JP5970166B2 - Method for producing glass container for liquor with reduced calcium ion elution - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a glass container for liquor that suppresses calcium ion elution, and more particularly, to a method for producing a glass container for liquor that can suppress the amount of calcium ions that are eluted from the inner surface of the glass container and suppress changes to the contents.

Conventionally, glass materials are used for pharmaceuticals by taking advantage of the stable properties found in airtightness, heat resistance, non-adsorption of components, non-eluting properties, durability, and corrosion resistance, as well as the property of being easily melted and molded. It is used as a container that can stably store contents such as reagents, foods, beverages, and alcoholic beverages. Glass materials such as soda lime glass, which are common as glass materials, are less expensive than quartz glass. Usually glass material, the glass skeleton is maintained by the silica component consisting of SiO _2, in addition to SiO _2, for example, various metal oxides including Na ₂ O, CaO, Al ₂ O _3, or the like is blended. Therefore, when a glass material is molded and commercialized, it is naturally considered that elements such as alkali metals and alkaline earth metals found in Na appear on the surface in addition to the silica component.

In the case where a conventional glass material is used as a container, in order to control the influence of the contents to be filled, dealkalization of the glass material is desired, and a treatment method has been developed. For example, in order to control the abundance ratio of Al in the glass product surface of aluminoborosilicate glass, which is known as a container material for ampules for pharmaceutical preparations, the surface of the glass product is washed with nitric acid, hydrofluoric acid, etc. (including mixed acids). And the glass container which suppressed the elution amount of ^{Al3 +} with respect to the content is also developed (refer patent document 1). Moreover, in order to make the inner surface of a glass container rich in silica, a method of blowing in CFC gas into the container has also been proposed (see Patent Document 2).

  As described above, various methods of dealkalizing using a glass material such as aluminoborosilicate glass and soda lime glass to control the surface of the glass material have been developed. However, in the case of the method disclosed in Patent Document 1, since an acid is used, handling is not easy. Among them, in the method of introducing chlorofluorocarbon into the molded glass material of Patent Document 2, a certain effect is exhibited in suppressing the oxidation reaction by controlling the ratio of Si, Na and Ca. Was revealed.

  For example, when a glass container is used for preserving distilled liquor such as whiskey, a precipitate called starch may be formed in the container during long-term storage. This starch is mainly crystals of calcium oxalate. The crystalline component of calcium oxalate is generated by the combination of oxalic acid contained in whiskey and calcium (ion) in water. Although calcium oxalate is harmless to the human body, it is easily recognized as a foreign substance because it is insoluble in water. Since calcium ions contained in whiskey itself are an important factor that determines taste, it is difficult to reduce itself. Therefore, if calcium ions eluted from the inner surface of the glass container can be reduced, it can be inferred that the crystal formation of calcium oxalate can be suppressed.

  However, in the existing dealkalized glass, there is no finding that focuses on calcium ions eluted from the glass material surface. Therefore, it is unclear exactly how much suppression is actually possible under what conditions. Therefore, paying attention to the usefulness of glass containers as liquor containers for which stability of quality is demanded, glass that leads to suppression of calcium ion elution by further analyzing the action of introducing CFCs into the glass material of Patent Document 2. The container has been developed.

JP 2001-294447 A JP 2005-170736 A

The present invention has been made in view of the above points, and manufacture of a glass container for liquor that suppresses the elution of calcium ions by reducing the surface of the glass material accompanying the use of Freon gas and reduces the influence on the contents. Provide a method .

That is, the invention of claim 1 is to form a glass molding by molding a molten glass obtained by melting a soda lime glass raw material into a predetermined container shape, and the surface temperature of the glass molding is below the glass softening point of the raw material. controlled to the temperature range, the injected CFC gas in the glass molded product, a manufacturing method of a glass container for subsequent liquor obtained by performing slow cooling in storage between the temperature range, The temperature range is 550 ° C. to 630 ° C., the Freon gas is 1,1-difluoroethane, and the injection amount thereof is 0.02 to 0.13% by volume of the content of the glass container. 6. Revised Japanese Pharmacopoeia General Test Method Test method for containers and packaging materials 7.01 Test method for glass containers for injections (ii) Prepare test water by adding distilled water to the glass containers based on the elution conditions of the second method, in accordance with JIS K0116 (2003) When the test water is measured by a measurement method using ICP-AES, the measured value of the elution amount of Ca ²⁺ eluted from the inner surface of the glass container satisfies 0.06 ppm or less. It concerns on the manufacturing method of the glass container for elution suppression liquors.

Invention of Claim 2 concerns on the manufacturing method of the glass container for calcium ion elution suppression alcoholic beverages of Claim 1 whose measured value of the elution amount of the said Ca < ²⁺ > is 0.03 ppm or less.

Invention of Claim 3 concerns on the manufacturing method of the glass container for calcium ion elution suppression alcoholic beverages of Claim 1 or 2 whose said liquor is whiskey.

According to the method for manufacturing a glass container for liquor suppressing calcium ion dissolution according to the invention of claim 1, molten glass obtained by melting a soda lime glass raw material is molded into a predetermined container shape to obtain a glass molded product, and the glass molding Storage of alcoholic beverages obtained by controlling the surface temperature of the product to a temperature range below the glass softening point of the raw material, injecting Freon gas into the glass molded product during the temperature range, and then performing slow cooling For manufacturing the glass container, wherein the temperature range is 550 ° C. to 630 ° C., the Freon gas is 1,1-difluoroethane, and the injection amount thereof is 0.02 of the inner capacity of the glass container. -0.13 vol%, 16th revised Japanese Pharmacopoeia General Test Method Test method for containers and packaging materials 7.01 Test method for glass containers for injections (ii) Prepare test water by adding distilled water to the glass containers based on the elution conditions of the second method, in accordance with JIS K0116 (2003) In the case where the test water is measured by a measurement method using ICP-AES, the measured value of the amount of Ca ²⁺ eluted from the inner surface of the glass container satisfies 0.06 ppm or less. Improvement of glass material surface due to the use of chlorofluorocarbon gas, which has less impact on destruction, effectively suppresses calcium ion elution, and realizes a low-priced liquor glass container with excellent storage performance and reduced impact on contents We were able to.

According to the method for producing a glass container for a calcium ion elution-suppressed liquor according to the invention of claim 2, in the invention of claim 1, the measured value of the elution amount of Ca ²⁺ is 0.03 ppm or less. An effect of suppressing calcium ion elution can be obtained.

According to the manufacturing method of the glass container for calcium ion elution suppression alcoholic beverages according to the invention of claim 3, in the invention of claim 1 or 2, since the alcoholic beverage is whiskey, the calcium ion elution suppression effect during long-term storage is excellent.

It is a schematic process drawing which shows the shaping | molding of a glass container, and a process process. It is the 1st observation photograph by the optical microscope of the glass container surface. It is a 2nd observation photograph by the optical microscope of the glass container surface. It is the 3rd observation photograph by the optical microscope of the glass container surface. It is a 4th observation photograph by the optical microscope of the glass container surface. It is the 1st imaging image data by the atomic force microscope of the glass container inner surface. It is the 2nd imaging image data by the atomic force microscope of the glass container inner surface. It is the 3rd imaging image data by the atomic force microscope of the glass container inner surface. It is the 4th image data by the atomic force microscope of the glass container inner surface.

The composition of a general soda lime glass is generally defined as follows. That is, SiO ₂ is 65 to 75% by weight, CaO is 5 to 15% by weight, Na ₂ O is 5 to 15% by weight, K ₂ O is 0 to 3% by weight, and other components such as Al ₂ O ₃ and MgO are contained. Composition. Since soda lime glass is inexpensive, it is most widely used and is mainly in demand as a glass container.

As can be grasped from the composition of soda lime glass, alkali metals such as Na and Ca and alkaline earth metals are always contained in a certain amount. It is considered that these reactive metal species appear on the inner surface of the glass container as described in the background art. Therefore, although it is very small amount, the influence with respect to the filling in a container is suggested. As will be described later, calcium ions often form a salt by bonding with an organic acid and precipitate. Therefore, with emphasis on the relationship with the contents to be filled, focusing on the behavior of calcium ions in particular rather than sodium ions, the glass components constituting the container from the inner surface of the glass container to the contents filled inside This is a glass container that has an enhanced inhibitory effect on the elution of calcium contained therein as calcium ions (Ca ²⁺ ).

6. In evaluating the elution amount of calcium ions (Ca ²⁺ ), the 16th revised Japanese Pharmacopoeia General Test Method Container / Packaging Material Test Method 7.01 Glass container test method for injection (ii) The second method was adopted. This is because this method is known as a test method for grasping component elution from the inner surface of a glass container enclosing a medicine, and is useful as an objective method for grasping the amount of elution. Distilled water is added to the glass container, and test water is prepared based on the elution conditions of the second method.

This test water is measured using ICP-AES (Inductively Coupled Plasma-Atomic Emission Spectrometry) in accordance with JIS K0116 (2003). ICP-AES was adopted as being suitable for measuring the amount of Ca ²⁺ eluted from the inner surface of the glass container in the present invention because it can measure the target element very sensitively.

Since it is essentially the concentration of Ca ²⁺ , it is defined as the amount of Ca ²⁺ (weight or number of moles) dissolved in unit weight or unit volume of distilled water. However, since it is a very small amount, it was defined as the calcium content (ppm). In addition, since calcium ions and calcium elements are considered to be only the mass difference of electrons, both were made equivalent when considering the quantity.

  From this, the manufacturing process of the glass container for liquor which suppresses calcium ion elution is demonstrated using the schematic process drawing of FIG. Silica sand, soda ash, limestone, glass cullet, etc., which are raw materials for glass containers of soda lime glass, and in addition, if necessary, metal oxides such as Cu, Fe, Cr and Ni are melted as coloring components in a melting furnace (S1) It becomes a molten glass. In addition, as another manufacturing method for manufacturing a colored glass container, a frit, a pellet, or the like containing a coloring component is added to the molten glass by connecting a colorant for hearth to the melting furnace.

  The molten glass is cut into a lump called a gob by a predetermined amount, sent to a known molding machine such as an IS machine, and molded into an appropriate container shape (Smd) to form a glass molding. When using the above-mentioned IS machine, in the molding step (Smd), first, either blow molding (S2) or press molding (S3) is performed as the primary molding using a rough mold (first stage), It becomes an intermediate molded body called a parison. Subsequently, in blow molding (S4), which is secondary molding using a finishing die, the parison is molded into a container-shaped glass molding (second stage). In addition, the shaping | molding in a shaping | molding process (Smd) can also be performed as a shaping | molding of only one step, selecting the optimal shaping | molding method according to a container shape.

  The glass molded product having a container shape is controlled to have a surface temperature range of 550 ° C. to 640 ° C., that is, to maintain the glass softening point or less when soda lime glass is employed. During this time, it is optimally adjusted by the time from the molding step (Smd) to the next fluorocarbon injection, slow cooling, adjustment of the distance, heating in the middle, and the like. The above-described temperature range of the surface temperature of 550 ° C. to 640 ° C. is a range that also takes into account the relationship between the temperature at the time of injecting Freon gas and the elution amount of calcium ions in Examples described later. That is, the elution of calcium ions is more suppressed when the temperature is in the range of 550 ° C. to 640 ° C., and particularly effective at 580 ° C. to 630 ° C., and the vicinity of 615 ° C. is the least suitable.

  Then, while the glass molded product is controlled within the above temperature range, chlorofluorocarbon gas is injected into the glass molded product (S5). The inner surface of the glass molding comes into contact with the injected chlorofluorocarbon gas. The fluorocarbon gas used is monochlorodifluoromethane, dichloromonofluoromethane, trifluoromethane, monochlorodifluoroethane, difluoroethane or the like. Since the opening of the glass molded product is open, the chlorofluorocarbon gas after injection diffuses into the atmosphere. For this reason, a type with less influence of ozone layer destruction is desirably selected. From this point, 1,1-difluoroethane is used as the chlorofluorocarbon gas used in this step.

  Many details of the action of CFCs on glass moldings (heated glass) are still unclear. However, as shown in the surface observations of FIGS. 2 to 9, the roughening of the surface region is apparent from the observation of the glass surface. First, FIGS. 2 to 5 are observations using an optical microscope (digital microscope). This corresponds to the fluorocarbon injection amount (volume percent (hereinafter referred to as vol%)) in Table 1 described later in the order of the figure numbers. If no Freon gas is injected, the glass surface is smooth on the photograph (see FIG. 2). The wrinkle appearing on the glass surface becomes more noticeable and the undulations increase as the injection amount of CFC gas increases to 0.07, 0.22, 0.65 vol% (refer to the order of FIGS. 3, 4 and 5).

  Next, an atomic force microscope (AFM) was used to investigate the state of change on the glass surface in more detail (see FIGS. 6, 7, 8, and 9). Each figure is an image image of observation in the non-contact mode using the Park Systems XE-100-ASN. FIGS. 6 and 7 are non-fluorocarbon-injected products, and FIGS. 8 and 9 are fluorocarbon-injected products. The scan area in FIGS. 6 and 8 is 2 μm × 2 μm, and the scan area in FIGS. 7 and 9 is 0.5 μm × 0.5 μm.

  The fluorocarbon gas non-injected products in FIGS. 6 and 7 have protrusions having a height of 1 to 2 nm at various locations on the glass surface, but there are no irregularities as a whole. These protrusions are assumed to be weathered crystals because they decreased by washing with water. On the other hand, in the chlorofluorocarbon gas-injected product of FIGS. 8 and 9, a lump-like projection having a height of 10 to 20 nm is present on one surface of the observation region, and the surface smoothness is lost. Even if the AFM observation is performed again after washing the CFC-injected product with water, the surface state does not change, so there is a strong possibility that it is caused by the action of the CFC gas introduced into the glass molding.

  It has been confirmed that chlorofluorocarbon gas, which is a fluorine compound, is thermally decomposed by coming into contact with the glass molded product having the above surface temperature to generate hydrogen fluoride and the like. Since halogen elements are known to be highly reactive, components such as alkali metals and alkaline earth metals excluding silicon and oxygen, which are the skeleton components of the glass, react with halogen elements in the chlorofluorocarbon gas and desorb from the glass surface. The possibility of separation, the possibility of film formation and volatilization associated with the combination of silicon and fluorine, or each element contained in the chlorofluorocarbon gas acts on the glass skeleton (silicon, oxygen, metal elements) constituting the glass molding It is suggested that the bond angle may be changed, and the combined factors are presumed.

  When the fluorocarbon gas was injected into the glass molded product in the above temperature range, the injection amount was initially sufficient to cover the inner surface of the glass molded product. Therefore, in consideration of gas diffusion into the container-shaped glass molded product, an attempt was made by injecting 1 to 5 vol% of CFC gas with respect to the internal volume of the glass molded product (that is, the glass container). As a result, as expected, Freon gas injection greatly improved the suppression effect of calcium ion elution compared to non-injection.

  The amount of elution of metal ions from the glass container was presumed to be correlated with the amount of fluorocarbon gas injected, and the upper limit of the gas injection amount that could minimize the amount of calcium ion elution was sought. However, contrary to the initial expectation, as disclosed in the examples described later, it has been clarified that the amount of calcium ions eluted increases as the amount of chlorofluorocarbon injection increases. Furthermore, it was clarified that the temperature of the glass container at the time of chlorofluorocarbon injection also has an effect.

  When suppressing the elution amount of calcium ions, a significant elution suppression effect can be confirmed even if the amount is smaller than the initial fluorocarbon gas injection amount. That is, the effect which is sufficient for suppression of the elution amount of calcium ions was clarified as the amount was as small as 0.02 to 0.22% by volume (vol%) of the content of the glass container. It is a new discovery even by the inventor who has obtained knowledge of silica enrichment of the glass surface accompanying the flow of Freon gas from Patent Document 2 presented in the background art. It is unclear how the effect of Freon gas on the surface of the glass container acts differently between calcium ions and sodium ions. Presumably, the bonding mode in the glass structure is different from the difference in ionic valence, and it is assumed that there is a difference in the desorption of the glass surface portion from the glass skeleton. The chlorofluorocarbon gas to be injected is a mixed gas with air, and is converted to volume% under room temperature conditions (the same applies to the examples described later).

  The calcium ion elution-suppressing glass container, which has mainly been described with respect to its composition and processing method, has been used exclusively for the purpose of stably storing acidic liquids that easily react with calcium ions. The target is not limited as long as the acidic liquid is stably stored from the elution of calcium ions, and examples thereof include liquid pharmaceuticals, preparations, reagents, and other chemical solutions.

  Among them, the acidic liquid is a beverage containing an organic acid and is used as a container (mainly a glass bottle). Since it is formed from soda lime glass, it is inexpensive and suitable for use in large quantities. That is, it is excellent in storage performance and suitable as an inexpensive beverage container. Examples of the beverage in this case include fruit beverages, carbonated beverages, and lactic acid beverages. Organic acids are acids containing a carboxyl group and the like, such as acetic acid, citric acid, malic acid, fumaric acid, maleic acid and the like. In addition, various acids derived from food and from fermented metabolites of food are also included.

  Furthermore, beverages containing organic acids and organic acids are liquors. Considering that the liquid is acidic due to the influence of components other than alcohol and is stored in units of years after filling into the container, the expectation for the calcium ion elution suppression effect during long-term storage is high. For example, containers for brewed sake such as sake and wine, distilled spirits such as shochu, awamori, whiskey, brandy, Shaoxing.

  Many liquors contain organic acids such as oxalic acid and tartaric acid. Calcium salts such as calcium oxalate and calcium tartrate may be generated by the combination of these organic acids with calcium ions contained in the liquor itself and calcium ions eluted from the glass container surface. For example, it is clear from experience that calcium oxalate occurs when the calcium ion concentration is about 1 ppm or higher.

  In alcoholic beverages with a high alcohol content such as whiskey, the proportion of water is relatively small. Calcium salts with low solubility are likely to precipitate and form precipitates called starches in the container. Although it is possible to reduce the calcium content in alcoholic beverages such as whiskey, it is not always desirable considering the effect on taste and aroma. Therefore, it is important to reduce calcium ion elution from glass containers used for filling and storage. Although starch itself such as calcium oxalate does not affect the human body, it is easily recognized as a foreign substance because it is precipitated in a container such as a bottle. Therefore, suppression of starch is desired in order to enhance the sense of security.

As is clear from the examples (acceleration test) described later, when the measured value of the calcium ion elution amount from the glass container based on the above elution and measurement method exceeds 0.1 ppm, the amount of starch (calcium oxalate) Insufficient generation suppression effect. On the other hand, when the measured value of the calcium ion elution amount is 0.1 ppm or less, the effect of suppressing the occurrence of starch is confirmed. In particular, a difference appears in whiskey and the like stored for a long time. Furthermore, as the measured value of the calcium ion elution amount decreased to 0.06 ppm or less and 0.03 ppm or less, a further effect of suppressing the occurrence of starch was revealed. Therefore, the amount of Ca ²⁺ eluted from the inner surface of the glass container is required to be 0.06 ppm or less, preferably 0.03 ppm or less.

[Glass container molding, Freon gas injection]
The inventor used a general soda lime glass raw material, and formed an alcoholic beverage bottle such as whiskey using an IS machine. This bottle is a glass container. Three types were prepared with an internal volume per bottle of 660 mL, 700 mL, and 500 mL. Each bottle is colorless and transparent and has the same raw material composition. The raw material composition was general soda lime glass, and the composition shown in Table 1 was obtained by measurement with a fluorescent X-ray analyzer. 1,1-difluoroethane was used for the chlorofluorocarbon gas. The fluorocarbon gas was injected by changing the amount of the molten glass gob and the air from the bottle mouth portion in the conveyance path until the molten glass gob was formed into a bottle shape and then entered into the slow cooling step. In the case where the fluorocarbon gas was not injected, it was gradually cooled without injection of the fluorocarbon gas.

[Preparation of test water for elution amount measurement]
Regarding the elution of components from the prepared glass container, the 16th revised Japanese Pharmacopoeia General Test Method mentioned above Container / Packaging Material Test Method 7.01 Glass Container Test Method for Injection (ii) First, the inner surface of the glass container was lightly washed with distilled water. Subsequently, an amount of distilled water corresponding to 90% of the actual capacity of the glass container was added, and the spout was properly plugged. And the glass container containing distilled water was put in the autoclave (high pressure steam sterilizer), and it heated at 121 degreeC for 1 hour, and left to cool to room temperature (cooling). Thus, test water for measuring the elution amount from the glass container was prepared.

  A weathering acceleration test (weathering acceleration test) was also performed in consideration of the storage period after filling the bottle with distilled liquor such as whiskey. The glass container containing distilled water that has been heated in the autoclave is left in a constant temperature room at 50 ° C., and the humidity in the constant temperature room is reduced to 90% for 12 hours and 2 hours, and then to 60% humidity for 8 hours. In addition, the humidity was increased over 2 hours and the mixture was left to stand for a total of 24 hours for exposure. Three repetitions of this 24-hour exposure correspond to one-year aging. Therefore, if it repeats 9 times, it can be assumed that 3 years have passed.

  The basis that three repetitions of 24-hour exposure can correspond to one-year deterioration over time is a condition that takes into account the result of measuring the calcium ion elution amount of a glass bottle that was actually stored for about one year. In this case, since the calcium ion elution amount may vary depending on the storage status of the product, the above 24-hour exposure is defined as three repetitions with a sufficient margin.

[Measurement by ICP-AES]
When measuring the amount of elution from a glass container into distilled water, ICP-AES (Inductively Coupled Plasma Atomic Emission Spectrometer) manufactured by PerkinElmer Japan Co., Ltd., Optima2000DV was used, and the emission spectroscopic analysis rules of JIS K0116 (2003) were specified. Based on the method, sodium, calcium, and silicon were measured. Since the mass difference between each element and ion is very small, it was regarded as the same amount. Regarding the quantitative detection limit when each sample was measured using the same analyzer, calcium was 0.001 ppm, and sodium and silicon were 0.01 ppm. The measurement range of 0.001 to 0.1 ppm was a measurement of two wavelengths in the axial direction, and the range of 0.01 to 2 ppm was a measurement of two wavelengths in the radial direction. Note that when calcium exceeds 0.1 ppm, a measurement range of 0.01 to 2 ppm is used, so the quantitative detection limit of a sample exceeding 0.1 ppm is 0.01 ppm. The measurement wavelength of calcium is 393.366 nm, 396.847 nm, the measurement wavelength of sodium is 5899.592 nm, 588.995 nm, and the measurement wavelength of silicon is 251.611 nm, 212.412 nm. The calibration value correlation coefficient r ² of the measured value is 0.990 or more, and the coefficient of variation (CV) at the lower limit of quantification concentration is 10% or less.

[Evaluation of the effect of the amount of chlorofluorocarbon injected]
The inventor manufactured a bottle by injecting chlorofluorocarbon gas at a time when the bottle surface temperature was 590 ° C. to 600 ° C. in the transport path after forming a 660 mL bottle and entering the slow cooling step. When injecting the chlorofluorocarbon gas into the glass container, a mixed gas of air and chlorofluorocarbon was used to obtain the jet pressure, and the chlorofluorocarbon gas injection pressure was controlled by adjusting the partial pressure of the chlorofluorocarbon gas. In the said manufacture, it was set as 0 vol% (Freon gas non-injection), 0.07 vol% (0.47 mL), 0.22 vol% (1.42 mL), and 0.65 vol% (4.26 mL). In addition, since an error inevitably occurs in the injection amount of chlorofluorocarbon, it is an approximate amount (the same applies hereinafter).

  The test water was prepared four times for each of four kinds of fluorocarbon injections, and a weathering acceleration test corresponding to the passage of two years was conducted. In addition, the elution amounts of sodium, calcium, and silicon were measured by the ICP-AES. The results are shown in Table 2, and the elution amount (ppm) was the average value of the four injections.

  From the results of Table 2, the effect of suppressing the elution of each element is remarkable by injecting Freon gas. Among them, the elution amount of sodium and silicon is almost constant regardless of the increase or decrease in the amount of fluorocarbon injection. However, although the elution amount of calcium was suppressed as compared with the case where the fluorocarbon gas was not injected, the elution amount of calcium increased as the injection amount of the fluorocarbon gas increased. The inventor initially anticipated a decrease in the calcium elution amount in correlation with an increase in the fluorocarbon injection amount. Therefore, even if the amount of chlorofluorocarbon was increased, the upper limit was reached when the decrease in calcium elution amount reached its peak. However, the result was reversed. As described above, the reason why the difference between sodium and calcium and the elements affects the dissolution behavior has not been elucidated. Presumably, the difference in ionization number and the reactivity with the halogen element contained in the chlorofluorocarbon gas are considered to have an effect.

  The inventor who obtained the knowledge in Table 2 focused on 0.22 vol% of the Freon gas injection amount in the table, and tried an experiment with an injection amount smaller than this amount. The inventor manufactured a bottle by injecting chlorofluorocarbon gas at a time when the bottle surface temperature was 590 ° C. to 600 ° C. in a conveyance path after forming a 700 mL bottle and entering the slow cooling step. In the production, 0 vol% (no fluorocarbon injection), 0.02 vol% (0.14 mL), 0.04 vol% (0.28 mL), 0.08 vol% (0.55 mL), and 0.21 vol% (1. 47 mL).

  After preparing three test waters for each of five types of fluorocarbon injections, the elution amounts of sodium, calcium, and silicon were measured by the ICP-AES. However, in this measurement, the weathering acceleration test is omitted, and the measurement is immediately after the preparation of the test water. The results are shown in Table 3, and the elution amount (ppm) was the average value of the three injection amounts.

  As a general tendency, the elution suppression effect of each element is remarkable even with a very small amount of fluorocarbon injection in the table. However, when the chlorofluorocarbon injection amount was about 0.02 vol%, the elution suppression effect decreased because the amount was too dilute. Therefore, the lower limit value of the Freon gas injection amount was set to 0.02 vol% from the tendency of 0.02 vol% and 0.04 vol% of the Freon gas injection amount.

  Furthermore, in order to grasp the tendency of the critical portion of the chlorofluorocarbon gas injection amount, the inventor newly formed a 660 mL bottle, and at the time when the bottle surface temperature was 590 ° C. to 600 ° C. in the conveyance path until the slow cooling process was started. By changing the injection amount, chlorofluorocarbon gas was injected to produce a bottle. In the production, 0.01 vol% (0.07 mL), 0.02 vol% (0.15 mL), 0.04 vol% (0.29 mL), and 0.13 vol% (0.87 mL), and 0.26 vol% (1.74 mL).

  After preparing three test waters for each of five types of fluorocarbon injections, the elution amounts of sodium, calcium, and silicon were measured by the ICP-AES. However, in this measurement, the weathering acceleration test is omitted, and the measurement is immediately after the preparation of the test water. The results are shown in Table 4, and the elution amount (ppm) was an average value of four injections.

  In Table 4, in the sample having a fluorocarbon gas injection amount of 0.01 vol%, the fluorocarbon gas injection amount is generally small. For this reason, the effect | action by CFC with respect to the glass surface does not fully appear. That is, it can be determined that the amount of Freon is too small. When the Freon gas injection amount is 0.02 vol% to 0.13 vol%, the measured value of calcium is uniformly small. And when the amount of flon gas injection reached 0.26 vol%, the measured calcium value increased again. According to the tendency in Table 4, it can be assumed that the elution of calcium is a U-shaped curve having a bottom of 0.04 vol.

  From the results in Table 4 in addition to Table 3 above, it can be estimated that the lower limit of the fluorocarbon gas injection amount is probably 0.02 vol%. From the results of Table 2, Table 3, and Table 4, there is a disconnection due to the difference in measured values between the amount of fluorocarbon gas injected 0.21 vol%, 0.22 vol%, and 0.26 vol%. Therefore, it can be estimated that the upper limit of the amount of chlorofluorocarbon injection is probably 0.22 vol%.

[Evaluation of Freon gas injection temperature]
In addition to the amount of chlorofluorocarbons injected, the temperature range in which chlorofluorocarbon gases were injected was also verified. The inventor, after forming a 500 mL bottle, in the conveyance path until entering the slow cooling step, the bottle surface temperature is 580 ° C. to 590 ° C., 590 ° C. to 600 ° C., and 600 ° C. to 610 ° C. In these three temperature ranges, chlorofluorocarbon gas was injected at different injection amounts to produce bottles. In the production, the amount of fluorocarbon gas injected was 0.02 vol% (0.08 mL) in each temperature range. A thermo viewer was used to control the temperature range of the glass bottle surface temperature. In addition, since temperature fluctuations occur depending on manufacturing conditions and gas injection conditions, the temperature range was adopted.

  After preparing three test waters for each temperature range, the elution amount of calcium was measured by the ICP-AES. However, in this measurement, the weathering acceleration test is omitted, and the measurement is immediately after the preparation of the test water. The results are shown in Table 5, and the elution amount (ppm) was the average value of the three injection amounts.

  From the results of Table 5, it was found that when chlorofluorocarbon gas was injected, the calcium elution suppression effect was small on the low temperature range side. Perhaps the amount of heat necessary for the reaction with chlorofluorocarbon gas is insufficient, and the reaction is not sufficient. Moreover, even when the temperature range reached 600 ° C. to 610 ° C., the effect of suppressing calcium elution was weakened. This is considered to be the result of the fluorocarbon gas reacting excessively with the glass surface, because the fluorocarbon gas is injected at a higher temperature.

  Based on the knowledge in Table 5, the difference in the calcium elution suppression effect depending on the temperature range, and the generation of starch when actually charged with acidic liquid (choose whiskey from liquor) were verified. The inventor made 0.03 vol. At 5 kinds of temperatures of 566 ° C., 586 ° C., 615 ° C., 626 ° C., and 640 ° C. in the conveying path after forming the 500 mL bottle until the slow cooling process is started. Bottles were manufactured as% (0.15 mL) Freon gas injection. As described above, a thermoviewer was used to manage the temperature range of the glass bottle surface temperature. However, since the glass bottle surface temperature has a fluctuation range, each display temperature is a reference value.

  After preparing the test water three by five at five different temperatures, the elution amount of calcium was measured by the ICP-AES. However, in this measurement, the weathering acceleration test is omitted, and the measurement is immediately after the preparation of the test water. The results are shown in Table 6, and the elution amount (ppm) was the average value of the three injection amounts.

  Prepare three glass bottles manufactured by injecting Freon gas at the above five temperatures, fill each with commercial whiskey, and leave it to stand every 3 months for 2 years. The presence or absence was confirmed. “○” for bottles that did not produce starch after 2 years (CFC gas injection temperature), “△” for bottles that produced starch within 6 months to less than 2 years, “×” for bottles that produced starch within 6 months ". At the same time, three bottles manufactured without injecting Freon gas were prepared, and whiskey was filled in the same manner as described above to check for the occurrence of starch.

  Based on the results of Table 6, the chlorofluorocarbon gas injection amount has the highest elution suppression effect from the transition of the fluorocarbon gas injection temperature and the measured calcium elution amount. Moreover, it turned out that the result of the U-shaped curve which shows bottom | bottom temperature 615 degreeC at the time of injection | pouring was shown similarly to the case of the fluorocarbon gas injection amount 0.02 vol% of the above-mentioned Table 5. Therefore, based on the measurement value of the calcium elution amount being 0.1 ppm or less, the upper limit of the temperature at the time of injecting the chlorofluorocarbon gas can be estimated. Furthermore, when the evaluation of starch generation is taken into consideration, it is possible to estimate that the upper limit is preferably 630 ° C to 635 ° C. Further, the lower limit of the temperature at the time of injecting the chlorofluorocarbon gas can be estimated to be around 550 ° C. in consideration of temperature measurement errors, actual manufacturing equipment, and manufacturing conditions.

In the results shown in Table 6, when the measured value of the calcium elution amount was 0.090 ppm, when the whiskey was stored for 2 years, the generation of starch could not be completely prevented. However, it exhibits a sufficient starch control effect due to the difference from the non-injected CFC gas. Therefore, the measured value of calcium (Ca ²⁺ ) elution amount of 0.1 ppm or less is a certain standard to be satisfied. And it is more desirable to suppress to 0.06 ppm, more preferably 0.03 ppm or less, because of a good elution suppression effect.

According to the method for producing a glass container for alcoholic beverages of the present invention, the surface of the glass material is modified by bringing the fluorocarbon gas into contact with the surface of the heated glass material, and the calcium ion is eluted as a result. It can be suppressed to a very small amount. Therefore, it is possible to reduce the influence on the contents such as the contents filled and stored in the glass container react with calcium ions. Therefore, it is possible to propose a new container for storing alcoholic beverages that are easily affected by calcium ions.

Claims (3)

The molten glass obtained by melting the soda lime glass raw material is molded into a predetermined container shape to form a glass molded product, and the surface temperature of the glass molded product is controlled to a temperature range below the glass softening point of the raw material, and the temperature A method for producing a glass container for storing alcoholic beverages obtained by injecting chlorofluorocarbon gas into the inside of the glass molded product between zones and then performing slow cooling,
The temperature range is 550 ° C. to 630 ° C., the Freon gas is 1,1-difluoroethane, and the injection amount is 0.02 to 0.13% by volume of the internal volume of the glass container,
Sixteenth revised Japanese Pharmacopoeia General Examination Method Test method for containers and packaging materials 7.01 Test method for glass containers for injections (ii) Prepare test water by adding distilled water to the glass containers based on the elution conditions of the second method, in accordance with JIS K0116 (2003) When the test water is measured by a measurement method using ICP-AES, the measured value of the amount of Ca ²⁺ eluted from the inner surface of the glass container satisfies 0.06 ppm or less. Manufacturing method of glass container for elution suppression alcoholic beverages. The method for producing a glass container for a calcium ion elution-suppressed liquor according to claim 1, wherein a measured value of the Ca ²⁺ elution amount is 0.03 ppm or less. The method for producing a glass container for a calcium ion elution-suppressed liquor according to claim 1 or 2, wherein the liquor is whiskey.

Images