WO2020235496A1 - Récipient en verre - Google Patents

Récipient en verre Download PDF

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Publication number
WO2020235496A1
WO2020235496A1 PCT/JP2020/019490 JP2020019490W WO2020235496A1 WO 2020235496 A1 WO2020235496 A1 WO 2020235496A1 JP 2020019490 W JP2020019490 W JP 2020019490W WO 2020235496 A1 WO2020235496 A1 WO 2020235496A1
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WIPO (PCT)
Prior art keywords
glass container
glass
cleaning
strain
container
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PCT/JP2020/019490
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English (en)
Japanese (ja)
Inventor
宮本　憲一
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大和特殊硝子株式会社
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Application filed by 大和特殊硝子株式会社 filed Critical 大和特殊硝子株式会社
Priority to JP2020528068A priority Critical patent/JP6768179B1/ja
Publication of WO2020235496A1 publication Critical patent/WO2020235496A1/fr

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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61J—CONTAINERS SPECIALLY ADAPTED FOR MEDICAL OR PHARMACEUTICAL PURPOSES; DEVICES OR METHODS SPECIALLY ADAPTED FOR BRINGING PHARMACEUTICAL PRODUCTS INTO PARTICULAR PHYSICAL OR ADMINISTERING FORMS; DEVICES FOR ADMINISTERING FOOD OR MEDICINES ORALLY; BABY COMFORTERS; DEVICES FOR RECEIVING SPITTLE
    • A61J1/00—Containers specially adapted for medical or pharmaceutical purposes
    • A61J1/05—Containers specially adapted for medical or pharmaceutical purposes for collecting, storing or administering blood, plasma or medical fluids ; Infusion or perfusion containers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D23/00—Details of bottles or jars not otherwise provided for
    • B65D23/02—Linings or internal coatings
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B25/00—Annealing glass products
    • C03B25/02—Annealing glass products in a discontinuous way
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C15/00—Surface treatment of glass, not in the form of fibres or filaments, by etching
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C23/00—Other surface treatment of glass not in the form of fibres or filaments

Definitions

  • the present invention relates to a glass container for storing, for example, pharmaceuticals, foods, cosmetic products, etc., such as ampoules and tube bottles.
  • Glass containers such as tube bottles, vials, ampoules, and syringes for storing pharmaceuticals, foods, cosmetics, etc. are often manufactured by molding glass tubes under heating.
  • a typical molding processing method there is a vertical molding method.
  • a glass tube having a constant diameter and open at both ends is erected vertically, and the lower end portion to be the mouth portion is heated to soften and processed into a desired shape to form the glass tube. Is cut to a desired length, and then the bottom of the glass container is formed to manufacture the target glass container.
  • the remaining glass tube that has been cut is shortened by the amount of one glass container manufactured, and the glass container can be mass-produced by repeating the above operation.
  • This method is performed automatically using a machine, and a vertical molding machine is usually used.
  • a method of reducing the processing deterioration of the glass by keeping the heating temperature during the molding process as low as possible is adopted, or a method of coating the inner surface of the glass after manufacturing the glass container (for example,).
  • (See Patent Document 1) was adopted, or a method of subjecting the inner surface of the glass to a sulfer treatment using ammonium sulfate was adopted.
  • the coating treatment of the glass surface, the sulfer treatment, or the processing of the glass tube by low-temperature heating has caused the process to be complicated and the manufacturing cost of the glass container to be high.
  • Patent Document 2 a glass container manufacturing process for obtaining a glass container by molding a glass tube under heating, a cleaning step for cleaning the inner surface of the glass container obtained in the glass container manufacturing process with a cleaning liquid, and cleaning A method for manufacturing a glass container including a strain-removing step of heating and heating a glass container washed in the step and then cooling the glass container to distort the strain is described.
  • Patent Document 2 describes that when the inner surface of a glass container was washed with a cleaning liquid before performing a strain-removing operation, it was found that a glass container in which alkaline components were hardly eluted from the glass surface of the inner surface could be manufactured. There is. Therefore, Patent Document 2 describes that the cleaning step is an important step for suppressing the elution of the alkaline component from the inner surface of the glass container. However, even if it is simply said that the inner surface of the glass container is cleaned, there are various cleaning means, and a sufficient cleaning effect cannot be obtained unless the cleaning process takes into consideration the surface characteristics of the glass. In this respect, Patent Document 2 does not describe that sufficient studies have been made on the cleaning process.
  • the strain removal step is necessary to remove strain due to thermal history when obtaining a glass container from a glass tube.
  • the strain-removing step is an extremely important step not only for removing strain but also for obtaining a glass container having excellent chemical durability, as will be described later.
  • Patent Document 2 does not describe this point at all.
  • a heat sterilization step after filling the manufactured glass container with a chemical solution or the like, or an alkaline component from the glass surface due to a reaction with the solution during storage. It is desired to provide a glass container in which such elution components do not elute or elute very little.
  • the present invention has been made in view of the problems of such conventional techniques, and an object of the present invention is to provide a glass container having extremely excellent chemical durability.
  • the present inventors have made extensive studies to solve the above problems.
  • the lower end of the vertically erected glass tube is heated with, for example, a gas burner to soften it, and when it is molded into a desired shape, the glass quality is altered by heating, and the volatile components of the glass from the heated glass (for example, Na 2 O, K 2 O, when the B etc. 2 0 3) is generated, these volatile components is increased by the chimney effect space between the open lower end and an upper end of the glass tube, these It was found that an alkaline component is formed by adhering a volatile component to the inner surface of a glass tube, and the adhering alkaline component is eluted from the glass surface after manufacturing a glass container.
  • the present inventors have obtained a glass container from a glass tube by the above-mentioned vertical molding method, and then washed the inner surface of the glass container with a cleaning liquid before performing a strain-removing operation for removing distortion due to thermal history. , It has been found that it is possible to manufacture a glass container in which the elution of alkaline components from the inner glass surface is extremely small.
  • glass generally refers to a substance that is in a glassy state, but usually refers to silicate glass.
  • Alkaline metals (Na, K, Li) and alkaline earth metals (Na, K, Li) and alkaline earth metals (Na, K, Li), which are network-like polymers and are called network-modified bodies or network-modified ions, are contained in the network-like structure of silicon oxide (SiO 2 ) which is a network-forming body.
  • SiO 2 silicon oxide
  • Ca, Mg, Ba etc. are partially contained to form a stable structure. With the exception of crystallized glass, the regularity extends only over very narrow meshes.
  • the network-forming body (ion) includes B, P, Ge, As, V and the like in addition to Si, and there is a borosilicate-based glass in which these oxides and silicon oxide are combined. Further, as the ions of the intermediate oxide that play a role of both network formation and network modification, there are Al, Ti, Zr and the like. There are many types of glass, more than 700. Among them, commonly used glass can be classified into the following five categories. Quartz glass, soda-lime glass, borosilicate glass, lead glass, and fluoride glass.
  • borosilicate glass has a network in which boric acid and silicic acid are copolymerized, and vitrification is facilitated even if the amount of alkali metal is small as compared with the case of silicate alone.
  • Low alkaline glass borosilicate has a small expansion coefficient of 3 ⁇ 10-6 / K, a Mohs hardness of about 7, is relatively hard, and has high corrosion resistance, so it is suitable for physics and chemistry instruments, medical instruments, chemical containers, etc. is there.
  • Borosilicate glass is preferable as the material of the glass container of the present invention.
  • the surface of glass is originally hydrophilic, rich in chemical activity, and has a strong ability to adsorb water and dirt by intermolecular suction force such as hydrogen bond.
  • it since it is an electrically defective conductor, it has a strong ability to adsorb dirt.
  • the surface of the glass reacts with the external atmosphere, and the deterioration accompanied by the composition change of the surface layer occurs. As a result, the transparency of the glass is impaired. This phenomenon has long been known as the "burnt" of glass. Therefore, it can be said that it is not easy to obtain a glass container having a desired cleanliness by cleaning without adversely affecting the glass substrate.
  • an acid or an alkali can be typically used as the cleaning liquid for such a glass container.
  • Table 2 below shows the weight loss (95 ° C., 24 hours (mg / cm 2 )) of soda-lime glass, borosilicate glass, and quartz glass having the glass composition (% by weight) shown in Table 1 due to acid and alkali. Shown.
  • borosilicate glass has the largest weight loss with respect to 5% sodium hydroxide. This is because silica, which is the main component, becomes sodium silicate and elutes.
  • the rate of elution into alkali is directly proportional to time, about doubling as the pH rises by 1, and doubling as the temperature rises by 10 ° C. Therefore, at 100 ° C., the elution rate is about 250 times that of room temperature.
  • what elutes in 5% hydrochloric acid is mainly the alkaline and alkaline earth components contained in the glass, and the silica component is hardly dissolved. Therefore, unlike elution with sodium hydroxide, the amount of elution is small.
  • the elution rate to acid is proportional to the square root of time and is much slower than the elution rate to alkali. Even if the pH drops by 1, the elution rate is only about 1.2 times. It can be seen from Table 2 that acid erosion is slower than that of alkaline. Further, it is known that the amount of elution into an organic acid is smaller than that of hydrochloric acid and an organic acid. Therefore, in the present invention, it is preferable to use an organic acid whose glass component is relatively slowly eroded as the cleaning liquid.
  • a hydroxyl group typified by a silanol group (SiOH) is present on the glass surface, and it is considered that this hydroxyl group acts as an adsorption base point of the substance. Therefore, if the time from the cleaning step of cleaning the inner surface of the glass container with the cleaning liquid to the subsequent strain-removing step is long, the surface characteristics of the glass may change. That is, the time between the cleaning step and the strain removing step is preferably 30 minutes or less. Further, in order to improve the cleaning effect, the spray pressure of the cleaning liquid is preferably 0.05 MPa or more.
  • FIG. 6A is a schematic view showing an example of a cross section of borosilicate glass before being heated to a temperature equal to or higher than the glass transition point for a long time.
  • the constituent components of the glass are homogeneous, and the network structure of the network-forming body is shown. It has a stable structure with a network modifier partially contained in it.
  • FIG. 6A is a schematic view showing an example of a cross section of borosilicate glass before being heated to a temperature equal to or higher than the glass transition point for a long time.
  • the constituent components of the glass are homogeneous, and the network structure of the network-forming body is shown. It has a stable structure with a network modifier partially contained in it.
  • FIG. 6B is a schematic view showing an example of a cross section of the borosilicate glass in a phase-separated state.
  • the portion indicated by the thick black line indicates the polar phase (Na 2 O, B 2 O 3, etc.), and the region excluding this polar phase is the silica phase. Glass separated into a two-phase structure has low chemical durability.
  • the present inventor has repeatedly studied the conditions that make it difficult for phase separation to occur.
  • the glass container washed in the washing step is heated and then cooled to remove strain. It was found that the heating temperature of the strain removing step is extremely important.
  • the present inventor properly controls the heating temperature in the strain-removing step to ensure that the temperature is homogeneous and contains a large amount of chemically stable SiO 2 without generating phase separation and free radicals. It was found that a film was formed on the inner surface of the glass container.
  • the borosilicate glass container having extremely excellent chemical durability of the present invention can be manufactured, for example, as follows.
  • a glass container made of borosilicate glass is molded under heating to obtain a glass container, and the inner surface of the glass container obtained in the glass container manufacturing process is coated with water, an aqueous solution of acid, an aqueous solution of a surfactant, or an aqueous solution of a surfactant.
  • a method for manufacturing a glass container which includes a cleaning step of cleaning with a cleaning solution consisting of an aqueous solution of an acid to which a surfactant is added, and a strain-removing step of heating and heating the glass container washed in the cleaning step and then cooling to distort the strain.
  • the temperature of the glass container in the cleaning step is 30 to 150 ° C.
  • the cleaning time with the cleaning liquid having a spray pressure of 0.05 MPa or more is 10 to 15 seconds
  • the time between the cleaning step and the strain removing step is 30 minutes or less.
  • the borosilicate glass container of the present invention having extremely excellent chemical durability is composed of the following inventions.
  • a borosilicate glass container characterized in that the oxide film formed on the inner surface is an oxide film mainly composed of SiO 2 .
  • the inner surface means a detection depth (about 1 to 10 nm) in X-ray photoelectron spectroscopy (XPS). This is because the component composition of the inner surface layer of the glass container is decisively important for enhancing the chemical durability.
  • the SiO 2 in the oxide film formed on the inner surface is preferably 80 to 92% by weight. If the SiO 2 coating is less than 80% by weight, sufficient chemical durability cannot be obtained. More preferably, the SiO 2 coating is 85% by weight or more.
  • the oxide film other than SiO 2 formed on the inner surface is a film of one or more oxides selected from Na 2 O, K 2 O, CaO, BaO, B 2 O 3 and Al 2 O 3. Is preferable. (5) It is preferable that no phase separation is generated on the inner surface of the borosilicate glass container and no free radicals are present.
  • the main body of the container has the characteristics of borosilicate glass, but the inner surface of the container has a siloxane structure in which silicon and oxygen are bonded by a siloxane bond which is a strong covalent bond, such as alkali metal or alkaline earth metal. Is preferably fixed by an ionic bond in a state where the oxygen radical freed in the siloxane structure is completely neutralized. (See FIG. 7 (c)) (6)
  • the borosilicate glass container is preferably for storing pharmaceuticals, foods or cosmetics.
  • a glass container made of borosilicate glass is molded under heating to obtain a glass container, and the inner surface of the glass container obtained in the glass container manufacturing process is coated with water, an aqueous solution of acid, and surface activity.
  • Manufactured by a manufacturing method including a cleaning step of cleaning with a cleaning solution consisting of an aqueous agent solution or an aqueous solution of an acid to which a surfactant is added, and a strain-removing step of heating and heating the glass container washed in the cleaning step and then cooling to distort the strain.
  • the temperature of the glass container in the cleaning step is 30 to 150 ° C.
  • the cleaning time with a cleaning liquid having a spray pressure of 0.05 MPa or more is 10 to 15 seconds
  • the period between the cleaning step and the strain removing step is set.
  • the borosilicate glass container of the present invention has no phase separation on the inner surface, no free radicals, no flakes or delamination, and silicon and oxygen existing on the inner surface are bonded by a siloxane bond. Therefore, the amount of the alkaline component eluted from the inner surface of the glass is extremely small, deterioration of the chemicals and the like as the contents is suppressed, and a predetermined quality can be reliably maintained.
  • FIG. 1A is a schematic view showing a state in which an alkaline eluent component is attached to the inner surface of the glass container
  • FIG. 1B is a glass container after removing the alkaline eluent component adhering to the inner surface.
  • the schematic diagram shown, FIG. 1 (c), is a schematic diagram showing a state after heating the glass container having the inner surface shown in FIG. 1 (b).
  • FIG. 2 is a schematic view showing an example of the method for manufacturing the borosilicate glass container of the present invention for each small step.
  • FIG. 3 is a schematic view showing an example of a manufacturing apparatus preferably used in the method for manufacturing a borosilicate glass container of the present invention.
  • FIG. 4 is a schematic configuration diagram showing a state in which a vial is washed with a washing machine.
  • FIG. 5A is a schematic cross-sectional view of an embodiment of the borosilicate glass container of the present invention
  • FIG. 5B is a schematic cross-sectional view of a glass container of a comparative example.
  • FIG. 6A is a schematic view showing an example of a cross section of the borosilicate glass before heating to a temperature equal to or higher than the glass transition point for a long time
  • FIG. 6B is an example of a cross section of the borosilicate glass in a phase-separated state. It is a schematic diagram which shows.
  • FIG. 6A is a schematic view showing an example of a cross section of the borosilicate glass before heating to a temperature equal to or higher than the glass transition point for a long time
  • FIG. 6B is an example of a cross section of the borosilicate glass in a phase-separated
  • FIG. 7 (a) is a diagram schematically showing the structure of commonly used silica-containing glass in a planar state
  • FIG. 7 (b) shows the glass shown in FIG. 7 (a) subjected to sulfer treatment.
  • FIG. 7 (c) is a diagram schematically showing the structure of the subsequent glass in a planar state
  • FIG. 7 (c) is a diagram schematically showing the structure of the inner surface of the borosilicate glass container of the present invention in a planar state.
  • FIG. 8 is a diagram comparing the amount of Na eluted with respect to the heating temperature in the strain removing step in the case of manufacturing the borosilicate glass container of the present invention.
  • the glass tube used as the material of the borosilicate glass container of the present invention is not particularly limited, but for example, a glass tube made of borosilicate glass is preferable.
  • the cross section of the glass tube is usually a perfect circle, but other shapes such as an elliptical shape may be used.
  • the diameter of the glass tube is not particularly limited, but is usually about 10 to 100 mm.
  • the length of the glass tube is not particularly limited, but usually it may be about 1 to 5 m.
  • the glass tube may be colorless and transparent, or may be colored, for example, brown.
  • the borosilicate glass container of the present invention can also be manufactured according to the method.
  • a glass tube having a constant diameter and open at both ends is erected vertically, and the lower end is inserted into a vertical molding machine usually equipped with a heating means, for example, with a gas burner having a temperature of about 1500 to 1800 ° C. It is heated to form a desired tube bottle shape, and then the molded product and the glass tube extending above the rest are separated under heating to form a glass bottle and a bottom. Next, the lower end of the separated glass tube is molded so that the cross section becomes the original perfect circle.
  • the temperature of the glass container after the molding process is usually about 300 to 400 ° C.
  • glass containers can be mass-produced.
  • the glass quality is usually altered by heating, and the volatile components of the glass (for example, Na 2 O and K 2 O) form a chimney in the space between the open lower end and the upper end of the glass tube. It is considered that it rises due to the effect and adheres to the inner surface of the glass tube to form an alkaline evaporative component.
  • the present invention removes or reduces the alkaline elution component adhering to the inner surface of the glass tube by going through the glass container cleaning step described in detail below after the glass container manufacturing step, and further, the cleaning step.
  • a strain-removing step within 30 minutes and subjecting the glass container to a strain-removing treatment controlled to an appropriate heating temperature, no phase separation is generated on the inner surface and free radicals are not present. It is possible to provide a borosilicate glass container in which silicon and oxygen existing on the inner surface are bonded by a siloxane bond without flakes or delamination.
  • a cleaning solution such as water, an aqueous solution of an acid, an aqueous solution containing a surfactant, or an aqueous solution of an acid to which a surfactant is added is applied to the inner surface of the glass container obtained in the process of manufacturing the glass container. It is preferable to use and wash.
  • the glass container If necessary, cool the glass container at about 300 to 400 ° C. after the molding process to, for example, an atmospheric temperature, and preferably wash the glass container at 150 ° C. or lower with a cleaning liquid. It is considered that the higher the temperature of the glass container, the higher the effect of removing or reducing the eluent component adhering to the inner surface of the glass container, but if the cleaning liquid is brought into contact with the high temperature glass container, the glass container may be damaged. Further, the lower limit temperature of the glass container at the time of cleaning is preferably 30 ° C. or higher in consideration of cleaning efficiency. Further, the washing time is preferably about 10 to 15 seconds because the washing is insufficient if it is less than 10 seconds and the productivity is lowered if it exceeds 15 seconds.
  • the temperature of the cleaning liquid in the cleaning step is not limited, but it is preferable to use a cleaning liquid of about 30 to 100 ° C, and more preferably to use a cleaning liquid of about 40 to 70 ° C. Within this range, a glass container having extremely excellent chemical durability, which is the object of the present invention, can be obtained.
  • the cleaning liquid water, an aqueous solution of acid, an aqueous solution containing a surfactant or an aqueous solution of an acid to which a surfactant is added are preferably used, and the solubility of the alkaline eluent component adhering to the inner surface of the glass container is high.
  • an aqueous acid solution or an acid aqueous solution to which a surfactant is added is more preferable.
  • Acids used in aqueous acid solutions are roughly classified into organic acids and inorganic acids.
  • organic acids include formic acid, acetic acid, oxalic acid, phthalic acid, citric acid and the like
  • inorganic acids include hydrochloric acid, sulfuric acid, nitric acid and the like. These acids may be used alone or in combination of two or more.
  • organic acids are preferable, and citric acid and oxalic acid are preferably used from the viewpoint of cleaning effect and handleability.
  • the organic acid is preferable in that the glass surface is kept very clean because it is burnt and decomposed into carbon dioxide and water in the strain removing step even if a residue is generated, and citric acid is particularly preferably used.
  • the acid concentration is usually about 0.005 to 1.0 mol / L, preferably about 0.005 to 1.0 mol / L. Is about 0.01 to 0.1 mol / L.
  • the surfactant used in the aqueous solution containing a surfactant or the aqueous solution of an acid to which a surfactant is added in the above cleaning liquid is not particularly limited, but a preferable surfactant is a nonionic surfactant. Agents can be mentioned.
  • Nonionic surfactants are roughly classified into polyethylene glycol type and polyhydric alcohol type, and the polyethylene glycol type includes higher alcohols, fatty acids, fats and oils, ethylene oxide adducts of polypropylene glycol or alkylphenol, and polyhydric alcohol fatty acid esters.
  • Examples thereof include ethylene oxide adducts of higher alkylamines and fatty acid amides, and examples of polyvalent alcohol types include fatty acid esters of glycerol, pentaerythritol, sorbitol or sucrose, and alkyl ethers of polyhydric alcohols.
  • concentration of the surfactant may be appropriately selected within a range that does not interfere with the object and effect of the present invention.
  • the glass container is inserted into an appropriate jig or suspended from the mouth to the bottom of the glass container, for example, from a nozzle.
  • the cleaning solution is usually blown up and sprayed under pressure. It is preferable to increase the spray pressure of the cleaning liquid by allowing the cleaning liquid spray port of the nozzle to discharge compressed air at the same time as the cleaning liquid (also referred to as jet spray cleaning).
  • the spray pressure of the cleaning liquid is preferably 0.05 MPa or more. Even if the spray pressure is too high, the cleaning effect is saturated, so the upper limit of the spray pressure is about 0.5 MPa.
  • the cleaning process is completed after cleaning with the cleaning liquid, a rinsing step with clean water, and a sufficient draining step by blowing air, for example.
  • the inner surface of the glass container may be cleaned by ultrasonic cleaning with the above cleaning liquid.
  • ultrasonic cleaning usually, not only the inner surface but the entire glass container is cleaned using the above-mentioned cleaning liquid, and rinse cleaning is performed. Whether or not to adopt ultrasonic cleaning is determined in consideration of the layout of the entire production line such as a vertical molding machine, a cleaning machine, and a strain-removing furnace, which will be described later.
  • the glass container washed in the cleaning step is fed to a strain-removing furnace controlled so that the target maximum atmospheric temperature is 685 to 700 ° C. It is carried out by heating and raising the temperature so as to secure a time of 1 minute from 685 ° C. to 710 ° C. and then cooling.
  • the entire time of the strain-removing treatment which consists of heating and heating the glass container at about 30 to 80 ° C. after cleaning to about 300 ° C., that is, the time spent in the strain-removing furnace ( Distortion time) is 3 to 40 minutes.
  • the borosilicate glass container of the present invention is characterized by an inner surface structure, and the process for obtaining a borosilicate glass container having an inner surface having a characteristic structure can be explained in an easy-to-understand manner as follows.
  • FIG. 1A is a schematic view showing a state in which the alkaline eluent component 3 is attached to the inner surface 2 of the glass tube 1.
  • Residual strain can be removed by heating the glass container after removing the alkaline eluent component. Further, as shown in FIG. 1C, the flatness of the inner surface 5 of the glass container 4 is also improved by the diffusion of atoms. However, depending on the heating conditions of the glass container, a phase separation state as shown in FIG. 6B is generated. Therefore, the heating conditions of the glass container are very important so as not to generate a phase separation state.
  • Borosilicate glass may undergo phase separation when heated to a temperature above the glass transition point for a long time. If the heating temperature is too high, the glass container will be deformed or wrinkled. Therefore, the selection of heating conditions is extremely important.
  • the time when the actual temperature of the glass container is 685 to 710 ° C. is controlled to be secured for 1 minute.
  • the glass container of the present invention can be manufactured. If the time at 685 to 710 ° C. is 1 minute, no phase separation is generated on the inner surface, no free radicals are present, silicon and oxygen existing on the inner surface are bonded by a siloxane bond, and the glass. It is possible to produce a glass container having a substantially smooth inner and outer surfaces by removing residual strain based on the thermal history without deforming or wrinkling the surface.
  • the temperature of the glass container itself exceeds 700 ° C for a long time (10 minutes or more), the glass surface may be deformed or wrinkles may occur.
  • the maximum atmospheric temperature of the strain-removing furnace is controlled below 650 ° C., the temperature of the glass container itself tends to fall below 600 ° C., and vitrification may be insufficient.
  • the present invention provides a glass container in which the amount of elution of alkaline components and the like is extremely small.
  • Pharmaceuticals, foods, and cosmetics stored in the manufactured glass container may have any shape.
  • it may be solid, liquid, or gaseous, and taking pharmaceuticals as an example, any shape and properties such as tablets, liquids, granules, powders, powders, ointments, sprays, powders, gels, etc. It may be.
  • foods and cosmetics may have any shape and properties.
  • the conductivity of the contained content liquid is extremely low.
  • a container for purified water Suitable as a container for sterile purified water or a container for injection water.
  • the 16th revision of the Japanese Pharmacopoeia, page 731 describes the conductivity of purified water in a container, sterilized purified water in a container, or water for injection in a container in the case of a container with an internal volume of 10 mL or less (25 ° C).
  • Example 1 A vial having a capacity of 2 mL was obtained by the following method using a glass tube made of borosilicate glass having an outer diameter of 16 mm and a length of 1 m and 60 cm. First, as shown in FIG. 2 (1), the glass tube 11 is inserted into the vertical molding machine 12 of the tube bottle with the end end facing up, and the lower end is heated with a gas burner to soften the glass and of the bottle. It was molded so that it had the shape of the opening.
  • the process order will be described in more detail based on FIG.
  • the lower end of the glass tube 11 was heated with a fishtail burner 13 at 1200 to 2000 ° C.
  • the shoulder portion was formed using the roller 14 and the plunger 15.
  • Heating was performed with a point burner 16 at 1200 to 2000 ° C.
  • the mouth portion was formed by the roller 14 and the plunger 15.
  • the bottle height was determined using the total height plate 17.
  • Cutting was performed using a cut burner 18 having a temperature of 1200 to 2000 ° C.
  • the bottom was homogenized using a point burner 16.
  • Air 19 was blown in, and the bottom molding of the vial 20 was completed using the point burner 16 at 1200 to 2000 ° C.
  • the vial 20 thus obtained is conveyed to the washing machine 22 in a state of being inserted into a jig placed on the net conveyor 21 (FIG. 3), and allowed to cool under a large temperature ((in FIG. 2). 9) Cooling step), the inner surface of the vial at about 30 ° C. was blown up and washed with 10 mL of a cleaning solution (citrate) at 25 ° C. for 10 seconds (spray pressure of citric acid 0.2 MPa) using a syringe (Fig. 2). (10) Washing step in FIG. 2), and after performing blow-up washing (0.2 MPa) with purified water for 10 seconds, air 19 was blown to sufficiently drain the water ((11) Draining step in FIG. 2). Although details are omitted in FIG. 3, the vial 20 can be conveyed to the washing machine 22 and the strain-removing furnace 24 by the net conveyor 21.
  • FIG. 4 is a schematic configuration diagram showing a state in which the vial 20 is washed by the washing machine 22.
  • 31 is a manifold
  • 32 is a nozzle
  • 33 is a needle valve
  • 34 is a flow meter
  • 35 is a pressure gauge
  • 36 is a pump
  • 37 is a storage tank for cleaning liquid.
  • strain removal step the target maximum atmospheric temperature in the strain removal furnace is controlled to be 670 ° C, and the strain is removed for 25 minutes (the time when the atmospheric temperature is 670 ° C or higher is 108 seconds, and the actual temperature of the glass container is 108 seconds.
  • the inlet side and the outlet side of the strain-removing furnace 24 are open, the inlet can be set to, for example, 670 to 700 ° C., even if the atmospheric temperature in the strain-removing furnace sensed by the thermocouple provided in the strain-removing furnace is set to 670 to 700 ° C. The side and outlet side will be lower than this temperature.
  • the ambient temperature in the strain-removing furnace was measured with thermocouples installed at three locations, and the burner heater 23 was turned on and off so that the temperature measured with one of the thermocouples became the target temperature. Furthermore, the actual temperature of the glass container was measured by a thermocouple fused to the glass container.
  • a glass container made of borosilicate glass of Comparative Example 1 was obtained through the same steps as in Example 1 except that washing with citric acid and purified water described in paragraph 0055 was not performed.
  • Table 3 below shows the atomic number ratios of the inner surfaces of the glass container of Example 1 and the glass container of Comparative Example 1 measured by X-ray photoelectron spectroscopy, and Table 4 below shows the base material boro.
  • the composition (% by weight) of the silicate glass and the ratio of the oxide film formed on the inner surface of the glass container obtained based on the atomic number ratio in Table 3 for the glass container of Example 1 and the glass container of Comparative Example 1. (% by weight) is shown.
  • X-ray photoelectron spectroscopy is an element on the sample surface that observes the kinetic energy of photoelectrons emitted from the sample surface into a vacuum by the photoelectric effect by irradiating the sample surface with soft X-rays under ultra-high vacuum. It is an analytical method that can obtain information on the composition and chemical state. Specifically, the necessary information can be obtained by the following equation.
  • E b hv-E kin- ⁇
  • E b the binding energy of bound electrons
  • hv the energy of soft X-rays
  • E kin the kinetic energy of photoelectrons
  • ⁇ the work function of the spectroscope
  • Example 2 After injecting 0.7 mL of purified water 40a into the glass container 40 of Example 1 made of borosilicate glass obtained by allowing to cool to room temperature in Example 1 above. , The autoclave treatment was carried out at 121 ° C. for 60 minutes. 41 is a rubber stopper. Further, a comparison of a cylindrical capacity of 2 mL as shown in FIG. 5 (b) obtained from a glass tube made of borosilicate glass having an outer diameter of 16 mm and a length of 1 m 60 cm in the same manner as described in paragraphs 0053 and 0054. 0.7 mL of purified water 50a was also injected into the glass container 50 made of borosilicate glass of Example 2.
  • Purified water is injected into a glass container, for example, in order to estimate how long the inner surface of the glass container deteriorates when a drug (for example, a liquid agent, a lyophilized product, a powder agent) is stored in the glass container. It has the meaning of an accelerated test, 1 hour after the injection of purified water corresponds to 1.6 years, 4 hours after the injection of purified water corresponds to 8 years, and 8 hours after the injection of purified water. Is equivalent to 13 years.
  • a drug for example, a liquid agent, a lyophilized product, a powder agent
  • the borosilicate glass container of Example 1 of the present invention in which an oxide film mainly composed of SiO 2 is formed on the inner surface has an extremely small amount of alkaline component eluted and has excellent chemical durability. It turns out to be extremely good. Further, it was confirmed by an electron microscope that no phase separation was generated on the inner surface of the glass container of the example, no free radicals were present, and there were no flakes or delamination.
  • FIG. 7A is a diagram schematically showing the structure of commonly used silica-containing glass in a planar state.
  • the ideal glass is 100% silica glass, which is generally called quartz glass, but 100% silica glass has a very high melting point of 2000 ° C. or higher and is difficult to mold. Therefore, in order to improve this, glass containing silica, which is generally used, is formed by adding an alkali metal such as sodium or potassium to break the siloxane bond of silica to lower the melting point and mold it. I'm trying to make it easier. Furthermore, in order to stably retain the added alkali metal in the glass, elements such as calcium and aluminum are added.
  • FIG. 7A is a diagram schematically showing the structure of commonly used silica-containing glass in a planar state. In FIG.
  • 100 is silicon, 101 is oxygen, 102a is an alkali metal, 102b is an alkaline earth metal, 103 is a covalent bond, and 104 is an ionic bond. That is, the silicon 100 and the oxygen 101 are connected by a covalent bond 103, and the alkali metal 102a or the alkaline earth metal 102b and the oxygen 101 are connected by an ionic bond 104. However, not all alkali metals 102a or alkaline earth metals 102b are bound to oxygen, and there are also free alkali metals 102a or alkaline earth metals 102b.
  • Silica which is the main component of glass, exhibits a strong siloxane bond in which silicon and oxygen are bonded by a covalent bond in which the outermost electrons of the atom are shared with each other.
  • the alkali metal breaks this covalent bond and exists in the state of an ionic bond in which the alkali metal neutralizes the free radical of oxygen.
  • the ionic bond has a weaker bond strength than the covalent bond, and as described above, in the glass container, the added alkali metal or alkaline earth metal elutes into the content liquid in the container over time. To do.
  • the amount of alkaline elution of glass containers used for pharmaceuticals is strictly specified by the Japanese Pharmacopoeia because the eluted alkali metals and the like affect the drug components.
  • FIG. 7 (b) is a diagram schematically showing the structure of the glass shown in FIG. 7 (a) after being subjected to the sulfer treatment in a planar state.
  • the sulfer treatment produces many free radicals 105 and causes many deficiencies in the siloxane bond.
  • the generation of free radicals 105 causes problems such as flakes (delamination) in which the physical strength of the glass surface deteriorates and the surface of the glass container peels off.
  • the method disclosed in the previous application is as follows. That is, the vials 20 having a capacity of 2 mL obtained as described in paragraphs 0053 and 0054 are subjected to the cleaning treatment as described in paragraph 0055 with two cleaning times of 10 seconds and 3 seconds selected. And, for those that were not cleaned, the maximum atmospheric temperature in the strain-removing furnace was controlled to be 670 ° C, and the strain was removed for 25 minutes (the time when the atmospheric temperature was 670 ° C or higher was 90 seconds, actually The temperature of the glass container was 670 to 700 ° C.), and the mixture was allowed to cool to room temperature.
  • the washing time is 10 seconds
  • the amount of eluted Na is 1/27 to 1/31 as compared with the case without washing.
  • the strain removal treatment (atmosphere temperature is 670 ° C.) is controlled for 25 minutes by controlling the target maximum atmospheric temperature in the strain relief furnace to be 670 ° C.
  • the above time is 108 seconds
  • the actual temperature of the glass container is 670 to 700 ° C.
  • the actual temperature of the glass container is 690 to 700 ° C. for 1 minute) with the glass container of Example 1.
  • Table 3 showing the atomic number ratio of the inner surface of the glass container of the comparative example in which the same heat treatment as in Example 1 was performed except that the cleaning treatment was not performed, and the table showing the weight ratio (% by weight) of the oxide film. 4 shows a result significantly different from that in Table 6. That is, in Table 3, Na has been shown to be reduced by 27% by performing the cleaning process, in Table 4, Na 2 O is to be decreased by 32% by performing the cleaning process shown Has been done. By comparing Tables 3 and 4 with Table 6, the temperature difference between "670 to 700 ° C.” disclosed in the previous application and "690 to 700 ° C.” in Example 1 of the present application is extremely large in the surface structure of the glass. It can be seen that it had a great influence on.
  • the difference between Tables 3 and 4 and Table 6 is considered to be derived from the actual temperature of the glass container after the cleaning treatment. That is, the siloxane bond between silicon and oxygen on the inner surface of the glass is strengthened by performing the heat treatment in which the actual temperature of the glass container is 690 to 700 ° C. for 1 minute, and the inner surface of free sodium inside the glass container is strengthened. It seems that the diffusion to the glass was suppressed.
  • Example 2 Therefore, in order to investigate the effect of the heating temperature on the structure of the glass, a glass tube made of borosilicate glass having a diameter of 16 mm and a length of 1 m 60 cm was used, and a vial having a capacity of 2 mL was obtained by the same method as in Example 1. .. Then, this vial was washed by the same method as in Example 1 except that the spray pressure of citric acid was set to 0.15 MPa or 0.10 MPa.
  • Strain elimination treatment for 25 minutes (the time when the atmospheric temperature is 655 ° C or higher is 180 seconds, the actual temperature of the glass container is 655 to 670 ° C, and the actual temperature of the glass container is 655 to 670 ° C.
  • the actual temperature of the glass container was 685 to 700 ° C.
  • the actual temperature of the glass container was 685 to 700 ° C. for 60 seconds)
  • the target in the strain-removing furnace In 180 seconds, the actual temperature of the glass container was 685 to 700 ° C., and the actual temperature of the glass container was 685 to 700 ° C. for 60 seconds), and 4) the target in the strain-removing furnace.
  • Distortion treatment for 25 minutes by controlling the maximum atmospheric temperature to 700 ° C (the time when the atmospheric temperature is 700 ° C or higher is 180 seconds, the actual temperature of the glass container is 700 to 710 ° C, the actual glass container.
  • the temperature of the glass container was 700 to 710 ° C. for 60 seconds), and 5) the target maximum atmospheric temperature in the strain-removing furnace was controlled to be 715 ° C for 25 minutes of strain-removing treatment (atmospheric temperature).
  • the time when the temperature is 715 ° C. or higher is 180 seconds, the actual temperature of the glass container is 715 to 730 ° C., and the actual temperature of the glass container is 715 to 730 ° C. for 60 seconds).
  • FIG. 8 is a diagram in which the heating temperature (° C.) is on the horizontal axis and the amount of Na eluted (ppm) is on the vertical axis based on the numerical values shown in Tables 7 and 8.
  • the heating temperature (° C.) on the horizontal axis of FIG. 8 indicates the target maximum atmospheric temperature (° C.) in the strain-removing furnace described in paragraph 0072.
  • the bar graph shown by the diagonal line on the left side shows the case where the citric acid spray pressure is 0.15 MPa
  • the bar graph shown by the dotted line on the right side shows the citric acid spray pressure. This is the case of 0.10 MPa.
  • FIG. 8 shows the case of 0.10 MPa.
  • the melting temperature of pure silica (SiO 2 ) represented by quartz is 2000 ° C. or higher, and it is extremely difficult to mold it into a glass container or the like. Therefore, in the production of practical glass, a certain amount of alkali metal such as sodium and potassium is added to cut the siloxane structure in silica everywhere to lower the melting temperature, and other materials such as boron, aluminum, calcium and barium. Together with the metal component, it is designed to impart temperature-viscosity characteristics that facilitate the molding of glass such as blow molding.
  • the behavior of the metal added for the production of practical glass as described above will be described below.
  • the added metal such as sodium cuts the siloxane structure everywhere and stays in the cut part in the state of ions to maintain the stability of the glass structure, but the ionic bond is as strong as the siloxane bond. Since it is not a bond, the movement of metals such as sodium becomes active at temperatures above the glass transition point.
  • the borosilicate glass used in the glass container of the present invention has excellent heat resistance and chemical resistance.
  • the molten glass surface is rich in silica.
  • a phenomenon called phase separation occurs that separates into phases of other metal oxides (oxides such as boron, sodium, and aluminum).
  • Metal oxides other than silica are concentrated and deposited on the glass surface where the phase separation phenomenon has occurred, which leads to deterioration of the glass surface.
  • a porous silicon dioxide (silica) phase exists on the glass surface where processing deterioration has occurred, and sodium, other metals, and their oxides are unevenly distributed in an island shape.
  • the glass container is heat-treated at 685 ° C to 710 ° C to vitrify the porous silica phase (siloxane bond between silicon and oxygen) and remain.
  • a metal such as sodium in the glass surface layer and immobilizing it in the siloxane structure of the surface layer portion in an ionic bond state, it is possible to obtain a structure having extremely little elution and high chemical durability.
  • the temperature is lower than 630 ° C to 650 ° C, the smoothing of the porous glass surface is insufficient, so that the metal such as sodium on the surface of the remaining pores is completely immobilized in the siloxane structure.
  • the temperature is higher than 730 ° C to 750 ° C, it is considered that the movement of metal ions from the deep layer of the glass container becomes active and the amount of alkali elution increases.
  • aluminum and boron which are other constituents of the borosilicate glass container of the present invention, are easily volatilized by heating during molding, like alkali metals and alkaline earth metals, so a considerable amount of aluminum and boron can be used. It adheres to and accumulates on the inner surface of glass during container molding. Aluminum and boron deposited on the inner surface of the glass are removed by a cleaning process under appropriate conditions, but aluminum and boron remaining in the container without being removed are subjected to a strain-removing process under appropriate conditions to form a glass network. It is firmly fixed in the glass structure.
  • the inner surface of the borosilicate glass container of the present invention is rich in silicic acid component and has a surface structure similar to that of quartz glass. Therefore, the borosilicate glass container of the present invention has no flakes or delamination on the surface, and the amount of alkaline component eluted from the glass surface is extremely small.
  • Example 3 Therefore, in order to confirm that the inner surface of the borosilicate glass container of the present invention does not generate phase separation and free radicals, and that silicon and oxygen existing on the inner surface are connected by a siloxane bond, further. , The following experiment was carried out.
  • the borosilicate glass container of the present invention is often used for storing medicines, and the medicines contain many chemical substances.
  • the amine compound has a high affinity for the borosilicate glass component and easily reacts with free radicals on the inner surface of the glass container.
  • a glass tube made of borosilicate glass having a diameter of 16 mm and a length of 1 m 60 cm was used, and a vial having a capacity of 2 mL was obtained by the same method as in Example 1. .. Then, this vial was washed by the same method as in Example 1 except that the spray pressure of citric acid was set to 0.2 MPa.
  • the target maximum atmospheric temperature in the strain removal furnace is controlled to be 685 ° C, and the strain is removed for 25 minutes (the time when the atmospheric temperature is 685 ° C or higher is 180 seconds, and the actual temperature of the glass container is 180 seconds. Is 685 to 700 ° C., and the actual temperature of the glass container is 685 to 700 ° C. for 60 seconds).
  • the glass container of Example 3-1 and Example 3-2 of the present invention and citric acid.
  • the glass containers of Comparative Example 3-1 and Comparative Example 3-2 were subjected to the same treatment except that they were not washed with purified water and drained, and these glass containers were allowed to cool to room temperature.
  • a constant concentration of low molecular weight (molecular weight is 100 or less) amine solution is injected into each glass container, and immediately after the injection of the low molecular weight amine solution (within 5 minutes), 1 week, 1 month, and 3 months later.
  • the amine concentration (%) in the glass container was measured with an infrared spectrophotometer.
  • Table 9 for low molecular weight amine solution A
  • Table 10 for low molecular weight amine solution B
  • the low amine concentration of the amine solution in the container measured by the infrared spectrophotometer means that the amine in the solution decreased due to the combination of free radicals abundant on the inner surface of the container and the amine in the solution. Is shown.
  • the high amine concentration of the amine solution in the container measured by the infrared spectrophotometer means that the amine in the solution is preserved because there are no free radicals on the inner surface of the glass container, and at the time of the first injection. Indicates that the state of is maintained or is very close to the state at the time of the first injection.
  • the borosilicate glass container of the present invention has an amine concentration of 100% in the amine solution immediately after injection of the low molecular weight amine solution (within 5 minutes). It can be seen that there are no free radicals on the inner surface of the borosilicate glass container.
  • Example 3 No phase separation was observed on the inner surface of the body of the glass containers of -1 and 3-2, but on the inner surface of the body of the glass containers of Comparative Examples 3-1 and 3-2, as shown in FIG. 6 (b). It was confirmed that a good phase was seen.
  • a glass container suitable as a container for storing pharmaceuticals, foods or cosmetics.

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Abstract

L'invention concerne un récipient en verre ayant une excellente durabilité chimique. Dans le récipient en verre, un film de revêtement d'oxyde formé sur sa surface interne comprend du SiO2 en tant que composant principal.
PCT/JP2020/019490 2019-05-17 2020-05-15 Récipient en verre WO2020235496A1 (fr)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02153846A (ja) * 1988-12-07 1990-06-13 Murase Glass Kk 低アルカリガラス容器の製法
JPH0437632A (ja) * 1990-05-30 1992-02-07 Nippon Glass Sangyo Kk ガラスアンプルまたは管瓶の製造方法
JPH0741335A (ja) * 1993-07-30 1995-02-10 Nippon Sheet Glass Co Ltd ガラス容器の処理方法
JPH10258110A (ja) * 1997-02-18 1998-09-29 Carl Zeiss:Fa 医療目的、特に薬剤または診断用の生成物の貯蔵のために滅菌し得るガラス容器
JP2003128439A (ja) * 2001-10-17 2003-05-08 Nippon Electric Glass Co Ltd ガラス容器及びその処理方法
JP2005289711A (ja) * 2004-03-31 2005-10-20 Nippon Glass Sangyo Kk アンプルまたはバイアル、およびその製造方法
WO2009116300A1 (fr) * 2008-03-21 2009-09-24 大和特殊硝子株式会社 Procédé de fabrication de récipients en verre à faible teneur alcaline

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02153846A (ja) * 1988-12-07 1990-06-13 Murase Glass Kk 低アルカリガラス容器の製法
JPH0437632A (ja) * 1990-05-30 1992-02-07 Nippon Glass Sangyo Kk ガラスアンプルまたは管瓶の製造方法
JPH0741335A (ja) * 1993-07-30 1995-02-10 Nippon Sheet Glass Co Ltd ガラス容器の処理方法
JPH10258110A (ja) * 1997-02-18 1998-09-29 Carl Zeiss:Fa 医療目的、特に薬剤または診断用の生成物の貯蔵のために滅菌し得るガラス容器
JP2003128439A (ja) * 2001-10-17 2003-05-08 Nippon Electric Glass Co Ltd ガラス容器及びその処理方法
JP2005289711A (ja) * 2004-03-31 2005-10-20 Nippon Glass Sangyo Kk アンプルまたはバイアル、およびその製造方法
WO2009116300A1 (fr) * 2008-03-21 2009-09-24 大和特殊硝子株式会社 Procédé de fabrication de récipients en verre à faible teneur alcaline

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