JPS5915144B2 - Manufacturing method for sanitary rubber products - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for manufacturing sanitary rubber products, and more particularly to a method for manufacturing sanitary rubber products such as closures or seals for pharmaceutical, medical, and food containers.

Conventional rubber caps, plugs, and sealing materials of this type are described in the known document [Rubber Association Journal Vol. 46 P. 703 (197
3), Vol48P537 (1975) - Rubber Industry Vol9N012], isoprene rubber (IR
), styrene-butadiene (S-SBR), polyethylene (PE), polybutadiene (BR), ethylene-propylene terpolymer copolymer (EPDM), epichlorohydrin rubber (CHR), and silicone rubber (Si). It has been introduced as a product suitable for pharmaceutical, medical, and food uses.

In addition, the material is specified in the Japanese Pharmacopoeia, Ninth Revision, General Test Methods, 38.
It meets the material test of the rubber stopper test method for infusions. These materials have also been studied from various angles, and regarding their formulation, Japanese Patent Publication No. 53-6177 discloses a method of crosslinking butyl rubber, polybutene, and polyisobutylene with paraquinone dioxime and lead dioxide. Japanese Patent Publication No. 50-158155 discloses a method of vulcanizing acrylic rubber with a triazine compound, and Japanese Patent Publication No. 53-8736 discloses a method of vulcanizing acrylic rubber with a triazine compound, and Japanese Patent Publication No. 53-8736 discloses a method of vulcanizing acrylic rubber with a triazine compound. -144054
In the publication, thermosetting synthetic resins are mixed with butyl rubber.
0 items are introduced. G. Melnikova also recommended butyl rubber for pharmaceutical rubber stoppers (Soviet Rough Technology Vol. 29 NO. 4, 1970).
This is because special properties are required, including physiological inertness and hydrophobicity, low toxicity and high heat absorption resistance, resistance to acids such as acetic acid or alkalis, and resistance to air, oxygen, and carbon dioxide. This is because it is a material that has excellent permeation resistance against, etc. However, butyl rubber also has properties that vary significantly depending on its compounding agents (types and ratios) and vulcanization methods, and butyl rubber has a high sensitivity to sulfur, organic sulfur-containing vulcanizing agents, and vulcanization accelerators. Since vulcanization is not difficult, a large amount of vulcanizing agent and accelerator must be used, and as a result, harmful substances are eluted even after vulcanization. In addition, vulcanization takes a long time, and in addition, the vulcanized rubber has adhesive properties. This makes high-speed automatic loading difficult. In addition, in order to solve this problem, research is being conducted on compounding agents for butyl rubber and anti-stick agents for the rubber surface.
Due to reasons such as an increase in leachables, we are unable to provide rubber products that meet the standard values of 38 Rubber Plug Test Method for Infusions in the Japanese Pharmacopoeia, Ninth Revised General Test Methods. Furthermore,
Rubber Chemistry and Te35 Technology Vo
l42P1147 (1969) contains butyl rubber
Although a rubber (DVIIR) obtained by crosslinking butyl rubber with an organic peroxide compound is described by bonding divinylbenzene to
Cross-linking with organic peroxide alone (DVIIR) has poor vulcanization physical properties, and when made into a rubber stopper, physical properties (fragment,
There is a problem with liquid leakage), making it unsuitable for practical use in this type of product.

In addition, polybutadiene, styrene-butadiene, and polyethylene are also polymer resins that are excellent in terms of safety and health as described by the US FDA, and can also be cross-linked with peroxide; It has hard physical properties, poor elasticity, and allows a large amount of oxygen, air, and carbon dioxide to permeate, so it cannot be used as an excellent rubber stopper.

The present invention is a manufacturing method that can solve the above-mentioned problems, fully utilize the characteristics and properties of butyl rubber, and provide sanitary rubber products with extremely excellent physical and chemical properties. and isobutylene rubber copolymer (
IIR) combined with divinylbenzene (DV
IIR), a simple substance or a composite of polybutadiene (BR), solution polymerized styrene-butadiene (S-SBR), or polyethylene (PE) is mixed with this, and this is co-crosslinked with an organic peroxide. It is characterized by

To explain in detail below, the main constituent material of the sanitary rubber product manufactured according to the present invention is a copolymer of isoprene rubber and isobutylene rubber, that is, rubber (DVIIR) in which divinylbenzene is bonded to butyl rubber (IIR). , its blending amount is 30 to 75%, preferably 40 to 7%.
It is 0%.

Polybutadiene, styrene-butadiene, and polyethylene are both solution-polymerized, and the blending amount is 10 to 30%, preferably 15 to 25%, and the blending ratio of these alone or in combination is adjusted as appropriate. and do it voluntarily. The organic peroxide is digyl peroxide, 2
・5-dimethyl-2,5-di(t-butyl peroxy)hexane, 2,5 dimethyl-2,5 di(t-butyl peroxy)
peroxy)hexane-3,1,4-bis(t-butyl peroxy isopropyl)benzene, 1,3-bis(t-butyl peroxy isopropyl)benzene, etc., and the blending amount is 0.03 to 0. 4 phr, and such a small amount is sufficient to form a co-crosslinked product, that is, a molded product.

White carbon is suitable as a filler, and it can also be used as a rubber reinforcing agent.The chemical name is silicic anhydride or calcium silicate, and the particle size is 0.01-3μ and the specific surface area is 50-50.
200 i/7, hydrogen ion concentration 6.0 to 10.5 pH. As other fillers, talc and clay may be used, and pigments may also be used.

Next, an example of manufacturing based on a specific formulation example will be explained.
The rubber (DVIIR) is molded into an appropriate shape in the same way as general synthetic rubber, that is, after compounding, it is processed on a mixing roll (50℃~
80℃), and polybutadiene (BR) is wrapped around it.
Alternatively, a simple substance or a composite of styrene-butadiene (S-SBR) is added, switched, and thoroughly mixed by thin-threading, and then molded and co-crosslinked using a vulcanization molding press. Table 1 below shows the blending ratio, test items, and test results. As is clear from the above test results, the value sufficiently satisfies the standard value stipulated in 38 Infusion Rubber Plug Test Method of the Ninth Revised General Test Methods of the Japanese Pharmacopoeia, and also the fragment test as a physical test. The leakage test values were also conducted in accordance with the German standard (DIN) and the British standard (BS), and the values fully conformed to the standard values.

Next, styrene-butadiene (S-
SBR) or polystyrene (PE) is added and similarly molded and co-crosslinked.

The blending ratio, test items, and test results are shown in Table 2 below.

As is clear from this, the test values fully complied with the Japanese Pharmacopoeia Ninth Revised General Tests 38 Rubber Plug Test Method for Infusions, German Standards, and British Standards.

Furthermore, in the above examples, if the decomposition products after crosslinking are removed by elution with a dilute alkaline solution, a more complete product can be produced.

Since the present invention is configured as described above, it is possible to provide a sanitary rubber product that fully satisfies each standard value.

Furthermore, it contains very few particulates, which have recently become a problem, and is ideal for pharmaceutical rubber stoppers, demonstrating excellent effectiveness.

Furthermore, the adhesiveness on the surface of the rubber stopper was extremely small compared to other IIR products, allowing for high-speed automatic loading. Furthermore, it was shown to be an extremely excellent rubber product that can be used effectively in blood sampling devices, blood transfusion devices, and disposable blood sampling devices.

As a result, we were able to provide sanitary rubber products and achieve the intended purpose.

Claims (1)

[Claims] 1 Divinylbenzene is bonded to a copolymer of isoprene rubber and isobutylene rubber, and polybutadiene or a simple substance or a composite of solution-polymerized styrene-butadiene or polyethylene is mixed therewith, and this is co-crosslinked with an organic peroxide. A method of manufacturing a sanitary rubber product characterized by the following.