Glass bottle and method to analyze gas composition using glass bottle

Abstract

To accurately quantify gas composition by effectively suppressing adsorption of the target component to the glass surface in analysis using glass bottles, even if the target component is gas component.SOLUTION: A glass bottle 11 has a silicone coating 3 on the surface 21 of the glass 2 of the glass bottle 11, and the silicone coating 3 has an inactivation treatment layer 4 that is treated to be inactivated.SELECTED DRAWING: Figure 2

Description

[Technical Field]

[0001] The present invention relates to a method for analyzing gas components and a glass bottle used for the analysis, and further to a surface treatment of the glass bottle. [Background technology]

[0002] Currently, gas components including volatile organic compounds (VOCs) are subject to total volume restrictions and odor restrictions in the atmospheric environment and automobile exhaust gases.

[0003] On the other hand, gas components, including volatile organic compounds (VOCs), are also important target components in skin gas analysis. That is, when conducting cancer screening, it has been customary to physically collect blood or actual affected tissue from the patient, and then perform processes such as liquid extraction on these biological samples before conducting component analysis. However, because collecting affected tissue places a heavy burden on the patient, skin gas analysis, which can provide highly accurate information that is intermediate between traditional urine or blood tests and detailed cell testing, has been attracting attention.

[0004] This skin gas analysis method involves placing a biological sample in a sealed glass bottle, collecting gas components generated from the biological sample in the bottle, and analyzing the collected gas. Regarding the application of headspace analysis to biological samples, a biological sample, particularly urine, is inserted into a closed and sealed test tube or bottle. Volatile compounds generated from the biological sample are then collected from the headspace, or collected in the headspace by solid-phase microextraction (SPME), followed by GC / MS analysis. A method for identifying specific bacteria in a biological sample has been disclosed (Patent Document 1). However, this method often fails to detect target components contained in gas components generated from the biological sample at low concentrations, potentially affecting the accuracy of the analysis of the target components. However, Patent Document 1 does not teach any means for reducing this effect.

[0005] Furthermore, even in a method of collecting gas components containing volatile inorganic compounds (VICs) in a glass bottle and analyzing the collected gas components, it is often impossible to detect the target component of analysis contained in the gas components generated from the sample if the concentration is low, which may affect the accuracy of the analysis of the target component of analysis.

[0006] Furthermore, in the method of collecting gas components in a glass bottle and analyzing the collected gas components, silanol groups are present on the glass surface of the glass bottle, and depending on the type of target component of the gas analysis, it may be adsorbed by the silanol groups on the glass surface, making it impossible to analyze trace components and reducing the analytical accuracy.

[0007] On the other hand, a method has been proposed in which silanol groups on the glass surface are alkylsilylated, i.e., end-capped, to reduce adsorption (Non-Patent Document 1), and glass bottles that have been deactivated to reduce component adsorption to active sites on the glass surface are commercially available as inactive glass bottles.

[0008] Furthermore, in synthetic resin containers, the absence of silanol groups prevents adsorption. However, there is a risk that volatile plasticizers and other substances may evaporate when the vials, which are often used to volatilize the components of interest in the headspace method, are kept warm or heated. In addition, the hydrophobic nature of resins reduces the recovery rate of hydrophobic compounds. For these reasons, glass bottles are more suitable than synthetic resin containers for analyzing volatile gas components. [Prior art documents] [Patent documents]

[0009] [Patent Document 1] Special Publication 2016-513259 [Non-patent literature]

[0010] [Non-Patent Document 1] Waters, Inert (DV) Glass Vials, [online], [Retrieved January 17, 2024], Internet <url: https: www.waters.com waters ja_jp %e4%b8%8d%e6%b4%bb%e6%80%a7%ef%bc%88dv%ef%bc%89%e3%82%ac%e3%83%a9%e3%82%b9%e3%83%90%e3%82%a4%e3%82%a2%e3%83%ab nav.htm?locale="ja_JP&cid=10091812"> Summary of the Invention [Problem to be solved by the invention]

[0011] However, conventional glass bottles that have been deactivated by alkylsilylation of silanol groups on the glass surface are primarily intended for storing solutions. The solution contains target components, such as acids and amines, as well as matrix components, such as surfactants present in environmental water and proteins present in cells and blood, present uniformly throughout the solution. These matrix components uniformly cover the glass surface before the target components, creating a masking effect that reduces the number of adsorption sites, thereby suppressing the adsorption of the target components to the glass surface. Therefore, when analyzing liquid samples, using glass bottles that have been deactivated in the conventional manner has not caused any problems in trace analysis.

[0012] On the other hand, when conventional glass bottles are used for analyzing gas components, the matrix components are difficult to vaporize, and even if they do vaporize, they adhere unevenly to the glass surface, making the vaporized target components, such as acids and amines, easily adsorb to the glass surface. Furthermore, the glass surface has irregularities and cracks, and gas components, which tend to diffuse, easily penetrate these irregularities and cracks and are adsorbed onto the glass surface. Therefore, even glass bottles that were not problematic for liquid samples have encountered problems when used for gas samples, such as the adsorption of target components.

[0013] Furthermore, in the method of alkylsilylating and end-capping silanol groups on the glass surface, it is difficult to end-capping all silanol groups, and many silanol groups remain on the glass surface. This does not adequately suppress the adsorption of target components onto the glass surface, making trace analysis impossible and reducing analytical accuracy.

[0014] Specifically, in headspace / gas chromatography (HS / GC) analysis of gas components as target components, the quantification area value of the target components varies depending on the size of the conventional inactivated glass bottle used. Specifically, the larger the capacity of the glass vial used as the deactivated glass bottle in the conventional technology, the larger the contact area between the target components and the glass surface, resulting in adsorption of the target components to the glass surface and a smaller quantification area value. This effect was particularly pronounced for carboxylic acids.

[0015] Here, we compare the quantitative area values ​​of carboxylic acids, a gas component collected with a syringe by the headspace method, using two commercially available deactivated glass vials without silicone coating, one 20 mL vial and the other 40 mL vial, which differ only in volume. Specifically, 2 μL of a solution of C1–C8 carboxylic acids (each concentration: 100 ppm) was added to each of two commercially available deactivated glass vials, which differ only in volume, and left at 35°C for 15 hours. The vaporized carboxylic acids were collected from the headspace in the vials with a syringe and analyzed using a gas chromatograph equipped with an FID detector (GC-FID). The analytical conditions are shown below. GC-FID:GC-2010 Plus (Shimadzu Corporation) Column: InertCap® Pure-WAX (GL Sciences) 0.32mm I.D. x 60m, df = 0.5μm Column oven temperature: 45°C (5 min) → 10°C / min → 220°C (5 min) Carrier gas: hydrogen Inlet: Split, 200℃ Pressure 70.4 kPa, total flow rate 15.2 mL / min, column flow rate 2.44 mL / min Linear velocity: 39.5 cm / sec, purge flow rate: 3.0 mL / min, split ratio: 4 Detector: FID, 220℃

[0016] As a result, as shown in Figure 9, the quantification area value for the carboxylic acid, the target component of analysis, was smaller in the 40 mL vial than in the 20 mL vial. This is because the contact area between the target component of analysis and the glass surface was larger when the vial volume was larger, and more of the target component of analysis was adsorbed onto the glass surface.

[0017] Furthermore, in the analysis of gas components using glass bottles, the stronger the adsorptivity of the target component of analysis, the more the target component of analysis is adsorbed to the glass surface, resulting in a smaller quantitative area value. Furthermore, for carboxylic acids, the lower the molecular weight, the stronger the adsorptivity to the glass surface, so that molecules smaller than caproic acid have a stronger tendency to adsorb.

[0018] As described above, in the headspace / gas chromatography (HS / GC) analysis using glass bottles that have been subjected to the conventional deactivation treatment, the target components of analysis are adsorbed onto the glass surface of the glass bottle, making it impossible to accurately quantify the target components of analysis.

[0019] Therefore, one object of the present invention is to provide a glass bottle that is more inert than glass bottles that have been subjected to conventional deactivation treatment. Another object is to effectively suppress adsorption of a target component to the glass surface, even if the target component is a gas, in an analysis using a glass bottle. Another object is to provide a glass bottle that can effectively suppress adsorption of a target component to the glass surface, even if the target component is a gas. Another object is to accurately quantify a gas component in an analysis using a glass bottle. Another object is to provide a glass bottle that can accurately quantify a gas component. Another object is to easily perform trace component analysis in an analysis of gas components using a glass bottle, even if the target component is a low concentration. Another object is to provide a glass bottle that can easily perform trace component analysis in an analysis of gas components using a glass bottle, even if the target component is a low concentration. [Means for solving the problem]

[0020] The present invention, which is a means for solving the above-mentioned problems, is a glass bottle having a glass surface subjected to a novel and distinctive surface treatment.

[0021] Specifically, it is a glass bottle with a silicone coating on the glass surface.

[0022] The glass bottle also has a silicone coating on the glass surface, and the silicone coating has a passivation treatment layer.

[0023] The glass bottle also has a silicone coating on the glass surface with a thickness of 1 nm or more and less than 80 nm.

[0024] The glass bottle also has a silicon coating on the glass surface with a thickness of 1 nm or more and less than 80 nm, and the silicon coating has a passivation treatment layer.

[0025] In the glass bottle, the raw material of the silicon coating is selected from the group consisting of tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, and tetrapropoxysilane, alkyltrialkoxysilanes such as methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, ethyltrialkoxysilane, and propyltrimethoxysilane, dialkyldialkoxysilanes such as dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldipropoxysilane, diethyldialkoxysilane, and dipropyldimethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, and the like. The glass bottle is made of one or more materials selected from the group consisting of trialkylmonoalkoxysilanes such as trimethylpropoxysilane, triethylmethoxysilane, and tripropylmethoxysilane, inorganic polysilazanes, perhydropolysilazanes, dimethyl-type cyclic siloxanes such as hexamethylcyclotrisiloxane and octamethylcyclotetrasiloxane, diethyl-type cyclic siloxanes, dipropyl-type cyclic siloxanes, hexamethyldisiloxane, linear polydimethylsiloxanes such as octamethyltrisiloxane and decamethyltetrasiloxane, linear polydiethylsiloxanes, and linear polydipropylsiloxanes.

[0026] The glass vial for analyzing gas components has a silicon coating on the glass surface.

[0027] The present invention also provides a glass vial for analyzing gas components, which has a silicon coating on the glass surface, the silicon coating having an inactivation treatment layer.

[0028] It is also a glass bottle for analyzing gas components that has a silicon coating on the glass surface with a thickness of 1 nm or more but less than 80 nm.

[0029] The glass bottle for analyzing gas components is also provided with a silicon coating having a thickness of 1 nm or more and less than 80 nm on the glass surface, the silicon coating having an inactivation treatment layer.

[0030] Also, there is an analytical method in which a sample is placed in a glass bottle with a silicon coating on the glass surface, left to stand at a predetermined constant temperature for a predetermined time, and the gas components generated from the sample are analyzed.

[0031] Also, there is provided an analytical method in which a sample is placed in a glass bottle having a silicon coating on the glass surface, the silicon coating having an inactivation treatment layer, and the sample is left at a predetermined constant temperature for a predetermined time, and the gas components generated from the sample are analyzed.

[0032] The analytical method also involves placing a sample in a glass bottle with a silicon coating on the glass surface that is 1 nm or more but less than 80 nm thick, leaving it at a predetermined constant temperature for a predetermined time, and analyzing the gas components generated from the sample.

[0033] Also, there is provided an analytical method in which a sample is placed in a glass bottle having a silicon coating with a thickness of 1 nm or more but less than 80 nm on the glass surface, the silicon coating having an inactivation treatment layer, and the sample is left at a predetermined constant temperature for a predetermined time, and the gas components generated from the sample are analyzed.

[0034] In addition, in the above analytical method, a sample is placed in the glass bottle and a collector is also placed therein, the gas components generated from the sample are collected by the collector, the gas components are recovered from the collector, and the gas components are analyzed.

[0035] In the above analytical method, the collector is a silica monolith collector.

[0036] In the above analytical method, the sample is a biological sample.

[0037] The glass surface treatment method also includes a cleaning process to remove organic matter adhering to the glass surface and / or an activation process to activate silanol groups on the glass surface, and then forms a silicon coating on the glass surface with a thickness of 1 nm or more and less than 80 nm.

[0038] Also, this is a glass surface treatment method that performs a cleaning treatment to remove organic matter adhering to the glass surface and / or an activation treatment to activate silanol groups on the glass surface, forms a silicon coating with a thickness of 1 nm or more and less than 80 nm on the glass surface, and then performs a passivation treatment on the silicon coating, thereby forming a silicon coating with a passivation treatment layer on the glass surface.

[0039] In addition, in the above-mentioned glass surface treatment method, after the silicon coating is formed on the glass surface, a cleaning treatment and / or a drying treatment is carried out.

[0040] Also provided is a method for manufacturing glass bottles using the above-mentioned glass surface treatment method. [Effects of the Invention]

[0041] According to the present invention as described above, it is possible to provide a glass bottle that is more inert than glass bottles that have been subjected to conventional deactivation treatment. Furthermore, in an analysis using a glass bottle, it is possible to effectively suppress adsorption of the target component to the glass surface, even if the target component is a gas component. Furthermore, it is possible to provide a glass bottle that can effectively suppress adsorption of the target component to the glass surface, even if the target component is a gas component. Furthermore, in an analysis using a glass bottle, it is possible to accurately quantify the target component, that is, the gas component. Furthermore, it is possible to provide a glass bottle that can accurately quantify the target component, that is, the gas component. Furthermore, in an analysis of gas components using a glass bottle, it is possible to easily perform trace component analysis, even if the target component, that is, the gas component, is at a low concentration. Furthermore, in an analysis of gas components using a glass bottle, it is possible to easily perform trace component analysis, even if the target component, that is, the gas component, is at a low concentration. [Brief explanation of the drawings]

[0042] [Figure 1] Partial cross-sectional view of one embodiment of the glass bottle of the present invention [Figure 2] Partial cross-sectional view of another embodiment of the glass bottle of the present invention [Figure 3] Partial cross-sectional view of another embodiment of the glass bottle of the present invention [Figure 4] Graphical representation of recovery of highly hydrophobic hydrocarbons [Figure 5] Graph showing the recovery rates of acetic acid, propionic acid, butyric acid, and valeric acid [Figure 6] Graph showing the recovery rates of octylamine and 2,6-dimethylaniline [Figure 7] Chromatogram of gas components generated from biological samples [Figure 8] Table showing the ratio of quantitative area values ​​of gas components generated from biological samples [Figure 9] A graph showing the quantitative area values ​​of C1 to C8 carboxylic acids measured using a conventional vial. DETAILED DESCRIPTION OF THE INVENTION

[0043] An embodiment of the present invention will be described below. The present invention is a glass bottle with a silicone coating. The silicone coating is formed on at least the gas contact portion where the glass surface of the glass bottle comes into contact with gas components generated from a sample, specifically, on the inner surface of the glass bottle. At least the entire inner surface of the glass bottle is covered with this silicone coating. Note that the portion to be covered with the silicone coating need only be the gas contact portion where the gas components in the glass bottle come into contact with the glass surface. However, when forming the silicone coating on the gas contact portion of the glass bottle, depending on the formation method, the silicone coating may be formed not only on the gas contact portion but also on the surface of the glass bottle including the gas contact portion, such as the outer surface of the glass bottle. A specific example of a glass bottle is a vial.

[0044] The term "sample" includes samples made of solids and / or liquids, as well as samples made of organic and / or inorganic compounds. Biological samples are also included in the term "sample." Furthermore, "gas components" are volatile compounds in the gaseous form generated from a sample, including volatile organic compounds (VOCs) and volatile inorganic compounds (VICs).

[0045] By providing a silicone coating on the inside surface of the glass bottle, the glass surface is not exposed, and recesses and cracks in the unevenness of the glass surface are filled or sealed, eliminating the influence of silanol groups on the glass surface and the influence of the unevenness and cracks on the glass surface, and preventing gas components, which are the components to be analyzed, from being adsorbed to the silanol groups or entering the recesses and cracks in the unevenness and being adsorbed to the glass surface.

[0046] Alternatively, a silicone coating may be provided on the inner glass surface of a glass bottle, and the silicone coating may be deactivated to form a deactivation layer on the silicone coating. This is because, depending on the raw materials and reaction conditions used to form the silicone coating, silanol groups may remain on the silicone coating. The silicone coating can be deactivated using a low-molecular-weight silylating agent capable of bonding organic compounds that do not nonspecifically adsorb to the silanol groups on the silicone coating surface to destroy the silanol groups remaining on the silicone coating. Forming a silicone coating on the glass surface results in a glass bottle with a uniform surface that is less susceptible to gas component adsorption, and deactivating the silicone coating can further enhance the inertness of the glass bottle surface.

[0047] The thickness of the silicone coating on the glass surface of the glass bottle may be 80 nm or more, but is preferably less than 80 nm. The glass surface of the glass bottle refers to one surface of the glass bottle. When a silicone coating is formed on both the inner and outer walls of the glass bottle, each thickness is preferably less than 80 nm, and the total thickness is preferably less than 160 nm. This is because if the thickness of the silicone coating formed on one surface of the glass is 80 nm or more, the transparency of the glass bottle will decrease. When forming a silicone coating on the glass surface, it is easy to form it on the entire glass bottle, including the inner and outer walls. In this case, if an 80 nm silicone coating is formed on each of the inner and outer walls of the glass bottle and the total thickness of the silicone coating is 160 nm or more, the glass bottle will turn white and the inside of the glass bottle will not be visible, but a transparent glass bottle is easier to use. In addition, a glass bottle with a silicone coating of 80 nm or more will have a highly hydrophobic surface, which will cause hydrophobic adsorption of fat-soluble gas components.

[0048] The glass bottle of the present invention is configured with a silicone coating on the inner glass surface of the glass bottle. Specifically, as shown in FIG. 1, glass bottle 1 is configured with a silicone coating 3 provided on the inner glass surface 21 of glass 2 of glass bottle 1, covering glass surface 21. The glass bottle of the present invention may also be configured with a silicone coating on the inner glass surface of the glass bottle, and a passivation treatment layer on the silicone coating, forming the outermost layer of the silicone coating. Specifically, as shown in FIG. 2, glass bottle 11 is configured with a silicone coating 3 provided on the inner glass surface 21 of glass 2 of glass bottle 11, covering glass surface 21, and a passivation treatment layer 4 provided on surface 31 of silicone coating 3 opposite glass surface 21, formed by alkylsilylation of silanol groups on surface 31 of silicone coating 3.

[0049] A silicon coating may be composed of 100% silicon oxide by mass, or may contain silicon oxide, unavoidable impurities, and other components. As described below, a silicon coating is formed by contacting the raw material of the silicon coating with the glass surface and processing it, and depending on the reaction conditions, the silicon coating may contain components other than silicon oxide. Therefore, a silicon coating can also be said to be a film containing silicon oxide.

[0050] Even if the silicon coating contains components other than silicon oxide, as long as it can cover the glass surface, it can prevent gas components from coming into contact with the glass surface and being adsorbed thereon.

[0051] The passivation treatment layer on the silicon coating also inactivates the silanol groups on the surface of the silicon coating with a silylating agent, and depending on the reaction conditions, etc., some silanol groups from the silylating agent may remain unreacted.

[0052] The silicon coating may consist of a single first layer made from one type of raw material, or a single first layer made from two or more types of raw materials. Alternatively, a multi-layer silicon coating may be formed by laminating one or more second layers made from one or more different raw materials on the surface of a first layer made from one or more raw materials. For example, as shown in FIG. 3 , a silicon coating 3 is provided on the inner glass surface 21 of the glass 2 of a glass bottle 12, covering the glass surface 21. The silicon coating 3 is composed of three silicon oxide layers 71, 72, and 73. A passivation treatment layer 4 is provided on the surface 31 of the silicon coating 3 opposite the glass surface 21, formed by silylation of silanol groups on the surface 31 of the silicon coating 3. Although not shown, a silicon coating composed of multiple silicon oxide layers without a passivation treatment layer may also be formed.

[0053] When a silicon coating is formed by stacking multiple layers in this way, the top layer, which forms the surface of the silicon coating, is preferably a film made from a dialkyldialkoxysilane as a raw material, because this configuration allows the dialkyldialkoxysilane to react with the remaining silanol groups, leaving alkyl groups on the surface of the silicon coating, thereby reducing the influence of the silanol groups on the surface of the silicon coating.

[0054] The method for manufacturing a glass bottle, particularly the glass surface treatment method for forming a silicone coating on the glass surface, includes a pretreatment step of cleaning and / or activating the glass surface, a silicone coating formation step, a passivation treatment layer formation step, and a posttreatment step of cleaning and / or drying the glass bottle. These steps may be performed separately or consecutively. Note that in these methods, the passivation treatment layer formation step and the posttreatment step may be omitted.

[0055] <Cleaning treatment and / or activation treatment> The manufacturing method for glass bottles involves preparing a glass bottle and first performing a cleaning and / or activation process on the glass surface as a pretreatment step. The cleaning process removes organic compounds adhering to the glass surface. Examples of cleaning processes include cleaning with organic solvents such as isopropanol, acetone, chloroform, and hexane to remove organic compounds adhering to the glass surface; baking the glass in the presence of oxygen at 450°C or higher to remove the organic compounds; immersing the glass bottle in ozone water to decompose and remove the organic compounds, followed by autoclaving and cleaning / activation; and simultaneously cleaning and activating the glass by decomposing the organic compounds on the glass surface in a vacuum chamber filled with ozone gas and then heating and removing them under reduced pressure. These methods completely remove organic compounds adhering to the glass surface. However, if there is no possibility of organic compounds adhering to the glass bottle, this cleaning process is not necessary.

[0056] The activation treatment hydrolyzes the siloxane bonds on the glass surface, activating them into silanol groups. When cleaning treatment is performed by baking the glass, the siloxane bonds that have undergone dehydration condensation during high-temperature treatment are hydrolyzed back into silanol groups by acid washing or the like, followed by thorough water rinsing and drying under reduced pressure at 120-150°C for 10 hours or more to activate the silanol groups on the glass surface. Alternatively, adsorbed water on the glass surface can be removed by heat treatment at 120-150°C for several hours, activating the silanol groups.

[0057] In the pretreatment, either the cleaning treatment or the activation treatment may be performed, but it is preferable to perform both treatments. The cleaning treatment and activation treatment of the glass surface can also be performed simultaneously by decomposing organic compounds on the glass surface in a vacuum chamber filled with ozone gas and then removing them under reduced pressure while heating. Any method can be used as the pretreatment step as long as it can remove organic compounds that inhibit the reaction and activate silanol groups to form a silicon coating.

[0058] <Silicon coating formation> Next, in the silicon film forming process, a silicon film is formed on the glass surface. This is to prevent the glass surface from being exposed and to fill or seal any recesses or cracks in the unevenness of the glass surface. Raw materials for the silicon film are not particularly limited, but include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, and tetrapropoxysilane; alkyltrialkoxysilanes such as methyltrimethoxysilane, methyltriethoxysilane, methyltrippropoxysilane, ethyltrialkoxysilane, and propyltrimethoxysilane; dialkyldialkoxysilanes such as dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldipropoxysilane, diethyldialkoxysilane, and dipropyldimethoxysilane; trimethylmethoxysilane, trimethylethoxysilane, trimethylpropoxysilane; It is possible to use one or more low molecular weight silicon compounds selected from the group consisting of silane, trialkylmonoalkoxysilanes such as triethylmethoxysilane and tripropylmethoxysilane, inorganic polysilazanes, perhydropolysilazanes, dimethyl cyclic siloxanes such as hexamethylcyclotrisiloxane and octamethylcyclotetrasiloxane, diethyl cyclic siloxanes, dipropyl cyclic siloxanes, hexamethyldisiloxane, linear polydimethylsiloxanes such as octamethyltrisiloxane and decamethyltetrasiloxane, linear polydiethylsiloxanes, and linear polydipropylsiloxanes.

[0059] The method for forming a silicon coating involves first applying a silicon coating raw material to the surface of a glass bottle. While the method for forming the silicon coating is not particularly limited, it is desirable to apply the silicon coating raw material to the entire glass surface in a uniform thickness. Next, the glass bottle with the silicon coating raw material applied thereto is reacted in an inert gas at a temperature appropriate for the silicon coating raw material used to form the silicon coating.

[0060] As described above, the silicon coating may be composed of a single layer made of one or more raw materials, but the silicon coating may also be composed of multiple layers by laminating one or more second layers made of one or more raw materials different from the raw materials of the first layer on the surface of the first layer made of one or more raw materials.

[0061] Although it depends on the reaction conditions for forming the layers that make up the silicon coating, the process of forming a silicon oxide layer is repeated one to several tens of times to thicken the silicon oxide layer and form the silicon coating. Specifically, the low molecular weight silicon compound bonds with the glass surface, and the low molecular weight silicon compound polymerizes to form a silicon oxide layer, which coats the glass surface and forms the silicon coating. Each layer may be made of the same silicon coating material and have the same composition, or the silicon coating may be made of multiple layers of different compositions, each made of different materials.

[0062] Although it varies depending on the formation conditions and type of reagent, film formation is generally achieved through the following reactions. With trifunctional reagents, three-dimensional polymerization and decomposition are repeated with an acid catalyst, forming a three-dimensional film. Alkaline catalysts also form planar films. With bifunctional reagents, polymerization basically occurs in a linear chain, but adding an oxidation catalyst or trifunctional reagent can cause it to grow three-dimensionally. With monofunctional reagents, polymerization can be stopped or added to incorporate the polymer into the film, allowing the density to be adjusted. Depending on the type of reagent, catalyst, temperature, and conditions, the film can become three-dimensionally thick or linearly long, and by combining these, it is possible to form a film tailored to the purpose.

[0063] <Silicon coating deactivation treatment> Next, the silicon coating is deactivated in the silicon coating deactivation process. Although the glass bottle with the silicon coating formed as described above exhibits sufficient inertness against volatile compounds, silanol groups may also be present on the silicon coating surface. In order to further increase the inertness, a low molecular weight silylating agent is used to chemically bond an organic compound that does not nonspecifically adsorb gas components to the silanol groups on the silicon coating surface, thereby deactivating the silicon coating surface. Note that this silicon coating deactivation process may not be performed.

[0064] The low molecular weight silylating agent is not particularly limited as long as it can bond an organic compound that does not nonspecifically adsorb gas components to a silanol group. Examples of the low molecular weight silylating agent include methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, trimethylchlorosilane, dimethyldichlorosilane, methyltrichlorosilane, hexamethyldisilazane, hexamethylcyclotrisiloxane, dimethyl-type cyclic siloxanes including octamethylcyclotetrasiloxane, diethyl-type cyclic siloxanes, dipropyl-type cyclic siloxanes, hexamethyldisiloxane, linear polydimethylsiloxanes such as octamethyltrisiloxane and decamethyltetrasiloxane, linear polydiethylsiloxanes, linear polydipropylsiloxanes, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldipropoxysilane, trimethylmethoxysilane, trimethylethoxysilane, and the like. It is preferable to use one or more selected from the group consisting of hydroxysilane, trimethylpropoxysilane, dimethoxymethylphenylsilane, dimethoxydiphenylsilane, diphenyltetramethyldisilazane, diphenyltetramethyldisilazane, phenyltrimethoxysilane, cyanotricyanopropyltrimethoxysilane, cyanoethyltriethoxysilane, cyanopropyltrimethoxysilane, aminopropyltriethoxysilane, aminopropyltrimethoxysilane, aminoethyltriethoxysilane, aminopropyltriethoxysilane, aminoethyltrimethoxysilane, (3-glycidyloxypropyl)trimethoxysilane, (3-glycidyloxypropyl)triethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-glycidoxypropyltriethoxysilane. By bonding an organic compound that does not nonspecifically adsorb gas components to the silanol groups on the silicon coating surface, it is possible to inactivate the silanol groups so that they do not come into direct contact with and adsorb gas components.

[0065] The silicon film can be deactivated by a conventionally known silylation method such as a solution reaction in a non-aqueous solution or a gas phase reaction in an inert gas.

[0066] By performing the deactivation treatment of the silicone coating, the glass surface of the glass bottle is provided with a silicone coating and a deactivation treatment layer composed of an organic compound that does not nonspecifically adsorb gas components and is bonded to the silanol groups on the surface of the silicone coating.

[0067] <Cleaning process and / or drying process> Finally, as a post-treatment step, after the silicon coating formation step or the silicon coating deactivation step, the glass bottle is washed and / or dried. As a post-treatment step, the glass bottle can be washed using a volatile solvent such as acetone or methanol and dried in a short time. However, this washing and / or drying step may be omitted.

[0068] Next, specific examples of the manufacturing method and glass surface treatment method for each step will be described. First, a cleaning treatment and / or activation treatment is carried out as a pretreatment step using the above-mentioned method, apparatus, tools, etc.

[0069] The formation of a silicon coating is carried out as follows. First, a container resistant to organic solvents, such as a glass beaker or an enamel beaker, is used to weigh out the silicon coating raw material. The silicon coating raw material is then dissolved in an alcohol solvent, an aromatic hydrocarbon solvent such as benzene, toluene, xylene, or cumene, or a hydrocarbon solvent such as hexane, octane, or decane to prepare a silicon reaction solution with a concentration of 1 to 20%. Hereinafter, the reaction solution in which a low-molecular-weight silicon compound, the silicon coating raw material, is dissolved in an organic solvent will be referred to as the silicon reaction solution. A convenient dip coating method involves immersing a pretreated glass bottle in the silicon reaction solution and coating the entire surface of the glass bottle with the silicon coating raw material, or pouring the silicon reaction solution into the glass bottle and coating only the inner surface of the glass bottle with the silicon coating raw material. In the dip coating method, it is preferable to place the glass bottle in the silicon reaction solution and then degas it under reduced pressure to remove any air bubbles on the glass surface. Alternatively, a spray coating method can be used in which the silicon reaction solution is formed into a gauze and sprayed onto the inner surface of the glass bottle, leaving the silicon coating raw material. In this way, any method can be used without particular limitations as long as it can uniformly deposit the raw material of the silicon coating onto the glass surface.

[0070] Next, the glass bottle with the silicon coating raw material attached is reacted in an inert gas, such as nitrogen or argon, using a vacuum dryer or vacuum chamber at a temperature appropriate for the silicon coating raw material used. While the reaction conditions are not particularly limited, a reaction time of 80 to 170°C for at least 4 hours is recommended. At temperatures below 80°C, the reaction progresses slowly due to the influence of volatile components contained in the raw materials. At temperatures above 170°C, the reaction rate increases, making it difficult to control the formation of an optimal film thickness. The reaction time varies depending on the presence or absence of a catalyst, the reaction temperature, the reagent raw materials used, and the synthesis scale, and is determined according to the reaction conditions. However, in a gas-phase reaction without the supply of oxygen and / or ozone, the silicon coating is formed slowly using the oxygen atoms contained in the raw material molecules. Therefore, unlike the continuous treatment method in which oxygen and / or ozone are supplied, which will be described later, time is required for the silicon coating to stabilize; therefore, a reaction time of at least 4 hours is preferred.

[0071] Alternatively, a silicon reaction solution can be placed in a separable flask equipped with a reflux tube or an enamel vessel with a glass glaze baked onto the surface of a metal vessel. The target glass bottle is then placed inside the solution, and the silicon reaction solution is heated using a mantle heater, a temperature-controlled bath, or a jacket. The solvent in the silicon reaction solution is refluxed for at least four hours, creating a silicon coating on the glass surface. The higher the concentration of the silicon reaction solution and the reaction temperature, the easier the silicon coating will form and the thicker it will be. While optimization of synthesis conditions is required based on the results of gas analysis, a standard approach is to reflux the silicon reaction solution in a 1-10% concentration cumene solvent for at least four hours. Repeated reactions with the addition of 0.1-5% oxidation catalysts such as hydrochloric acid, acetic acid, formic acid, hydrogen peroxide, and citric acid can promote the formation of a silicon coating and increase its thickness. This method allows the production of transparent silicon coatings with thicknesses of 1 nm to less than 80 nm.

[0072] Next, as a silicon coating deactivation treatment using a solution reaction silylation method, a glass bottle with a silicon coating formed thereon is placed in a silylation reaction solution prepared by mixing a low-molecular-weight silylating agent with an aromatic hydrocarbon solvent such as benzene, toluene, xylene, or cumene, or a hydrocarbon solvent such as hexane, octane, or decane, and the solvent is refluxed and heated for at least four hours. By bonding an organic compound that does not nonspecifically adsorb gas components to the silanol groups on the silicon coating surface, the inertness of the glass bottle can be increased. While optimization of the silicon coating deactivation treatment conditions is necessary depending on the evaluation of the gas component analysis results, it is preferable to reflux the solvent and heat for at least four hours in a 1-10% concentration silylation reaction solution in decane solvent.

[0073] Alternatively, a vapor-phase silylation method can be used to deactivate silicon coatings. A glass bottle containing a silicon coating and a low-molecular-weight silylating agent are placed in a vacuum chamber, and the silicon coating can be deactivated in the vapor phase. While optimization of the silicon coating deactivation conditions is necessary based on the analysis of gas components, a reaction time of 150–350°C for at least four hours is recommended. While the deactivation process using a low-molecular-weight silylating agent proceeds more easily at higher reaction temperatures, since this is a post-silicon coating deactivation process, it is also important that the silicon coating does not degrade due to the reaction temperature. Therefore, a reaction temperature of 150°C or higher is recommended for any silylating agent, at which a deactivation reaction can be expected. However, it is preferable to keep the reaction temperature below 350°C, at which the silicon coating does not degrade. Furthermore, the thicker the silicon coating, the greater the surface roughness. This requires time for the low-molecular-weight silylating agent to diffuse evenly, and deactivation proceeds from the contact points with the low-molecular-weight silylating agent. Considering the thickness of the silicon film is less than 80 nm, a reaction time of 4 hours or more is recommended.

[0074] Next, a specific example of a continuous treatment method for a glass bottle manufacturing method and a glass surface treatment method, including a method for forming a silicon coating on the surface of a glass bottle and / or a method for inactivating the silicon coating, will be described. The continuous treatment method uses a vacuum chamber vessel that has a raw material supply port, an oxygen and / or ozone gas supply port, and a vacuum pump suction and exhaust port, and through which glass bottles can be put in and taken out. The temperature inside the reactor can be controlled to 40 to 400°C, and the pressure can be controlled to 0.75 to 910 mmHg. The vessel has a supply port for supplying silicon reaction solution with an inert gas such as nitrogen, and a supply port for oxygen and / or ozone gas at 10 to 100 g / m. 3 Oxygen and / or ozone gas is used to decompose and remove organic compounds on the glass surface, to activate the glass surface, and as a reaction catalyst.

[0075] The cleaning and activation processes for decomposing organic compounds on the glass surface are carried out as follows: The glass bottle is placed in a vacuum chamber, and the pressure is 1 to 5 mmHg, the temperature is 250 to 400°C, and the concentration is 10 to 100 g / m 3 Oxygen and / or ozone are introduced into a vacuum chamber. The reaction is allowed to proceed for at least 0.5 minutes, decomposing the organic compounds on the glass surface and simultaneously activating the silanol groups on the glass surface. The pressure is increased to 1-5 mmHg, and the decomposed organic compounds are evacuated. If there is a large amount of visible deposits on the glass surface, these procedures are repeated.

[0076] Next, the silicon film formation process is divided into a base formation process and a main process. In the base formation process, the silicon reaction solution is supplied into a vacuum chamber at a pressure of 1 mmHg or less and a temperature of 250 to 400°C with an inert gas such as nitrogen, argon, or helium so that the concentration of low-molecular-weight silicon compounds in the chamber is 0.01 to 10%. The reaction is carried out for 0.5 minutes or more, forming a silicon film base on the glass surface.

[0077] Furthermore, in this process, a low molecular weight silicon compound, which is the raw material for the silicon film, is supplied into the vacuum chamber at a pressure of 1 mmHg or less and a temperature of 250 to 400°C with an inert gas such as nitrogen, argon, or helium so that the concentration of the raw material for the silicon oxide film in the chamber is 0.01 to 10%. 3 Oxygen and / or ozone are supplied into the vacuum chamber and allowed to react for at least 0.5 minutes to form a silicon coating on the glass surface. Unreacted silicon coating raw materials are then evacuated until the pressure inside the vacuum chamber reaches 5 mmHg or less. This process is then repeated 1 to 50 times until the silicon coating reaches the target thickness. To maintain the transparency of the glass bottle, it is recommended to repeat the process approximately 10 times to form a silicon coating less than 80 nm thick.

[0078] Next, the silicon film is deactivated. At a pressure of 1 mmHg or less and a temperature of 250°C to 400°C, the low-molecular-weight silylating agent described above, the raw material for the deactivation process, is supplied into the vacuum chamber with an inert gas such as nitrogen, argon, or helium so that the concentration inside the chamber is 0.01 to 10%. The reaction is allowed to continue for 0.5 minutes or more, and the silicon film is deactivated. Unreacted low-molecular-weight silylating agent is evacuated until the pressure drops below 1 mmHg. This deactivation process is repeated until a level of inertness suitable for gas component analysis is achieved.

[0079] One analytical method for assessing the effectiveness of glass surface treatment on glass bottles involves placing a fixed amount of three or more representative compounds—acidic, hydrophobic, and basic—in a surface-treated glass bottle and leaving it at 35°C for at least 30 minutes. The gas components inside the bottle are then analyzed, and an adsorption assessment is performed based on the quantitative area value to determine whether any gas components are adsorbed to the glass bottle. By evaluating adsorption and optimizing the glass surface treatment method, the accuracy of gas component analysis can be improved. If direct analysis of the gas components inside the glass bottle is difficult, a recommended method is to place an adsorbent inside the glass bottle and then perform a solvent extraction of the gas components from the adsorbent for analysis.

[0080] A method for analyzing gas components generated from a sample using the glass bottle of the present invention will be described. The analytical method can employ a headspace method. In static headspace sampling (SHS), for example, a sample is placed in a glass bottle, the bottle is capped, and the bottle is left standing for a predetermined time at a constant temperature, e.g., room temperature (25°C) or higher, to generate gas components from the sample, and the concentration of the gas components is analyzed. The gas components generated from the sample in the glass bottle are then collected using a syringe or other device and introduced into a gas chromatograph (GC) or gas chromatograph mass spectrometer (GC-MS) equipped with various detectors such as FID. The peak areas of the chromatogram can be measured for analysis. The sample includes liquid samples such as solutions and solid samples, as well as biological samples, including liquid biological samples such as urine, blood, plasma, and serum, and solid biological samples such as tissue and skin fragments.

[0081] Another analytical method within the headspace method (Headspace Sorptive Extraction (HSSE) or Headspace-Monolithic Material Sorptive Extraction (HS-MMSE)) involves placing a sample in a glass bottle and a collector, which is then placed in the gas phase space within the bottle by, for example, suspending it from the lid. The lid is then closed and the bottle is left to stand for a predetermined time at a predetermined temperature, e.g., a constant temperature above room temperature (25°C), to generate gas components from the sample. The generated gas components are then collected by the collector and concentrated. The gas components are then recovered from the collector by elution with a solvent or by desorption or desorption by heating. The recovered gas components are then introduced into a gas chromatograph (GC) or gas chromatograph mass spectrometer (GC-MS) equipped with various detectors, such as an FID, and analyzed by measuring the peak areas of the chromatogram. The timing of adding the scavenger to the glass bottle is not particularly limited, and it can be added at the same time as the sample is added, or after the sample is added, for example, after gas components are generated from the sample.

[0082] The type of collector is not particularly limited, and the shape may be powder, granules, monolithic, or the like, and the material may be silica gel, etc. For ease of insertion and removal from a glass bottle, a collector in which a glass stirrer is coated with polydimethylsiloxane or a silica monolith collector may be used, but a silica monolith collector is preferred because it has a large surface area and can collect a large amount of gas components, making it easier to detect, qualify, and quantify the gas components when analyzing them.

[0083] In addition to these, headspace methods also include headspace-solid phase microextraction (HS-SPME), headspace-in-tube extraction (HS-ITEX), dynamic headspace sampling (DHS), purge and trap (PT), and gas stripping, which are methods that collect gas components generated in the gas phase space (the so-called headspace) inside a glass bottle and introduce them into analytical equipment such as GC or GC-MS equipped with various detectors such as FID. [Example]

[0084] Glass bottles were manufactured by performing glass surface treatment in separate steps. One hundred commercially available untreated glass bottles and 20 mm diameter borosilicate glass headspace vials (GL Sciences) were baked in air at 450°C for 10 hours to decompose and remove organic matter from the glass surface. Next, the bottles were placed in a 0.1% aqueous hydrochloric acid solution and ultrasonically cleaned for 30 minutes. The aqueous hydrochloric acid solution was discarded, and the waste liquid was repeatedly washed with ion-exchanged water until it became neutral. The bottles were dried under reduced pressure in a vacuum dryer at 150°C for 10 hours to activate the silanol groups on the glass surface.

[0085] Next, the vacuum-dried glass bottle was placed in a 5% dimethyldiethoxysilane hexane solution and degassed under reduced pressure for several minutes to remove surface bubbles. The solution was discarded by decantation, and the surface of the glass bottle was coated with a low-molecular-weight silicon compound (dimethyldiethoxysilane), the raw material for the silicon coating. The glass bottle coated with the silicon coating raw material was reacted in an inert gas atmosphere at 120°C for 4 hours, forming a silicon coating on the surface of the glass bottle.

[0086] Furthermore, to increase the thickness of the silicon coating, the glass bottle was placed in a 3% methyltriethoxysilane, 0.1% hydrochloric acid, and ethanol solution and degassed under reduced pressure for several minutes to remove surface bubbles. The solution was discarded by decantation and coated with the silicon coating raw material (methyltriethoxysilane). The glass bottle coated with the silicon coating raw material was reacted in an inert gas atmosphere at 120°C for 4 hours to form a silicon coating on the surface of the glass bottle and increase the thickness. The thickness of the silicon coating could be adjusted by the number of treatments used to create the silicon coating; a silicon coating of 2 nm was obtained after one treatment, 4 nm after two treatments, and 12 nm after three treatments. The glass bottle with the 12 nm silicon coating was designated Example 1-1.

[0087] Next, the surface of the silicon coating was deactivated. The glass bottle with the 12 nm silicon coating was deactivated in a vacuum chamber containing 0.1% trimethylmethoxysilane (a low-molecular-weight silylating agent) at 100°C for 4 hours, and the resulting glass bottle was designated Example 1-2. In this way, glass bottles suitable for gas component analysis, such as those used in Examples 1-1 and 1-2, were obtained.

[0088] For Comparative Example 1, two types of glass bottles were prepared that had undergone only conventional deactivation treatment without a silicone coating on the glass surface. The glass bottles, whose glass surface had been activated using the same method as in Example 1, were then subjected to deactivation treatment at 100°C for 4 hours in a vacuum chamber containing 0.1% trimethylmethoxysilane (a low-molecular-weight silylating agent). The resulting glass bottles were designated Comparative Example 1-1. The glass bottles, whose glass surface had been activated using the same method as in Example 1, were then subjected to deactivation treatment at 100°C for 4 hours in a vacuum chamber containing 0.2% hexamethyldisilazane (a low-molecular-weight silylating agent). The resulting glass bottles were designated Comparative Example 1-2. [Example]

[0089] Glass bottles were manufactured by performing the glass surface treatment by successively carrying out the steps of forming a silicon coating on the glass surface and deactivating the silanol groups on the silicon coating surface. A commercially available untreated glass bottle and a 20 mm diameter borosilicate glass headspace vial (GL Sciences) were placed in a 75 L vacuum chamber equipped with a silicon coating raw material supply port, oxygen and / or ozone gas supply port, and a vacuum pump suction and exhaust port, and heated to 300°C at 1 mmHg pressure. A concentration of 20 g / m 3 One liter of ozone gas was added and reacted for one minute to decompose and clean the organic compounds on the glass surface, while also activating the silanol groups on the glass surface. After that, the vacuum chamber, whose pressure had risen due to the generated decomposition products, was evacuated to 1 mmHg pressure and the decomposition products were removed.

[0090] Next, at a pressure of 1 mmHg and a temperature of 300°C, 2 g of a low molecular weight silicon compound, which is the raw material for the silicon coating, in this case dimethyldiethoxysilane, was supplied into the chamber with nitrogen. The reaction was allowed to proceed for 1 minute, forming a silicon coating base on the glass surface. Next, as film-forming process 1, 1 g of dimethyldiethoxysilane was supplied into the chamber with nitrogen at a pressure of 5 mmHg and a temperature of 300°C. Subsequently, as film-forming process 2, 1 g of dimethyldiethoxysilane was supplied into the chamber with nitrogen at a concentration of 10 g / m 3 One liter of ozone gas was added and reacted for one minute to form a silicon film. Then, in film formation process 3, the pressure inside the chamber was set to 5 mmHg and unreacted materials were evacuated. This silicon film formation process from film formation process 1 to film formation process 3 was repeated five times to adjust the thickness of the silicon film to 35 nm. The vacuum chamber was evacuated to a pressure of 1 mmHg and unreacted materials were removed.

[0091] Next, 1 g of dimethyldiethoxysilane as a low-molecular-weight silylating agent was supplied into the chamber with nitrogen at a pressure of 1 mmHg and a temperature of 300°C. The reaction was carried out for 1 minute to inactivate the surface of the silicon coating, and the resulting glass bottle was designated as Example 2-1.

[0092] The silicone coating was formed 10 times using the same process as in Example 2-1, and the thickness of the silicone coating was adjusted to 60 nm. The pressure was reduced to 1 mmHg and unreacted materials were removed. The silicone coating surface was not deactivated. The resulting glass bottle was designated Example 2-2.

[0093] The silicone coating was formed 15 times using the same process as in Example 2-1, and the thickness of the silicone coating was adjusted to 80 nm. The pressure was reduced to 1 mmHg and unreacted materials were removed. The silicone coating surface was not deactivated. The resulting glass bottle was designated Example 2-3.

[0094] The glass bottles of Example 2-1 with a 35 nm silicone coating and Example 2-2 with a 60 nm silicone coating were transparent, while the glass bottle of Example 2-3 with an 80 nm silicone coating turned white. [Example]

[0095] Glass bottles were evaluated using volatile, highly hydrophobic hydrocarbons, which are gas components. The adsorption of gas components by volatile, highly hydrophobic hydrocarbons, which are gas components, was compared for nine types of glass bottles: Example 1-1 (12 nm silicone coating only), Example 1-2 (12 nm silicone coating + deactivation treatment), Example 2-1 (35 nm silicone coating + deactivation treatment), Example 2-2 (60 nm silicone coating only), Example 2-3 (60 nm silicone coating only), and Comparative Example 3-1, which is a 20 mm diameter borosilicate glass headspace vial (GL Sciences) as an untreated glass bottle; Comparative Example 3-2, which is a commercially available glass bottle 1 (a product without a silicone coating and advertised as having no deactivation treatment); Comparative Example 3-3, which is a commercially available glass bottle 2 (a product without a silicone coating and advertised as having deactivation treatment); and Comparative Example 3-4, which is a commercially available glass bottle 3 (a product without a silicone coating and advertised as having deactivation treatment).

[0096] First, 1 μL of a 100 ppm acetonitrile solution of octane or dodecane was dropped onto the bottom of the glass bottle, and the lid of the glass bottle was then closed. The gas components were collected at 35°C for 5 minutes using a silica monolithic collector, Monotrap® RGC18 TD (GL Sciences), which was placed in the gas phase space inside the glass bottle. Next, the Monotrap® RGC18 TD, which had already collected the gas components, was placed in a portable thermal desorber (HandyTD TD265, GL Sciences) connected to the front stage of a gas chromatograph (GC-FID) equipped with an FID detector. The gas components, i.e., the components to be analyzed, were thermally desorbed from the Monotrap® RGC18 TD, and the peak areas of the chromatogram obtained using GC-FID were measured.

[0097] The same amount of the same sample was then added directly to a monolithic silica collector, the Monotrap® RGC18 TD. The Monotrap® RGC18 TD, to which the sample had been added directly, was then placed in a HandyTD TD265 connected to the front end of a GC-FID. The target components were then thermally desorbed from the Monotrap® RGC18 TD, and the peak areas of the resulting chromatogram were measured using a GC-FID. The area values ​​obtained when the sample was dropped onto the bottom of a glass bottle were plotted as the recovery rate (%), relative to the quantitative area values ​​obtained when the sample was added directly to the Monotrap® RGC18 TD. The results are shown in Figure 4. Figure 4(a) shows the results for the octane solution, and Figure 4(b) shows the results for the dodecane solution.

[0098] The analytical conditions are as follows: GC-FID:GC-2010 Plus (Shimadzu Corporation) Column: InertCap (registered trademark) 5 (GL Sciences) 0.25mm ID x 60m, df = 1.0μm Column oven temperature: 60°C (1 min) → 4°C / min → 250°C (4 min) Carrier gas: hydrogen Inlet: Split, 200℃ Pressure 96.4 kPa, total flow rate 11.3 mL / min, column flow rate 1.24 mL / min Linear velocity: 31.2 cm / sec, purge flow rate: 3.0 mL / min, split ratio: 5.7 Detector: FID, 220℃ <HandyTD TD265> Desorption temperature 45℃(0.5min)→45℃ / sec→200℃(1.5min) Desorption pressure 110kPa

[0099] As shown in Figure 4, Examples 1-1 and 1-2, which had a 12 nm silicon coating, Example 2-1, which had a 35 nm silicon coating, and Example 2-2, which had a 60 nm silicon coating, achieved nearly 100% recovery. However, in Example 2-3, which had a silicon coating of 80 nm or more, the silicon coating formed a hydrophobic surface, resulting in a 68% recovery rate for the highly hydrophobic hydrocarbon dodecane, resulting in hydrophobic adsorption. Therefore, if there is a possibility that highly hydrophobic volatile compounds, which are gas components, may be included in the target components for analysis, it is recommended to use a silicon coating of less than 80 nm. Note that while some Examples have lower recovery rates than Comparative Examples, these are evaluation results for the hydrocarbons octane and dodecane only. For other gas components, such as acidic and basic volatile compounds, the Examples have better recovery rates than the Comparative Examples. Overall, the glass bottles of the Examples have better recovery rates than the Comparative Examples. [Example]

[0100] Glass bottles were evaluated for the adsorption of acidic volatile compounds, which are gas components. The adsorption of acidic volatile compounds, which are gas components, was compared for ten glass bottles: Example 1-1 (silicon coating 12 nm only), Example 1-2 (silicon coating 12 nm + inactivation treatment), Example 2-1 (silicon coating 35 nm + inactivation treatment), Example 2-2 (silicon coating 60 nm only), Comparative Example 1-1 (inactivation treatment only), and Comparative Example 1-2 (inactivation treatment only) produced in Example 1 and Example 2, and Comparative Example 3-1, which is a 20 mm diameter borosilicate glass headspace vial (GL Sciences) as an untreated glass bottle; Comparative Example 3-2, which is a commercially available glass bottle 1 (a product without a silicone coating and claimed to be inactivated); Comparative Example 3-3, which is a commercially available glass bottle 2 (a product without a silicone coating and claimed to be inactivated); and Comparative Example 3-4, which is a commercially available glass bottle 3 (a product without a silicone coating and claimed to be inactivated).

[0101] First, 1 μL of a 100 ppm methanol solution of acetic acid, propionic acid, butyric acid, or valeric acid was dropped onto the bottom of the glass bottle. The bottle was then closed and the gas components (gaseous acetic acid, propionic acid, butyric acid, and valeric acid) were collected at 35°C for 5 minutes using a silica monolith collector, Monotrap® RGC18 TD (GL Sciences Inc.), placed in the gas phase space inside the glass bottle. Next, the Monotrap® RGC18 TD with the collected gas components was placed in a portable thermal desorber (HandyTD TD265, GL Sciences Inc.) connected to the front stage of a gas chromatograph (GC-FID) equipped with an FID detector. The gas components, i.e., the target components for analysis (acetic acid, propionic acid, butyric acid, and valeric acid), were thermally desorbed from the Monotrap® RGC18 TD, and the peak areas of the resulting chromatogram were measured using GC-FID.

[0102] The same amount of sample (1 μL of 100 ppm methanol solution of acetic acid, propionic acid, butyric acid, and valeric acid) was then directly added to a monolithic silica collector, the Monotrap® RGC18 TD. The Monotrap® RGC18 TD with the sample directly added was then placed in a HandyTD TD265 connected to the front end of a GC-FID. The target components were then thermally desorbed from the Monotrap® RGC18 TD, and the peak areas of the resulting chromatogram were measured using a GC-FID. The area values ​​obtained when the sample was dropped onto the bottom of a glass bottle were plotted as recovery percentages (%), relative to the area values ​​obtained when the sample was directly added to the Monotrap® RGC18 TD. The results are shown in Figure 5. Figure 5(a) shows the recovery percentages for acetic acid, Figure 5(b) shows the recovery percentages for propionic acid, Figure 5(c) shows the recovery percentages for butyric acid, and Figure 5(d) shows the recovery percentages for valeric acid.

[0103] The analytical conditions are as follows: GC-FID:GC-2010 Plus (Shimadzu Corporation) Column: InertCap® Pure-WAX (GL Sciences) 0.25mm ID x 60m, df = 0.5μm Column oven temperature: 45°C (5 min) → 20°C / min → 220°C (5 min) Carrier gas: hydrogen Inlet: Split, 200℃ Pressure 70.4 kPa, total flow rate 15.2 mL / min, column flow rate 2.44 mL / min Linear velocity: 39.5 cm / sec, purge flow rate: 3.0 mL / min, split ratio: 4 Detector: FID, 220℃ <HandyTD TD265> Desorption temperature 45℃(0.5min)→45℃ / sec→200℃(1.5min) Desorption pressure 110kPa

[0104] As shown in Figures 5(a) to 5(d), the comparative examples showed recovery rates ranging from 5 to 60%. It was revealed that conventional commercially available glass bottles (Comparative Examples 3-3 and 3-4) that claim to have been inactivated but do not have a silicone coating cannot be used for the analysis of acidic volatile compounds in gas components. Furthermore, even Comparative Example 1-1, which was inactivated with a typical low-molecular-weight silylating agent without a silicone coating, and Comparative Example 1-2, which was inactivated with a basic low-molecular-weight silylating agent, only achieved recovery rates comparable to those of the commercially available products in Comparative Examples 3-1 to 3-4, making them unusable for the analysis of acidic volatile compounds in gas components. On the other hand, Examples 1-1, 1-2, 2-1, and 2-2, which were equipped with the silicone coating of the present invention, all achieved recovery rates of 85% or higher. Furthermore, Examples 1-2 and 2-1, which were further inactivated with a silicone coating, achieved recovery rates of nearly 100%. It became clear that for the analysis of acidic volatile compounds in gas components, glass bottles using only conventional technology, such as those in the comparative example, could not be used, and that a configuration with a silicone coating on the glass surface, such as that in the example of the present invention, was necessary. [Example]

[0105] The glass bottle was evaluated by the basic volatile compound, which is a gas component. The glass bottles of Example 1-1 (silicon coating 12 nm only), Example 1-2 (silicon coating 12 nm + inactivation treatment), Example 2-1 (silicon coating 35 nm + inactivation treatment), Example 2-2 (silicon coating 60 nm only), Comparative Example 1-1 (inactivation treatment only), and Comparative Example 1-2 (inactivation treatment only) manufactured in Example 1 and Example 2, and the untreated glass bottles of Comparative Example 3-1, which is a 20 mm diameter borosilicate glass headspace vial (GL Sciences), Comparative Example 3-2, which is a commercially available glass bottle 1 (a product without a silicone coating and claimed to be inactivated), Comparative Example 3-3, which is a commercially available glass bottle 2 (a product without a silicone coating and claimed to be inactivated), and Comparative Example 3-4, which is a commercially available glass bottle 3 (a product without a silicone coating and claimed to be inactivated), were compared for the adsorption of the basic volatile compound, which is a gas component.

[0106] First, 1 μL of a methanol solution containing 100 ppm of octylamine or 2,6-dimethylaniline was dropped onto the bottom of the glass bottle. The lid was then closed, and the gas components (gaseous octylamine and 2,6-dimethylaniline) were collected at 35°C for 5 minutes using a silica monolithic collector, Monotrap® RGC18 TD (GL Sciences), placed in the gas phase space inside the glass bottle. Next, the Monotrap® RGC18 TD with the collected gas components was placed in a portable thermal desorber (HandyTD TD265, GL Sciences) connected to the front stage of a gas chromatograph (GC-FID) equipped with an FID detector. The gas components, i.e., the target components for analysis (octylamine and 2,6-dimethylaniline), were thermally desorbed from the Monotrap® RGC18 TD, and the peak areas of the resulting chromatogram were measured using GC-FID.

[0107] The same amount of sample (1 μL of 100 ppm methanol solution of octylamine and 2,6-dimethylaniline) was then added directly to a monolithic silica collector, the Monotrap® RGC18 TD. The Monotrap® RGC18 TD with the sample added directly was then placed in a HandyTD TD265 connected to the front end of a GC-FID. The target components were then thermally desorbed from the Monotrap® RGC18 TD, and the peak areas of the resulting chromatogram were measured using a GC-FID. The area values ​​obtained when the sample was dropped onto the bottom of a glass bottle were plotted as recovery percentages (%), relative to the area values ​​obtained when the sample was added directly to the Monotrap® RGC18 TD. The results are shown in Figure 6. Figure 6(a) shows the recovery percentages for octylamine, and Figure 6(b) shows the recovery percentages for 2,6-dimethylaniline.

[0108] The analytical conditions are as follows: GC-FID:GC-2010 Plus (Shimadzu) Column: InertCap (registered trademark) 5 (GL Sciences) 0.25mm ID x 60m, df = 1.0μm Column oven temperature: 60°C (1 min) → 4°C / min → 250°C (4 min) Carrier gas: hydrogen Inlet: Split, 200℃ Pressure 96.4 kPa, total flow rate 11.3 mL / min, column flow rate 1.24 mL / min Linear velocity: 31.2 cm / sec, purge flow rate: 3.0 mL / min, split ratio: 5.7 Detector: FID, 220℃ <HandyTD TD265> Desorption temperature 45℃(0.5min)→45℃ / sec→200℃(1.5min) Desorption pressure 110kPa

[0109] 6(a), for octylamine, Examples 1-1, 1-2, 2-1, and 2-2, which are equipped with the silicone coating of the present invention, achieved recovery rates of 70% or more, and Examples 1-2 and 2-1, which were subjected to a silicone coating deactivation treatment, achieved recovery rates of nearly 100%. On the other hand, Comparative Examples 1-1, 1-2, and 3-1 to 3-4, which are not equipped with a silicone coating, achieved recovery rates of only 20% or less, indicating that basic volatile compounds are strongly adsorbed to the glass bottle and cannot be used to analyze basic volatile compounds in gas components.

[0110] 6(b), for 2,6-dimethylaniline, Examples 1-1, 1-2, 2-1, and 2-2, which were provided with the silicone coating of the present invention, achieved recovery rates of 85% or more, and Examples 1-2 and 2-1, which underwent inactivation treatment of the silicone coating, achieved recovery rates of nearly 100%. On the other hand, Comparative Examples 1-1 and 3-3, which were not provided with the silicone coating, achieved recovery rates of about 80%, while Comparative Examples 1-2, 3-1, 3-2, and 3-4 achieved recovery rates of about 50 to 60%.

[0111] Amines adsorb to silanol groups, and the higher the pKa (acid dissociation constant) of the amine, the easier it is to adsorb. In this example, octylamine, with a pKa of 10.6, and 2,6-dimethylaniline, with a pKa of 3.89, are used as gas components. By testing with two gas components in this way, it is possible to confirm not only whether or not adsorption occurs, but also the strength of adsorption for each gas component.

[0112] In Comparative Example 3-3, a recovery rate of 80% or more was achieved for 2,6-dimethylaniline, which has a low pKa. However, in Comparative Example 3-4, the recovery rate of 2,6-dimethylaniline was less than 60%, indicating that Comparative Example 3-3 adsorbed less amines than Comparative Example 3-4. The evaluation method of the present invention allows the amount of gas component adsorption by the vial to be quantified, making it possible to determine which vial is more suitable. Even in Comparative Example 3-3, which can be used for amine compounds with a low pKa, the recovery rate for octylamine, a high pKa amine compound, was less than 20%, indicating that it was strongly adsorbed to the glass vial. This indicates that conventional vials cannot be used for amines and are not suitable for analyzing basic, volatile gas components.

[0113] No comparative vials were found that could analyze highly adsorbent volatile compounds, such as amines with high pKa, without adsorption, and it was found that vials treated with conventional methods could not be used. In Examples 1-1 and 2-2 equipped with the silicone coating of the present invention, recovery rates of over 70% were obtained even for octylamine, which is easily adsorbed and could not be analyzed with conventional vials, demonstrating that they can be used for quantitative analysis. Furthermore, by adding a deactivation treatment to the silicone coating, recovery rates of around 100% were obtained even for octylamine, as in Examples 1-2 and 2-1.

[0114] From the above results, it became clear that the examples of the present invention can be used to analyze any amine as a gas component, while the comparative examples cannot be used to analyze gas components depending on the type of amine. Therefore, it became clear that the conventional vials used in the comparative examples cannot be used to analyze volatile compounds in gas components, and that the glass bottles of the present invention, which have a silicone coating on the glass surface, are necessary. It was also proven that providing a silicone coating on a glass bottle and an inactivation treatment layer further reduces adsorption of gas components. [Example]

[0115] Raw chicken meat (commercially available raw ground chicken meat) was used as a biological sample, and glass bottles were evaluated by analyzing the gas components emitted from the raw chicken meat. The glass bottle of Example 2-1 (35 nm silicone coating + inactivation treatment) and the commercially available glass bottle 2 of Comparative Example 3-3 (a product without a silicone coating and advertised as inactivation treatment) were analyzed and compared for the gas components emitted from the raw chicken meat. A steel wire was passed through and fixed into the septum, and 2 g of raw chicken meat was suspended from the wire. The septum was then fastened together with the lid, and 2 g of raw chicken meat was fixed in the gas space at the top of the glass bottle. Each gas component was collected at 35°C for 1 hour using a silica monolithic collector, Monotrap® RGC18 TD (GL Sciences), placed in the gas phase space inside the glass bottle. The collected gas components were then placed in a multifunction gas chromatograph mass spectrometer inlet (OPTIC-4, Shimadzu Corporation) connected to the front end of a gas chromatograph mass spectrometer (GC-MS). The gas components, i.e., each target component for analysis, were thermally desorbed from the Monotrap® RGC18 TD, and the peak areas of the resulting chromatogram were measured using GC-MS. The results are shown in the chromatogram in Figure 7. The top chromatogram is for the glass bottle of Comparative Example 3-3, and the bottom chromatogram is for the glass bottle of Example 2-1.

[0116] The analytical conditions are as follows: Multi-function inlet for gas chromatograph mass spectrometer: OPTIC-4 (Shimadzu Corporation) Gas chromatograph mass spectrometer: GCMS-QP2020 NX (Shimadzu Corporation) Software: Evolution Workstation (Shimadzu Corporation) LabSolutions (registered trademark) (Shimadzu Corporation) conditions: <optic-4> Time: 65 min Inlet: 40℃ (10sec) → 60℃ / min → 200℃ Cryofocus (liquid nitrogen): -150℃ (5 min) → 60℃ / min → 200℃ Carrier gas: He Column flow rate: 2.0 mL / min Septum purge: 5mL / min Splitless: 20 mL / min, Splitless time: 5 min <gc> Column: InertCap® Pure-WAX (GL Sciences) Inner diameter 0.32mm, length 60m, film thickness 0.5μm Column oven temperature: 40°C (5 min) → 5°C / min → 220°C (20 min) Ion source temperature: 200℃ Interface temperature: 220℃ Measurement time: 1 to 61 minutes Measurement method: Scan Mass range: m / z 29~500 Event: 0.30 seconds Library: NIST14

[0117] As shown in the chromatograms in Figure 7, in the analysis of gas components generated from raw chicken meat, Example 2-1 (lower chromatogram, 35 nm silicone coating + inactivation treatment) showed less adsorption of gas components to the glass surface than Comparative Example 3-3 (upper chromatogram, product without silicone coating and advertised as inactivated), and tended to yield larger peak heights and peak areas, improving quantitation (for example, the peak indicated by the arrow in the upper part of Figure 7).

[0118] The table in Figure 8 shows the peak area ratios of the 17 volatile compounds, which are gas components in the chromatogram in Figure 7, for the glass bottle in Comparative Example 3-3 (top row) and the glass bottle in Example 2-1 (bottom row). The area ratios for volatile compounds without polar groups (n-hexane and cyclopropane, butyl-) were all 1.01. The chromatogram obtained with the glass bottle in Example 2-1 had slightly larger peak areas, but the difference was small. Among alcohols, the area ratios for ethanol, 1-butanol, and 1-hexanol were 1.69, 1.21, and 1.12, respectively. Volatile compounds with a higher proportion of polar hydroxyl groups in the molecule tend to be more polar and have a higher area ratio. Benzene, 1,3-dichloro-, is a highly polar volatile compound due to the presence of two chloro groups in its molecule, which increase its polarity due to the influence of the benzene ring, but its area ratio was a large 1.74. That is, it is clear that for polar volatile compounds, the glass bottle of Example 2-1 of the present invention gave a higher recovery rate than the glass bottle of Comparative Example 3-3.

[0119] Furthermore, glass bottles of the present invention (Examples 1-1 and 2-2) characterized by having a silicone coating on the glass surface showed less adsorption of gas components and a higher recovery rate than glass bottles inactivated by conventional technology in evaluations using acidic volatile compounds of gas components and basic volatile compounds of gas components, as shown in Examples 4 and 5. This is because the silicone coating formed on the glass surface covered the silanol groups on the glass surface, reducing the number of silanol groups onto which gas components adsorb.

[0120] Furthermore, glass bottles (Examples 1-2 and 2-1) of the present invention, which have a silicone coating on the glass surface and a passivation layer on the silicone coating surface, characterized in that the passivation layer is composed of a film in which the silanol groups on the silicone coating surface have been alkylsilylated, exhibited higher recovery rates than the glass bottles of Examples 1-1 and 2-2 when evaluated using acidic volatile compounds and basic volatile compounds of gas components, as shown in Examples 4 and 5. Furthermore, as shown in Example 6, the glass bottle of Example 2-1, when evaluated using gas components generated from a biological sample, exhibited particularly low adsorption of polar gas components compared to glass bottles passivated by conventional techniques, resulting in a higher recovery rate. This is because the silicone coating formed on the glass surface covers the silanol groups on the glass surface, and the silanol groups on the silicone coating surface are further alkylsilylated, further reducing the number of silanol groups to which gas components are adsorbed.

[0121] Furthermore, the glass bottles of the present invention (Examples 1-1 and 2-2) characterized by having a silicone coating on the glass surface and the glass bottles of the present invention (Examples 1-2 and 2-1) characterized by having a silicone coating on the glass surface, a passivation treatment layer on the surface of the silicone coating, and the passivation treatment layer being composed of a film in which the silanol groups on the surface of the silicone coating have been alkylsilylated, did not reduce the recovery rate of highly hydrophobic gas components compared to glass bottles deactivated by conventional technology, as shown in Example 3.

[0122] These glass bottles of the present invention can be suitably used in headspace analysis, which involves collecting and analyzing gas components generated in the gas phase inside the glass bottle, when it is desired to reduce the adsorption of gas components compared to conventional glass bottles. Furthermore, because the silanol groups in the portion that comes into contact with the target component in the sample have been reduced, the bottles can be suitably used not only for the headspace analysis but also for storing liquid samples. [Industrial Applicability]

[0123] According to the present invention, in the analysis of volatile compounds, which are gas components, including volatile organic compounds (VOCs) and volatile inorganic compounds (VICs), it is possible to prevent the components to be analyzed from being adsorbed to silanol groups on the glass surface of the glass vial used for the analysis, thereby enabling trace analysis of volatile compounds and improving analytical accuracy. Therefore, the glass vial of the present invention can be suitably used for a variety of analyses, such as analyzing atmospheric environments and automobile exhaust gases, and can be used in the automotive industry. It can also be suitably used for analyzing volatile compounds emitted from biological samples, and can be used in the medical industry. Therefore, it can be used in a variety of industries that require the analysis of volatile compounds, which are gas components. < / gc> < / url:>

Claims

1. A glass bottle having a silicone coating on the glass surface.

2. A glass bottle having a silicone coating on the glass surface, the silicone coating having a passivation treatment layer.

3. A glass bottle characterized by having a silicon coating on the glass surface with a thickness of 1 nm or more but less than 80 nm.

4. A glass bottle characterized in that a silicon coating having a thickness of 1 nm or more and less than 80 nm is provided on the glass surface, and the silicon coating has a passivation treatment layer.

5. The raw material of the silicon coating is tetraalkoxysilane such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, etc.; alkyltrialkoxysilane such as methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, ethyltrialkoxysilane, propyltrimethoxysilane, etc.; dialkyldialkoxysilane such as dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldipropoxysilane, diethyldialkoxysilane, dipropyldimethoxysilane, etc.; trimethylmethoxysilane, trimethylethoxysilane, trimethylpropoxysilane, triethyltrialkoxysilane, etc.

5. The glass bottle according to claim 1, wherein the polysilazane is one or more selected from the group consisting of trialkylmonoalkoxysilanes such as trimethylmethoxysilane and tripropylmethoxysilane, inorganic polysilazanes, perhydropolysilazanes, dimethyl-type cyclic siloxanes such as hexamethylcyclotrisiloxane and octamethylcyclotetrasiloxane, diethyl-type cyclic siloxanes, dipropyl-type cyclic siloxanes, linear polydimethylsiloxanes such as hexamethyldisiloxane, octamethyltrisiloxane and decamethyltetrasiloxane, linear polydiethylsiloxanes, and linear polydipropylsiloxanes.

6. A glass bottle for analyzing gas components, characterized by having a silicon coating on the glass surface.

7. A glass bottle for analyzing gas components, characterized in that the glass surface is provided with a silicon coating, and the silicon coating is provided with an inactivation treatment layer.

8. A glass bottle for analyzing gas components, characterized in that the glass surface has a silicon coating having a thickness of 1 nm or more but less than 80 nm.

9. A glass bottle for analyzing gas components, characterized in that the glass surface is provided with a silicon coating having a thickness of 1 nm or more but less than 80 nm, and the silicon coating is provided with an inactivation treatment layer.

10. An analytical method characterized by placing a sample in a glass bottle with a silicone coating on the glass surface, leaving it at a predetermined constant temperature for a predetermined time, and analyzing the gas components generated from the sample.

11. An analytical method characterized by placing a sample in a glass bottle having a silicon coating on the glass surface, the silicon coating having an inactivation treatment layer, leaving it at a predetermined constant temperature for a predetermined time, and analyzing the gas components generated from the sample.

12. An analytical method characterized by placing a sample in a glass bottle having a silicon coating with a thickness of 1 nm or more but less than 80 nm on the glass surface, leaving it at a predetermined constant temperature for a predetermined time, and analyzing the gas components generated from the sample.

13. An analytical method characterized by placing a sample in a glass bottle having a silicon coating with a thickness of 1 nm or more but less than 80 nm on the glass surface, the silicon coating having a passivation treatment layer, leaving it at a predetermined constant temperature for a predetermined time, and analyzing the gas components generated from the sample.

14. The analytical method according to any one of claims 10 to 13, characterized in that a sample and a collector are placed in the glass bottle, the gas components generated from the sample are collected by the collector, the gas components are recovered from the collector, and the gas components are analyzed.

15. The analytical method according to claim 14, wherein the collector is a silica monolith collector.

16. 14. The analytical method according to claim 10, wherein the sample is a biological sample.

17. The analytical method according to claim 14, wherein the sample is a biological sample.

18. The analytical method according to claim 15, wherein the sample is a biological sample.

19. A glass surface treatment method characterized by carrying out a cleaning treatment to remove organic matter adhering to a glass surface and / or an activation treatment to activate silanol groups on the glass surface, and then forming a silicon coating on the glass surface with a thickness of 1 nm or more and less than 80 nm.

20. A glass surface treatment method comprising: performing a cleaning treatment to remove organic matter adhering to a glass surface and / or an activation treatment to activate silanol groups on the glass surface; forming a silicon coating having a thickness of 1 nm or more and less than 80 nm on the glass surface; and performing a passivation treatment on the silicon coating to form a silicon coating having a passivation treatment layer on the glass surface.

21. 21. The glass surface treatment method according to claim 19, further comprising the step of performing a cleaning treatment and / or a drying treatment after the silicon coating is formed on the glass surface.

22. A method for manufacturing glass bottles, comprising manufacturing glass bottles using the glass surface treatment method according to claim 19 or 20.

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