Container surface treatment method and surface structure of container treated by said method

Abstract

The present invention provides a glass container having extremely excellent chemical durability, which includes a cleaning step of cleaning the inner surface of the glass container with a cleaning solution consisting of water, an acid aqueous solution, a surfactant aqueous solution, or an acid aqueous solution containing a surfactant, a distortion removing step of heating and then cooling the glass container cleaned in the cleaning step to remove distortion, the glass container is then placed in a plasma processing device, and a plasma atmosphere formed by a plasma generating unit is used to modify the film-forming surface of the glass container to make the film-forming surface hydrophilic in a state in which an evaporation source for imparting hydrophilic groups is supplied into a vacuum chamber of a predetermined vacuum degree of the plasma processing device, the glass container having the hydrophilized film-forming surface is then supplied into a vacuum chamber of the predetermined vacuum degree with an evaporation source for promoting hydrolysis or nucleophilic reaction of a precursor material for a SAM film or a self-assembled multilayer film, an evaporation source for a precursor material for a SAM film or a self-assembled multilayer film is supplied to form a SAM film or a self-assembled multilayer film on the hydrophilized film-forming surface, and finally, the bonding between the film-forming surface and the SAM film or the self-assembled multilayer film is strengthened in the vacuum chamber of the predetermined vacuum degree.

Description

[Technical field]

[0001] The present invention relates to a method for treating the surface of pharmaceutical and physicochemical containers, such as ampoules and tube bottles, and to the surface structure of containers treated by said method. [Background technology]

[0002] Medical containers filled with medicinal liquids, blood, etc., are required to have transparency to check for contamination by foreign matter and changes due to drug compounding, heat resistance to withstand sterilization, flexibility to facilitate discharging of medicinal liquids, gas barrier properties to prevent deterioration of the quality of medicinal liquids due to intrusion of water vapor and oxygen into the container, and reduction of elution of trace substances from the container surface. In addition, after filling the containers with the contents, heat sterilization is generally performed. In particular, infusion preparations that are administered directly into the bloodstream are strictly required to be kept in a sterile state, and sterilization at 121°C is becoming the global standard.

[0003] Conventionally, glass containers have been used as such medical containers, but due to problems such as the container being damaged by impact or being dropped, plastic containers, which have excellent impact resistance, are also being used.

[0004] Glass containers such as ampoules and tube bottles are often manufactured by forming glass tubes under heating. A typical forming method is the vertical forming method. In this method, a glass tube with a certain diameter and open ends is vertically set, and the lower end that becomes the mouth is heated to soften and processed into a desired shape, and then the glass tube is cut to a desired length, and the bottom of the glass container is formed to produce the desired glass container. The remaining glass tube after cutting is shortened by the length of one glass container produced, and by repeating the above process, glass containers can be mass-produced.

[0005] However, when a glass container manufactured in this manner is used to store, for example, a liquid medicine, components of the glass may leach out from the inner glass surface of the glass container, contaminating the medicine or the like. For example, alkali metals in the components of the glass may increase the pH value. In some cases, the components of the glass leach out from the glass surface may react with the liquid contained therein to form a precipitate, compromising the quality of the liquid contained therein.

[0006] In order to solve these problems, the conventional method of coating or sulfurizing the glass surface makes the process complicated and increases the manufacturing cost of the glass container, making it impossible to obtain a glass container with excellent chemical durability. Therefore, the present inventor has previously filed a patent application for a method for manufacturing a glass container with excellent chemical durability (Patent Document 1). This Patent Document 1 describes a method for manufacturing a glass container, which includes a manufacturing process of a glass container in which a glass tube is molded under heating to obtain a glass container, a cleaning process in which the inner surface of the glass container obtained in the manufacturing process of the glass container is cleaned with a cleaning liquid, and a distortion removing process in which the glass container cleaned in the cleaning process is heated to a higher temperature and then cooled to remove distortion. However, Patent Document 1 does not fully describe the cleaning process that takes into account the surface characteristics of the glass and the distortion removing process, which is an important process for obtaining a glass container with excellent chemical durability. Patent Document 2 describes a chemical vapor deposition method for a silicon dioxide film, which is characterized by depositing a silicon dioxide film by a plasma CVD method using tetraisocyanate silane as a raw material gas. However, the method described in Patent Document 2 cannot provide a container that does not elute eluted components such as alkaline components from the surface due to reaction with liquid during storage, or that elute only in small amounts. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Patent No. 6159304 specification [Patent Document 2] Patent No. 3305826 specification Summary of the Invention [Problem to be solved by the invention]

[0008] In the case of pharmaceutical or physicochemical containers, it is desirable to provide containers that do not elute, or only slightly elute, alkaline components and other elutable components from the surface due to reactions with liquids during storage or during heat sterilization after filling the manufactured container with a medicinal solution or the like.

[0009] The present invention has been made in consideration of the problems inherent in the conventional technology, and an object of the present invention is to provide a container that is extremely excellent in chemical durability. [Means for solving the problem]

[0010] The present inventors have conducted extensive research to solve the above problems, and have found that when the lower end of a vertically standing glass tube is heated, for example, with a gas burner to soften it and then processed into a desired shape, the glass quality is altered by the heat, and volatile components of the glass (e.g., Na2O, KO) are generated from the heated glass, and as the volatile components rise in the space between the open lower and upper ends of the glass tube due to the chimney effect, they adhere to the inner surface of the glass tube to form alkaline components, and the adhered alkaline components are eluted from the glass surface after the glass container is manufactured.

[0011] Furthermore, the present inventors have found that when a glass container is obtained from a glass tube by the above-mentioned vertical molding method and the inner surface of the glass container is washed with a cleaning liquid before a distortion removing operation for removing distortion due to thermal history, a glass container can be produced with extremely little elution of alkaline components from the inner glass surface.

[0012] However, when it comes to cleaning the inside of glass containers, there are many different cleaning methods, and unless the cleaning process takes into account the surface characteristics of the glass, sufficient cleaning results cannot be achieved. There are more than 700 types of glass, and among these, borosilicate low alkali glass has an expansion coefficient of 3 x 10 -6 / K, is relatively hard with a Mohs hardness of about 7, and has high corrosion resistance, making it suitable for use in lab and chemical instruments, medical instruments, drug containers, etc. Borosilicate glass is preferred as the material for the glass container of the present invention.

[0013] By the way, the surface of glass is inherently hydrophilic, highly chemically active, and has a strong ability to adsorb moisture and dirt due to intermolecular attractive forces such as hydrogen bonds. It is also a poor conductor of electricity and has a strong ability to adsorb dirt. For example, if glass is left in the air, the surface of the glass reacts with the external atmosphere, causing deterioration accompanied by a change in the composition of the surface layer. Therefore, it can be said that it is not easy to obtain a glass container with a desired cleanliness by cleaning without adversely affecting the glass base material.

[0014] Typically, an acid or an alkali can be used as a cleaning liquid for such glass containers. Table 1 below shows the weight loss (95°C, 24 hours (mg / cm)) of soda-lime glass, borosilicate glass, and quartz glass due to acid and alkali. 2 )) is shown. [Table 1]

[0015] As shown in Table 1, borosilicate glass shows the greatest weight loss in response to 5% sodium hydroxide. This is because silica, the main component, becomes sodium silicate and dissolves. On the other hand, what dissolves in 5% hydrochloric acid is mainly the alkali and alkaline earth components contained in the glass, and the silica component hardly dissolves. Therefore, unlike dissolution in sodium hydroxide, the amount of dissolution is small. The dissolution rate in acid is proportional to the square root of time and is much slower than the dissolution rate in alkali. It can be seen from Table 1 that acid corrosion is slower than alkali corrosion. It is also known that hydrochloric acid and organic acids are compared to dissolution in organic acids, and the amount of dissolution in organic acids is smaller. Therefore, in the present invention, it is preferable to use an organic acid, which corrodes glass components relatively slowly, as the cleaning liquid.

[0016] In addition, hydroxyl groups, such as silanol groups (SiOH), are generally present on the glass surface, and it is believed that these hydroxyl groups act as adsorption sites for substances. Therefore, if there is a long time between the cleaning process, in which the inner surface of a glass container is cleaned with a cleaning solution, and the subsequent distortion removal process, the surface characteristics of the glass may change. In other words, it is preferable to keep the time between the cleaning process and the distortion removal process to within 30 minutes. Furthermore, in order to improve the cleaning effect, it is preferable to set the spray pressure of the cleaning solution to 0.05 MPa or more.

[0017] Furthermore, when borosilicate glass is heated for a long period of time above its glass transition point, it can separate into two phases (phase separation): a polar phase (Na2O, B2O3, etc.) in which ionic bonds are predominant, and a silica phase in which covalent bonds are predominant. Glass that has separated into two phases has low chemical durability.

[0018] Therefore, the present inventors have repeatedly studied conditions that make phase separation less likely to occur. As a result, they have found that in order to obtain a glass container with excellent chemical durability, in the manufacturing method of a glass container described in Patent Document 1, the heating temperature in the distortion removing step in which the glass container washed in the washing step is heated to an elevated temperature and then cooled to remove distortion is extremely important. Based on the above findings, the present inventors have found that by appropriately controlling the heating temperature in the distortion removing step, a homogeneous coating containing a large amount of chemically stable SiO2 can be formed on the inner surface of the glass container without causing phase separation or free radicals.

[0019] Furthermore, some pharmaceutical and physicochemical containers are required to suppress the amount of contamination of the liquid inside the container with the substances that make up the inner wall of the container to the detection limit (ppm or less). For example, the hydrolytic stability of pharmaceutical glass containers in the European Pharmacopoeia is evaluated by the resistance to the release of water-soluble inorganic substances into water under the contact conditions between the inner surface of the container and water. The European Pharmacopoeia classifies glass containers into Type I glass containers, which are suitable for most preparations, regardless of whether they are administered parenterally, Type II glass containers, which are suitable for most acidic and neutral preparations, regardless of whether they are administered parenterally, and Type III glass containers, which are suitable for non-aqueous preparations, powders (excluding freeze-dried preparations), and oral preparations that are generally administered parenterally, and specifies a limit value of 0.5 for the oxide concentration expressed as sodium oxide (μg / mL) for Type I and II glass containers with a filling volume of more than 500 mL (milliliters) in surface water resistance tests using flame atomic absorption spectrometry.

[0020] To meet the strict requirements mentioned above, it is necessary to apply an appropriate treatment to the inner surface of the container to form a thin film with excellent water resistance. There are several thin film formation methods, including the "vacuum deposition method," in which film-forming materials such as metals and oxides are evaporated in a vacuum container and then attached to the opposing substrate surface to form a thin film; the "ion plating method," which uses almost the same principle as the vacuum deposition method, but in which evaporated particles are passed through plasma to give them a positive charge and the substrate on which the film is to be formed is given a negative charge, so that the positively charged particles are attracted to the negatively charged substrate to form a thin film with excellent adhesion to the substrate surface; the "sputtering method," in which the metal to be applied as a thin film is placed as a target in a vacuum chamber, and a high voltage is applied to collide positively ionized rare gas (usually argon) or nitrogen with the negatively charged target to flick off atoms on the target surface to form a thin film on the substrate surface; and the "chemical vapor deposition method," in which a source gas containing the components of the desired thin film is supplied to a heated substrate in a reaction tube made of quartz or the like, and a thin film is formed on the substrate by a chemical reaction in the gas phase.

[0021] The above "vacuum deposition method," "ion plating method," and "sputtering method" belong to the category of physical vapor deposition (hereinafter also referred to as PVD), which is carried out in a high vacuum. This is because if the film-forming precursor collides frequently with other particles, the precursor will not reach the substrate. In the high vacuum in which physical vapor deposition is carried out, the precursor is transported to the substrate in a state almost similar to that of a molecular beam. Also, since the precursor is often a highly reactive atom, when it lands on the substrate surface, there is an almost 100% probability that it will adhere to the substrate. On the other hand, the raw materials for chemical vapor deposition (hereinafter also referred to as CVD) are gaseous molecules, and molecules containing the atoms to be deposited are supplied to a vessel in which a substrate is placed, and some energy is applied to dissociate the molecules (chemical reaction). If the dissociation products containing the atoms to be deposited (precursors) are adhesive, thin film deposition is possible. The degree of vacuum in which CVD is performed does not need to be as high as in PVD. In other words, it is performed in a high-pressure environment. The reason is that this is not necessary. Since the density of the raw material increases with higher pressure, increasing the pressure moderately has the advantage of improving the film formation speed. In addition, the directionality of the raw material molecules is lost due to collisions in the gas phase, making it possible to supply the raw material molecules to recesses, which was not possible with PVD.

[0022] In addition, while PVD does not cause chemical reactions during the transport of raw material particles, CVD allows many chemical reactions to occur simultaneously in addition to the dissociation reaction of the raw materials. Therefore, if the appropriate chemical reaction occurs, it is possible to incorporate functional groups possessed by the raw material molecules into the film, making it possible to obtain highly functional films that cannot be obtained by PVD. In this way, because CVD involves complex chemical reactions, it is possible to impart various functions to the film.

[0023] However, the raw materials used in the CVD method are stable molecules, so they need to be dissociated in some way. Thermal CVD is a method in which a substrate is heated and the raw material molecules are heated by the thermal energy. In contrast, in plasma CVD, the electrons in the plasma containing the raw material molecules are the main decomposition agents. Therefore, since there is no need to heat the substrate to dissociate the raw material molecules, the plasma CVD method has the advantage of being able to form films on substrates that are sensitive to heat. In addition, in thermal CVD, where heat (vibrational excitation) is the driving force behind all reactions, the reactions that occur and their products are all in a state of thermal equilibrium, whereas plasma CVD, which uses electronic excitation, makes it possible to create materials that are out of thermal equilibrium.

[0024] Therefore, the present inventors decided to adopt the plasma CVD method. However, the plasma CVD method also has a drawback. The ions necessary to maintain the plasma state damage the deposited film. Therefore, the inventors devised an improved plasma CVD method that overcomes this drawback and at the same time uses a different reaction system from the CVD method using tetraisocyanate silane as a raw material described in Patent Document 2.

[0025] That is, the method for treating the surface of a container of the present invention is characterized by a washing step in which the inner surface of a glass container is washed with a washing liquid consisting of water, an aqueous solution of an acid, an aqueous solution of a surfactant, or an aqueous solution of an acid to which a surfactant has been added, a distortion removing step in which the glass container washed in the washing step is heated to a higher temperature and then cooled to remove distortion, the glass container is then placed in a vacuum chamber, water vapor is supplied into the chamber to a predetermined pressure, and discharged to irradiate plasma to hydrophilize the surface of the glass container, and then tetraisocyanate silane or 1H,1H,2H,2H-heptadecafluorodecyltrimethoxysilane is supplied into the chamber so as not to dissociate, and a reaction is allowed to proceed at a predetermined temperature for a predetermined time to form a thin film on the glass container, and finally, a treatment is performed to strengthen the bond between the glass container surface and the thin film, and in the case where tetraisocyanate silane is supplied, the surface functional group is replaced with a hydroxyl group. In the case where tetraisocyanate silane is supplied, the surface structure of the container treated by such a method is composed of a silicon-based polymer containing a urethane bond, a urea bond, and a biuret bond. Furthermore, when 1H,1H,2H,2H-heptadecafluorodecyltrimethoxysilane is supplied, the surface structure of the container is composed of siloxane bonds.

[0026] The surface treatment method for a container of the present invention comprises placing a resin container in a vacuum chamber, irradiating plasma by discharging while supplying water vapor into the chamber until a predetermined pressure is reached, and after completion of the plasma irradiation, supplying tetraisocyanate silane or 1H,1H,2H,2H-heptadecafluorodecyltrimethoxysilane into the chamber and allowing a reaction to proceed at a predetermined temperature for a predetermined time to form a thin film on the resin container, and finally carrying out a treatment to strengthen the bond between the surface of the resin container and within the thin film, and is characterized in that when tetraisocyanate silane is supplied, surface functional groups are replaced with hydroxy groups. Effect of the Invention

[0027] According to the container surface treatment method of the present invention and the surface structure of a container treated by said method, the amount of alkaline components leaching from the inner surface of the container is extremely small, and deterioration of the contents, such as medicines, is suppressed, thereby ensuring the maintenance of the specified quality. [Brief description of the drawings]

[0028] [Figure 1] FIG. 1(a) is a schematic diagram showing a state in which alkaline soluble components have adhered to the inner surface of a glass container, FIG. 1(b) is a schematic diagram showing the glass container after the alkaline soluble components adhered to the inner surface have been removed, and FIG. 1(c) is a schematic diagram showing the state of a glass container having the inner surface shown in FIG. 1(b) after being heated. [Diagram 2] FIG. 2 is a schematic diagram showing each sub-step of an example of a method for producing a borosilicate glass container of the present invention. [Diagram 3] FIG. 3 is a schematic diagram showing an example of a manufacturing apparatus suitably used in the method for manufacturing a borosilicate glass container of the present invention. [Figure 4] FIG. 4 is a schematic diagram showing how a vial is washed by a washer. [Diagram 5] FIG. 5 is a schematic cross-sectional view of one embodiment of the borosilicate glass container of the present invention. [Figure 6] FIG. 6 is a schematic diagram showing the overall configuration of a plasma processing apparatus according to one embodiment for performing plasma processing on a glass container. [Figure 7] FIG. 7 is a cross-sectional view of the vacuum chamber of the plasma processing apparatus shown in FIG. [Figure 8] FIG. 8 shows the results of measuring the surface structure of a glass container using a Fourier transform infrared spectrophotometer, with the horizontal axis showing wave number ( / cm) and the vertical axis showing absorbance. [Figure 9] FIG. 9 is a partial extract of FIG. 8 and shows the results of measuring the surface structure of a glass container using a Fourier transform infrared spectrophotometer, with the horizontal axis indicating wave number ( / cm) and the vertical axis indicating absorbance. [Figure 10]FIG. 10 is a partial extract of FIG. 8 and shows the results of measuring the surface structure of a glass container using a Fourier transform infrared spectrophotometer, with the horizontal axis indicating wave number ( / cm) and the vertical axis indicating absorbance. [Figure 11] FIG. 11 is a partial extract of FIG. 8 and shows the results of measuring the surface structure of a glass container using a Fourier transform infrared spectrophotometer, with the horizontal axis indicating wave number ( / cm) and the vertical axis indicating absorbance. [Figure 12] FIG. 12 is a diagram showing chemical reactions on the surface of a glass container. [Figure 13] FIG. 13 is another diagram showing chemical reactions on the surface of a glass container. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0029] The glass tube used as the material of the glass container of the present invention is not particularly limited, but is preferably made of borosilicate glass. The cross section of the glass tube is usually circular, but may be elliptical or other shapes. 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 also not particularly limited, but is usually about 1 to 5 m. The glass tube may be colorless and transparent, or may be colored, for example, brown.

[0030] Since a method for producing a glass container using such a glass tube has been well established, the glass container of the present invention can be produced in accordance with the method. For example, a glass tube with a certain diameter and open ends is set vertically, and the lower end is usually inserted into a vertical molding machine equipped with a heating means, and heated, for example, with a gas burner at a temperature of about 1500 to 1800°C to form a desired tube bottle shape, and then the molded product and the glass tube extending above the remaining part are separated under heating, and a glass bottle and a bottom are formed. Next, the lower end of the separated glass tube is shaped so that the cross section is the original perfect circle. The temperature of the glass container after shaping is usually about 300 to 400°C.

[0031] By repeating this process, glass containers can be mass-produced. During this process, as described above, the glass is usually altered by heating, and the volatile components of the glass (e.g., Na2O, KO) rise through the space between the open upper and lower ends of the glass tube due to the chimney effect, adhere to the inner surface of the glass tube, and form alkaline soluble components.

[0032] In the present invention, after the above-mentioned glass container manufacturing process, a glass container cleaning process is carried out, as described in detail below, to remove or reduce alkaline soluble components adhering to the inner surface of the glass tube, and the glass container is then subjected to a distortion removal process within 30 minutes after the cleaning process. By subjecting the glass container to a distortion removal treatment controlled at an appropriate heating temperature, it is possible to provide a borosilicate glass container in which no phase separation is generated on the inner surface, no free radicals are present, no flakes or delamination are present, and the silicon and oxygen present on the inner surface are bonded by siloxane bonds.

[0033] The glass container at about 300 to 400°C after the molding process is cooled, for example, to atmospheric temperature as necessary, and preferably washed with a washing liquid at 150°C or less. It is considered that the higher the temperature of the glass container, the higher the effect of removing or reducing the elutable components attached to the inner surface of the glass container, but the glass container may be damaged if the washing liquid is brought into contact with the high-temperature glass container. In addition, the lower limit temperature of the glass container during washing is preferably 30°C or higher, taking into account the washing efficiency. In addition, the washing time is preferably about 10 to 15 seconds, since washing is insufficient if it is less than 10 seconds, and productivity decreases if it exceeds 15 seconds.

[0034] Although there are no limitations on the temperature of the cleaning solution in the cleaning step, it is preferable to use a cleaning solution at about 30 to 100° C., and more preferably about 40 to 70° C. If it is within this range, it is possible to obtain a glass container having extremely excellent chemical durability, which is the objective of the present invention.

[0035] As the cleaning liquid, water, an aqueous solution of an acid, an aqueous solution containing a surfactant, or an aqueous solution of an acid with the addition of a surfactant is preferably used, and an aqueous solution of an acid or an aqueous solution of an acid with the addition of a surfactant is more preferred in terms of high solubility of alkaline elutable components adhering to the inner surface of the glass container.

[0036] The acids used in the aqueous acid solution are broadly classified into organic acids and inorganic acids. Examples of organic acids include formic acid, acetic acid, oxalic acid, phthalic acid, and citric acid, and examples of inorganic acids include hydrochloric acid, sulfuric acid, and nitric acid. These acids may be used alone or in combination of two or more. For the reasons mentioned above, organic acids are preferred, and citric acid and oxalic acid are preferred from the viewpoints of cleaning effect and handling.

[0037] The higher the acid concentration, the higher the solubility of the alkaline component tends to be. However, from the viewpoint of ease of handling, including the treatment of waste liquid, the acid concentration is usually set to about 0.005 to 1.0 mol / L, preferably about 0.01 to 0.1 mol / L.

[0038] The surfactant used in the aqueous solution containing a surfactant or the aqueous solution of an acid to which a surfactant has been added among the above cleaning solutions is not particularly limited, but a preferred surfactant is a nonionic surfactant. The concentration of the surfactant may be appropriately selected within a range that does not impede the object and effect of the present invention.

[0039] To clean the inner surface of a glass container with the above-mentioned cleaning liquid, the glass container is usually inserted or hung in a suitable jig, and the cleaning liquid is sprayed from the mouth of the glass container to the bottom, usually by blowing up under pressure from a nozzle. It is preferable to increase the spray pressure of the cleaning liquid by making the nozzle's cleaning liquid spray outlet capable of ejecting compressed air simultaneously with the cleaning liquid (also called jet spray cleaning). Specifically, the spray pressure of the cleaning liquid is preferably 0.05 MPa or more. If the spray pressure is too high, the cleaning effect will be saturated, so the upper limit of the spray pressure is about 0.5 MPa.

[0040] When a cleaning liquid other than water is used as the cleaning liquid, after cleaning with the cleaning liquid, a process of rinsing with clean water and a process of thoroughly draining the water, for example by blowing air, are performed, and then the cleaning process is completed.

[0041] The cleaning of the inner surface of the glass container with the above cleaning solution may be performed by ultrasonic cleaning. In the case of ultrasonic cleaning, not only the inner surface but also the entire glass container is usually cleaned with the above cleaning solution, followed by rinsing. Whether or not to use ultrasonic cleaning is determined in consideration of the layout of the entire production line including the vertical molding machine, cleaning machine, and distortion removal furnace, which will be described later.

[0042] The distortion removing process of the glass container in the present invention is carried out by feeding the glass container washed in the washing process to a distortion removing furnace controlled to have a target maximum atmospheric temperature of 685 to 700°C, heating and then cooling the glass container so that the actual temperature of the glass container is between 685°C and 710°C for 1 minute. The total time of the distortion removing process, which consists of heating and heating the glass container to about 30 to 80°C in the distortion removing furnace and then cooling it to about 300°C, that is, the time in the distortion removing furnace (distortion removing time), is 3 to 40 minutes. This distortion removing process removes the distortion remaining in the glass container based on the thermal history when the glass tube is molded into the glass container, and at the same time, no phase separation is generated on the inner surface of the glass, no free radicals are present, and a homogeneous coating containing a large amount of chemically stable SiO2 is formed on the inner surface, and a glass container is obtained in which there are no flakes or delaminations and silicon and oxygen present on the inner surface are bonded by siloxane bonds.

[0043] The process for obtaining the glass container of the present invention can be easily explained as follows.

[0044] (1) Adhesion of alkaline soluble components to the inner surface of the glass tube As described above, when the glass tube is heated by a gas burner at a temperature of about 1500 to 1800°C and molded into the desired shape of a tube bottle, the glass quality is altered by the heat, and the volatile components of the glass (e.g., Na2O, K2O) rise in the space between the open lower and upper ends of the glass tube due to the chimney effect and adhere to the inner surface of the glass tube, forming alkaline elutable components. Figure 1(a) is a schematic diagram showing the state in which alkaline elutable components 3 are adhered to the inner surface 2 of a glass tube 1.

[0045] (2) Removal of alkaline eluable components by washing Although the alkaline elutable components can be removed by washing, as a result of washing, the inner surface 5 of the glass container 4 becomes microscopically uneven, as shown in FIG. 1(b).

[0046] (3) Removal of residual distortion caused by thermal history during molding Residual distortion can be removed by heating the glass container after removing the alkaline eluting components, and the flatness of the inner surface 5 of the glass container 4 is also improved by atomic diffusion, as shown in Figure 1(c).

[0047] (4) Forming the inner surface of glass containers Borosilicate glass can undergo phase separation when heated to a temperature above its glass transition point for a long period of time. Also, if the heating temperature is too high, the glass container can become deformed or wrinkled. Therefore, the selection of heating conditions is extremely important.

[0048] Therefore, in a distortion removing furnace controlled to a target maximum atmospheric temperature of 685 to 700° C., the glass container of the present invention can be produced by controlling the time during which the actual temperature of the glass container is 685 to 710° C. for one minute. If the time during which the temperature is 685 to 710° C. is one minute, no phase separation occurs on the inner surface, no free radicals exist, silicon and oxygen present on the inner surface are bonded by siloxane bonds, the glass surface does not deform or wrinkle, and residual distortion due to thermal history is removed, making it possible to produce a glass container with almost smooth inner and outer surfaces.

[0049] If the temperature of the glass container itself exceeds 700°C for a long period of time (10 minutes or more), the glass surface may deform or wrinkle. On the other hand, if the maximum atmospheric temperature of the distortion removal furnace is controlled to less than 650°C, the temperature of the glass container itself is likely to fall below 600°C, which may result in insufficient vitrification.

[0050] (5) Plasma treatment Organic molecules exhibit a unique adsorption phenomenon to solid surfaces, and in the process of adsorption, a densely assembled and aligned molecular film may be formed. When the adsorbed molecular layer is one layer, that is, when a monolayer is formed, this is called a self-assembled monolayer (hereinafter, sometimes referred to as a SAM film). When the adsorbed molecular layer is two or more layers, it is called a self-assembled multilayer film. Therefore, the glass container manufactured as described above is placed in the vacuum chamber of a plasma processing device, and a SAM film or a self-assembled multilayer film is formed on the surface of the glass container. That is, in a state where an evaporation source that imparts hydrophilic groups is supplied into a vacuum chamber of a predetermined vacuum degree of the plasma processing device, a surface hydrophilization mode is executed in which the film formation surface of the glass container is modified by the plasma atmosphere formed by the plasma generating unit to make the film formation surface hydrophilic, and in a state where an evaporation source that promotes hydrolysis or nucleophilic reaction of a precursor material of the SAM film or self-organized multilayer film is supplied into a vacuum chamber of a predetermined vacuum degree to the glass container with the film formation surface hydrophilized, an evaporation source of the precursor material of the SAM film or self-organized multilayer film is supplied to the hydrophilized film formation surface, and a self-organization mode is executed in which a SAM film or self-organized multilayer film is formed on the hydrophilized film formation surface, and finally, a final processing mode is executed in a vacuum chamber of a predetermined vacuum degree to strengthen the bond between the film formation surface of the glass container and the SAM film or self-organized multilayer film. Note that a similar process can be performed in the plasma processing device on a resin container instead of a glass container to form a SAM film or self-organized multilayer film on the resin container. Examples of such resins include propylene (PP), polyethylene (PE), cycloolefin (COP, COC), polyethylene terephthalate (PET), and polyvinyl chloride (PVC).

[0051] The present invention provides a container with an extremely small amount of elution of alkaline components and the like. EXAMPLES

[0052] Although the embodiments of the present invention will be described below, it goes without saying that various changes and modifications can be made without departing from the technical scope of the present invention.

[0053] A glass tube made of borosilicate glass having an outer diameter of 16 mm, a length of 1.6 m, and a composition (weight %) shown in Table 2 below was used to obtain a 2 mL vial by the following method. First, as shown in FIG. 2 (1), the glass tube 11 was inserted into a vertical tube bottle molding machine 12 with the end facing up, and the lower end was heated with a gas burner to soften the glass, which was then molded into the shape of the opening of the bottle. The steps are explained in more detail below with reference to FIG. 2.

[0054] [Table 2]

[0055] (1) The lower end of the glass tube 11 was heated by a fishtail burner 13 at 1200 to 2000°C. (2) A shoulder was formed using a roller 14 and a plunger 15. (3) Heated with a point burner 16 at 1200 to 2000°C. (4) The mouth portion was formed using a roller 14 and a plunger 15. (5) The bottle height was determined using the total height board 17. (6) Cutting was performed using a cut burner 18 with a temperature of 1200 to 2000°C. (7) The bottom was homogenized using point burner 16. (8) Air 19 was blown in and the bottom of the vial 20 was formed using a point burner 16 at 1200 to 2000°C.

[0056] The vial 20 thus obtained is inserted into a jig placed on a net conveyor 21 (FIG. 3), and is transported to a cleaning machine 22 and allowed to cool at ambient temperature (cooling step (9) in FIG. 2). The inner surface of the vial at about 30° C. is spray-cleaned with 10 mL of a cleaning solution (citric acid) at 25° C. using a syringe for 10 seconds (citric acid spray pressure 0.2 MPa) (cleaning step (10) in FIG. 2). After spray-cleaning with purified water for 10 seconds (0.2 MPa), air 19 is blown in to thoroughly drain the water (draining step (11) in FIG. 2). Although details are omitted in FIG. 3, the vial 20 can be transported to the cleaning machine 22 and the distortion removal furnace 24 by the net conveyor 21.

[0057] Fig. 4 is a schematic diagram showing how vial 20 is washed by washer 22. In Fig. 4, 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, and 37 is a storage tank for the washing liquid. By adjusting the opening of needle valve 33, the spray pressure of the washing liquid can be adjusted.

[0058] The vial 20, which has been washed with citric acid and purified water and drained off, is transported to a 5 m effective length heating furnace 24 equipped with a burner heater 23 within 30 minutes ((12) strain relief step in FIG. 2), and strain relief treatment is performed for 25 minutes (the time during which the atmospheric temperature is 670°C or higher is 108 seconds, the actual temperature of the glass container is 670-700°C, and the time during which the actual temperature of the glass container is 690-700°C is 1 minute) while controlling the target maximum atmospheric temperature in the strain relief furnace to be 670°C. A borosilicate glass container is obtained, and the glass container is allowed to cool to room temperature. FIG. 5 is a schematic cross-sectional view of the borosilicate glass container 40 thus obtained. Note that the inlet and outlet sides of the strain relief furnace 24 are open, so even if the atmospheric temperature in the strain relief furnace detected by a thermocouple installed in the strain relief furnace is, for example, 670-700°C, the temperature on the inlet and outlet sides is lower than this temperature. The atmospheric temperature in the distortion removal furnace was measured by thermocouples installed at three locations, and the burner heater 23 was controlled to turn on and off so that the temperature measured by 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.

[0059] FIG. 6 is a schematic diagram showing the overall configuration of one embodiment of a plasma processing apparatus for performing plasma processing on the glass container thus obtained to form a SAM film or a self-assembled multilayer film, and FIG. 7 is a cross-sectional view of the vacuum chamber of the plasma processing apparatus shown in FIG. 6.

[0060] As shown in FIG. 6, the plasma processing apparatus 51 has a vacuum chamber 52 that accommodates a glass container V on which a SAM film or a self-assembled multilayer film is formed, a lower electrode 53 that also serves as a stage for placing the glass container V in the vacuum chamber 52, and an upper electrode 54 that faces the lower electrode 53, and a plasma generation power supply 57 is connected to the lower electrode 53. FIG. 6 shows a structure in which the lower electrode 53 supports the glass container V, but a structure in which the upper electrode 54 supports the glass container V may also be used, or a structure in which both the lower electrode 53 and the upper electrode 54 support the glass container V may also be used. In addition, the plasma generation power supply 57 may be a low-frequency power supply or a high-frequency power supply. In addition, a pressure gauge 55 that monitors the pressure in the vacuum chamber 52, an earth 56, and a vacuum pump 59 are connected to the vacuum chamber 52. In addition, the system has a structure in which a gas inlet 60 used for plasma treatment, a bubbler 65 for reactant substances necessary for plasma treatment and for forming a SAM film or a self-assembled multilayer film, and a raw material chamber 68 for the SAM film or the self-assembled multilayer film are connected by piping and introduced into the vacuum chamber 52.

[0061] Further, as shown in FIG. 7, the vacuum chamber 52 in this embodiment has an upper chamber 77 and a lower chamber 78, and the lower chamber 78 has an O-ring 80. In this embodiment, the upper chamber 77 and the lower chamber 78 are made of an electrically grounded electric conductor, and the entire inner wall surface of the vacuum chamber 52 is a ground potential surface with a ground potential. The electric conductor constituting the upper chamber 77 and the lower chamber 78 is a metal material composed of, for example, transition metals such as copper, nickel, titanium, alloys thereof, stainless steel, molybdenum, tungsten, and other high melting point metals. In this embodiment, the upper chamber 77 has a gas inlet 71 at its top, and a gas inlet 60 used for plasma processing, a bubbler 65 for a reactant material necessary for plasma processing and the film formation process of the SAM film or self-assembled multilayer film, and a pipe connected from the raw material chamber 68 for the SAM film or self-assembled multilayer film are connected to the gas inlet 71.

[0062] In this embodiment, the lower electrode 53 is composed of a current introduction terminal 72 and an electrode stage 73, and an insulating member 76 is arranged around the current introduction terminal 72 and under the electrode stage 73. The current introduction terminal 72 is connected to a plasma generation power supply 57. The upper electrode 54 facing the lower electrode 53 has a structure that also serves as a gas shower plate 74. In this embodiment, the lower chamber 78 has a structure in which an earth ring 75 is provided in a form surrounding the electrode stage 73. It is preferable that the difference in height between the electrode stage 73 and the earth ring 75 is approximately 0 mm, but the earth ring 75 may be slightly higher than the electrode stage 73. The earth ring 75 is formed so that the distance between the electrode stage 73 and the earth ring 75 is 1 mm or more and 5 mm or less. By forming such a distance, it is possible to control the flow of gas and expand the uniform plasma region as much as possible. If the distance between the earth ring 75 and the electrode stage 73 is less than 1 mm, the distance is too narrow when the gas is drawn by the vacuum pump, and in addition, abnormal discharge occurs, making it impossible to generate the desired plasma. Furthermore, if the distance between the earth ring 75 and the electrode stage 73 is greater than 5 mm, abnormal discharge will occur between the electrode stage 73 and the earth ring 75, making it impossible to generate a desired uniform plasma.

[0063] Furthermore, the lower chamber 78 has a vacuum exhaust port 79 connected to a vacuum pump 59 between the current introducing terminal 72 and the earth ring 75, and the degree of vacuum in the vacuum chamber 52 can be adjusted by an exhaust flow rate control valve 58. Therefore, by using the device of this embodiment, it is possible to satisfactorily carry out hydrophilization treatment by plasma treatment in the pretreatment step of forming a SAM film or a self-assembled multilayer film.

[0064] In this embodiment, three gas introduction pipes, consisting of a system from a gas inlet 60 for introducing gas used in plasma treatment, a system from a bubbler 65 for reactant substances necessary for plasma treatment and the film formation process of a SAM film or a self-assembled multilayer film, and a system from a raw material chamber 68 for the SAM film or the self-assembled multilayer film, are connected to the vacuum chamber 52. For the piping of the gas introduction pipes, piping with a structure surrounded by a heat insulating material or a heater (not shown) is used to prevent the gas from liquefying.

[0065] In this embodiment, the gas used in the plasma treatment introduced from the gas inlet 60 is supplied from a gas cylinder (not shown) and introduced into the vacuum chamber 52 via a flow rate control valve / mass flow controller 61. As the gas used in the plasma treatment, a gas that imparts hydroxyl groups (OH groups) to the surface of the glass container V, or a pre-treatment gas for the step of imparting OH groups is selected. Examples include water vapor (H2O), oxygen (O2), and argon (Ar). There is no limitation on the gas as long as it is a gas that imparts OH groups to the surface, or a gas that can be used for pre-treatment of the step of imparting OH.

[0066] When the gas used for plasma treatment is supplied to the vacuum chamber 52, the degree of vacuum in the vacuum chamber 52 is controlled by the exhaust flow rate control valve 58 and the vacuum pump 59, and by discharging between the lower electrode 53 and the upper electrode 54, the above gas functions as a plasma generating gas and performs plasma hydrophilization treatment on the glass container V.

[0067] In this embodiment, the bubbler 65 into which the vapor source 67, which is a reactant material necessary for plasma processing and for forming a SAM film or a self-assembled multilayer film, is provided with a mantle heater 66, and generates vapor of the vapor source 67, which is a reactant material necessary for plasma processing and for forming a SAM film or a self-assembled multilayer film, by heating, and supplies the vapor to the vacuum chamber 52. The bubbler 65 is connected to a pipe through which a carrier gas is supplied from an inlet 62 for carrier gas for carrying the vapor of the vapor source 67 via a flow rate control valve / mass flow controller 63, and a pipe having a bypass valve 64 through which a carrier gas that can be mixed with the vapor from the bubbler 65 passes without passing through the bubbler 65 is configured. If the carrier gas is not required, it is not necessary to flow the carrier gas.

[0068] As the vapor source 67, which is a reactant material necessary for plasma treatment and deposition of the SAM film or self-assembled multilayer film, an evaporation source that imparts OH groups to the surface of the glass container V or an evaporation source that promotes hydrolysis or nucleophilic reaction of the precursor of the SAM film or self-assembled multilayer film is selected. For example, water (H2O) is exemplified.

[0069] When the vapor of the vapor source 67, which is a reactant material necessary for plasma processing and for forming the SAM film or self-assembled multilayer film, is supplied to the vacuum chamber 52, the above-mentioned H2O gas (water vapor) functions as a plasma generating gas by discharging between the lower electrode 53 and the upper electrode 54, and this is a process for providing OH groups to the surface of the glass container V. In the SAM film or self-assembled multilayer film forming process immediately afterwards, the residual component (water vapor) of the plasma at the time of discharging promotes hydrolysis or nucleophilic reaction with the SAM film or self-assembled multilayer film precursor material. By controlling the degree of vacuum in the vacuum chamber 52 with the exhaust flow rate control valve 58 and the vacuum pump 59, the subsequent hydrolysis or nucleophilic reaction of the SAM film or self-assembled multilayer film precursor may occur during or after the discharge has stopped, as long as the SAM film or self-assembled multilayer film precursor is not decomposed or dissociated.

[0070] In this embodiment, the SAM film or self-assembled multilayer film raw material chamber 68 into which a vapor source 70 of the SAM film or self-assembled multilayer film precursor material is injected is equipped with a mantle heater 69, and vapor of the SAM film or self-assembled multilayer film raw material chamber 68 is generated by heating with the mantle heater 69 and supplied to the vacuum chamber 52. As the vapor source 70 of the SAM film or self-assembled multilayer film precursor material, an evaporation source that undergoes dehydration condensation between OH groups generated by hydrolysis of the SAM film or self-assembled multilayer film precursor material and OH groups formed on the surface of the glass container V, or an evaporation source that undergoes dehydration condensation between the material molecules of the evaporation source of the SAM film or self-assembled multilayer film precursor material themselves and OH groups formed on the surface of the glass container V is selected. For example, chlorosilanes such as 1H,1H,2H,2H-perfluorodecyldimethylchlorosilane, tetrahydrooctylmethyldichlorosilane (FOMDS), dichlorodimethylsilane (DDMS), 1H,1H,2H,2H-perfluorodecyltrichlorosilane (FDTS), octadecyltrichlorosilane (OTS), and tetrahydrooctyltrichlorosilane (FOTS); dimethyldimethoxysilane, dimethyldiethoxysilane, isobutylmethyldimethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, dodecyltriethoxysilane, 1H,1H,2H,2H-perfluorodecyltrimethoxysilane, 1H,1H,2H,2H-tridecafluorooctyl Examples of the material include alkoxysilane-based materials such as n-octadecyltrimethoxysilane, n-octadecyltrimethoxysilane, and tetraethoxysilane (TEOS); phosphonic acid-based materials such as octadecylphosphonic acid and 1H,1H,2H,2H-perfluorooctylphosphonic acid; isocyanate-based materials such as tetraisocyanatesilane; alkoxysilane-based and isocyanate-based materials such as triethoxy(3-isocyanatopropyl)silane; and disilazanes such as hexamethyldisilazane (HMDS). The material is not limited to chlorosilane-based materials, alkoxysilane-based materials, isocyanate-based materials, phosphonic acid-based materials, and disilazanes that can form a SAM film or a self-assembled multilayer film.

[0071] When the vapor source 70 of the SAM film or self-assembled multilayer film precursor material is supplied to the vacuum chamber 52, it is preferable that no discharge occurs between the lower electrode 53 and the upper electrode 54. In the SAM film or self-assembled multilayer film formation process, when the vapor source 70 of the SAM film or self-assembled multilayer film precursor material is tetraisocyanate silane, the residual components of the plasma during discharge and H2O react with the self-assembled multilayer film precursor material through a nucleophilic reaction, while the unreacted isocyanate groups among the four isocyanate groups react with the OH groups applied to the glass container surface or the resin container surface to form urethane bonds, and the first layer of the self-assembled multilayer film is formed. When the vapor source 70 of the SAM film or self-assembled multilayer film precursor material is 1H,1H,2H,2H-perfluorodecyltrimethoxysilane, the residual components of the plasma during discharge and H2O react with the SAM film precursor material through hydrolysis, and then the OH groups applied to the glass container surface or the resin container surface and the OH groups of the SAM film precursor material self-assemble through hydrogen bonds, and then a dehydration condensation reaction proceeds to form the SAM film.

[0072] As described above, the plasma processing apparatus in this embodiment includes a plasma generating unit that forms a plasma atmosphere in a vacuum chamber, and has modes for performing each of the following three processes. (1) A surface hydrophilization mode in which, in a state in which an evaporation source that imparts hydrophilic groups is supplied into a vacuum chamber, the film-forming surface of a glass container or a resin container is modified by a plasma atmosphere formed by a plasma generating unit to make the film-forming surface hydrophilic. (2) A self-assembly mode in which an evaporation source that promotes the hydrolysis or nucleophilic reaction of a precursor material for a SAM film or a self-assembled multilayer film is supplied to a glass or resin container having a hydrophilized film formation surface in a vacuum chamber of a specified vacuum level, and a SAM film or a self-assembled multilayer film is formed on the hydrophilized film formation surface by supplying an evaporation source of the precursor material for the SAM film or the self-assembled multilayer film. (3) A final treatment mode consisting of a heat treatment in a vacuum chamber of a specified vacuum level to strengthen the bond between the film formation surface and the SAM film or the self-assembled multilayer film, and a silanol treatment of the outermost surface in the case where the self-assembled multilayer film precursor material is tetraisocyanate silane.

[0073] In this embodiment, the surface hydrophilization mode, the self-assembly mode, and the final processing mode are preferably performed in a common vacuum chamber. This allows the transition from the surface hydrophilization mode to the self-assembly mode, and from the self-assembly mode to the final processing mode, to be performed without opening the vacuum chamber to the atmosphere. Note that, when the surface hydrophilization mode, the self-assembly mode, and the final processing mode are performed in separate vacuum chambers, it is preferable that the vacuum chamber be a load-lock type that can transport containers while maintaining a vacuum state.

[0074] In this embodiment, both the evaporation source for providing hydroxyl groups to the surface of the container and the evaporation source for promoting hydrolysis of the precursor material of the self-assembled monolayer are preferably water vapor. Note that the water vapor in the self-assembly mode may be water vapor remaining in the surface hydrophilization mode.

[0075] According to this embodiment, by performing vacuum plasma treatment on the substrate surface immediately before forming a SAM film or self-assembled multilayer film on the container, it is possible to impart hydrophilic groups such as hydroxyl groups at a high density, and it is possible to form a high-density SAM film on the container surface before the hydrophilicity of the hydrophilic groups imparted to the container changes over time, without opening the vacuum chamber to the atmosphere.

[0076] Furthermore, the method for forming a SAM film or self-assembled multilayer film in this embodiment includes the steps of: (A) placing a glass container in a vacuum chamber; (B) supplying an evaporation source that imparts hydrophilic groups to the surface of the glass container into the vacuum chamber, and generating plasma from the evaporation source by turning the vacuum chamber into plasma, thereby hydrophilizing the surface of the glass container; (C) supplying an evaporation source of a precursor material of the SAM film or self-assembled multilayer film into the vacuum chamber after step (B), while the evaporation source that promotes hydrolysis or nucleophilic reaction of the precursor material of the SAM film or self-assembled multilayer film is supplied into the vacuum chamber, thereby forming a SAM film or self-assembled multilayer film on the surface of the glass container; and (D) strengthening the bond between the glass container surface and the SAM film or self-assembled multilayer film, and performing a silanol treatment on the outermost surface when the precursor material of the self-assembled multilayer film is a tetrafunctional alkoxysilane such as tetraisocyanate silane or tetraethyl orthosilicate, and at least steps (B) and (C) are performed without opening the vacuum chamber to the atmosphere. Step (D) may be performed in a series of processes in a vacuum chamber without being exposed to the atmosphere, or may be performed after being temporarily exposed to the atmosphere.

[0077] Then, the borosilicate glass container V obtained as described in paragraphs 0053 to 0058 was placed in the plasma processing apparatus shown in FIG. 6, and the surface of the glass container V was subjected to the processing described below to form a self-assembled multilayer film.

[0078] The atmospheric pressure in vacuum chamber 52 was reduced to 5 to 10 Pa. Thereafter, bubbler 65 into which water was injected as vapor source 67, a reactant substance necessary for plasma treatment and formation of a SAM film, was heated to 70° C. by mantle heater 66, water vapor was introduced into vacuum chamber 52, and the atmospheric pressure in vacuum chamber 52 was maintained at 100 Pa. A 13.56 MHz high-frequency power source was used as plasma generation power source 57, and water vapor plasma irradiation was performed for 3 minutes at a power of 200 W.

[0079] The raw material chamber 68 for the SAM film or self-assembled multilayer film, into which 5 cc of tetraisocyanate silane was injected as a vapor source 70 of the SAM film or self-assembled multilayer film precursor material, was heated to 50° C. by a mantle heater 69. After plasma irradiation was completed, the valve of the bubbler 65 was closed, and then, without opening the vacuum chamber 52 to the atmosphere, the valve of the raw material chamber 68 for the SAM film or self-assembled multilayer film was opened to introduce tetraisocyanate silane into the vacuum chamber 52, and the glass container V was exposed to the vapor of tetraisocyanate silane for 20 minutes to form a self-assembled multilayer film on the glass container V.

[0080] Furthermore, the glass container on which the self-assembled multilayer film was formed was heated to 100-120°C to strengthen the bond between the glass container surface and the inside of the self-assembled multilayer film. After that, water vapor plasma was again irradiated to form silanol groups on the outermost surface, realizing a hydrophilic surface.

[0081] Next, the same treatment as above was performed on glass container V made of borosilicate glass obtained as described in paragraphs 0053 to 0058 and paragraphs 0078 to 0079, except that 1H,1H,2H,2H-perfluorodecyltrimethoxysilane was used instead of tetraisocyanatesilane as the vapor source 70 of the SAM film or self-assembled multilayer film precursor material. Thereafter, glass container V on which the SAM film of 1H,1H,2H,2H-perfluorodecyltrimethoxysilane was formed was heated to 100 to 120° C., thereby strengthening the bond between the glass container surface and the SAM film.

[0082] Then, using a Fourier transform infrared spectrophotometer, the molecules formed on the surface of glass container V, which had been treated using the above-mentioned tetraisocyanate silane as the raw material for the self-assembled multilayer film, were identified. Since infrared light is absorbed as the energy of vibration and rotational motion of molecular bonds, information on the molecular structure and functional groups can be obtained from the spectrum. Figure 8 shows the results of measuring the surface structure of the glass container using a Fourier transform infrared spectrophotometer, with the horizontal axis indicating wave number ( / cm) and the vertical axis indicating absorbance. Figures 9, 10, and 11 are partial extracts of Figure 8.

[0083] It can be seen that by subjecting the surface of glass container V to plasma treatment according to the method of the present invention, urethane bonds (chemical formula 1) are formed on the surface of the glass container, as shown in FIG. 12, and urea bonds (chemical formula 2) and biuret bonds (chemical formula 3) are formed on the surface of the glass container, as shown in FIG. 13.

[0084] [ka]

[0085] [ka]

[0086] [ka]

[0087] In addition, a glass container made of borosilicate glass of Comparative Example 1 was obtained through the same steps as those described in paragraphs 0053 to 0058, except that no surface treatment using plasma was performed, and a glass container made of borosilicate glass of Comparative Example 2 was obtained through the same steps as those described in paragraphs 0053 to 0058, except that no surface treatment using plasma was performed and no washing with citric acid and purified water was performed.

[0088] Thereafter, for the borosilicate glass container (Example 1) surface-treated with tetraisocyanate silane using a plasma processing device, the borosilicate glass container (Example 2) surface-treated with perfluorocarbon using a plasma processing device, the borosilicate glass container of Comparative Example 1, and the borosilicate glass container of Comparative Example 2, 0.7 mL of purified water 40a was poured into each glass container 40 as shown in FIG. 5, and then autoclaved at 121°C for 2 hours or 4 hours. 41 is a rubber stopper. Then, for the purified water in these glass containers, the amount of eluted Na (ppm) was measured using an atomic absorption spectrophotometer at the time when 1 hour had elapsed after the purified water was poured, and the amount of eluted B (ppm), the amount of eluted Al (ppm), the amount of eluted Si (ppm), the amount of eluted Ca (ppm), and the amount of eluted Ba (ppm) were measured using an inductively coupled plasma emission spectrophotometer. As a result, the measurement results shown in Tables 3 to 8 below were obtained. Injecting purified water into a glass container serves the purpose of accelerated testing to estimate how long it will take for the inner surface of a glass container to deteriorate when a pharmaceutical product (e.g., liquid, freeze-dried preparation, powder) is stored in the glass container; one hour after the injection of purified water corresponds to 1.6 years.

[0089] [Table 3]

[0090] [Table 4]

[0091] [Table 5]

[0092] [Table 6]

[0093] [Table 7]

[0094] [Table 8]

[0095] As shown in Tables 3 to 8, the borosilicate glass containers of Examples 1 and 2 had extremely low elution amounts of all six elements, and were found to have extremely excellent chemical durability. On the other hand, the borosilicate glass container of Comparative Example 1 had the same elution amounts of elements other than Na as the borosilicate glass containers of Examples 1 and 2, but the elution amount of Na was greater than that of the borosilicate glass containers of Examples 1 and 2. Moreover, the borosilicate glass container of Comparative Example 2, which was not subjected to a surface treatment, had a large amount of elution of all six elements.

[0096] Furthermore, the so-called contact angle, which is the angle between the liquid surface and the solid surface at the location where the free surface of the stationary liquid comes into contact with the solid wall, was measured for the glass container of Example 2, the glass container of Comparative Example 2, the polypropylene container (PP container), and the cycloolefin container (COP container). This contact angle is determined by the magnitude relationship between the cohesive force between the liquid molecules and the adhesive force between the liquid and the solid wall, and is defined as the contact angle θ, and the surface tension of the liquid is defined as σ. L Let the surface tension of the σ solid be σ S Let the interfacial tension between the solid and liquid be σ SL Then, it is expressed by the following equation. COSθ=(σ S -σ SL ) / σ L The PP container and the COP container were obtained by injection molding so as to have the same external shapes as the glass containers of Examples 1 and 2 and Comparative Examples 1 and 2.

[0097] The contact angles (degrees) were then measured for the four types of containers using the sessile drop method, which involves "actually measuring the coordinates of the droplet contour curve, assuming that the droplet contour shape is represented by a Young-Laplace theoretical curve, calculating the parameters of the curve from the coordinates of the contour shape, specifically determining a function that represents the curve, differentiating the function with respect to the endpoint coordinates to find a tangent, and finding the contact angle from the gradient of the tangent." The liquids used were water, 85% ethanol, acetone, and salad oil. The measurement results for the contact angles (degrees) are shown in Tables 9 to 12 below.

[0098] [Table 9]

[0099] [Table 10]

[0100] [Table 11]

[0101] [Table 12]

[0102] As shown in Table 9, the contact angle of the glass container of Example 2 exceeds 90° when the liquid is water, and it is found to have water repellency like the PP and COP containers. However, the contact angle of the glass container of Comparative Example 2 is less than 90° when the liquid is water, and it is found to be hydrophilic.

[0103] When the liquid was 85% ethanol, acetone, or salad oil, as shown in Tables 10 to 12, the glass container of Comparative Example 2 was impossible to measure, and the PP container and COP container were also almost impossible to measure, but the glass container of Example 2 had a certain contact angle and cannot be said to be lipophilic. [Industrial Applicability]

[0104] According to the present invention, a container suitable for use in pharmaceuticals and physicochemical applications can be provided. [Explanation of symbols]

[0105] 51 Plasma processing equipment 52 Vacuum Chamber 53 Lower electrode 54 Upper electrode 55 Pressure Gauge 56 Earth 57 Power supply for plasma generation 58 Exhaust flow control valve 59 Vacuum Pump 60 Gas inlet 62 Carrier gas inlet 65 Reactant material bubbler 66, 69 Mantle heater 67 Vapor source of reactant material 68 Raw material chamber for SAM film or self-assembled multilayer film 70 Vapor source of precursor material for SAM film or self-assembled multilayer film 71 Gas inlet 72 Current introduction terminal 73 Electrode Stage 74 Gas shower plate 75 Earth Ring 76 Insulating materials 77 Upper Chamber 78 Lower Chamber 79 Vacuum exhaust port 80 O-ring

Claims

1. a washing step of washing the inner surface of a glass container with a washing liquid consisting of water, an aqueous acid solution, an aqueous surfactant solution or an aqueous acid solution containing an added surfactant; a distortion removing step of heating and then cooling the glass container washed in the washing step to remove distortion; then, placing the glass container in a plasma processing device, and in a state in which an evaporation source for imparting hydrophilic groups is supplied into a vacuum chamber of a predetermined vacuum degree of the plasma processing device, the film-forming surface of the glass container is modified to be hydrophilic by a plasma atmosphere formed by a plasma generating unit; supplying an evaporation source for promoting hydrolysis or nucleophilic reaction of a precursor material for the SAM film or self-assembled multilayer film to the glass container with the hydrophilic film-forming surface, to form a SAM film or self-assembled multilayer film on the hydrophilic film-forming surface; and finally, strengthening the bond between the film-forming surface and the SAM film or self-assembled multilayer film in the vacuum chamber of the predetermined vacuum degree.

2. A method for treating the surface of a container, comprising the steps of: placing a resin container in a plasma processing device; supplying an evaporation source that imparts hydrophilic groups into a vacuum chamber of the plasma processing device having a predetermined vacuum degree; modifying a film-forming surface of the resin container by a plasma atmosphere formed by a plasma generating unit to make the film-forming surface hydrophilic; after completion of plasma irradiation by the plasma atmosphere, without opening to the atmosphere, supplying an evaporation source of a precursor material of the SAM film or self-assembled multilayer film to the resin container whose film-forming surface has been made hydrophilic in a vacuum chamber of the predetermined vacuum degree and supplying an evaporation source of a precursor material of the SAM film or self-assembled multilayer film into the vacuum chamber of the predetermined vacuum degree to form a SAM film or self-assembled multilayer film on the hydrophilized film-forming surface; and finally strengthening the bond between the film-forming surface and the SAM film or self-assembled multilayer film in the vacuum chamber of the predetermined vacuum degree.