JPS59200649A - Rubber stopper for medicine - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Goods The present invention relates to an improved rubber stopper for pharmaceutical use. In particular, the surface is not sticky and the slipperiness is high quality. This invention relates to an improved medical rubber stopper.

△ Chlorinated butyl rubber, which has excellent gas impermeability and chemical resistance, is usually used as the sealing rubber stopper for ampoule bottles, which are used to enclose medicines and take out the contents through the rubber stopper with a syringe. .

However, since such rubber stoppers have adhesive surfaces and poor slip properties, they often stick to each other during automatic stoppering operations, which often causes trouble.

In order to eliminate this drawback, a method of applying silicone oil or the like to the surface of the rubber stopper has traditionally been used, but with this method, the surface of the rubber stopper is wet, so there is no chance of foreign matter such as dust adhering to it. It is not suitable for water scales, and the coating film tends to peel off when cleaning and sterilizing the rubber stopper, which is not desirable. In addition, a method has been proposed in which the surface of the rubber stopper is covered with a vulcanized film of fluororubber, but the vulcanized film of fluororubber itself is not very good in terms of adhesiveness and slipperiness, which sufficiently eliminates the above-mentioned problems. The reality is that this is not the case.

The present inventors have discovered that the above-mentioned problems can be essentially solved by providing a coating containing fluororubber and fluororesin on at least a portion of the surface of the rubber stopper.
The present invention has now been completed.

The coating containing fluororubber and fluororesin according to the present invention has the inherent elasticity of fluororubber, and the fluororesin imparts appropriate non-adhesiveness and slipperiness to its surface, so the above-mentioned troubles will not occur. Moreover, it is difficult for foreign substances to adhere to the rubber stopper, and blooming or bleeding of the compounded chemicals in the rubber stopper is prevented.

The fluororubber referred to in the present invention is a highly fluorinated elastic copolymer, and particularly preferred fluororubber is usually 40 to 85 mol% of vinylidene fluoride and at least one species copolymerizable with it. and other fluorine-containing ethylenically unsaturated monomers. Further, as the fluororubber, a fluorocomb containing iodine in the polymer chain can also be preferably used. For example, this fluororubber containing iodine has 0.001 to 10% by weight at the end of the polymer chain.
Preferably, 0.01 to 5% by weight of iodine is bonded, and the same 40 to 85 mol% of vinylidene fluoride as mentioned above and at least one other fluorine-containing ethylenically unsaturated monomer copolymerizable therewith. This is a fluororubber whose main composition is an elastic copolymer (see JP-A-52-40543). Other fluorine-containing ethylenically unsaturated monomers that can be copolymerized with vinylidene fluoride to provide an elastic copolymer include hexafluoropropylene, pencfluoropropylene, and 3. Wonofluoroethylene, trifluorochloroethylene, tetrafluoroethylene, vinyl fluoride, perfluoro(methyl vinyl ether), perfluoro(ethyl vinyl ether), perfluoro(
Typical examples include flobyl vinyl ether). Particularly preferred fluororubbers are vinylidene fluoride/hexafluoropropylene dielastic copolymers and vinylidene fluoride/tetrafluoroethylene/hexafluoropropylene terelastic copolymers.

In addition, the fluororesin referred to in the present invention includes polytetrafluoroethylene, tetrafluoroethylene, and at least one other ethylenically unsaturated monomer copolymerizable therewith (for example, olefins such as ethylene and propylene,
hexafluoropropylene, vinylidene fluoride,
Examples include copolymers of chlorotrifluoroethylene, vinyl fluoride (nato halogenated olefins, perfluoroalkyl vinyl ethers, etc.), polychlorotrifluoroethylene, polyvinylidene fluoride, and the like. Among these, preferred fluororesins are at least one of polytetrafluoroethylene, tetrafluoroethylene and hexafluoropropylene, perfluoroethyl vinyl ether, perfluoroethyl vinyl ether, and perfluoropropyl vinyl ether (usually 40 mol% based on tetrafluoroethylene). (included below).

A coating comprising fluororubber and fluororesin is usually obtained by applying a fluororubber paint comprising fluororubber, fluororesin, and a liquid carrier to the surface of a rubber stopper by a conventional means. This fluorocomb paint also contains coupling agents, vulcanizing agents, acid acceptors, pigments,
A filler or the like may be added, and the coating film obtained by applying the fluororubber paint can be vulcanized under appropriate conditions if necessary.

Here, the coupling agent refers to a compound that acts on the interface between an organic material and an inorganic material and forms a strong bridge between the image materials through chemical or physical bonding, and is usually a compound such as silicon, titanium, zirconium, hafnium, Thorium, tin, and aluminum are compounds of magnesium, and are compounds that have a group that can bond an organic material and an inorganic material.

Among these coupling agents, preferred are silane coupling agents and orthoacid esters of Group IV reduction elements of the periodic table (such as titanium or zirconium) and derivatives thereof, with aminosilane compounds being the most preferred.

Representative examples of the aminosilane compounds preferably used include γ-aminopropyltriethoxysilane (hereinafter referred to as A-1100), N-β-aminoethyl-γ-aminopropyltrimethoxysilane, N-(
)rimethoxysilylpropyl)ethylenediamine, N-
β-aminoethyl-γ-aminopropylmethyldimethoxysilane, γ-ureidopropyltriethoxysilane,
Compounds such as β-aminoethyl-β-aminoethyl-γ-aminopropyltrimethoxysilane are mentioned, and this aminosilane compound not only functions as a vulcanizing agent for fluororubber, but also improves its adhesion to the base material. also contributes.

The vulcanizing agent mainly functions as a vulcanizing agent for fluororubber, and together with the coupling agent, improves mechanical properties. Typical examples thereof include ethylamine, propylamine, and butylamine. , benzylamine, allylamine, n-amylamine, monoamines such as ethanolamine, ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, 3,9-bis(3-aminopropyl)
-2,4,8,10-tetraoxaspiro[5,5:
] Diamines such as undecane (hereinafter referred to as V-11), polyamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, among others, amine compounds having two or more terminal amine groups. is preferred.

As the acid acceptor, those commonly used in the vulcanization of fluororubber can be similarly used, such as one or more divalent metal oxides or hydroxides. Specific examples include oxides or hydroxides of magnesium, calcium, zinc, lead, and the like. Further, as the filler, silica, clay, diatomaceous earth, talc, carbon, etc. are used.

The ratio of fluororubber and fluororesin in the fluororubber paint is preferably 95:5 to 35:65 by weight, and when the ratio of fluororesin is less than the above lower limit, the desired non-adhesiveness and lubricity can be achieved. The improvement is not sufficient, and conversely, if the amount exceeds the above upper limit, a coating film of the desired thickness cannot be obtained.
Cracks and pinholes are likely to occur in the paint film.

The liquid carrier contained in the fluororubber paint used in the present invention is selected from organic solvents such as lower ketones, lower esters, and cyclic ethers, water, and a mixture of water and a water-soluble organic liquid. Alcohols can be exemplified.

The film thickness of the film containing the fluororubber and fluororesin of the present invention is preferably 1 μm to 20 μm.

As mentioned above, chlorinated butyl rubber has been used for pharmaceutical rubber stoppers due to its gas impermeability and chemical resistance, but coatings containing fluororubber and fluororesin are more sensitive to air and air than chlorinated butyl rubber. It has low water vapor permeability and even better chemical resistance.

Therefore, according to the present invention, since a coating containing such fluororubber and fluororesin is used, the material of the rubber stopper body may be chlorinated butyl rubber, for example, butadiene rubber,
Various synthetic rubbers such as styrene-butadiene rubber, chloroprene rubber, nitrile rubber, epichlorohydrin rubber, ethylene-propylene rubber, and ethylene-propylene-diene rubber are used.

One embodiment of the rubber stopper of the present invention is shown in the drawings. FIG. 1 is a perspective view thereof, and FIG. 2 is a sectional view thereof.

As clearly shown in FIG. 2, a coating 2 containing fluororubber and fluororesin is provided on the surface of the rubber stopper body 1.

It is preferable that the

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples and Comparative Examples. Note that parts indicate parts by weight.

Example 1 and Comparative Examples 1 and 2 Non-adhesiveness test on the surface of a paint film A paint with the following composition was applied to the surface of a chlorinated butyl rubber vulcanized plate (the uncoated one is referred to as Comparative Example 1), and the test was carried out for 10 minutes at room temperature. It was further dried at 150° C. for 3 minutes to form a coating film with a thickness of 10 μm.

Paint composition: Example 1 Comparative Example 21) Fluororubber 100 parts 100 parts 2) Fluorine resin 30 parts Acetone 520 parts 400 parts Note 1) Vinylidene fluoride/tetrafluoroethylene/hexafluoropropylene elastic copolymer 2) Cut each tetrafluoroethylene/hexafluoropropene copolymer test piece into pieces of 10 wn in length and 20 wn in diameter, overlap them so that the coating film forming surfaces are in contact with each other, and apply 1.
It was pressed for 0 seconds. The peel strength of the crimped piece was measured by performing a 180° peel test using an autograph. The results are shown in Table 1.

Table 1 Example 2 and Comparative Examples 3 to 4 Using the test pieces prepared in Example 1 and Comparative Examples 1 to 2,
Using a Baudenleben type friction tester, the friction coefficient, i, and the hunting width appearing on the torque line of the friction surface, which is a guideline for stick-slip, were measured under the following conditions.

Measurement condition: Indenter: 2d chlorinated butyl rubber vulcanized plate Load: 50g Movement speed: 0.24cm/sec Note 1) Stick slip

[Brief explanation of the drawing]

FIG. 1 is a perspective view of one embodiment of the rubber stopper of the present invention, and FIG. 2 is a sectional view of the rubber stopper of FIG. 1. 1...Rubber stopper body, 2...Coating. Patent applicant: Daikin Industries, Ltd. Agent: Attorney: Qingbai Ao (2 others) Figure 1 Figure 2 Procedural amendment (.e) October 19, 1980 Director General of the Japan Patent Office 1, Indication of the case 1982 Patent Application No. 074527 2 Name of the invention Rubber stopper for pharmaceuticals 3 Relationship with the case of the person making the amendment Patent applicant address Osaka prefecture person t2 (+lI, Ie Ig kU:
;i l 'J Month 112 City No. 39 New Hankyu Pill Name (
285) Daikin Industries (Main company representative: Mt.
1) Minoru 4, Agent 5, date of amendment order: (voluntary) and column 7 of detailed explanation of the invention, amend the following points in the statement of contents of the amendment. ■As per the appendix in the claims section. ■1 Column for detailed description of the invention (1) In the 5th line from the bottom of page 1, insert a container such as [after "ampule bottle"]. (2) On page 3, line 4, “Bloom” was corrected to “Bloom”. (31+', ' Delete ``(hereinafter referred to as A-1100)'' in the 5th line from the bottom of page 7. (4) Delete ``(hereinafter referred to as V-11)'' in the 4th line from the bottom of page 7. Above (attached sheet) Patent Claims 1. A rubber stopper for pharmaceuticals, characterized in that a coating containing fluororubber and fluororesin is provided on at least a portion of the surface of the com stopper. 2. Harm between the fluorocarbon resin and the fluorine resin. The rubber stopper according to claim 1, wherein the ratio of jj to weight is 95=5 to 35:65.

Claims (1)

[Scope of Claims] 1. A medical rubber stopper, characterized in that a coating containing fluororubber and fluororesin is provided on at least a portion of the surface of the rubber stopper. 2. The ratio of fluororubber and fluororesin is 95:5 by weight
~35:65 The rubber stopper according to claim 1.