JPH0741065B2 - Medical and pharmaceutical rubber products - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention is a product used for rubber parts of medical devices or stoppers of containers for pharmaceuticals, eleventh revision “Japanese Pharmacopoeia” and British Standard 3263. , DIN 58363, 58367, etc., relating to medical and pharmaceutical rubber products excellent in hygiene and physical properties that can pass various regulations established in other countries.

[Conventional technology]

The medical and pharmaceutical rubber products differ greatly in performance and evaluation method from rubber products such as automobile tires, hoses and packing. Medical and pharmaceutical rubber products are required to have a high degree of hygiene, followed by aging resistance, heat resistance, compression strain resistance,
Impermeable resistance, flexibility, etc. are required. From this viewpoint, isobutylene-isoprene rubber (IIR) is the first, followed by ethylene-propylene terpolymer rubber (EPM, EPDM), butadiene rubber (BR). It is preferable to use a compounded crosslinked product mainly composed of, for example, isoprene rubber (IR). As an invention relating to a compounding agent such as IIR and a crosslinking agent, the one proposed in Japanese Examined Patent Publication No. 60-57870 is known.

The inventors of the present invention described in JP-A-59-5046, IIR, EPD
We have proposed a technology to further enhance the properties of rubber stoppers for medical and pharmaceutical products by laminating cross-linked rubbers such as M, BR and IR with fluorine-based copolymer film. As a rubber stopper, it shows a very satisfactory result.

[Problems to be solved by the invention]

By the way, in the case of chemicals that are insoluble in water or unstable in aqueous solutions, or when it is desired to prolong the efficacy, for example vegetable oil
Preparations using non-aqueous solvents such as glycols, suspension milk preparations using vegetable oil, high calorie nutritional infusion preparations (mixed with high calorie preparations) containing fatty acids, glucose, amino acids, vitamins, minerals, etc., intraocular It may be a sustained release preparation for administration, a sustained release preparation for intrauterine, buccal or transdermal administration. However, when a rubber stopper according to a conventional known technique is used for such a pharmaceutical product, the drug itself, the solvent and additives of the pharmaceutical agent permeate and permeate into the rubber stopper, the rubber substance swells, and the rubber and the rubber compound are A phenomenon in which the drug is adsorbed by the rubber which is eluted in the drug formulation liquid or swollen on the contrary and the potency of the drug is reduced occurs, and there are still many problems in terms of long-term hygiene.

The present invention has been made in view of the present situation, and is excellent in hygiene without swelling of rubber as described above, rubber, elution of a compound, adsorption of drugs, additives, etc., and flexibility and gas resistance. The purpose is to propose medical and pharmaceutical rubber products with sufficient permeability and hermeticity.

[Means for solving problems]

The present invention has a rubber surface of a rubber composed of 20 to 80% by weight of a copolymer rubber containing acrylonitrile and butadiene as main components and having a thickness of 0.
The present invention relates to a medical / pharmaceutical rubber product in which a fluorine-based resin film of 001 to 1.0 mm is laminated, and rubber cross-linking, molding and the above lamination are simultaneously performed.

In a particularly preferred embodiment of the present invention, the rubber is a rubber comprising 20 to 60% by weight of a copolymer rubber containing acrylonitrile and butadiene as main components, and epichlorohydrin rubber and / or ethylene-acrylic copolymer rubber. Pharmaceutical rubber products can be mentioned.

1 to 3 show an embodiment of the medical / pharmaceutical rubber product of the present invention. In each drawing, E is a fluorine resin film, and F is a rubber body made of NBR rubber. FIG. 1 is a cross-sectional view of a container A (here, a vial) filled with a chemical solution B, the laminated rubber stopper C of the present invention being stoppered, and the aluminum cap D being wound up. In FIG. 1, the rubber stopper C
The outer peripheral portion of the leg base is a rubber surface. FIG. 2 shows a syringe J equipped with a laminated stopper G of the present invention having a sucker H.
In the cross-sectional view of (combined container A), I shows an injection needle and K shows the laminated stopper of the present invention. FIG. 3 is also an example of the laminated rubber stopper of the present invention.

In the present invention, vegetable oil added to several pharmaceutical products,
Acrylonitrile and butadiene are the main components as a rubber elastic body that is not attacked by simple substances and / or complexes of alcohol compounds, surfactants, preservatives, anti-aging agents and chemicals such as vitamins, glucose, amino acids, minerals. By using a copolymer (hereinafter abbreviated as NBR), the fluorine-based resin film is overlaid on the surface of the copolymer and pressure-molded with a mold or the like to crosslink the rubber, laminate with the fluorine-based resin film,
The present invention solves the above-mentioned problems in conventional medical products by simultaneously molding and laminating a fluorine-based resin on at least a part of the surface thereof to obtain a medical / medical rubber product.

The reason why NBR is selected as the elastic body in the present invention is that the NBR molecule contains a nitrile group (-C≡N) having a strong cohesive force, so that it is excellent in oil resistance and chemical resistance. NBR
Are classified into extremely high, high, medium high, medium low and low nitrile depending on the content of acrylonitrile (CH ₂ = CH—CN), and their SP value (Solubility Panameter) is 8.5 to 10.5.
The NBR used in the present invention has an acrylonitrile content of 31.
It is preferably about 56 to 56% by weight of medium to high.

Thus, even in NBR having excellent oil resistance and chemical resistance, since commercial products are manufactured by emulsion polymerization, there is a risk that the emulsifier, the polymerization activator, the terminating agent, etc. migrate to the drug or solvent and contaminate. Therefore, if it is used as it is, it will be a low grade hygienic rubber product. Therefore, in the present invention, NBR is used as the main component of the rubber body that constitutes the internal structure of the rubber product, and a fluorine-based resin film is laminated on at least a part of the rubber body, so that the 11th revision "Japanese Pharmacopoeia" ( (Hereinafter abbreviated as "Nippon Yakuhin") standard, British Standard 3263, DIN583
It is a high-grade sanitary rubber product that can pass the standards of foreign countries such as 63 and 58367.

Examples of the NBR used in the present invention include acrylonitrile-butadiene-isoprene terpolymer, ethylene-acrylonitrile-butadiene terpolymer (manufactured by Zeon Corporation, Settopol), acrylonitrile-butadiene-methacrylic acid terpolymer. Combined, acrylonitrile-
Butadiene-1,1 dihydroperfluoroethyl acrylate terpolymer, butadiene-acrylonitrile-butyl acrylate terpolymer, carboxylated NBR,
Examples thereof include NBR partially crosslinked with divinylbenzene, and NBR obtained by copolymerizing these with an antioxidant.

Depending on the characteristics and prescription of the drug or the like applied to the device, the container using the rubber part or the rubber stopper of the present invention, the above NBR is mainly used, and further, epichlorohydrin rubbers (hereinafter CO
And / or ethylene-acrylic copolymer rubber (hereinafter abbreviated as EA) can be mixed, whereby the resistance to a polar solvent preparation can be further improved.

Examples of COs used in the present invention include epichlorohydrin polymers, epichlorohydrin-ethylene oxide copolymers (ECO), and terpolymers of ECO and allyl glycidyl ether (AGE) (GW, GECO). ,
By mixing these, heat resistance, oxidation resistance, gas impermeability, ultraviolet resistance and elasticity are improved.

As the EA used in the present invention, a terpolymer copolymerized with ethylene and methyl acrylate as a main component and an unsaturated organic acid ester (manufactured by Dyupon Co., Baymatsu (trade name),
SP value of 8.9 to 9.7]. The rubber is generally cross-linked with an amine, but in the present invention, cross-linking with an organic peroxide is preferred, and a cross-linking aid such as N-N'-m-phenylene dimeride or triacryl isocyanurate. Used together. In addition to the above, for example, ethylene-ethyl acrylate maleic anhydride terpolymer [Sumitomo Chemical Co., Ltd., Bondyne (trade name)], ethylene acrylic acid ester-vinyl acrylate copolymer [Electrochemical Co., Denka ER
(Trade name)], ethylene acrylate-acrylonitrile copolymer, ethylene-acrylate copolymer, acrylate-butadiene copolymer (ABR), etc. can be used, and all contain vitamins, glucose, fats, etc. Oil resistance and water resistance can be improved with respect to the composite preparation.

The composition of the rubber body constituting the internal constitution of the medical / pharmaceutical rubber product of the present invention has an NBR content of 20 to 80% by weight, COs, EA
When not mixed, the NBR content is preferably 40 to 80% by weight, particularly preferably 60 to 80% by weight. Also NBR to CO
When the compounds or EA are mixed, the NBR content is preferably 20 to 60% by weight, and the COs and / or EA is preferably 5 to 50% by weight.

In addition, as the other compounding agent in the rubber component of the rubber element,
Reinforcing agents such as clays, titanium oxide, barium carbonate, white carbon, carbon black, fillers, processing aids,
A well-known technique is applied to blending a pigment or the like. Further, the action of the cross-linking agent, the cross-linking activator, etc. is complicated, but it is an important matter in the present invention to use a combination of additives so that the cross-linking network of the highest concentration can be constituted with a small amount of these compounds. is there.

In the present invention, as the fluorine-based resin film laminated on at least a part of the rubber body containing NBR or the like as a main component, for example, tetrafluoroethylene-ethylene copolymer (ETF
E), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA),
Chlorotrifluoroethylene-ethylene copolymer (ECTF
E), polyvinyl fluoride (PVF), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), polytetrafluoroethylene (PTFE) and the like.

The thickness of the fluorine-based resin film is preferably 0.001 to 1.0 mm.If it is 0.001 mm or less, it may be damaged during processing and the product warranty may be insufficient.On the other hand, if it is 1.0 mm or more, the rigidity will be too strong and it will be a rubber product. It is unsuitable because it reduces the tightness of the container / object.

In order to obtain a strong adhesive surface between the fluorine-based resin film and the rubber surface, the film surface is pretreated by a known technique such as corona discharge treatment, plasma discharge treatment, glow discharge treatment, arc discharge treatment, and spatter etching. It is preferable to keep.

Also, the rubber composition and the type of fluorine resin film (for example,
With PVDF, PVF, etc.), a strong adhesive surface can be obtained only by cleaning the film surface or applying a primer treatment. Whichever method is used, it is important that the adhesive force between the rubber surface and the film is 3 to 30 kg / cm.

The method for producing a medical / pharmaceutical rubber product of the present invention is described in JP-B-57
-53184, JP-A-59-5046, a known technique and Japanese Patent Application No. 60-113255, the technique proposed in the specification, on the mold surface of a mold having a concave shape of the product shape, First, the fluorine-based resin film is placed, and the uncrosslinked compounded rubber containing the above-mentioned rubber as a main component is overlaid thereon, and then, by heating and pressurizing, the crosslinking and molding are simultaneously performed, and the adhesion and lamination with the fluorine-based resin are performed. To do. If a fluororesin film is further placed on the uncrosslinked rubber surface for molding and lamination, a product in which the fluororesin is laminated on the entire surface of the product can be obtained.

〔Example〕

Below, various experiments and examples leading to the present invention and comparative examples are shown.
The present invention will be specifically described. Common items for each experiment are as follows.

1) The rubber composition was as shown in each table, and the rubber compounding operation was performed using an open roll and an internal mixer in accordance with JIS K6384 (1975).

2) The cross-linking method conforms to JIS K6384, and the laminating technique as shown in FIG. 4 described in JP-A-59-5046 described above is applied. The shape of each product is added to the notes in the table.

3) The physical properties of the crosslinked product and the adhesive strength between the rubber and the resin film were measured according to JIS K6301. The preferred characteristic values for the rubber product of the present invention include, for example, tensile strength of 60 to 160 kg / cm ² , elongation of 300 to 600%, hardness of 38 to 55 (H
s).

4) For hygiene tests, refer to 41 of “Nippon Yakuhin,” in accordance with the rubber stopper test method for infusion, temperature 121 ° C. for 60 minutes, and extract for pH, potassium permanganate reducing substance (abbreviated as KMnO ₄ ), The evaporation residue (abbreviated as RE) and ultraviolet absorption spectrum (abbreviated as UV) were measured. The pass value of “Nichiyaku” standard is pH fluctuation value ± 1.0 or less, KMnO ₄ 2.0 ml or less, RE 2.0 mg or less, UV 0.2 or less.

5) The hygiene test of laminated rubber products is based on
Oil, solvent, etc. were brought into contact with each other to extract the substance transferred to the solvent, etc., and pH, KMnO ₄ , RE and UV of the extract were measured in the same manner as in the previous item 4), and migration / contamination from the rubber product was examined. .

6) As the fluorine-based resin film to be laminated, one of the following two kinds was used.

i) 1-1 ETFE, tetrafluoroethylene: ethylene = 65:35 (molar ratio), melting point 235 ° C, manufactured by Daikin Industries, thickness
0.05mm resin film, 1x atmospheric pressure on one side of this film
Sputter etching processing at 10 ^-2 Torr, Rf voltage 800W, winding speed 0.3mm / min.

ii) 1-2 PVDF, KF film (trade name) manufactured by Kureha Chemical Industry, one side of which was cleaned with an alcohol mixture.

Experiment 1. Preliminary test Using a medium-high nitrile having an acrylonitrile content of 33% as an NBR, a crosslinked product was obtained under the composition and the crosslinking conditions shown in Table 1. The measured physical properties of the obtained crosslinked product and the results of hygiene test are also shown in Table 1.
Are shown together.

As is clear from Table 1, when the NBR content is 84.4% by weight (formulation 1), the crosslinked product has low physical properties and cannot be used as a practical rubber product. The physical properties are preferably 36.7% by weight of NBR (Compound 2) with a relatively large amount of filler. However, when a vial rubber stopper for injection composed of a cross-linked product of this formulation 2 was prototyped and evaluated, it was found that the injection needle puncture test according to British test standard 3263 (1960), exfoliation of fine particles, RE value (by Japanese medicine 16 injection), etc. From this point of view, it was unsuitable as a hygiene product.

Experiment 2. NBR test (a) When non-laminated NBR is cross-linked and molded, medium-high nitrile with a non-staining antioxidant is used as NBR with acrylonitrile content of 35%, and NBR content is 61.3 to 70.7.
%, And sulfur crosslinking, organic donating sulfur crosslinking or peroxide crosslinking was performed under the compounding and crosslinking conditions shown in Table 2, and molding was performed simultaneously with crosslinking. Thus, an injection vial No. 2 rubber stopper having the shape shown in FIG. 1 and having no fluorine-based resin film laminate E was produced. The evaluation of the obtained rubber plug is also shown in Table 2 (formulations 5 to 7).

Table 2 also shows, for comparison, those obtained by using IIR or natural rubber instead of NBR in the same manner (compounds 8 and 9).

As is clear from the results of Table 2, all of the formulations 5 to 9 were unsatisfactory products because of high values of pH, KMnO ₄ , RE and UV in the hygiene test.

(B) In the case of cross-linking / molding fluorine resin film laminated NBR, the diameter is 12.9 mm and the depth is 5.0 mm, which is equivalent to the leg of injection vial No. 2 (see Fig. 1) described in the table below. The 1-1ETFE film and the rubber of each composition shown in Table 2 above were overlaid on the plate surface of the mold provided with the depressions, and the laminated mold rubber was heated and pressed under the first crosslinking condition of Table 3 by the upper mold. Cross-linking at the same time as molding
Obtained by laminating and subsequently cut with burrs. Next, place the laminated leg rubber molded product in the same leg die cavity as above, place the same compounded rubber as the leg on the plate upper surface, and press under the second cross-linking condition of Table 3 with the flange cavity die.・ The rubber stopper was completed by heating. At this time, the adhesive force between the ETFE film and the rubber is 3
It was ~ 8 kg / cm.

As shown in FIG. 1, a vial for injection (JI
SR 3521) No. 2 was used, and olive oil was added to this as chemical solution B.
7 ml was charged, the laminated rubber stopper obtained above was completely stoppered as the stopper F, and the aluminum cap D was further wound. Next, the vial was left in an inverted state in a thermostat at a temperature of 30 to 40 ° C for 90 days so that the laminated portion and olive essential oil were immersed. The same vial for injection was separately prepared, and the same procedure as above was performed using a mixture of 7 ml of olive essential oil and 0.7 g of beeswax as the drug solution B and purified water. After 90 days, each solution in the vial was extracted three times with 7 ml of a mixed solution of water and methyl alcohol. Table 3 shows the evaluation results of the extract.

As shown in Table 3, in the laminated bottle stopper filled with the olive essential oil and the olive essential oil / beeswax mixed liquid, the product of the present invention has the same degree of purification water and high hygiene. On the other hand, Comparative Example 1
In (IIR) and Comparative Example 2 (natural rubber NR), both the olive essential oil and the olive essential oil / beeswax mixture have high pH and UV values. It has become unsanitary because it penetrates and elutes. When comparing the hygiene properties of Table 3 (laminated product) and Table 2 (non-laminated product), it was found that there was no contamination of the purified water filled by laminating with ETFE film.
It can be seen that the difference between NR and IIR, NR is also small.

Calcium chloride (1.00 g) was precisely weighed in a vial, a laminated rubber stopper was capped on the vial, an aluminum cap was tightened and left at room temperature for 90 days. Although it was 2.42 g, Comparative Example 2 (NR) was 4.1
Increased to 2g. This is due to an increase in moisture absorption through the laminated rubber plug, indicating that the product of the present invention has a low hygroscopic property.

Experiment 3. Experiment on mixed composition of NBR and GECO (a) When non-laminated material was cross-linked and molded As shown in Table 4, rubber in which GECO was mixed as COs in NBR (compounds 10 and 11) and IR as comparison First, a rubber stopper (compound 12) was used to prepare a sliding plug with a sucker for a syringe as shown in FIG. 2 in which a fluorine-based resin film was not laminated. Use a mold with a rubber stopper with a rubber stopper (diameter 13 mm, height 12 mm), and use both molds with spiral protrusions on the upper plate and the root of the sucker. Was molded and crosslinked.

As shown in Table 4, the rubber obtained by mixing GECO with NBR has good physical properties, but each value in the hygiene test is generally high and not preferable. (Note that the standard for disposable syringes for syringes is based on the Ministry of Health and Welfare Notification No. 442.
Since it is 0 minutes, the pH difference is 2.0 or less and RE is 1.0 mg or less, which is different from the standard value of “Nichiyaku”. The “Nichiyaku” standard applies to syringes and drug containers and stoppers. ) (B) When fluorine-based resin film is crosslinked, molded, and laminated Next, the same mold as above is used, and 1-1 ETFE film and each rubber of compounding numbers 10 to 12 are placed on the plate surface of the mold, and other conditions are shown in Table 4. In the same manner as above, a laminated stopper was molded, laminated and crosslinked with the 1-1ETFE film having the shape shown in FIG. 1-1 ETFE at this time
The adhesive force between the film and the rubber was 5 to 9 kg / cm. The ETFE film laminated syringe with a stopper (5 ml) is used as a container for medicines and also as an injector that can be administered in an emergency. The laminated stopper prepared in 1 above was attached. In addition, an injection needle should be attached for administration. A penicillin oil preparation (soybean essential oil + penicillin G) was filled in an injection cylinder (made of glass), and the laminate, sliding stopper and laminate stopper of Examples 4 and 5 and Comparative Example 3 were stoppered and completely sealed. Further, as a control, purified water was filled in the same manner. This filling container (syringe) was left in a thermostatic chamber at 30 to 40 ° C. for 3 months to test the contact contamination between the drug product and the laminated rubber. Next, the oil formulation is washed and extracted with 5 ml of purified water / alcohol mixed solution about 5 times, and these extracts are collected,
A hygiene test was conducted. The results are shown in Table 5.

As is clear from Table 5, the sanitary test results in the case where the purified water was put into the injection cylinder show that the purified water was not contaminated equally in Examples 4 and 5 and Comparative Example 3. However, when filled with soybean essential oil, Examples 4 and 5 are similar to purified water,
The extraction cleaning liquid of Comparative Example 3 has high pH and UV. This indicates that the IR crosslinking compound migrated and contaminated the soybean essential oil mixture.

Experiment 4. Experiment on mixed composition of NBR and EA (a) In case of non-laminated cross-linking / molding As shown in Table 6, NBR has ethylene and methyl acrylate as main components and unsaturated organic acid ester. Using the blends 13, 14 and 15 containing the above terpolymer composition and the blend 16 using EPDM instead of NBR, a fluorine resin film is laminated in the same shape as that shown in FIG. A rubber stopper which was not present was prepared under the crosslinking conditions shown in Table 6 and then washed.

As is clear from Table 6, the crosslinked physical properties of the rubber blended with NBR and EA are high, but slightly higher than the standard value of Nichiyaku, so that it is suitable for general rubber products rather than high-grade sanitary rubber products.

(B) When laminating, cross-linking, and molding a fluorine-based resin film Next, using the same lower mold as used in (a), 1-2 PVDF film thickness 1.0 mm and the rubber of compound 13 to 16 in Table 6 were used. It was used under pressure and heating under the same conditions as in (a), and simultaneously subjected to crosslinking, lamination and molding to obtain PVDF film laminated rubber stoppers (Examples 6 to 8 and Comparative Example 4).

100 ml of soybean oil fat emulsion (10% oil solution, manufactured by Otsuka Chemical Co., Ltd.) was charged into a medicine bottle, the PVDF film laminated stopper obtained above was stoppered, and an aluminum cap was further wound. Further, instead of the fat emulsion, 100 ml of purified water was similarly filled to serve as a control. Next, in a thermostat at a temperature of 30-40 ° C, invert the laminated plug so that it is immersed in the fat emulsion, and leave it for 90 days, and wash the fat emulsion in the vial about 3 times with 70 ml of water / methyl alcohol mixture. , Extracted. Table 7 also shows the evaluation results of the washed extract. As is clear from Table 7, the PVDF film laminated rubber stopper has high hygiene even when used in a fat emulsion as in purified water. The hygienic properties of the soybean oil fat emulsions are almost the same in Examples 6, 7 and 8. However, Comparative Example 4 EPD
As shown in Table 7, it can be seen that the pH and UV of the extraction / washing water of the laminated rubber plug of M are high and contaminated.

Although not listed in the above experimental examples, the composition obtained by mixing GECO and EA in NBR, the rubber plug of the present invention obtained by laminating / crosslinking / molding a fluorine-based resin film on the composition is also the same,
It was as excellent as each example product.

As is clear from the above experimental results, the medical / pharmaceutical rubber stopper of the present invention has neither swelling of rubber nor elution from the rubber and its compound, nor adsorption of the drug / additive to the rubber, which is extremely hygienic. It has excellent properties, and also has good physical properties such as tensile strength, elongation and hardness, and is made flexible so that chemical resistance, solvent resistance, oil resistance, gas permeation resistance and airtightness are sufficient.

The laminated rubber product of the present invention is used in pharmaceutical preparations such as vegetable oil-soluble, alcohol-soluble, oil, water-based suspension preparations, and the like, for example, hormonal agents, vitamins A and D agents, penicillin, and other gram-positive drugs. And negative bacterial agents, injection solutions such as oily contrast agents, enteric agents, spreading agent preparations such as kanamycin, fatty oils and fat emulsions, preparations for high-calorie infusion therapy,
It can be advantageously used for container devices used for sustained-release preparations such as eye drops, and rubber parts of medical device tools.

(Effect of the invention) As described above, NBR or N is used as a medical / pharmaceutical rubber product.
By using BR mixed with CO or EA as a base material and stacking a fluororesin film on it to perform cross-linking, molding and lamination at the same time, it is extremely high grade with excellent physical properties and hygiene. A sanitary rubber product is obtained, which can pass the "Japanese Pharmacopoeia" standard.

Further, the rubber product of the present invention is a hygienic rubber product having strong resistance to animal and vegetable oils and solvents, and is made into a vegetable oil formulation, a glycol-based formulation, etc. It can be used for rubber parts of sustained-release drugs made into formulations, etc., and can be kept and stored hygienically for a long period of time.
It has a great effect that cannot be obtained with conventional products.

[Brief description of drawings]

FIG. 1 is a cross-sectional view showing a state in which a drug solution is put into a vial, the laminated rubber stopper of the present invention is stoppered, and an aluminum cap is wound and tightened, and FIG. 2 is a laminated slip stopper of the present invention and a syringe with the laminated stopper attached. FIG. 3 is a sectional view of an example of the laminated rubber stopper of the present invention.

Claims (4)

[Claims] 1. A rubber surface of a rubber composed of 20 to 80% by weight of a copolymer rubber containing acrylonitrile and butadiene as main components is laminated with a fluorine resin film having a thickness of 0.001 to 1.0 mm,
In addition, a medical / medical rubber product obtained by simultaneously performing rubber cross-linking, molding, and laminating. 2. The medical / medical use according to claim 1, wherein the rubber comprises 20 to 60% by weight of a copolymer rubber containing acrylonitrile and butadiene as main components and 5 to 50% by weight of epichlorohydrin rubber. Rubber product. 3. The rubber composition according to claim 1, wherein the rubber comprises 20 to 60% by weight of a copolymer rubber containing acrylonitrile and butadiene as main components and 5 to 50% by weight of an ethylene-acrylic copolymer rubber. Medical and pharmaceutical rubber products. 4. A patent comprising 20-60% by weight of a copolymer rubber containing acrylonitrile and butadiene as main components, 5-50% by weight of epichlorohydrin rubbers, and 5-50% by weight of an ethylene-acrylic copolymer rubber. Claim scope (1)
The medical / pharmaceutical rubber product according to the item.