JPH0437632A - Glass ampoule or bottle, and its production - Google Patents

Abstract

PURPOSE:To easily improve the productivity of glass ampoules produced by a hot-molding method from a glass tube into an ampoule form, etc., by treating the inner surface of a hot-molded product with a silicon compd. in vapor phase. CONSTITUTION:Borosilicate glass, etc., is heated and molten at 800-1000 deg.C and molded to obtain an ampoule or bottle-shape hot-molded product (A). On the inner surface of (A), a liquid silicon compd. [e.g. Si(NCO)4] is dropped on the inner surface of the product (A) in an environment at 400-600 deg.C for the vapor phase treatment. The treated product (B) is then slowly cooled and left to stand. Thus, the glass ampoule or bottle with inner surface coated with a silica film is produced.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to a glass ampoule or tube bottle formed from a glass tube, which is used as a storage container for drugs or test samples mainly in the medical and physical and chemical fields. , and its manufacturing method.

[Prior Art] As a method of manufacturing glass ampoules or tube bottles used as storage containers for drugs or test samples in the medical and physical and chemical fields, a glass tube is heated and melted into the shape of an ampoule or tube bottle using a burner flame. However, a method is known in which the molded product is slowly cooled.

Glass often contains an alkali component as a main raw material or as a fluxing agent, and when the glass tube is heated and melted, the alkali components such as alkali boric acid contained in the glass volatilize and become oxidized. Adheres to and condenses on the inner walls of molded products. This encapsulated and condensed alkaline component can hardly be removed by ordinary cleaning. Therefore, the glass ampoule or tube column manufactured in this manner has extremely high alkali elution from the inner surface. If chemicals or test samples are stored in such glass ampoules or tube bottles, the internal solution will deteriorate due to alkaline elution.

As a method to prevent the elution of the alkaline components mentioned above, silicone resin is applied to the inner surface of the obtained molded product. how to cloth,
Another method is to subject the inner surface of the molded product to sulfur treatment with ammonium sulfate. Although these treatment methods are effective in preventing the elution of attached alkaline substances, they add a separate process to the manufacturing process of glass ampoules or tube bottles, resulting in low productivity and high costs. .

In addition, as a method to prevent the adhesion of alkaline components, methods such as lowering the temperature of the burner flame to reduce the volatilization of alkaline components, or venting the volatilized components by passing pressurized air through the mouth of the molded product are also available. However, these methods do not sufficiently prevent the adhesion of alkaline components and have low productivity.

[Problems to be Solved by the Invention] Therefore, the present invention provides a method for efficiently producing glass ampoules or tube bottles with low alkali elution over a long period of time from the above-mentioned type of glass tube, and The object of the present invention is to provide an ampoule or a tube bottle.

[Means for Solving the Problems] In order to solve the above problems, in the present invention, the inner surface of a hot-formed product that has been heat-formed from a glass tube is coated with a stable silica film by vapor-phase treatment with a silicon compound. I'm wearing it.

That is, the present invention provides a method for manufacturing a glass ampoule or a tube bottle by heating and forming a glass tube into an ampoule or tube bottle shape and slowly cooling the tube, in which the inner surface of the hot-formed product is coated with a silicon compound in a vapor phase after the heat forming. Provided is a method for manufacturing a glass ampoule or tube bottle, which is characterized in that it is treated to coat a silica film.

The present invention also provides a glass ampoule or tube bottle having a silica film formed by hot vapor phase treatment of a silicon compound on its inner surface.

The present invention will be explained in more detail below.

To produce glass ampoules or vials according to the invention, glass ampoules or tubes can be produced using methods known per se.
A tube of borosilicate glass is heated and melted and formed into an ampoule or tube bottle shape. The heating temperature is usually about 800°C to 1000°C.

Next, the inner surface of the obtained hot-formed product is subjected to a vapor phase treatment with a silicon compound, and a silica film is deposited and formed on the inner surface of the molded product by decomposition (hydrolysis, etc.).

The silicon compound used in the present invention is used to deposit and form a silica film on the inner surface of a hot-formed product by vapor phase treatment, and contains oxygen atoms in addition to silicon. A preferred silicon compound is a silicon compound that forms and deposits a silica film by hydrolysis in the gas phase and generates gas as a by-product.

Examples of such silicon compounds include silyltetrisonaneto compounds, especially silyltetrisonaneto (S i
(NGO) 4).

This compound is hydrolyzed by moisture in the atmosphere to form a silica film, and carbon dioxide gas and nitrogen gas are produced as by-products.

Now, gas phase treatment of the inner surface of a hot molded product with a silicon compound can be carried out, for example, by dropping liquid silyl isocyanate into the inside of the molded product, which is at a temperature of about 400 to 600°C immediately after hot molding (for example, 1 to 2a). This can be done by doing. The dropped silyl isocyanate instantly volatilizes to form a gas phase.

Alternatively, the gas phase treatment involves passing similarly heated air as a carrier gas through the silyl isocyanate heated to about 100 to 200°C (at a flow rate of, e.g., 2 liters/min to 3 liters/min). This can also be carried out by entraining the isocyanate and passing this carrier gas through the interior of the molded article, which is at a temperature of about 400 to 600 DEG C. immediately after hot molding.

In any of these methods, silyl isocyanate is considered to be hydrolyzed by atmospheric moisture in the gas phase to form a silica film, and the by-products, carbon dioxide gas and nitrogen gas, are removed by volatilization.

After the inner surface of the hot molded product is subjected to gas phase treatment with a silicon compound, the molded product is slowly cooled by a conventional method and left to cool to obtain a glass ampoule or tube bottle whose inner surface is coated with a silica film. The silica film thus formed is stable and can prevent elution of alkaline components contained in the glass over a long period of time.

[Function] As mentioned above, the silica compound that comes into contact with the hot molded product in the gas phase is hydrolyzed and deposits a silica film on the inner surface of the molded product.
This silica film acts as a film that prevents elution of alkaline components over a long period of time.

In addition, since the formation of the silica film is carried out in a series of manufacturing processes for ordinary glass ampoules or tube bottles, the time required for gas phase treatment is not added to the manufacturing time, and productivity is also reduced. good.

[Example] The present invention will be explained in detail below.

Example 1 Ampules and tube bottles having the specifications shown in Table 1 below were heat-molded from borosilicate glass tubes.

Table 1 Ampoule 12.5 77.5 0.42 2 Tube bottle 24.3 46.5 1.2 10 Inside each molded product at a temperature of 580°C immediately after heat molding,
1 drop of silyl tetraisocyanate (0.04~0.0
5 grams) was added dropwise, subjected to gas phase treatment, and then gradually cooled and left to cool to obtain desired glass ampoules and tube bottles.

When the inner surface of the obtained product was analyzed by Auger electron spectroscopy, it was confirmed that only a silica film was formed.

Next, the amount of alkali elution from the obtained ampoules and tube bottles is
Immediately after production, the consumption of 0.02N□-H2S04 was measured by titration.For comparison, similar measurements were also made for conventional non-treated products.

The results are shown in Table 2 below.

Table 2 Ampoule 0.875 0.098 Tube
LIOI 0.142 As is clear from the results shown in Table 2, the glass ampoules and tube bottles of the present invention have significantly less alkali elution than conventional products.

In addition, regarding the product of the present invention after 100 days of manufacture,
Similarly, the amount of alkali elution was measured. The results are shown in Table 3 below.
Shown below.

Table 3 Type Titration amount (ml) Blank (water only) 0.04 Ampoule 0.07 Tube 0. o5 As can be seen from the results shown in Table 3, the glass ampoules and tube bottles of the present invention can effectively prevent alkali elution over a long period of time.

[Effects of the Invention] As described above, unlike conventional methods, the present invention forms a silica film as an alkali elution prevention film in the normal manufacturing process of glass ampoules or tube bottles, but it is relatively simple. Ampules or tube bottles can be easily manufactured from glass tubes with excellent productivity1, and the formed silica film can prevent alkali elution over a long period of time.

Claims (2)

[Claims] (1) In a method of manufacturing a glass ampoule or tube via a process of heating and forming a glass tube into the shape of an ampoule or tube and slow cooling, after the heating and forming, the inner surface of the hot-formed product is treated with a silicon compound in a vapor phase. 1. A method for producing a glass ampoule or tube bottle, which comprises applying a silica film to the glass ampoule or tube. (2) A glass ampoule or tube bottle having a silica film formed by hot vapor phase treatment of a silicon compound on its inner surface.