JP2895293B2 - Laminated sanitary rubber products - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminated sanitary rubber product which is safe and sanitary for use in various containers, especially containers for food and medicine, transporters, utensils, packaging materials and the like. The rubber product of the present invention satisfies the standard test pass values of various official standards required for this kind of field, has excellent properties that can meet the test items that have recently been regarded as problematic from a medical point of view, and is economical. It also has sex.

[0002]

2. Description of the Related Art The Food Sanitation Law is a law concerning packaging and utensil materials for food containers, and is described as non-toxic, tasteless, and odorless. This hygiene includes heat resistance and hot water resistance. The details are Notification No. 370 of the Ministry of Health and Welfare (December 1972) and Notification No. 20 of the Ministry of Health and Welfare (April 1957
Month).

[0003] Pharmaceutical containers are required to have a high degree of hygiene and safety because they greatly affect the human body. For example, "11th revised Japanese Pharmacopoeia" (hereinafter abbreviated as JP11) International Standards Organization (abbreviated as ISO), European Pharmacopoeia (abbreviated as EP), US Pharmacopoeia XXI (abbreviated as USP), West German Industrial Standard DIN 58,366- 58,368 (abbreviated as DIN), British Standard 3263 (abbreviated as BS), and the like define test methods and quality standards. More recently, test items from a medical point of view and high-grade standards are being added.

[0004] Regarding medical equipment supplies, the Ministry of Health and Welfare Notification No. 4
No. 42 and No. 413 (injection syringe standard), Ministry of Health and Welfare Notification No. 3
No. 00 and No. 301 (standards for blood collection instruments and transfusion sets) and the like define test methods and quality standards.

In contrast to the above official documents, isoprene rubber (abbreviated as IR), butadiene rubber (abbreviated as BR),
Terpolymer rubber of ethylene-propylene rubber (abbreviated as EPM) and ethylene-propylene terpolymer (EPDM)
), Isobutylene-isoprene copolymer rubber (II
R) or chlorinated rubber of IIR (abbreviated as CIIR)
Or, IIR brominated rubber (abbreviated as BIIR), isobutylene-isoprene-divinylbenzene terpolymer rubber (abbreviated as DIIR) and the like are excellent rubbers.

However, in order to make the rubber product for food use suitable for the application and to meet the requirements of the standard, for example, styrene-
Heat is improved by blending isoprene copolymer and polyethylene (abbreviated as PE) (JP-A-48-76939 and JP-A-48-76940), and EPDM is blended with tocophenol for heat sterilized food packaging. A laminate (JP-A-53-134574), zinc flower, EPDM,
Various rubber compositions such as fatty acid zinc and calcium oxide blended for use in food hygiene applications (Japanese Patent Publication No. 62-25175) or a method for producing a rubber product for food use described in Japanese Patent Publication No. 58-12907. The technology has been developed.

[0007] In the technology for producing rubber products for pharmaceuticals and medical devices, a method for preventing the formation of N-nitroso compounds by blending ascorbic acid or a derivative thereof (Japanese Patent Publication No. 1-3426).
2. JP-A-1-53696, JP, JP-B 1-20, BR, BIIR and nipple obtained by crosslinking natural rubber with an organic peroxide.
650), rubber stoppers in which fine powder PE is blended with IR (Japanese Patent Publication No. 45-8789), rubber products for pharmaceuticals with no elution of zinc salt (Japanese Patent Publication No. 61-40257), and rubber stoppers further improved (Japanese Patent Publication No. 60-57870).
Rubber products for pharmaceuticals and medical products in which ultra high molecular weight PE is blended with IIR, BIIR and CIIR (Japanese Patent Publication No. 1-55666)
Publication).

Further, as a rubber product for medical supplies and medical devices having a resin film laminated on the surface thereof, a technique of laminating a polypropylene (PP) film on a vulcanized rubber (Japanese Utility Model Publication No. 44-5751 and 44-27753). JP-A-49-21346), a plug coated entirely with a fluororesin having excellent chemical resistance (JP-B-45-17831), and a rubber plug whose chemical surface is wrapped with ethylene trifluoride resin (JP-B-49-21346). ), A method of manufacturing a stopper in which the surface of a rubber stopper, in particular, a chemical solution is laminated with a fluororesin film (Japanese Patent Publication Nos. 52-1355 and 54-9)
119, 57-53184, JP-A-61-27213.
4, JP-A-2-23961, and rubber stoppers in which IIR is laminated with a fluororubber (JP-B-63-43104, JP-A-55-47850) are known.

[0009] In the above-mentioned known techniques, no matter how much the rubber compounding agent is studied, eluate or exfoliated matter is generated from the rubber compounding agent and the rubber, thereby contaminating external chemicals and the like. Therefore, by wrapping in a fluororesin, PE or PP resin film, it has been used as a means for preventing external (chemical solution) contamination. However, films made of sanitary fluororesins, PE, PP, etc., have a weak adhesive force surrounding the rubber surface and easily peel off. In addition, although there is a technique for strongly bonding the film surface by corona discharge treatment or the like, it is an advanced technique and causes a problem in economy.

[0010]

SUMMARY OF THE INVENTION A resin film that adheres to a rubber surface with a very simple method with a strong adhesive force, and is a pharmaceutically and chemically inert substance.
It is an object of the present invention to find a hygienic resin film that can satisfy various standardized test standards.

[0011]

Means for Solving the Problems As a means for solving the above-mentioned problems, the present invention provides a sanitary product comprising a resin having a polymer component of a cyclic olefin compound or a crosslinked polycyclic hydrocarbon compound, which is laminated on a rubber surface. Provide rubber products. As the cyclic olefin-based compound in the present invention, monocyclic olefin-based compounds or their alkyl derivatives and acrylate derivatives are particularly preferred. Further, as the crosslinked polycyclic hydrocarbon-based compound in the present invention, a compound having one or more unsaturated bonds in a ring or a substituent thereof is particularly preferable. In the present invention, a resin containing the cyclic olefin-based compound or the crosslinked polycyclic hydrocarbon-based compound as a polymer component (hereinafter, also referred to as a cyclic resin of the present invention) may be a lower olefin, an aromatic or a lower olefin, or It may contain an aromatic vinyl monomer as a copolymer component, or may be a mixture with an olefin resin. Further, it is particularly preferable that the cyclic resin of the present invention has any one of the characteristic values having a bromine value of 5 or less and a softening point of 90 ° C. or more.

[0012]

SUMMARY OF THE INVENTION In recent years, coal tar, separation of each monomer of C ₅ fraction obtained by naphtha cracking or the like, purification techniques and, there by new technologies related to the polymerization catalyst and the like of each monomer, while distinctive resin body have been developed, among them Significant progress has been made in polymers of cyclic olefinic monomers, especially crosslinked polycyclic hydrocarbon monomers. For example cyclopentadiene by naphtha cracking of petroleum fractions obtained from C ₅ fraction obtained is industrially inexpensively abundantly obtained monomer. Cyclopentadiene (abbreviated as CPD)
Is dimerized at room temperature to obtain dicyclopentadiene (abbreviated as DCP).
C. to 160 C.) to CPD. This CPD, DC
Petroleum resins are produced as polymers using P as a raw material, and are used in the rubber industry as tackifiers for adhesives, sizing resins for papermaking, raw resins for paints, and the like.

The present inventors have found that a resin containing such a cyclic olefin compound or a crosslinked polycyclic hydrocarbon compound as a polymer component can easily and firmly adhere to a general-purpose molded rubber, and the adhesion surface is Focusing on the fact that the resin does not easily peel off in operations such as high-temperature water sterilization, and that the resin is inert, highly hygienic, and non-crystalline, the sanitary rubber products laminated on the surface are manufactured by the Japanese Pharmacopoeia, etc. It was found that a product having a very good hygiene was obtained in conformity with the test, and the present invention was able to be achieved.

The compound as a polymer component of the cyclic resin of the present invention will be described in more detail. First, as the cyclic olefin-based compounds, for example, cyclopentadiene,

Embedded image Cyclopentene,

Embedded image Cyclooctene,

Embedded image 4-methyl-cyclohexene,

Embedded image 4,5-dimethyl-cyclohexene

Embedded image And the like, and lower alkyl derivatives and acrylate derivatives obtained by substituting one to three lower alkyl groups such as methyl group and ethyl group.

The crosslinked polycyclic hydrocarbon compounds include:
Bicyclic or higher crosslinked cyclic hydrocarbon compounds, especially crosslinked polycyclic olefin compounds and derivatives thereof, or crosslinked polycyclic saturated hydrocarbon compounds having an unsaturated double bond in the substituent Is particularly preferred. That is, cross-linked polycyclic cycloalkene compounds and their lower alkyl derivatives, allyl derivatives, aralkyl derivatives, vinyl derivatives of cross-linked polycyclic cycloalkane compounds, allyloxycarboxy derivatives, (meth) acryloxy derivatives and the like can be mentioned. .

More specifically, the following compounds can be mentioned. Bicyclo [2,2,1] -2-heptoene,

Embedded image Bicyclo [2,2,1] 2,5-heptodiene (2,5
-Norbornadiene),

Embedded image 6-ethyl-bicyclo [2,2,1] -2-heptoene,

Embedded image 6-ethylidene-bicyclo [2,2,1] -2-heptoene (also referred to as 5-ethylidene-2-norbornene),

Embedded image 6-phenyl-bicyclo [2,2,1] hept-2-ene,

Embedded image Tricyclo [4,3,0,1 ^2,5 ] -3-decene,

Embedded image Tricyclo [4,3,0,1 ^2,5] -3,8 Deseten (3,8-dihydro - also referred to as dicyclopentadiene),

Embedded image Tricyclo [4,4,0,1 ^2,5 ] -3-undecene,

Embedded image Pentacyclo [4,7,0,1 ^2,5, 0,0 ^{8 and 13,} 1
^9,12 ] -3-pentadecene,

Embedded image 5,10-dimethyl-tetracyclo [4,4,0,1
^{2,5,1 7,10} ] -3-dodecene,

Embedded image Tetracyclo [4,4,0,1 ^2,5, 1 ^7,10] -3-dodecene,

Embedded image 11,12-dimethyl-hexacyclo [6,6,1,1
^{3,6, 1 10,13, O 2,7,} 0 9,14 ] -4-heptadecene,

Embedded image Pentacyclo [6,5,1,1 ^3,6, O ^2,7, 0 ^9,13]
-4-pentadecane,

Embedded image 8-ethylidene-9-ethyltetracyclo [4,4
0,1 ^2,5 , 1 ^7,10 ] -3-dodecene,

Embedded image Bis (allyloxycarboxy) tricyclo [4,3
0,1 ^2,5 ] -decane,

Embedded image Bis (methacryloxy) tricyclo [4,3,0,1
^2,5 ] -decane,

Embedded image Bis (acryloxy) tricyclo [4,3,0,1
^2,5 ] -decane

Embedded image

In the cyclic resin of the present invention, at least one selected from the above-mentioned cyclic olefin compounds and cross-linked polycyclic hydrocarbon compounds is used as a polymer component, but is copolymerizable with these polymer components. Lower olefins, aromatics or lower olefins or aromatic vinyl monomers can be contained as copolymer components. Specific examples of such other polymer components include, for example, ethylene,
Examples thereof include propylene, isoprene, butadiene, methylpentene, norbornene, butene, and vinyltoluene. Two or more of such other copolymer components may be used in combination.

In order to polymerize the cyclic resin of the present invention, known techniques may be used. For example, Japanese Patent Publication Nos.
8-43412, 61-1442, 62-1976
1, JP-A-50-75700, JP-A-55-129434,
58-127728, 60-168708, 61
-115916, 61-271308, 63-22
118, 63-221118, 63-24310
3. Known techniques described in JP-A-2-180976.

More specifically, the following three methods can be used. (1) Cyclopentadiene and a corresponding olefin or cyclic olefin are subjected to a cycloaddition reaction (Diels-Alder reaction) to obtain a crosslinked cyclic hydrocarbon monomer, and the monomer is converted into aluminum, tungten, Vanadium, polymerized using boron compounds as catalysts,
A method for obtaining a crosslinked cyclic hydrocarbon resin by purifying the resin into a resinous material. (2) a monomer as a polymer component of the cyclic resin of the present invention,
For example, a polymerization reaction of a lower alkylcycloalkene compound, a cycloalkadiene compound, a crosslinked polycyclic alkadiene compound, a crosslinked polycyclic alkene compound, or the like in a solvent using vanadium, aluminum, tungsten, boron compound, or the like as a catalyst. To obtain a high molecular weight resinous material. Next, a method of hydrogenating the resinous material with a nickel, platinum catalyst or the like to obtain the cyclic resin of the present invention. (3) A method in which an acryloyl derivative of a crosslinked polycyclic compound is polymerized with light and / or an organic peroxide to obtain a crosslinked cyclic resin, which is purified to obtain the cyclic resin of the present invention. In the above three kinds of polymerization reactions, a copolymer can be obtained by further adding a monomer such as an olefin compound or an aromatic compound.

In any of the above-mentioned polymerization methods, the presence of a monomer, a low-molecular-weight oligomer, a metal catalyst or the like as a polymerization component in the cyclic resin body of the present invention reduces generation of odor and deterioration of sanitary properties. It is not preferable in respect of the point. Therefore, it is preferable that the cyclic resin used in the present invention has a softening point of 90 ° C. or higher (JIS K 2207, 2531 ring and ball type). Further, the cyclic resin body preferably has a bromine value (JIS K 2543) of 5 or less. If the cyclic resin body has a bromine number of more than 5, the sanitary rubber product is colored and discolored after lamination on the rubber surface. As one measure against this coloring and discoloration,
Add anti-aging agent.

The antioxidants added to the cyclic resin body of the present invention include 2-6-di-tert-butyl-4-methylphenol (BHT) and octadecyl-3- (4'-hydroxy-3 ', 5 '-Di-t-butylphenyl) propionate (trade name: Irganox 1076, manufactured by Ciba Geigy), tetrakis [methylene (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane (trade name: Irga Knox 1010, manufactured by Ciba Geigy), tocophenol, 4,4'-thiobis (6-t-
Butyl-3-methylphenol) (trade name: Antage RC, manufactured by Kawaguchi Chemical), bis (2,2,6,6-tetramethylpiperidyl) sebacate (trade name: SANOL LS)
-770, manufactured by Sankyo Co., Ltd.), 1,3,8-triaza-
7,7,9,9-Tetramethyl-n-octyl-spiro [4,5] decane-2,4-dione (trade name: SANOL LS-772, manufactured by Sankyo Co., Ltd.) and the like. These antioxidants prevent the resin from gelling due to heat, light and oxygen of the cyclic resin body. The amount of the antioxidant added is 0.1 to 1 part by weight.

The content of the cyclic olefin monomer in the cyclic resin body of the present invention is preferably at least 30% by weight. The molecular weight of the cyclic resin body is 5,000 to 100,000,000, and the low molecular weight resin body is a highly viscous body. Therefore, when the lamination to rubber and the processing operation are difficult, it is preferable to use a processing aid. As the processing aid, at least one kind of higher fatty acid, higher fatty acid ester, silicone oil, fluorine oil and the like is used.
-5% by weight.

As a method of laminating the cyclic resin of the present invention on the rubber surface, the cyclic resin is soluble in a general-purpose solvent.
It is mixed with an aliphatic or aromatic hydrocarbon solvent such as n-hexane, cyclohexane, butane, pentane, cyclooctane, heptane, ethylbenzene, propylbenzene or the like or a mixed solvent thereof at about 1 to 8% by weight, and coated on the rubber surface. Alternatively, a method of spraying and then drying, or a method of laminating the cyclic resin on a rubber surface by a known technique such as a T-die method, a stretching method, an inflation method or the like may be used. Further, the cyclic resin of the present invention may be mixed with an olefin resin and laminated on the rubber surface. In this case, the processing operability is facilitated by using polyethylene or polybutene having a low to medium molecular weight of 10% by weight or less.

The cyclic resin of the present invention has a high softening point,
Since it is stable against oxygen and oxidation and has hygienic properties, it is formed into a film having a thickness of 0.1 to 1 mm, and is laminated on the compounded unvulcanized rubber. Can be adopted, and this method is economically preferable. Examples of such techniques include a method described in Japanese Patent Publication No. 59-5046 and a method of laminating a plurality of resin films on a rubber stopper, which the present inventors have already disclosed in Japanese Patent Publication No. 57-53184. No.
Furthermore, the cyclic resin of the present invention can also be applied to the rubber surface of a rubber stopper of a plastic container (see the techniques described in Japanese Patent Application Laid-Open Nos. 2-1275 and 2-399). The laminated rubber product obtained by laminating the cyclic resin of the present invention in the form of a film and laminating the rubber can pass the standards of JP-11 "44 Plastic container test for infusion" or "43 Rubber stopper test for infusion". Further, the film of the cyclic resin absorbs water,
The film was found to have extremely excellent resistance to moisture absorption and moisture transmission.

The rubber for laminating the cyclic resin of the present invention includes natural rubber, IR, IIR, BR, EPDM, CR,
General-purpose rubber such as NBR can be applied. The reason is,
Since the annular resin body can be strongly adhered and wrapped around the rubber surface even with an extremely thin film, a compounding agent in the rubber such as a vulcanizing agent, a vulcanization accelerator, a reinforcing material, etc. is not eluted, that is, It is in that unsanitary unsuitable substances do not elute and contaminate the external contact substances (pharmaceuticals, food, etc.) of the rubber product. In addition, the annular resin body film is a flexible and elastic film, and is characterized in that it retains the same flexibility and elasticity as the laminated rubber.

[0026]

EXAMPLES The present invention will be described below in more detail with reference to examples, but the present invention is not limited to these examples. Synthesis Example of Resin of the Present Invention: Synthesis Example 1 (DCP resin polymer) Using a 5000 ml three-necked flask equipped with a stirrer, 1800 ml of purified and dehydrated toluene and 600 g of dehydrated and purified DCP were charged in a nitrogen atmosphere, and then triethylaluminum [as a catalyst] Al (C ₂ H ₅ ) ₃ ] 140 g, triethylamine [N (C ₂ H ₅ ) ₃ ] 365 g and titanium tetrachloride [TiCl ₂ ] 46 g (both as dry matter)
Are sequentially added under a nitrogen atmosphere, and the mixture is stirred and polymerized at 25 ° C. for 6 hours. After the polymerization, 10 ml of hydrochloric acid was added to 2000 ml of a mixed solvent of acetone-isopropyl alcohol (1: 1) to cause precipitation, and the precipitated resin was washed with the above-mentioned mixed solvent and dried.
360 g of a CP ring-opened polymer was obtained.

Next, an autoclave with a stirrer 2000 m
10% by weight of the ring-opening polymer, 1 kg of a cyclohexane solution and 5 g of Raney nickel were placed in the reactor, the temperature in the reactor was increased to 120 ° C., and a hydrogenation reaction was performed at a hydrogen pressure of 70 atm for 8 hours. The catalyst in the mixture was removed by centrifugation and filtration, and acetone-isopropyl alcohol (1:
1) Precipitate in 1000 ml of the mixed solution and prepare resin (a) 100
g was obtained. The resin (a) has a softening point of 136 ° C., an average molecular weight of about 30,000, and is soluble in a 5% solution of n-hexane.

To 100 parts by weight of the resin (a) obtained above, 0.3 part by weight of an antioxidant Irganox 1010 was added. N-Hexane was used as a solution, and 1.5 parts by weight of dimethylpolysiloxane and 1.5 parts by weight of sorbitan stearate were added for film formation.

Synthesis Example 2 (DCP-ethylene copolymer) A stirrer was placed at the center of a dried 5000 ml three-necked flask.
A dropping funnel was attached. Under nitrogen atmosphere, 2,500 ml of dehydrated toluene and 150 g of dehydrated DCP were put, and 31 g of ethylene aluminum sesquichloride was used as a catalyst.
4.2 g of dichloroethoxyoxovanadium was added, and a mixed gas (1/2) of a dry ethylene gas and a nitrogen gas was passed for 7 minutes, and the mixture was further polymerized at 20 ° C. for 60 minutes through the mixed gas for 30 minutes. The copolymerization was stopped by adding 30 ml of methanol to precipitate a resin body, washed with acetone, and dried at about 60 ° C. to obtain 88 g of a copolymer. DCP in this copolymer is 68 mol%.

An autoclave with a stirrer having a capacity of 1000 ml, 500 g of a cyclohexane solution containing 10% by weight of the copolymer resin obtained above and 5 g of palladium carbon were charged. After the inside of the reactor was replaced with hydrogen, the temperature was raised to 120 ° C. while stirring. . Next, the hydrogen pressure is increased to 70 atm at the same temperature, and hydrogen is added for 8 hours while replenishing hydrogen to the same pressure. Next, the catalyst in the reaction product was removed by centrifugation and filtration, precipitated in a large amount of a mixed solvent of acetone-isopropyl alcohol (1: 1), filtered and dried to obtain 60 g of a resin (b). The softening point of the resin (b) was 130 ° C. and the bromine value was 0.3.

The copolymer resin (b) obtained above was formed by adding 3% by weight of sorbitan stearate, 1% by weight of dimethylpolysiloxane, and 0.5% by weight of BHT to form a film. In the case of brush application or scattering, the solution is applied to the rubber surface as a cyclohexane solution (5% by weight).

Synthesis Example 3 (Ternary copolymer of DCP) Purified DCP8 in an autoclave equipped with a stirrer
After adding 0 g and 10 g of isoprene, the mixture is gradually heated with stirring under a nitrogen atmosphere, and polymerized at a temperature of 250 ° C. for 7 hours. After cooling, low volatiles are distilled off at about 120-200 ° C,
Vacuum was removed at ７０70 ° C. to remove volatiles. Next, the polymer was put in an autoclave, 80 g of cyclohexane and 2 g of Raney nickel catalyst were added, and hydrogen pressure was 100 kg / cm ² ,
Hydrogenate at a temperature of 200 ° C. for 4 hours. After cooling, the catalyst is filtered off and distilled to remove the solvent. 0.7% by weight of BHT
Addition, bromine value of resin (c) 1.5, softening point 12
At 2 ° C., there is an insoluble matter in n-hexane.

Synthesis Example 4 (Polymerized crosslinked polycyclic compound) 8-Methyloxycarbonyltetracyclo [4,4
0,1 ^7,10 ] -3-dodecene

Embedded image 250 g, 1,2-dichloroethane 1000 ml, 1-
To 1.9 g of hexene, a chlorobenzene solution 4 having a concentration of 0.05 mol / liter of tungsten hexachloride as a catalyst was used.
6 ml, 35 ml of a 1,2-dichloroethane solution having a concentration of 0.1 mol / l of paraaldehyde and 19 ml of a toluene solution having a concentration of 0.5 mol / l of triisobutylaluminum were added to a reactor equipped with a stirrer purged with nitrogen gas. The polymerization reaction is carried out at 10 ° C. for 10 hours. The polymerization is stopped by adding methanol to the polymer, the solvent is evaporated, washed with an acetone / methanol solution and dried. Next, the polymer was dissolved in 4500 ml of tetrahydrofuran, 23 g of a palladium-alumina catalyst containing 5% by weight of palladium was added, and the temperature was 170 ° C. under a hydrogen gas pressure of 100 kg / cm ^2.
For 5 hours. Hereinafter, the same treatment as in Example 1 is performed to obtain a polymer resin. 0.5 parts by weight of BHT is added to 100 parts by weight of the polymer resin to obtain resin (d). The resin (d) had a bromine value of 0.05 and a softening point of 112 ° C.

[0034] Synthesis Example 5 (crosslinked polycyclic binary copolymer) 2 liter equipped with a stirrer vessel, placed cyclohexane 1 liter of dry purified, 8,9-dimethyl - tetracyclo [4,4,0,1 ^{2 , 5} 1 ^7,10 ] -3-Dodecene (synthesized by cycloaddition of cyclopentadiene and dimethylnorbornene)

Embedded image 30 g were charged under flowing nitrogen, and then ethyl aluminum sesquichloride [Al (C ₂ H ₅ ) _1.5 Cl _1.5 ] 12
g, dichloroethoxyoxovanadium [VO (C ₂ H
₅ ) ₂ g of Cl ₂ ] was dropped, and a 1/2 mixed gas of dry ethylene and nitrogen gas was blown in at a temperature of 10 ° C. for 15 minutes for 15 liters to carry out a copolymerization reaction. 12m methanol
The polymerization reaction is stopped by adding 1 and washed with acetone and dried under vacuum. 0.3 parts by weight of Irganox 1010 was added to 100 parts by weight of the copolymer obtained above (yield 28 g, bromine value 0.5, softening point 118 ° C.). This is referred to as resin (e).

[0035] Synthesis Example 6 (crosslinked polycyclic terpolymer) 2 liter equipped with a stirrer vessel, were charged 1 liter of toluene of dehydrated and purified, tetracyclo [4,4,0,1 ^2,5 under a nitrogen stream 1 ^7,10 ] -3-dodecene 30.
4 g, 3.8 g of 4-methyl-cyclohexene,
Next, 3.6 g of ethyl aluminum sesquichloride and 2.2 g of vanadium oxytrichloride are added. Next, 13 liters of a dry mixed gas of ethylene and nitrogen gas １ ／ is blown in at a temperature of 10 ° C. for 30 minutes from a gas blowing pipe to carry out a polymerization reaction. Next, the reaction was stopped by adding 20 ml of methanol, and methanol was further added to the polymer.
g (bromine value 0.3, softening point 124 ° C.). The polymer
To 100 parts by weight, 0.3 parts by weight of Irganox 1076 was added to obtain resin (f).

Synthesis Example 7 (Polymer of crosslinked polycyclic compound) Bis (methacryloxy) tricyclo [4,3,0,1
^2,5 ] -3-decane (100 g) and cyclohexane (100)
g of benzoyl peroxide 2 under a nitrogen flow.
g is added, mixed uniformly, gradually heated, and the polymerization reaction is carried out at 120 ° C. for 5 hours. The solvent was removed and 4 g of t-butyl peroxybenzoate and 4,4'-thiobis (6
-T-butyl-3-methylphenol).
It is used as a 2% by weight solution of cyclohexane. The obtained resin (g) had a softening point of 112 ° C. and a bromine number of 3.3.

Synthesis Example 8 100 parts by weight of the copolymer resin (g) obtained in Synthesis Example 7 was
3 parts by weight of microwax having a softening point of 80 ° C. and 3 parts by weight of low molecular weight polyethylene are added, and mixed with a Brabender plastomill at a temperature of 120 to 130 ° C., followed by a T-die method. Into a film. This mixed resin is referred to as (h).

Resins (a) of the present invention obtained in Examples 1 to 8 and Synthesis Examples 1 to 8 of Comparative Example 1 to
Laminate coating was performed on the rubber stopper base using (h). The BR rubber used as the base was produced as follows. BR rubber compounding: BR (Nipol BR 1242S, manufactured by Nippon Zeon Co., Ltd., cis content 37.2%, ML _{1 + 4} 100 ° C 53): 100 parts by weight Powdered polyethylene (manufactured by Iron and Steel Chemicals): 3 parts by weight Part Titanium oxide (manufactured by Ishihara Sangyo) ... 15 parts by weight Calcined clay (manufactured by Burgess Pigment) ... 20 parts by weight 2,5-dimethyl-2,5-di (t-butylperoxy) hexane ... 1 part by weight Vinyl tris (β-methoxy) silane 1 part by weight BR rubber compounding operation and vulcanization operation are performed in accordance with SRIS (Japanese Rubber Association Standard) 3603. Vulcanization conditions are temperature 1
Mold at 60 ° C. for 12 minutes. Fig. 1 shows the molded rubber product.
Rubber substrate 1 is immersed twice or more in an n-hexane solution of the resin bodies (a) to (g) of the present invention to a thickness of about 0.1 mm, The coating was completely dried at a temperature of about 90 ° C. to form a coating on the rubber surface as shown in FIG. 1 (Examples 1 to 8).

For each of the samples obtained above and the rubber substrate alone without resin lamination (Comparative Example 1), a sanitary test was performed in accordance with JP11 "43. Test method for rubber stopper for infusion". Table 1 shows the results. As shown in FIG. 2, these rubber stoppers were plugged into a glass container filled with a chemical solution, and an aluminum cap was tightly wound thereon. A special hygiene test was conducted, and the results are shown in Table 2.

[0040]

[Table 1]

[0041]

[Table 2]

The details of the special hygiene test are as follows. Other special hygiene test Number of fine particles (test of the number of particles generated from rubber stoppers): Put 10 rubber stoppers in a hard glass bottle, add 300 ml of dust-free water, wrap the container opening with a film, and rotate twice by hand Vibration for about 20 seconds per second. Then, after standing still for one hour, the number of fine particles in water is measured by a light shielding type automatic fine particle measuring device (manufactured by HIAC). The presence of fine particles of 5 μm or more in the injection solution is a most important item because it causes problems such as blockage of blood vessels.

Separation of rubber fragments (Fragmentati
on); bottle of the shape shown as 4 in FIG. 2 (10 ml capacity)
, 5 ml of water is put into the flask, a rubber stopper is stoppered, and then the aluminum cap 6 is tightly wound. Test needle 22G (0.70 × 32m
2 ml of water is poured into the syringe with m), and this is penetrated 20 times through the needle insertion portion 8 of the rubber stopper. At the time of the 20th penetration, the water in the syringe is poured into the bottle, and then the injection needle is pulled out. After vibrating inside the bottle, remove the rubber stopper, filter the contents,
Count the number of rubber pieces on the filter paper. This test method is an improvement of the BS method. Although the BS standard specifies that the rubber pieces are three or less, the industry currently requires that the number be two or less.

Test of gas component in head space: 8 ml of a 2% by weight saline solution is put into the glass bottle 4 of FIG. 2, the rubber stopper 3 is closed, and the aluminum cap 6 is further tightened. The glass bottle is steam-heated in a pressure vessel at a temperature of 121 ± 1 ° C. for 60 minutes and then left for about 10 hours. Next, 5 ml of gas in the head space 7 in the bottle is sampled with a gas syringe, and this is measured by gas chromatography. Column: 10% OV-101 (180-200 mesh WH
P), carrier gas He 50 ml / min, column temperature 1
00 to 200 ° C (4 ° C / min temperature rise), the presence or absence of a peak, and the magnitude are observed. This test is a test for examining the generation of trace amounts of gas by rubber and compounding agents, which has become a problem in recent years.

Alkali-resistant solution test: 10 rubber stoppers were placed in an alkali-resistant container, and a 0.5% by weight solution of sodium carbonate, which was 10 times the weight of the rubber stopper, was added. And tighten. Next, the temperature 121
Heat at 30 ° C. for 30 minutes. After leaving to cool to room temperature and cooling, the rubber stopper was removed.
The transmittance of the visible part at 0 nm is measured. Pass 95% or more. This test is a basic test for examining the relationship between rubber and a chemical solution, and rubber products with low transmittance are unsuitable.

Water absorption test; vulcanized rubber product
Dry at 05 ° C under normal pressure for 3 hours. Next, after being left in a desiccator containing a desiccant for about 1 hour, the weight (A) is precisely weighed. Next, the rubber stopper is immersed in purified water 10 times as much as the rubber stopper, and steam-heated as it is in a pressure vessel at a temperature of 121 ± 1 ° C. for 30 minutes. After cooling, leave only the rubber stopper in a desiccator for 30 minutes to remove water on the surface, weigh the weight (B) at that time, and ((B)-
(A) / (A) × 100) (%) is determined, and a weight increase of 2% by weight or less is regarded as acceptable.

Slip test: A rubber stopper is placed on a fluororesin plate, one end of the plate is fixed, and the rubber stopper moves when the other end is raised at a constant speed. The angle at which this movement starts is measured.

As shown in Table 1, the rubber stoppers of Examples 1 to 5 of the present invention passed the JP11 standard. Also, as shown in Table 2, it is excellent in special hygiene tests. On the other hand, the rubber stopper not laminated in the comparative example is
As shown in Tables 1 and 2, there are items whose standard values are rejected.
Since PE, PP, PET, and fluororesin do not dissolve in a solvent (eg, n-hexane), these resins cannot be dissolved in the solvent to form a thin resin coating.

Examples 9 to 13 and Comparative Examples 2 to 4 (Injection in which resin was laminated)
Hygiene test of instrumental stopper) Two rolls of the cyclic resin of the present invention or a press temperature of 100 to
By pressing at 140 ° C., a film plate having a thickness of 0.3 to 0.4 mm was prepared. Next, molding of the laminated rubber stopper was performed by the method of laminating the resin film of the present invention simultaneously with rubber crosslinking and molding. Specifically, a lower mold having a depression of a slip stopper mold and an upper mold having a protrusion at the tip of a push rod were used. First place the resin film sheet of the present invention described above on the lower mold surface, placing the compounded rubber of the BR thereon into a sheet, temperature 160 ° C. superimposed upper die, pressurizing it to about 80 kg / cm ² As a result, a plug with a laminated resin film is obtained (see FIGS. 4 and 5). Using a BR rubber having the same composition as that of the above-mentioned mold, a laminated stopper (comparative product) was obtained by laminating each of PE, PP, and fluororesin (abbreviated as F) films in the same manner.

The thus obtained laminated stopper of the present invention and the comparative product were evaluated for the difficulty of adhesion of the film to the rubber, the elongation of the film, and the state of the film when sterilized with high-temperature water after lamination. Table 3 shows the results.

[Table 3]

As shown in Table 3, the stoppers (Examples 9 to 13) in which the cyclic resin film of the present invention was laminated strongly adhered to the rubber surface from the time of molding, and the lamination failure such as tearing of the film and wrinkles was observed. Did not. In addition, there was no defective product even after the high-temperature water treatment. On the other hand, in PE and F (Comparative Examples 2 and 4), the film was broken at the time of molding. Although PP (Comparative Example 3) was good in molding, water bubbles were generated by high-temperature water treatment.

Example 14 According to the technique described in JP-A-61-272134,
In the plug shown in FIG. 6, first, the rubber molding of the leg 15 of the plug and the lamination of the fluororesin film (using a film whose surface is subjected to a sputter treatment) 16 are performed simultaneously, and then the rubber molding of the flange 17 and the book The lamination molding of the resin film 1 of the invention is performed simultaneously. The rubber plug shown in FIG. 7 and FIG. 8 is made of a rubber stopper according to the technique described in Japanese Patent Application Laid-Open No. 61-272134. The rubber stopper having the ring-shaped resin body 1 of the present invention laminated thereon has an excellent feature that, when a drug is prepared in a container, fine particles are not generated from the rubber due to the movement of the rubber stopper.

Example 15 In accordance with the technique described in Japanese Patent Application Laid-Open No. 2-1275, the annular resin body of the present invention was laminated on rubber on a chemical solution surface as shown in FIG. 3, and a plug was welded to a plastic container. As a feature of this type of the present invention, without contaminating the chemical solution,
It has the feature that a high-quality drug solution can be administered to the human body.

[0054]

According to the present invention, there is provided a novel sanitary rubber product in which a rubber surface is laminated with a special annular resin body.
The cyclic resin body of the present invention has high sanitary properties, is inert,
It can pass the test standards for pharmaceuticals and medical devices such as 1.
It is also odorless for food. (B) The annular resin body of the present invention easily adheres to the rubber surface, and the adhered surface is not easily peeled off. (C) Since the rubber surface is coated with the ring-shaped resin body, the rubber and the rubber compounding agent do not contaminate the outside (chemical solution or the like).

[Brief description of the drawings]

FIG. 1 is a cross-sectional view of a rubber stopper of the present invention in which the entire surface is laminated with an annular resin film of the present invention.

FIG. 2 is a cross-sectional view showing a product state in which a glass container is filled with a chemical solution, the laminated rubber stopper of the present invention is stoppered, and an aluminum cap is wound thereon.

FIG. 3 shows a state in which the rubber stopper laminated with the annular resin film of the present invention is inserted into the outer support of the plastic container, the upper pig is placed thereon, and the rubber stopper laminated portion is welded to the outer support and the upper pig. Cross section shown

FIG. 4 is a cross-sectional view in which an annular resin body film of the present invention is laminated on a push rod tip stopper of a syringe.

FIG. 5 is a cross-sectional view showing a state in which the surface of the plug of FIG. 4 is laminated with the annular resin film of the present invention.

FIG. 6 is a cross-sectional view showing a rubber stopper of a freeze-dried preparation, in which a leg portion is laminated with a fluororesin, and a flange portion is laminated with an annular resin film of the present invention.

FIG. 7 is a longitudinal sectional view showing a state in which the annular resin film of the present invention is laminated on the leg portion and the flange portion of the rubber stopper which come into contact with the chemical solution.

8 is a cross-sectional view of the laminated rubber stopper (eglue type rubber stopper) of FIG.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 The cyclic | annular resin body film of this invention 2 Rubber part 3 The rubber stopper which laminated | stacked the cyclic resin body of this invention 4 Glass container 5 Chemical solution 6 Aluminum cap 7 Headspace 8 Needle stab position 9 Plastic external support 10 Plastic upper pig 11 Outside a syringe Cylinder 12 Push rod of syringe 13 Slipper with laminated cyclic resin body film of the present invention 14 Tip of push rod of syringe 15 Leg of rubber stopper 16 Fluororesin film 17 Flange

Continuation of the front page (58) Field surveyed (Int. Cl. ⁶ , DB name) B32B 1/00-35/00 A61J 1/00-1/08 A61L 31/00

Claims (7)

(57) [Claims] 1. A sanitary rubber product obtained by laminating a resin containing a cyclic olefin compound or a crosslinked polycyclic hydrocarbon compound as a polymer component on a rubber surface. 2. The sanitary rubber product according to claim 1, wherein the cyclic olefin-based compound is at least one selected from monocyclic olefin-based compounds and their alkyl derivatives and acrylate derivatives. 3. The sanitary rubber product according to claim 1, wherein the crosslinked polycyclic hydrocarbon compound has at least one unsaturated bond in a ring or in a substituent. 4. A resin comprising the above-mentioned cyclic olefin-based compound or cross-linked polycyclic hydrocarbon-based compound as a polymer component, wherein a lower olefin, an aromatic or a lower olefin or an aromatic vinyl monomer is a copolymer component. The sanitary rubber product according to any one of claims 1 to 3, wherein the product is contained as: 5. The resin according to claim 1, wherein the resin containing the cyclic olefin compound or the crosslinked polycyclic hydrocarbon compound as a polymer component is a mixture with an olefin resin.
The sanitary rubber product according to claim 4. 6. The resin according to claim 1, wherein the resin containing the cyclic olefin compound or the crosslinked polycyclic hydrocarbon compound as a polymer component has a bromine value of 5 or less. Sanitary rubber products. 7. The resin according to claim 1, wherein the resin containing the cyclic olefin-based compound or the crosslinked polycyclic hydrocarbon-based compound as a polymer component has a softening point of 90 ° C. or higher. The sanitary rubber product as described.