermediate layer does not have a function as an ultraviolet shielding layer. The copolymer polyester, isocyanate compound, and additives contained in the protective layer are the same as the copolymer polyester, isocyanate compound, and additives contained in the coating liquid, and therefore description thereof is omitted here.

[0068] The protective layer may be a single layer or a multi-layer consisting of two or more layers. When the protective layer is a multi-layer, each layer may have the same composition or different compositions.

[0069] The thickness of the protective layer is preferably 0.1 μm or more and 100 μm or less, more preferably 0.5 μm or more and 50 μm or less, and further preferably 0.7 μm or more and 30 μm or less, whereby the deterioration resistance of the barrier layer can be further improved. The thickness of the protective layer can be measured, for example, at the body of the container, and means the thinnest point. When the protective layer has multiple layers, the thickness of the protective layer is the sum of the thicknesses of all the layers.

[0070] (evaporated film) The container of the present disclosure may have a vapor deposition film in order to further improve the gas barrier properties.

[0071] Examples of the vapor-deposited film include vapor-deposited 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, organic silicon compounds such as hexamethyldisiloxane, and hard carbon films such as DLC (Diamond Like Carbon) films. In addition, the hard carbon film made of DLC is also called i-carbon film or hydrogenated amorphous carbon film (aC:H), and is a hard carbon film. 3 It is an amorphous carbon film that is mainly composed of bonds.

[0072] The thickness of the deposited film is not particularly limited, and can be, for example, 1 nm or more and 150 nm or less. The thickness of the deposited film can be measured, for example, at the body of the container, and refers to the location where the thickness is the thinnest.

[0073] The deposition film can be formed by a conventional method, for example, physical vapor deposition methods (PVD methods) such as vacuum deposition, sputtering, and ion plating, and chemical vapor deposition methods (CVD methods) such as plasma chemical vapor deposition, thermal chemical vapor deposition, and photochemical vapor deposition.

[0074] Hereinafter, an embodiment of the structure of a container according to the present disclosure will be described with reference to the drawings, taking a vial and a syringe as examples. Each figure is a schematic illustration. Therefore, the size and shape of each part are appropriately exaggerated to facilitate understanding. In addition, the present invention can be implemented by appropriately changing the size and shape within the scope of the technical concept. In addition, the numerical values ​​of the dimensions and material names of each member described in this specification are examples of embodiments, and are not limited thereto, and can be appropriately selected and used. In this specification, terms that specify shapes and geometric conditions, such as parallel, orthogonal, and vertical, are interpreted to include substantially the same state in addition to their strict meanings.

[0075] Fig. 1 is a schematic half-sectional view showing a vial, which is one embodiment of the container of the present disclosure. As shown in Fig. 1, a vial 50 includes a cylindrical body 53 for storing an item such as a medicine, a bottom 54 closing the lower end of the body 53, a cylindrical neck 52 provided above the body 53 and having a smaller outer diameter than the body 53, and a cylindrical mouth 51 provided above the neck 52 and having a larger outer diameter than the neck 52.

[0076] The body 53 in Fig. 1 has a cylindrical shape with a generally uniform diameter as a whole, but is not limited thereto, and may have a polygonal cylindrical shape such as a rectangular 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. Furthermore, the body 53 in Fig. 5 has a generally flat surface without any irregularities, but is not limited thereto. For example, the body 53 may have irregularities such as panels or grooves.

[0077] 1, in the vial 50, the mouth 51 is constituted by a container body 55, and the neck 52, the body 53, and the bottom 54 are constituted by the container body 55, an intermediate layer 56, and a protective layer 57. As shown in FIG. 1, in the neck 52, the body 53, and the bottom 54, the intermediate layer 56 and the protective layer 57 are provided on the entire outside of the container body 55 so as to surround the container body 55. In one embodiment, the intermediate layer 56 and the protective layer 57 may be provided on the entirety or a part of one or more regions selected from the mouth portion 51, the neck portion 52, the body portion 53, and the bottom portion .

[0078] An intermediate layer 56 and a protective layer 57 may be provided on the inside of the vial 50 (not shown). The vial 50 may be provided with a vapor deposition film (not shown) on at least one selected from the group including the inside and outside of the vial.

[0079] When the vial 50 is used to store medicines or the like, the medicines or the like are placed in the body 53, and then a rubber stopper (not shown) having gas barrier properties is fitted into the mouth 51. Furthermore, the vial 50 is sealed by crimping (rolling) a cap (not shown) made of a relatively soft metal such as aluminum on top of the stopper. This allows the vial 50 to have gas barrier properties.

[0080] Fig. 2 is a schematic half-sectional view showing a syringe as one embodiment of the container of the present disclosure. As shown in Fig. 6, a syringe 60 includes a cylindrical outer tube 61 having a generally uniform diameter, a nozzle 62 formed at the upper end of the outer tube 61 for injecting or discharging a medicinal solution, a gasket 63 housed in the outer tube 61 and capable of sliding liquid-tightly inside the outer tube 61, a plunger 64 attached to the gasket 63 to slide the gasket 63 up and down inside the outer tube 61, and a flange 65 for hooking a finger when pushing the plunger 64 upward and downward to move it.

[0081] 2, the syringe 60 has a tip 62 and a flange 65 that are formed by a container body 66, and an outer cylinder 61 that is formed by the container body 66, an intermediate layer 67, and a protective layer 68. As shown in FIG. 2, in the outer cylinder 61, the intermediate layer 67 and the protective layer 68 are provided on the entire outside of the container body 66 so as to surround the container body 66. In one embodiment, the intermediate layer 67 and the protective layer 68 may be provided on the entire or partial area of ​​one or more selected from the outer cylinder 61 , the cylinder tip 62 , and the flange 65 .

[0082] The intermediate layer 67 and the protective layer 68 may be provided on the inside of one or more selected from the outer cylinder 61, the cylinder tip 62, and the flange 65 (not shown). The syringe 60 may have a vapor-deposited film (not shown) 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 nozzle 62, and the flange 65.

[0083] The cylindrical tip 62 is sealed with a sealing cap (not shown), thereby providing the syringe 60 with gas barrier properties. The sealing cap may be a cap-shaped product made of an elastic material such as rubber or elastomer, which is wrapped around the tip 62. Alternatively, a sealing cap may be formed by producing a cap-shaped molded product from a synthetic polymer resin composition, disposing an elastic material such as rubber or elastomer on the tip 62 to close the tip 62, and then covering the tip 62 with the cap-shaped product. Alternatively, a cap-shaped molded product having a through hole on the top surface of the synthetic polymer resin composition may be produced, and disposing a resealable material such as rubber or elastomer on the tip 62 to close the through hole, and then covering the tip 62 with the cap-shaped sealing cap. As the synthetic polymer resin composition, a composition containing polypropylene or cyclic polyolefin as a constituent component is preferable.

[0084] In the container of the present disclosure, the oxygen permeability is preferably 0.1000 cc / pkg·day·0.21 atm or less, more preferably 0.0100 cc / pkg·day·0.21 atm or less, and even more preferably 0.0010 cc / pkg·day·0.21 atm or less. In this specification, oxygen permeability is a value measured in accordance with JIS K 7126-2:2006 using an oxygen permeability measuring device (manufactured by MOCON, product name: OX-TRAN 2 / 20) under conditions of 23°C and humidity of 40% RH, and is a value measured on the entire container with the opening blocked with a jig.

[0085] The cross-sectional thickness of the container of the present disclosure is preferably 0.1 mm or more and 5.0 mm or less, and more preferably 0.5 mm or more and 3.0 mm or less. The cross-sectional thickness of the container can be measured, for example, at least in the body of the container having the container body, the barrier layer, and the protective layer. The cross-sectional thickness of the container means the point where the cross-sectional thickness is the thinnest.

[0086] In one embodiment of the container, the transmittance of ultraviolet light having a wavelength of 400 nm or less is preferably 20% or less. This makes it possible to prevent the contents from being deteriorated by ultraviolet light. The transmittance is more preferably 15% or less, even more preferably 5% or less, and even more preferably 1% or less. Such a transmittance can be achieved by forming the intermediate layer from a material having a low transmittance of ultraviolet light. The transmittance of ultraviolet light can be obtained by measuring the transmittance of light having a wavelength of 400 nm or less at 0.5 nm intervals using a spectrophotometer. As the spectrophotometer, an ultraviolet-visible spectrophotometer manufactured by Shimadzu Corporation can be used. The transmittance of the container is measured, for example, at least in the body of the container having the container body, the intermediate layer, and the protective layer.

[0087] The container according to an embodiment of the present disclosure may be printed on its surface. The image formed by printing is not particularly limited, and may be, for example, a pattern, a character, etc. 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. Printing can be carried out by a known method, such as 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 stamp method, or a cold stamp method.

[0088] <Container manufacturing method> Hereinafter, a method for manufacturing a container according to one embodiment of the present disclosure will be described using a vial as an example.

[0089] In one embodiment, the vial 50 shown in FIG. 1 can be manufactured by the following procedure. First, a container body 55 having a mouth portion 51, a neck portion 52, a body portion 53, and a bottom portion 54 is produced by a conventionally known method. Next, an intermediate layer coating liquid containing the material for forming the intermediate layer 56 and a solvent is prepared. Next, the coating liquid for the intermediate layer is applied to the neck portion 52, the body portion 53 and the bottom portion 54 of the container body 55 to form a coating film. The coated film is then dried to remove the solvent, thereby forming the intermediate layer 56. Next, the coating liquid of the present disclosure containing a copolymer polyester and an isocyanate compound is prepared. Next, the coating liquid of the present disclosure is applied to the surface of the intermediate 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 bottle 50 shown in FIG. 1 can be manufactured. The syringe 60 shown in FIG. 2 can be manufactured by appropriately selecting the shape of the container body 66 and the application locations of the intermediate layer coating fluid and the coating fluid of the present disclosure.

[0090] The solvent used in the intermediate layer coating liquid is one that can dissolve or emulsify and disperse the material that constitutes the intermediate 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. The solvent used is preferably water, an alcohol, or a mixture thereof, and more preferably a mixed solvent of water and isopropyl alcohol.

[0091] In the intermediate layer coating liquid, the total concentration of the solid content of the materials constituting the intermediate layer is preferably 2% by mass or more and 15% by mass or less, more preferably 3% by mass or more and 10% by mass or less, which allows the formation of an intermediate layer with a uniform thickness.

[0092] The viscosity of the intermediate layer coating liquid is preferably 150 mPa·s or more and 4000 mPa·s or less, and more preferably 200 mPa·s or more and 2500 mPa·s or less, which can further improve the productivity of the container. The viscosity of the intermediate layer coating liquid can be measured using a rotational viscometer at a temperature of 20° C. in accordance with JIS Z 8803:2011.

[0093] The intermediate layer coating liquid can be applied by a conventional method, for example, a method of applying the intermediate layer coating liquid with a brush, a method of immersing a container in the intermediate layer coating liquid, a method of spraying the intermediate layer coating liquid on the surface of the container body, etc.

[0094] The drying temperature of the coating film formed from the intermediate layer coating liquid is a temperature at which the solvent can be removed, and is preferably 20° C. or higher and 180° C. or lower, more preferably 40° C. or higher and 150° C. or lower, and even more preferably 50° C. or higher and 120° C. or lower.

[0095] The coating liquid of the present disclosure can be applied by a conventionally known method, for example, a method of applying the coating liquid with a brush or the like, a method of immersing a container in the coating liquid of the present disclosure, a method of spraying the coating liquid of the present disclosure onto the surface of a container, etc.

[0096] The drying temperature of the coating film formed from the coating solution of the present disclosure is a temperature at which the solvent can be removed, and is preferably 40° C. or higher and 180° C. or lower, more preferably 50° C. or higher and 150° C. or lower.

[0097] A method for manufacturing a container according to one embodiment may include a step of printing images, such as patterns and letters, on the surface of the container. Printing can be performed by a known method. Examples of printing methods include inkjet printing, gravure printing, offset printing, flexographic printing, thermal transfer printing, silk screen printing, pad printing, hot stamping, and cold stamping. For example, when printing is performed by the inkjet method, a UV-curable ink is applied to the container, and then irradiated with UV light to harden the ink. Printing may also be performed using a thermal transfer sheet. EXAMPLES

[0098] The present disclosure will now be described in more detail with reference to examples, but the present disclosure is not limited to these examples.

[0099] [Example 1] Vylon 200 (trade name, manufactured by Toyobo Co., Ltd.) was prepared as a copolymer polyester containing ethylene glycol and neopentyl glycol as diol copolymer components and terephthalic acid and isophthalic acid as dicarboxylic acid copolymer components. The Tg of the copolymer polyester was 67° C., and the Mw of the copolymer polyester was 17,000. The copolymer polyester was dissolved in a mixed solvent of ethyl acetate and methyl ethyl ketone (1:1 mixed solution) so that the content of the copolymer polyester was 25% by mass, to prepare a base material. Further, Takenate A-10 (product name, manufactured by Mitsui Chemicals, Inc.) was prepared as a curing agent. Takenate A-10 contained 0.3 mass % of metaxylylene diisocyanate as an isocyanate compound. A curing agent was added in an amount of 3 mass % relative to the base resin to prepare a coating liquid of Example 1. In the coating liquid of Example 1, the compounding ratio of the isocyanate compound to the copolymer polyester was 1 / 2778 in terms of mass ratio.

[0100] [Example 2] A coating liquid of Example 2 was prepared in the same manner as in Example 1, except that 5% by mass of a curing agent was added to the base resin. In the coating liquid of Example 2, the compounding ratio of the isocyanate compound to the copolymer polyester was 1 / 1667 in terms of mass ratio.

[0101] [Example 3] A coating liquid of Example 3 was prepared in the same manner as in Example 1, except that Takenate A-50 (product name, manufactured by Mitsui Chemicals, Inc.) was used as the curing agent instead of Takenate A-10. Takenate A-50 contained 0.5% by mass of isophorone diisocyanate and 0.2% by mass of metaxylylene diisocyanate as isocyanate compounds. In the coating liquid of Example 3, the compounding ratio of the isocyanate compound to the copolymer polyester was 1 / 1190 in terms of mass ratio.

[0102] [Example 4] A coating liquid of Example 4 was prepared in the same manner as in Example 3, except that a curing agent was added in an amount of 5% by mass relative to the base resin. In the coating liquid of Example 4, the blending ratio of the isocyanate compound to the copolymer polyester was 1 / 714 in terms of mass ratio.

[0103] [Example 5] A coating liquid of Example 5 was prepared in the same manner as in Example 1, except that Takenate D-131N (product name, manufactured by Mitsui Chemicals, Inc.) was used as the curing agent instead of Takenate A-10. Takenate D-131N contained less than 1 mass% of metaxylylene diisocyanate as an isocyanate compound. In the coating liquid of Example 5, the blending ratio of the isocyanate compound to the copolymerized polyester was less than 1 / 833 in terms of mass ratio.

[0104] [Example 6] A coating liquid of Example 6 was prepared in the same manner as in Example 5, except that 5% by mass of a curing agent was added to the base resin. In the coating liquid of Example 6, the compounding ratio of the isocyanate compound to the copolymerized polyester was less than 1 / 500 in terms of mass ratio.

[0105] [Example 7] A coating liquid of Example 7 was prepared in the same manner as in Example 1, except that 083-7100 Hardener H-1 (product name, manufactured by Rock Paint Co., Ltd.) was used as the curing agent instead of Takenate A-10, and the curing agent was added in an amount of 10 mass% relative to the base resin. 083-7100 Hardener H-1 contained 55 to 60 mass% of metaxylylene diisocyanate as an isocyanate compound. In the coating liquid of Example 7, the blending ratio of the isocyanate compound to the copolymer polyester was 1 / 4.5 in terms of mass ratio.

[0106] [Comparative Example 1] A coating liquid of Comparative Example 1 was prepared in the same manner as in Example 1, except that no curing agent was added. In the coating liquid of Comparative Example 1, the blending ratio of the isocyanate compound to the copolymer polyester was 0 / 1 in terms of mass ratio.

[0107] [Comparative Example 2] A coating liquid of Example 2 was prepared in the same manner as in Example 3, except that 1% by mass of a curing agent was added to the base resin. In the coating liquid of Comparative Example 2, the blending ratio of the isocyanate compound to the copolymer polyester was 1 / 3571 in terms of mass ratio.

[0108] [Container creation] As the container body, a syringe body (product name: ClearJect (registered trademark), manufactured by Taisei Kako Co., Ltd.) made of cycloolefin polymer, with a cross-sectional thickness of the outer cylinder of 1.5 mm and a capacity of 5 mL was prepared. Next, 18.75 g of PVA (manufactured by Kuraray Co., Ltd., product name: PVA-124, degree of polymerization: 2400, degree of saponification: 98-99%) was added to 462.5 g of water, and then 18.75 g of polyacrylic acid (manufactured by Nippon Shokubai Co., Ltd., product name: AS-58, number average molecular weight: 106,000) was added and stirred to prepare an intermediate layer coating liquid with a solids concentration of 7.5 mass% (viscosity: 1933 mPa s (20°C)). The intermediate layer coating solution was applied to the outer cylinder of the syringe body with the cap attached to the tip 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 mass ratio of polyacrylic acid to PVA was 1 / 1. The coating liquids of Examples 1 to 7 and Comparative Examples 1 and 2 were each applied to the surface of the barrier layer with a cap attached to the tip of the syringe body 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 a syringe was produced. The syringe had a structure as shown in FIG. 2, except that it did not have a gasket or a plunger.

[0109] [Transparency rating] The protective layer of each of the syringes produced using the coating solutions of Examples 1 to 7 and Comparative Examples 1 and 2 was visually observed, and the transparency was evaluated according to the following criteria. The results are shown in Table 1. A: The protective layer was not cloudy and was transparent. B: The protective layer became cloudy.

[0110] [Heat resistance evaluation] The syringes prepared using the coating solutions of Examples 1 to 7 and Comparative Examples 1 and 2 were autoclaved (heating temperature: 120°C, heating time: 20 minutes) while placed in a test tube rack, and the heat resistance of the syringes was evaluated according to the following criteria. The results are shown in Table 1. A: The protective layer did not stick to the test tube rack, and no air bubbles were observed on the surface of the protective layer. B: The protective layer stuck to the test tube rack or air bubbles appeared on the surface of the protective layer.

[0111] [Oxygen barrier property evaluation] For each of the syringes produced using the coating liquids of Examples 1 to 7 and Comparative Examples 1 and 2, the heat resistance was evaluated, and then the oxygen permeability of the syringe was measured to evaluate the oxygen barrier property of the syringe. The oxygen permeability was measured in accordance with JIS K 7126-2:2006 using an oxygen permeability measuring device (manufactured by MOCON, product name: OX-TRAN2 / 20) under conditions of 23°C and 40% RH. The oxygen permeability value was measured for the entire syringe with the opening blocked with a jig. The results are shown in Table 1.

[0112] [Table 1]

[0113] As is clear from Table 1, in the syringes made using the coating solutions of Examples 1 to 7, even after autoclaving, the protective layer does not soften due to heat and stick to the test tube rack, and air bubbles do not form on the surface of the protective layer, and it is understood that the protective layer has excellent heat resistance. As a result, it is also understood that the barrier layer covered with the protective layer is not easily damaged, has a small oxygen permeability even after autoclaving, and has excellent oxygen barrier properties. It is also clear that the syringes produced using the coating solutions of Examples 1 to 6 have transparent protective layers and are suitable for medical use. [Explanation of symbols]

[0114] 50: Vial 51: Mouth 52: Neck 53: Torso 54: Bottom 55: Container body 56: Middle class 57:Protective layer 60: Syringe 61: Outer cylinder 62:Tip tip 63: Gasket 64: Plunger 65: Flange 66: Container body 67: Middle class 68:Protective layer

Claims

1. A coating liquid containing a copolymer polyester and an isocyanate compound, The copolymer polyester contains, as a diol component, ethylene glycol and neopentyl glycol or propylene glycol, The copolymer polyester contains terephthalic acid as a dicarboxylic acid component, The weight average molecular weight of the copolymer polyester is more than 1,000 and not more than 20,000, The isocyanate compound has two or more isocyanato groups in the molecule, a blending ratio of the isocyanate compound to the copolymer polyester (isocyanate compound / copolymer polyester) is 1 / 3500 or more and 1 / 1 or less in mass ratio.

2. The coating fluid according to claim 1 , wherein the copolymer polyester further contains isophthalic acid as a dicarboxylic acid component.

3. The coating fluid according to claim 1 or 2, wherein the copolymer polyester has a glass transition temperature of 35° C. or higher and 100° C. or lower.

4. The coating liquid according to claim 1 or 2, wherein the isocyanate compound is at least one selected from the group consisting of metaxylylene diisocyanate and isophorone diisocyanate.

5. A container comprising a container body, a protective layer provided on at least a portion of a surface of the container body, and an intermediate layer provided between the container body and the protective layer, the protective layer contains a copolymer polyester and an isocyanate compound, The copolymer polyester contains, as a diol component, ethylene glycol and neopentyl glycol or propylene glycol, The copolymer polyester contains terephthalic acid as a dicarboxylic acid component, The weight average molecular weight of the copolymer polyester is more than 1,000 and not more than 20,000, The isocyanate compound has two or more isocyanato groups in the molecule, a blending ratio of the isocyanate compound to the copolymer polyester (isocyanate compound / copolymer polyester) is 1 / 3500 or more and 1 / 1 or less in mass ratio.

6. The container according to claim 5 , wherein the copolymerized polyester further contains isophthalic acid as a dicarboxylic acid component.

7. 7. The container according to claim 5 or 6, wherein the copolymer polyester has a glass transition temperature of 35°C or higher and 100°C or lower.

8. The container according to claim 5 or 6, wherein the isocyanate compound is at least one selected from the group consisting of metaxylylene diisocyanate and isophorone diisocyanate.

9. 7. The container according to claim 5 or 6, wherein the protective layer has a thickness of 0.1 μm or more and 100 μm or less.

10. The container according to claim 5 or 6, wherein the container body comprises at least one selected from the group consisting of polyolefins, cyclic polyolefins, cyclic olefin copolymers, polycarbonates, and polyesters.

11. The container according to claim 5 or 6, wherein the intermediate layer is at least one selected from the group consisting of an ultraviolet shielding layer and a barrier layer.

12. 7. The container according to claim 5 or 6, which is a vial.

13. 7. The container according to claim 5 or 6, which is a syringe.

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