Reinforced glass container, manufacturing method of medicine container, and manufacturing method of reinforced glass container

Abstract

The present invention provides a reinforced glass vessel that is impact resistant and can be used for processes involving high-temperature exposure or UV ray irradiation.　The reinforced glass vessel according to the present invention comprises a glass vessel and a polymer layer which is disposed on the outer surface of the glass vessel and has a thickness of more than 1 μm. The polymer layer includes a tetrafluoroethylene polymer that has a melting point greater than 260°C and has a carbonyl group-containing group or a hydroxyl group-containing group.

Description

[Technical Field]

[0001] The present invention relates to a reinforced glass container, a method for manufacturing a medicine container, and a method for manufacturing a reinforced glass container. [Background technology]

[0002] Glass containers have excellent chemical resistance, airtightness, transparency, and the like. Therefore, glass containers are useful as containers for storing pharmaceuticals, and are widely used as ampoules and vials. However, glass is easily broken by impact, and glass containers are easily damaged by transportation or contact during filling with contents. Therefore, a method of providing a polymer layer on the outer surface of a glass container to improve the impact resistance of the glass container has been adopted, but it is not easy to firmly adhere the glass and the polymer layer.

[0003] Patent Document 1 proposes a glass container in which a primer layer is provided on the outer surface using a silane coupling agent, and a polymer layer is further provided on the primer layer. Patent Document 2 also proposes a glass container having an undercoat layer made of a copolymer of tetrafluoroethylene and hexafluoropropylene (FEP) on the outer surface, and further having a topcoat layer made of a fluoroolefin-based polymer on the undercoat layer. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Special Publication No. 2015-515433 [Patent Document 2] Japanese Patent Application Publication No. 9-206606 Summary of the Invention [Problem to be solved by the invention]

[0005] In recent years, glass containers have increasingly been required to undergo high-level hygiene control, and for example, glass containers used to store pharmaceuticals are often subjected to sterilization treatment by prolonged exposure to high temperatures or ultraviolet radiation. However, the present inventors have found that the glass containers described in Patent Documents 1 and 2 are insufficient to satisfy such requirements.

[0006] Specifically, the glass container described in Patent Document 1 has the problem that its original impact resistance is still insufficient. In addition, as the primer layer or polymer layer deteriorates due to exposure to high temperatures or ultraviolet light, not only does the impact resistance further decrease, but the polymer layer itself is also prone to peeling. The glass container described in Patent Document 2 has a problem in that the adhesion between the outer surface and the coating layer is still insufficient, and the coating layer melts when exposed to high temperatures, making it impossible to perform the sterilization treatment sufficiently.

[0007] As a result of extensive research, the present inventors have discovered that by providing a specific tetrafluoroethylene-based polymer layer on the outer surface of a glass container, a reinforced glass container can be obtained that is impact resistant and can be subjected to treatments involving exposure to high temperatures and ultraviolet radiation. An object of the present invention is to provide such a reinforced glass container and a method for manufacturing the same, as well as a method for manufacturing a medicine container using such a reinforced glass container. [Means for solving the problem]

[0008] The present invention has the following aspects. [1] A reinforced glass container comprising: a glass container; and a polymer layer having a thickness of more than 1 μm provided on the outer surface of the glass container, wherein the polymer layer has a melting temperature of more than 260°C and contains a tetrafluoroethylene-based polymer having a carbonyl group-containing group or a hydroxyl group-containing group. [2] The reinforced glass container according to [1], wherein the compressive strength of the tetrafluoroethylene-based polymer exceeds 12 MPa. [3] The tetrafluoroethylene-based polymer has a main chain carbon number of 1 × 10 6The reinforced glass container according to [1] or [2], which is a tetrafluoroethylene-based polymer having 10 to 5,000 carbonyl-containing groups per container. [4] The reinforced glass container according to any one of [1] to [3], wherein the tetrafluoroethylene-based polymer is a tetrafluoroethylene-based polymer containing units based on perfluoro(alkyl vinyl ether). [5] The tempered glass container according to any one of [1] to [4], wherein the glass container is made of borosilicate glass or alkali aluminosilicate glass. [6] The reinforced glass container according to any one of [1] to [5], wherein the thickness of the glass container is 2 mm or less.

[0009] [7] The reinforced glass container according to any one of [1] to [6], wherein the polymer layer further contains polytetrafluoroethylene. [8] The reinforced glass container according to any one of [1] to [7], wherein the thickness of the polymer layer exceeds 20 μm. [9] The reinforced glass container according to any one of [1] to [8], wherein the polymer layer has a thickness of less than 40 μm.

[10] The reinforced glass container according to any one of [1] to [9], wherein the glass container is a vial, an ampoule, a bottle, or a cartridge.

[11] The reinforced glass container according to any one of [1] to

[10] , which is for pharmaceuticals.

[0010]

[12] A method for producing a pharmaceutical container, comprising exposing the glass reinforced container according to any one of [1] to

[11] to ultraviolet light or an atmosphere having a temperature of 200°C or higher and lower than the melting temperature of the tetrafluoroethylene-based polymer to obtain a sterilized glass reinforced container, filling the glass reinforced container with a pharmaceutical, and sealing the glass reinforced container to obtain a pharmaceutical container in which the pharmaceutical is contained in the glass reinforced container.

[13] A method for producing a reinforced glass container, comprising: applying a liquid composition having a melting temperature of more than 260°C and containing particles of a tetrafluoroethylene-based polymer having a carbonyl group-containing group or a hydroxyl group-containing group to the outer surface of a glass container; and heating the composition to form a polymer layer containing the tetrafluoroethylene-based polymer and having a thickness of more than 1 μm on the outer surface of the glass container; and obtaining a reinforced glass container having the glass container and the polymer layer provided on the outer surface of the glass container.

[14] The manufacturing method according to

[13] , wherein the liquid composition is applied to the outer surface of the glass container by dip coating.

[15] The method according to

[13] or

[14] , wherein the viscosity of the liquid composition is 1000 mPa·s or less. [Effects of the Invention]

[0011] According to the present invention, a tempered glass container having excellent impact resistance, heat resistance, and UV resistance can be obtained, and containers for medicines and the like that require high levels of hygiene control can be produced with high efficiency. DETAILED DESCRIPTION OF THE INVENTION

[0012] The following terms have the following meanings: "Average particle size (D50)" is the volume-based cumulative 50% diameter of a target object (particle or filler) determined by laser diffraction / scattering. In other words, particle size distribution is measured by laser diffraction / scattering, and a cumulative curve is calculated with the total volume of the particle group as 100%. The particle size is the point on that cumulative curve where the cumulative volume is 50%. The "melting temperature" is the temperature corresponding to the maximum value of the melting peak of a polymer as measured by differential scanning calorimetry (DSC). The "glass transition temperature (Tg)" is a value measured by analyzing a polymer using the dynamic mechanical analysis (DMA) method. The "viscosity" is the viscosity of the liquid composition measured using a Brookfield viscometer at 25° C. and 60 rpm. The measurement is repeated three times, and the average value of the three measurements is used. The "thixotropy ratio" is a value calculated by dividing the viscosity of a liquid composition measured at a rotation speed of 30 rpm by the viscosity of the liquid composition measured at a rotation speed of 60 rpm. Each viscosity measurement is repeated three times, and the average value of the three measurements is used. The "specific surface area" is a value calculated by measuring particles or fillers by the gas adsorption (constant volume method) BET multipoint method, and is determined using a NOVA4200e (manufactured by Quantachrome Instruments). The term "unit" in a polymer refers to an atomic group formed directly from one monomer molecule by polymerization, or an atomic group formed by converting a part of the atomic group into a different structure by treating the resulting polymer. Hereinafter, a unit based on monomer a will also be referred to simply as a "monomer a unit."

[0013] The reinforced glass container of the present invention (hereinafter also referred to as "the container") comprises a glass container and a polymer layer (hereinafter also referred to as "F layer") having a thickness of more than 1 μm that is provided on the outer surface of the glass container. The F layer has a melting temperature of more than 260°C and contains a tetrafluoroethylene-based polymer (hereinafter also referred to as "F polymer") that has a carbonyl group-containing group or a hydroxyl group-containing group. The container has excellent impact resistance, heat resistance, and UV resistance. The reasons for this are not entirely clear, but are thought to be as follows.

[0014] The F polymer in this container is a heat-resistant and UV-resistant fluoropolymer with a melting temperature of over 260°C, which improves the shape retention of the F layer when exposed to high-temperature atmospheres or UV rays. Furthermore, F polymer, which has a melting point, has a certain degree of plasticity and elasticity, and can be said to be highly flexible. For this reason, by forming the F layer to a certain thickness or more, the impact resistance of this container is improved. Furthermore, the F polymer has a carbonyl group-containing group or a hydroxyl group-containing group, which interacts with polar functional groups such as silanol groups present on the outer surface of the glass container, resulting in strong adhesion between the outer surface and the F polymer. It is believed that these effects work synergistically to provide a tempered glass container that is excellent in impact resistance and can be subjected to treatments involving exposure to high temperatures and ultraviolet radiation.

[0015] The F layer in the present container is preferably provided directly on the outer surface of a glass container. In other words, the present container has a glass container and an F layer provided directly on the outer surface of the glass container, and the F layer is preferably a glass container containing an F polymer. In this case, the above-mentioned mechanism of action becomes more pronounced, and the impact resistance, heat resistance, and UV resistance of the present container are more likely to be improved.

[0016] The F polymer is a heat-meltable polymer containing units (TFE units) based on tetrafluoroethylene (hereinafter also referred to as "TFE"). Therefore, the F layer has excellent flexibility and adhesiveness and adhesion to the outer surface of a glass container. Note that "heat-meltable" means a polymer with melt fluidity that has a melt flow rate of 0.1 to 1,000 g / 10 min at a temperature 20°C or more higher than the melting temperature of the polymer under a load of 49 N. The melting temperature of the F polymer is more than 260° C., and preferably 280 to 320° C. In this case, the F layer tends to have excellent heat resistance.

[0017] The fluorine atom content in the F polymer is preferably 70% by mass or more, more preferably 74 to 76% by mass, which makes it easier to improve the UV resistance of the F layer. The glass transition point of the F polymer is preferably from 75 to 125°C, more preferably from 80 to 100°C.

[0018] Examples of F polymers include polymers containing TFE units and ethylene units, polymers containing TFE units and propylene units, polymers containing TFE units and units based on perfluoro(alkyl vinyl ether) (hereinafter also referred to as "PAVE") (PFA), and polymers containing TFE units and units based on fluoroalkylethylene, with PFA being preferred. Using PFA as the F polymer makes it easier to improve the impact resistance of the container. The polymers may further contain units based on other comonomers. Preferred PAVEs are CF2=CFOCF3, CF2=CFOCF2CF3 and CF2=CFOCF2CF2CF3 (PPVE), with PPVE being more preferred.

[0019] The F polymer has a carbonyl group-containing group or a hydroxyl group-containing group (hereinafter, these are also collectively referred to as "oxygen-containing polar groups"). Because the F polymer has such oxygen-containing polar groups, the F layer adheres firmly to the outer surface of the glass container and also exhibits excellent high-temperature adhesion. The oxygen-containing polar group may be contained in a unit in the F polymer or in a terminal group of the main chain of the F polymer. Examples of the latter include an F polymer having an oxygen-containing polar group as a terminal group derived from a polymerization initiator, a chain transfer agent, etc., and an F polymer having an oxygen-containing polar group obtained by subjecting an F polymer to plasma treatment or ionizing radiation treatment. The F polymer preferably has a carbonyl group-containing group, which provides excellent adhesion and close contact between the F layer and the outer surface of the glass container.

[0020] As the hydroxyl group-containing group, a group containing an alcoholic hydroxyl group is preferred, and -CF2CH2OH, -C(CF3)2OH and a 1,2-glycol group (-CH(OH)CH2OH) are more preferred. The carbonyl group-containing group is a group containing a carbonyl group (>C(O)). Preferred examples of the carbonyl group-containing group include a carboxyl group, an alkoxycarbonyl group, an amide group, an isocyanate group, a carbamate group (-OC(O)NH), an acid anhydride residue (-C(O)OC(O)-), an imide residue (-C(O)NHC(O)-, etc.), and a carbonate group (-OC(O)O-), with an acid anhydride residue being more preferred. When the F polymer has a carbonyl group-containing group, the number of carbonyl group-containing groups in the F polymer is 1×10 6 The number of carbonyl-containing groups per polymer is preferably 10 to 5,000, more preferably 50 to 4,000, and even more preferably 100 to 2,000. In this case, the adhesion of the F layer to the outer surface of the glass container is more likely to be improved. The number of carbonyl-containing groups in the F polymer can be determined by the composition of the polymer or the method described in WO 2020 / 145133.

[0021] The F polymer is preferably a polymer having an oxygen-containing polar group containing TFE units and PAVE units, more preferably a polymer containing TFE units, PAVE units and units based on a monomer having an oxygen-containing polar group, and even more preferably a polymer containing these units in the following amounts, in that order, relative to all units: 90 to 99 mol %, 0.5 to 9.97 mol %, and 0.01 to 3 mol %. Moreover, as the monomer having an oxygen-containing polar group, itaconic anhydride, citraconic anhydride, and 5-norbornene-2,3-dicarboxylic anhydride (hereinafter also referred to as "NAH") are preferred. Specific examples of such polymers include the polymers described in WO 2018 / 16644.

[0022] The F polymer is more likely to be distributed densely and uniformly in the F layer. Furthermore, it is more likely to form microspherulites in the F layer, which increases adhesion to other components. As a result, it is easier to obtain an F layer with high adhesion to the outer surface of a glass container. The compressive strength of the F polymer is a value measured according to ASTM-D695. Specifically, the compressive strength of the F polymer is preferably greater than 12 MPa, more preferably 15 MPa or greater. The compressive strength of the F polymer is preferably 40 MPa or less. In this case, the high-temperature adhesiveness of the F layer is likely to be improved.

[0023] The F layer preferably has a light transmittance of 80% or more for wavelengths of 255 to 355 nm. In this case, the contents (e.g., pharmaceuticals) housed in the container can be easily visible from the outside. In such a container with excellent visibility, the F layer preferably contains an F polymer as a main component, and preferably consists essentially of an F polymer. "An F layer consisting essentially of an F polymer" means that the F layer contains 90% by mass or more of the F polymer. The peel strength between the glass container and the F layer is preferably 5 N / cm or more, more preferably 8 N / cm or more, which prevents the F layer from easily peeling off from the glass container. The thickness of the F layer is greater than 1 μm, preferably greater than 20 μm, and preferably less than 40 μm. The present container including an F layer of such a thickness is likely to have improved impact resistance, heat resistance, and UV resistance.

[0024] The porosity of the F layer is preferably 5% or less, more preferably 4% or less, and is preferably 0.01% or more, more preferably 0.1% or more. The porosity of the F layer is determined by determining the void area of ​​the F layer using image processing from an SEM photograph of the cross section of the F layer observed using a scanning electron microscope (SEM), and is the percentage (%) obtained by dividing the area occupied by the void area by the area of ​​the F layer. The area occupied by the gap portion is determined by approximating the gap portion to a circle.

[0025] The F layer may also contain a resin material other than the F polymer, which will be described later in the manufacturing method of the present container, and preferably contains polytetrafluoroethylene (PTFE). The present container, in which the F layer contains the F polymer and PTFE, has excellent low friction properties, and not only can it suppress adhesion of foreign matter, but it also tends to improve handling during transportation, etc. Furthermore, it is easier to improve the resistance (heat resistance and UV resistance) of the F layer to sterilization treatment. When the F layer contains an F polymer and PTFE, the F polymer content and the PTFE content in the F layer are each preferably independently 10 to 90% by mass. The mass ratio of the PTFE content to the F polymer content in the F layer is preferably 1 or more. The mass ratio is preferably 20 or less, more preferably 10 or less. PTFE refers to a non-thermofusible tetrafluoroethylene polymer whose main unit is TFE, and examples thereof include TFE homopolymers and copolymers of TFE and a trace amount of a comonomer (HFP, PAVE, FAE, etc.).

[0026] Glass containers are not particularly limited in their applications, but are suitable for use as containers for containing and storing pharmaceuticals. Examples of such containers include vials, ampoules, bottles, cartridges, syringes (outer cylinders and plungers), beakers, and petri dishes, with vials, ampoules, bottles, and cartridges being preferred. Glass containers can be chemically strengthened prior to the formation of an F layer, which can be used to improve the mechanical durability of the glass container. Therefore, glass containers can also be ion-exchange strengthened prior to the formation of an F layer. In this case, the glass is also called "ion-exchange glass." A specific example of ion-exchange strengthening of glass containers is immersing the glass container in a 100% KNO3 molten salt bath at 450°C for about 8 hours. Glass containers can also be strengthened by other strengthening methods, such as heat strengthening and flame polishing.

[0027] The glass container may also be formed from a glass composition containing ion-exchangeable glass and non-ion-exchangeable glass, and may be formed from a Type 1B glass composition such as Schott Type 1B aluminosilicate glass. The glass container is preferably formed from glass that meets the standards for pharmaceutical glass as set forth by regulatory agencies such as the United States Pharmacopoeia, the European Pharmacopoeia, and the Japanese Pharmacopoeia, based on its resistance to hydrolysis.

[0028] The glass constituting the glass container is preferably made of soda-lime glass, alkali aluminosilicate glass, or borosilicate glass, and more preferably made of alkali aluminosilicate glass or borosilicate glass, because these glasses have a low coefficient of linear expansion, high resistance to thermal shock, and excellent chemical resistance. Also, the glass is 25 x 10 -7 ~80×10 -7 It is preferred that the material has a coefficient of linear thermal expansion (CTE) of 1 / °C. The compressive stress of the glass container is preferably 300 MPa or more, more preferably 350 MPa or more, and is preferably 900 MPa or less. The thickness (wall thickness) of the glass container is preferably 50 μm or more, more preferably 100 μm or more. The thickness of the glass container is preferably 2 mm or less, more preferably 1 mm or less. Because the container has an F layer, even a glass container with a relatively small thickness can exhibit high impact resistance.

[0029] Alkali aluminosilicate glasses generally contain Na2O and / or K2O, SiO2, and Al2O3, and optionally contain at least one alkaline earth metal oxide and at least one alkali metal oxide. The alkali aluminosilicate glass is preferably free of boron and boron-containing compounds. The alkali aluminosilicate glass may contain a trace amount of at least one additional oxide selected from the group consisting of SnO2, ZrO2, ZnO, TiO2, and As2O3. These components are added as a clarifying agent and / or a chemical durability improver. Furthermore, a coating containing SnO2, ZrO2, ZnO, TiO2, As2O3, or the like may be formed on the outer surface of the glass container.

[0030] Specific examples of borosilicate glasses include Corning® Pyrex® 7740, 7800, Wheaton 180, 200, 400, Schott Duran, Schott Fiolax, KIMAX® N-51A, Gerrescheimer GX-51 Flint, and the like. Specific examples of soda lime glass include Wheaton 800 and 900. As the soda lime glass, ammonium sulfate-treated soda lime glass may also be used.

[0031] The method for producing a reinforced glass container of the present invention (hereinafter also referred to as "this method") is a method in which a liquid composition containing particles of an F polymer (hereinafter also referred to as "F particles") is applied to the outer surface of a glass container, and heated to form an F layer containing the F polymer and having a thickness of more than 1 μm on the outer surface of the glass container, thereby obtaining the present container. For the reasons mentioned above, the resulting container has excellent impact resistance, heat resistance, and UV resistance. In this method, it is preferable to apply the liquid composition directly to the outer surface of the glass container. In other words, it is preferable to apply the liquid composition to the outer surface of the glass container and heat it to directly form an F layer on the outer surface of the glass container. In this case, for the reasons mentioned above, the impact resistance, heat resistance, and UV resistance of the resulting container are likely to be further improved.

[0032] In the liquid composition, the D50 of the F particles is preferably 10 μm or less, more preferably 5 μm or less. The D50 of the F particles is preferably 0.1 μm or more, more preferably 1 μm or more. With a D50 in this range, the F particles tend to have good fluidity and dispersibility. The specific surface area of ​​F particles is 1 to 25 m 2 / g is preferred, and 1 to 8m 2 / g is more preferred.

[0033] The F particles may contain resins or inorganic substances other than the F polymer, but preferably contain the F polymer as the main component. The content of the F polymer in the F particles is preferably 80% by mass or more, more preferably 100% by mass. Examples of the resin include heat-resistant resins such as aromatic polyester, polyamideimide, (thermoplastic) polyimide, polyphenylene ether, polyphenylene oxide, and maleimide. Examples of the inorganic filler include silicon oxide (silica), metal oxides (beryllium oxide, cerium oxide, alumina, soda alumina, magnesium oxide, zinc oxide, titanium oxide, etc.), boron nitride, and magnesium metasilicate (steatite). At least a portion of the surface of the inorganic filler may be surface-treated with a silane coupling agent (3-aminopropyltriethoxysilane, vinyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-isocyanatopropyltriethoxysilane, etc.).

[0034] F particles containing a resin or inorganic substance other than an F polymer may have a core-shell structure with an F polymer as the core and the above-mentioned component as the shell, or may have a core-shell structure with an F polymer as the shell and the above-mentioned component as the core. Such F particles are obtained, for example, by coalescence (by collision, aggregation, etc.) of particles of an F polymer with particles of the above-mentioned component.

[0035] The liquid composition may contain an inorganic filler in addition to the F particles. If the liquid composition contains an inorganic filler, an F layer having excellent low linear expansion properties can be easily formed. Examples of inorganic fillers include silicon oxide (silica), metal oxides (beryllium oxide, cerium oxide, alumina, soda alumina, magnesium oxide, zinc oxide, titanium oxide, etc.), boron nitride, and magnesium metasilicate (steatite). The D50 of the inorganic filler is preferably 0.01 to 20 μm. The shape of the inorganic filler may be any of granular, needle-like (fibrous), and plate-like. Specific shapes of the inorganic filler include spherical, scale-like, layer-like, leaf-like, apricot-like, columnar, cockscomb-like, equiaxed, leaf-like, micaceous, block-like, flat, wedge-like, rosette-like, net-like, and prismatic shapes. When the liquid composition contains an inorganic filler, the amount thereof is preferably from 1 to 50 mass %, more preferably from 5 to 40 mass %, based on the total mass of the liquid composition.

[0036] The liquid composition may further contain a resin material other than the F particles (F polymer) from the viewpoint of improving the adhesiveness and low linear expansion of the F layer. Such resin materials may be thermosetting or thermoplastic, and may also be modified. The resin material may be dissolved in the liquid composition, or may be dispersed as particles without being dissolved in the liquid composition.

[0037] Examples of such resin materials include tetrafluoroethylene polymers other than F polymers, aromatic polyimides, aromatic polyamic acids which are aromatic polyimide precursors, aromatic maleimides, acrylic resins, phenolic resins, liquid crystalline polyesters, liquid crystalline polyesteramides, polyolefin resins, modified polyphenylene ethers, polyfunctional cyanate ester resins, polyfunctional maleimide-cyanate ester resins, polyfunctional maleimides, aromatic elastomers such as styrene elastomers, vinyl ester resins, urea resins, diallyl phthalate resins, melamine resins, guanamine resins, melamine-urea co-condensation resins, polycarbonates, polyarylates, polysulfones, polyarylsulfones, aromatic polyamides, aromatic polyetheramides, polyphenylene sulfides, polyaryl ether ketones, polyamideimides, polyphenylene ethers, and epoxy resins.

[0038] As the tetrafluoroethylene-based polymer other than the F polymer, PTFE is preferred, as described above. When the liquid composition contains PTFE particles, the D50 thereof is preferably 0.1 to 6 μm. Furthermore, when the liquid composition contains PTFE particles, the amount thereof is preferably 10 to 50 mass % based on the total mass of the liquid composition. When the liquid composition contains a resin material other than PTFE, the amount thereof is preferably 40% by mass or less based on the total mass of the liquid composition.

[0039] In addition to the above components, the liquid composition may further contain other components such as a thixotropy-imparting agent, a viscosity modifier, an antifoaming agent, a silane coupling agent, a dehydrating agent, a plasticizer, a weathering agent, an antioxidant, a heat stabilizer, a lubricant, an antistatic agent, a whitening agent, a colorant, a conductive agent, a release agent, a surface treatment agent, and a flame retardant.

[0040] The liquid composition preferably contains a liquid dispersion medium, which is a liquid that has the function of dispersing or dissolving the components that make up the liquid composition, and is a liquid compound that is inactive at 25°C. The liquid dispersion medium may be water or a non-aqueous liquid dispersion medium. As the liquid dispersion medium, from the viewpoint of enhancing the dispersion stability of each component in the liquid composition, a liquid compound selected from the group consisting of water, amides, ketones, and esters is preferred, and water, N-methyl-2-pyrrolidone, γ-butyrolactone, methyl ethyl ketone, cyclohexanone, and cyclopentanone are more preferred.

[0041] Two or more liquid dispersion media may be used in combination, and in this case, it is preferable that the different liquid dispersion media are compatible with each other. The boiling point of the liquid dispersion medium is preferably 125 to 250° C. Within this range, when the liquid dispersion medium is removed from the liquid composition, the F particles are highly fluidized and densely packed, and as a result, a dense F layer is easily formed. The content of the liquid dispersion medium in the liquid composition is preferably 40 to 80 mass %, more preferably 50 to 70 mass %.

[0042] The liquid composition may contain a nonionic surfactant from the viewpoint of improving dispersion stability and handling properties. Specific examples of such surfactants include the "Ftergent" series (manufactured by Neos Corporation, Ftergent is a registered trademark), the "Surflon" series (manufactured by AGC Seimi Chemical Co., Ltd., Surflon is a registered trademark), the "Megafac" series (manufactured by DIC Corporation, Megafac is a registered trademark), the "Unidyne" series (manufactured by Daikin Industries, Ltd., Unidyne is a registered trademark), "BYK-347", "BYK-349", "BYK-378", "BYK-3450", "BYK-3451", "BYK-3455", "BYK-3456" (manufactured by BYK Japan KK), and "KF-6011" and "KF-6043" (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0043] The viscosity of the liquid composition is preferably 10 mPa·s or more, more preferably 20 mPa·s or more, and is preferably 1000 mPa·s or less, more preferably 500 mPa·s or less, and even more preferably 100 mPa·s or less. The thixotropy ratio of the liquid composition is preferably 1.0 or more, and more preferably 3.0 or less, and more preferably 2.0 or less. In this case, the liquid composition having the above properties has excellent coatability (particularly coatability by dip coating) and uniformity, and is likely to form a denser F layer.

[0044] Examples of methods for applying the liquid composition to the outer surface of a glass container include coating methods such as dip coating, spraying (spraying using a spray gun), roll coating, spin coating, gravure coating, microgravure coating, gravure offset, knife coating, kiss coating, bar coating, die coating, fountain-meyer bar coating, and slot die coating, with dip coating being particularly preferred. The dip coating method can more easily form an F layer on the outer surface of a glass container.

[0045] The liquid composition applied to the outer surface of the glass container is preferably heated to remove the liquid dispersion medium (dry) to obtain a dry coating, and then the dry coating (F polymer) is baked by further heating to form an F layer. The heating temperature when removing the liquid dispersion medium is preferably a temperature lower than the boiling point of the liquid dispersion medium by 0 to 150°C. For example, when N-methyl-2-pyrrolidone (NMP), which has a boiling point of approximately 200°C, is used, the heating temperature is preferably 150°C or lower, more preferably 100 to 120°C. When removing the liquid dispersion medium, air drying may be performed.

[0046] After removing the liquid dispersion medium, the mixture is preferably heated at a temperature at which the F polymer is baked, more preferably at a temperature of 300 to 400°C. The F layer may be formed by applying and drying the liquid composition once or twice or more times. For example, the F layer may be formed by applying and drying the liquid composition to obtain a dry film, applying and drying another liquid composition on this dry film to obtain a thick dry film, and baking the dry film (F polymer) by heating.

[0047] The method for producing a pharmaceutical container of the present invention is a method of exposing the container to an atmosphere (high-temperature atmosphere) at a temperature of 200°C or higher and lower than the melting temperature of the F polymer or to ultraviolet light to obtain a sterilized pharmaceutical container, filling the container with a pharmaceutical, and sealing it to obtain a pharmaceutical container in which the pharmaceutical is contained in the container. The specific temperature of the high-temperature atmosphere is preferably 250 to 300°C. The time for which the container is exposed to a high-temperature atmosphere is preferably 0.5 to 12 hours, more preferably 1 to 6 hours.

[0048] On the other hand, the wavelength of the ultraviolet light to be irradiated is preferably 240 to 290 nm. The cumulative dose of ultraviolet light is 1 to 200 mJ / cm 2 is preferred. The pharmaceuticals contained in this container include chemical substances themselves that can be used for the diagnosis, treatment, cure, or prevention of diseases, compositions containing at least one such chemical substance, etc. The pharmaceuticals may be in any form, such as liquid, solid, gel, suspension, emulsion, or powder.

[0049] The reinforced glass container, the manufacturing method of the medicine container, and the manufacturing method of the reinforced glass container of the present invention have been described above, but the present invention is not limited to the configurations of the above-described embodiments. For example, in the glass reinforced container of the present invention, any other configuration may be added to the configuration of the above embodiment, or any configuration that exhibits the same function may be substituted. Furthermore, in the manufacturing method of the pharmaceutical container and the manufacturing method of the glass reinforced container of the present invention, in the configuration of the above embodiment, any other process for any purpose may be added, or any process that performs a similar function may be substituted. [Example]

[0050] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. 1.Details of each ingredient [particle] F particle 1: Contains 97.9 mol%, 0.1 mol%, and 2.0 mol% of TFE units, NAH units, and PPVE units, in that order, and has a main chain carbon number of 1×10 6 Particles (D50: 2.1 μm) made of a polymer (melting temperature: 300°C, compressive strength: 15 MPa) containing 1,000 carbonyl groups per particle F Particle 2: Particles (D50: 2.3 μm) made of a polymer containing 75 mol% and 25 mol% of TFE units and hexafluoropropylene-based units, respectively, based on the total units (melting temperature: 255°C, compressive strength: 10 MPa). [Glass container] Glass container 1: Borosilicate glass vial (thickness: 2 mm)

[0051] 2. Example of production of liquid composition A powder of F particles 1, a nonionic silicone surfactant (BYK, product name: BYK-3450), a pH buffer, and water were placed in a pot, followed by the addition of zirconia balls. The pot was then rolled at 150 rpm for 1 hour to obtain Liquid Composition 1 (viscosity: 30 mPa s, pH: 8-9) containing F particles 1 (40 parts by mass), a silicone surfactant (2 parts by mass), a pH buffer (2 parts by mass), and water (56 parts by mass). Liquid composition 2 (viscosity: 20 mPa·s, pH: 9) was obtained in the same manner as liquid composition 1, except that the powder consisting of F particles 1 was changed to a powder consisting of F particles 2. Furthermore, a commercially available aqueous dispersion of PTFE (manufactured by AGC, trade name: AD-915E) containing 60 mass % of non-thermofusible PTFE particles (D50: 0.3 μm) was used as liquid composition 3. Furthermore, a powder of F particles 1, a silicone surfactant, and liquid composition 3 were mixed to obtain liquid composition 4 (viscosity: 50 mPa s) containing PTFE particles (50 parts by mass), F particles 1 (5 parts by mass), a silicone surfactant (0.25 parts by mass), and water (44.75 parts by mass). The pH of liquid composition 4 was adjusted to 10 by adding an appropriate amount of ammonia water.

[0052] 3. Example of manufacturing a reinforced glass container A liquid coating was formed on the outer surface of a glass container 1 by a dip coating method in which the glass container 1 was immersed in the liquid composition 1. Next, the glass container 1 on which this liquid coating had been formed was passed through a drying oven at 120°C for 5 minutes and dried by heating to obtain a dry coating. The dried coating was then heated in a nitrogen oven at 380°C for 3 minutes, thereby obtaining a reinforced glass container 1 having a glass container 1 and an F layer (thickness: 25µm) containing the molten and fired product of F particles 1 on its outer surface. Reinforced glass containers 2 to 4 were obtained in the same manner as in the production of reinforced glass container 1, except that liquid compositions 2 to 4 were used instead of liquid composition 1. The F layer of each of the reinforced glass containers 1 to 4 had a light transmittance of 80% or more for wavelengths of 255 to 355 nm.

[0053] A glass container 1 was immersed in a solution containing 0.1% by mass of aminopropylsilsesquioxane to form a liquid coating on its outer surface, and then heated in a convection oven at 100°C for 15 minutes to form a primer layer. Subsequently, the glass container 1 having the primer layer was immersed in the liquid composition 3 to form a liquid coating on the primer layer. Next, the glass container 1 having the liquid coating formed thereon was passed through a drying oven at 120°C for 5 minutes and dried by heating to obtain a dry coating. The dried coating was then heated in a nitrogen oven at 380°C for 3 minutes, thereby forming an F layer (thickness: 25µm) containing the molten and fired product of the F particles 1, and obtaining a reinforced glass container 5 having the glass container 1 and the primer layer and F layer in that order on its outer surface.

[0054] 4. Evaluation 4-1. Adhesion A strip-shaped cut was made in the F layer of each of the glass reinforced containers 1 to 5, and the strip was peeled off at a 90° angle from one end of the longitudinal direction at a pulling speed of 50 mm / min using a tensile tester. The maximum load measured was taken as the peel strength (N / cm) and evaluated according to the following criteria. [Evaluation criteria] ◯: Peel strength is 8N / cm or more. △: Peel strength is 5 N / cm or more and less than 8 N / cm. ×: Peel strength is less than 5 N / cm.

[0055] 4-2. Heat resistance After heating the reinforced glass containers 1 to 5 in an oven at 260°C for 1 hour, the appearance of the F layer was visually inspected and evaluated according to the following criteria: The reinforced glass container 3 was not evaluated because the adhesion of the F layer was insufficient. [Evaluation criteria] ○: The entire F layer is in close contact with the glass container 1. ×: The F layer is peeled off from the glass container 1.

[0056] 4-3.UV resistance After irradiating the glass reinforced containers 1 to 5 with ultraviolet light at a wavelength of 270 nm for 1 hour, the appearance of the F layer was visually inspected and evaluated according to the following criteria: Note that the glass reinforced container 3 was not evaluated because the adhesion of the F layer was insufficient. [Evaluation criteria] ◯: The F layer is not deteriorated and the surface is smooth. ×: The F layer is deteriorated and the surface is not smooth. The evaluation results are summarized in Table 1 below.

[0057] [Table 1]

[0058] The F layer formed on the container surface had the highest transparency and the highest internal visibility in Glass Reinforced Container 1. The F layer formed on the container surface had the lowest friction, the lowest foreign matter adhesion, and the best transportability in Glass Reinforced Container 4. [Industrial Applicability]

[0059] The tempered glass container of the present invention has excellent impact resistance, heat resistance and UV resistance, and is therefore useful as a container for storing pharmaceuticals and the like, which require high levels of hygiene control. The entire contents of the specification, claims and abstract of Japanese Patent Application No. 2021-002416, filed on January 8, 2021, are hereby incorporated by reference as part of the disclosure of the specification of the present invention.

Claims

1. A reinforced glass container has a glass container and a polymer layer having a thickness of more than 1 μm, which is provided directly on the outer surface of the glass container, and the polymer layer has a melting temperature of more than 260° C. and contains a tetrafluoroethylene-based polymer containing units based on perfluoro(alkyl vinyl ether) having 100 to 2000 carbonyl-containing groups per 1×10 6 carbon atoms in the main chain.

2. 2. The reinforced glass container according to claim 1, wherein the tetrafluoroethylene-based polymer has a compressive strength of greater than 12 MPa.

3. 3. The tempered glass container according to claim 1, wherein the glass container is made of borosilicate glass or alkali aluminosilicate glass.

4. The glass reinforced container according to any one of claims 1 to 3, wherein the glass container has a thickness of 2 mm or less.

5. The reinforced glass container according to any one of claims 1 to 4, wherein the polymer layer further contains polytetrafluoroethylene.

6. The reinforced glass container according to any one of claims 1 to 5, wherein the polymer layer has a thickness of more than 20 µm.

7. The reinforced glass container according to any one of claims 1 to 6, wherein the polymer layer has a thickness of less than 40 µm.

8. The reinforced glass container according to any one of claims 1 to 7, wherein the glass container is a vial, an ampoule, a bottle, or a cartridge.

9. The glass reinforced container according to any one of claims 1 to 8, which is for pharmaceuticals.

10. A method for manufacturing a pharmaceutical container, comprising exposing the glass reinforced container according to any one of claims 1 to 9 to ultraviolet light or an atmosphere having a temperature of 200°C or higher and lower than the melting temperature of the tetrafluoroethylene-based polymer to obtain a sterilized glass reinforced container, filling the glass reinforced container with a pharmaceutical, and sealing the glass reinforced container to obtain a pharmaceutical container in which the pharmaceutical is contained in the glass reinforced container.

11. A method for producing a reinforced glass container, comprising: applying a liquid composition containing particles of a tetrafluoroethylene-based polymer having a melting temperature of above 260°C and containing units based on perfluoro(alkyl vinyl ether) having 100 to 2000 carbonyl-containing groups per 1 x 10 carbon atoms in the main chain directly to the outer surface of a glass container; and heating the composition to directly form a polymer layer containing the tetrafluoroethylene-based polymer and having a thickness of above 1 μm on the outer surface of the glass container; and obtaining a reinforced glass container having the glass container and the polymer layer directly provided on the outer surface of the glass container.

12. The method of claim 11 , wherein the liquid composition is applied to the outer surface of the glass container by dip coating.

13. The method according to claim 11 or 12, wherein the viscosity of the liquid composition is 1000 mPa·s or less.

Images