JP3518553B2 - Medical equipment - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a medical device, and more particularly to a medical device which does not deteriorate the contacting drug and is not easily damaged even in the process of filling the drug.

[0002]

2. Description of the Related Art Medical devices have recently been replaced with disposable devices in order to prevent secondary infection of viruses by repeated use. In addition, for example, injectable drugs have also been conventionally used by aspirating from a sterilized ampoule at the time of injection with a syringe, but recently, a prefilled syringe in which the injectable drug has been previously inhaled in a syringe is distributed, After injection, the syringe was discarded.

[0003] In medical chemical containers, it is necessary to have a certain level of transparency so that the contents can be easily visually recognized. Conventionally, glass, polyethylene, polypropylene,
Polyvinyl chloride is used. However, the glass sometimes breaks and is heavy, and alkali ions and the like are sometimes eluted. In addition, it is sometimes difficult to dispose of it because it is difficult to burn it, or it is dangerous to dispose of debris. Polyethylene and polypropylene have poor heat resistance and cannot be steam sterilized.
The low-molecular organic components were sometimes eluted. Further, polyvinyl chloride is inferior in heat resistance, and chlorine may be eluted to alter the contents.

Recently, a thermoplastic norbornene resin has been proposed as a material for medical equipment, and medical equipment made of the resin has excellent gas barrier properties, does not allow water to permeate, and has little elution. It has been reported that the performance is excellent (JP-A-3-61025). But,
It has been found that the thermoplastic norbornene-based resin is liable to be scratched when transferring or using medical equipment such as a chemical container, and the stain may cause stains which are difficult to remove. That is, in the process of actually filling the chemicals with a machine, it was confirmed that scratches were generated on the outer surface due to contact with a metal or the like and that stains that were difficult to remove with machine oil were attached.

[0005]

DISCLOSURE OF THE INVENTION As a result of intensive studies on the above problems, the present inventors have found that the surface of a medical instrument made of a thermoplastic norbornene resin is not contacted with a drug, a living body, or a device that comes into contact with a living body. By forming a hard coat layer, it was found that scratches were less likely to occur, stains due to machine oil could be easily removed, and steam sterilization at high temperature was possible, and the present invention was completed. .

[0006]

Thus, according to the present invention, it does not deform even when sterilized, it does not change the chemicals that come into contact due to the elution of impurities or the adsorption of chemical components, and it is unlikely that scratches will occur on the external surface and that the mechanical oil It is easy to remove dirt caused by
Also provided is a medical device made of a thermoplastic norbornene-based resin that can be steam sterilized at high temperature.

(Thermoplastic Norbornene Resin) The thermoplastic norbornene resin of the present invention is disclosed in JP-A-3-14882.
No. 3,122,137, and 4-63807.
Known resins such as ring-opening polymers of norbornene-based monomers, hydrogenated products thereof, addition-type polymers of norbornene-based monomers, addition of norbornene-based monomers and olefins. Type polymers and the like.

Norbornene-based monomers are also known monomers in the above-mentioned publications, JP-A-2-227424 and JP-A-2-276842, and examples thereof include norbornene, its alkyl, alkylidene and aromatic substituted derivatives. And halogens, hydroxyl groups of these substituted or unsubstituted olefins,
Polar group substituents such as ester group, alkoxy group, cyano group, amide group, imide group and silyl group, for example, 2-norbornene, 5-methyl-2-norbornene, 5,5-dimethyl-2-norbornene, 5- Ethyl-2-norbornene, 5-butyl-2-norbornene, 5-ethylidene-
2-norbornene, 5-methoxycarbonyl-2-norbornene, 5-cyano-2-norbornene, 5-methyl-5-methoxycarbonyl-2-norbornene, 5-phenyl-2-norbornene, 5-phenyl-5-methyl- 2-norbornene, 5-hexyl-2-norbornene, 5-octyl-2-norbornene, 5-octadecyl 2-norbornene and the like; a monomer in which one or more cyclopentadiene is added to norbornene, a derivative similar to the above Substitutes, for example 1,4: 5,8-dimethano-
1,2,3,4,4a, 5,8,8a-2,3-cyclopentadienonaphthalene, 6-methyl-1,4: 5,8
-Dimethano-1,4,4a, 5,6,7,8,8a-octahydronaphthalene, 1,4: 5,10: 6,9-trimethano-1,2,3,4,4a, 5,5a , 6, 9,
9a, 10,10a-dodecahydro-2,3-cyclopentadienoanthracene, etc .; a polycyclic monomer that is a multimer of cyclopentadiene, a derivative or substituent similar to the above, for example, dicyclopentadiene, 2,3-dihydrodicyclopentadiene and the like; adducts of cyclopentadiene and tetrahydroindene and the like, derivatives and substitution products similar to the above, for example, 1,4-methano-1,4,4
a, 4b, 5,8,8a, 9a-octahydrofluorene, 5,8-methano-1,2,3,4,4a, 5,8,
8a-octahydro-2,3-cyclopentadienonaphthalene and the like; and the like.

In the present invention, when the norbornene-based monomer is polymerized, other copolymerizable cycloolefins and the like are used in combination within a range that does not substantially impair the effects of the present invention. Can be Specific examples of the copolymerizable cycloolefin in the case of ring-opening polymerization include, for example, cyclopentene, cyclooctene, 5,6.
Examples thereof include compounds having one or more reactive double bonds such as dihydrodicyclopentadiene.

The norbornene-based monomer may be polymerized by a known method. Generally, TiCl ₄ , WC is used as a polymerization catalyst.
Polymerization is carried out by combining a transition metal compound such as l ⁶ , MoCl ₅ , VCl ₅ , NiCl ₂ and PdCl _{2 with} an alkyl compound of a typical metal such as Al, Li, Na and Mg.
If necessary, a known method such as Ni or Pd may be used.
By hydrogenating the above as a catalyst, a hydrogenated product of a thermoplastic norbornene-based resin can be obtained.

In the conventionally known polymerization method, the transition metal derived from the polymerization catalyst remains in the polymer. Medical equipment
Upon contact with a living body or a drug, it is not preferable that the remaining transition metal elutes, and it is preferable that the transition metal does not substantially remain in the medical device. As a method for obtaining such a polymer, the pore volume is 0.5 cm ³ / g or more, preferably 0.1.
Hydrogenation of the polymer using a heterogeneous catalyst in which a hydrogenation catalyst metal such as nickel is supported on an adsorbent such as alumina having a specific surface area of 7 cm ³ / g or more, preferably 250 m ² / g or more, The transition atom derived from the polymerization catalyst can be reduced to 1 ppm or less by treating the resin solution with such an adsorbent to adsorb metal atoms or repeatedly washing the resin solution with acidic water and pure water. .

The method for producing the heterogeneous catalyst may be according to a known method, such as JP-B-50-15474 and JP-B-49-3.
2187, Japanese Patent Publication No. 49-11312, Japanese Patent Publication No. 51-
According to No. 48479, etc., depending on the drying and firing conditions,
The adsorption capacity of the carrier may be controlled. For example, in the case of a heterogeneous catalyst in which nickel is supported on activated alumina, the concentration is 10
Aluminum hydroxide powder is suspended in a 20% nickel sulfate or nickel nitrate aqueous solution at a concentration of 10 to 20% and hydrolyzed with sodium hydroxide to support nickel hydroxide on the surface of aluminum hydroxide. This powder is collected by filtration and solidified by extrusion,
Calcination at 450 ° C., contact with hydrogen at 100 to 200 ° C. to reduce the surface, and 80 to 120 ° C. in the presence of oxygen.
The nickel catalyst supported on the activated alumina is obtained by heating the metal surface to oxidize the metal surface and form an oxide film. Although the surface of nickel is covered with nickel oxide, the nickel oxide becomes nickel by reduction in the hydrogenation reaction system and functions as a catalyst.

[0013] Extrusion conditions, the temperature and pressure, etc. of the firing, since the fine structure of the activated alumina is changed, the pore volume of 0.5 cm ³ / g or more, preferably 0.7 cm ³ / g or more, preferably The conditions are selected so that the specific surface area is 250 m ² / g or more. Further, when hydrogenation is performed at a high temperature, the thicker the oxide film is, the more heat resistant it is. Therefore, the temperature, time, oxygen concentration, etc. of the oxidation may be adjusted to select preferable conditions. The fired product thus obtained may be crushed to obtain a heterogeneous catalyst.

When a transition metal chloride is used as a transition metal compound of a general polymerization catalyst, the chlorine atom is usually 2
Remains above ppm. It is preferable that chlorine atoms as well as transition metal atoms do not remain in medical devices,
It is preferable to remove. As a method for removing, transition metal atoms can be removed by the same treatment, and the residual amount can be reduced to 1 ppm or less.

The glass transition temperature of the thermoplastic norbornene resin used in the present invention is preferably 105 ° C. or higher,
More preferably 120 ° C or higher, particularly preferably 130 ° C
That is all. Some sterilization methods do not require heating, such as γ-ray irradiation, but the simplest sterilization methods are methods that require heating, particularly boiling and steam sterilization. In sterilization by boiling, there is no problem if the glass transition temperature of the thermoplastic norbornene-based resin is 105 ° C. or higher, but in steam sterilization, the required heat resistance differs depending on the temperature setting during sterilization. The most common steam sterilization is an autoclave method at 121 ° C. In order to prevent deformation by steam sterilization, a glass transition temperature of 130 ° C. or higher is preferable. In general,
The glass transition temperature of the thermoplastic norbornene-based resin becomes higher as the number of monomers having a larger number of rings is used. For example, a hydrogenated product of a ring-opening polymer of ethyl tetracyclododecene, which is a tetracyclic compound, usually has a temperature of 130 ° C or higher. However, in the hydrogenated product of the norbornene ring-opening polymer, which is a bicyclic compound, it is usually 30
It is about ℃. On the other hand, the glass transition temperature of the addition type polymer of norbornene is 300 ° C. or higher, and measurement may not be possible in some cases. If the glass transition temperature is too high, injection molding may be difficult. Therefore, a monomer or comonomer may be selected to produce a thermoplastic thermoplastic norbornene-based resin having a glass transition temperature according to the purpose.

The number average molecular weight of the thermoplastic norbornene resin used in the present invention is 10,000 to 200,000 in terms of polystyrene measured by the GPC (gel permeation chromatography) method using a toluene solvent.
It is 0, preferably 20,000 to 100,000, more preferably 25,000 to 50,000. If the number average molecular weight is too small, the mechanical strength will be poor, and if it is too large, the moldability will be poor. The content of the resin component having a polystyrene reduced molecular weight of 2,000 or less by the high performance liquid chromatography analysis using toluene in the thermoplastic norbornene-based resin as a solvent is 1% by weight or less, preferably 0.5% or less. When the amount of the low molecular weight component is large, the medical device may be eluted by contact with a living body or a drug.

When the thermoplastic norbornene-based resin is hydrogenated, the hydrogenation rate is 90% or more, preferably 95% or more, more preferably 99% or more from the viewpoint of heat deterioration resistance and light deterioration resistance. To do.

(Compounding agent) The thermoplastic norbornene-based resin is substantially free from any shape change such as deformation in the steam sterilization treatment which is often used for medical devices, but it is turbid and transparent depending on the treatment conditions. May deteriorate. In order to prevent this, it is preferable to add a compounding agent that is incompatible with the thermoplastic norbornene-based resin and use it as a resin composition. An organic compound or an inorganic filler may be used as long as it can be finely dispersed until transparency is exhibited.

The inorganic filler has an average particle size of 1 μm.
In particular, those having a thickness of 0.5 μm or less, particularly 0.2 μm or less are preferable. Further, it is preferably transparent and water-insoluble. For example, silica, alumina, glass, and the like made into ultrafine powder having the above particle size can be used.

The organic compound is preferably a high molecular compound which does not easily deteriorate the drug by being eluted into the drug which comes into contact with the medical device of the present invention, and has a glass transition temperature of 40 in order to finely disperse the drug. A rubbery polymer having a temperature of ℃ or less is preferable. Note that the block copolymerized rubbery polymer or the like may have two or more glass transition temperatures. In that case, the lowest glass transition temperature may be 40 ° C. or lower.

Examples of the polymer compound used as a compounding agent include emulsion- or solution-polymerized styrene-butadiene-rubber, high-styrene rubber and other random or block-styrene-butadiene copolymers, and hydrogenated products thereof. Isoprene rubber, hydrogenated product thereof; chloroprene rubber, hydrogenated product thereof; saturated polyolefin rubber such as ethylene / propylene copolymer, ethylene / α-olefin copolymer, propylene / α-olefin copolymer; ethylene / Propylene / diene copolymer, α-
Diene polymers such as olefin / diene copolymers, diene copolymers, isobutylene / isoprene copolymers, isobutylene / diene copolymers, halides thereof,
Hydrogenated products of diene polymers or their halides;
Acrylonitrile / butadiene copolymer, hydrogenated product thereof; vinylidene fluoride / trifluoroethylene copolymer, vinylidene fluoride / hexafluoropropylene copolymer, vinylidene fluoride / propylene hexafluoride / tetrafluoroethylene copolymer Fluorine rubbers such as polymers and propylene / tetrafluoroethylene copolymers; special urethane rubbers, silicone rubbers, polyether rubbers, acrylic rubbers, chlorosulfonated polyethylene rubbers, epichlorohydrin rubbers, propylene oxide rubbers, ethylene acrylic rubbers, etc. Rubber; copolymer of norbornene-based monomer and ethylene or α-olefin, terpolymer of norbornene-based monomer and ethylene and α-olefin, ring-opening polymer of norbornene-based monomer, norbornene-based monomer Ring-opening polymers of polymers such as hydrogenated products of norbornene type Incompatible with the thermoplastic norbornene-based resin, which is the main component of the resinous composition of the humic polymer; styrene / butadiene / styrene / rubber, styrene / isoprene / styrene / rubber, styrene / ethylene / butadiene / styrene / Aromatic vinyl monomers such as rubber
Random copolymers of conjugated dienes, their hydrogenated products;
Linear or radial block copolymer of styrene / butadiene / styrene / rubber, styrene / isoprene / styrene / rubber, styrene / ethylene / butadiene / styrene / rubber aromatic vinyl monomer / conjugated diene
In addition to styrene-based thermoplastic elastomers such as hydrogenated products thereof, urethane-based thermoplastic elastomers, polyamide-based thermoplastic elastomers, 1,2-polybutadiene-based thermoplastic elastomers, vinyl chloride-based thermoplastic elastomers, fluorine-based thermoplastic elastomers, etc. A thermoplastic polymer having a glass transition temperature of 20 ° C. or lower, a cyclohexyl group, an isobornyl group,
Tricyclo [4.3.0.1 ^2,5 ] decan-3-yl group, tricyclo [4.3.0.1 ^2,5 ] -7-decene-
Poly (meth) acrylate resins having a cyclic substituent such as 3-yl group; copolymers of styrenes with (meth) acrylates such as octyl acrylate and hexyl acrylate butyl acrylate, poly (aminocarbonyltetramethylenecarbonylaminomethylene- Polyamide resins such as 1,3-cyclohexylenemethylene); poly [oxycarbonyl (1,3-phenylene) carbonyloxymethylene (tricyclo [4.3.0.1 ^2,5 ]-
3,8-diyl) methylene] and other polyester resins;
Polybutylene oxide, poly [oxy (2-methyl-
2-hydroxytrimethylene) oxy (1,4-phenylene) isopropylidene (1,4-phenylene)] and other polyether resins; poly [oxycarbonyloxy (2-methyl-1,4-cyclohexylene] isopropylidene ( 3-methyl-1,4-cyclohexylene)] and other polycarbonate resins; polyurethane resins; and other polymer compounds.

Among these, copolymers of aromatic vinyl monomers and conjugated diene monomers, hydrogenated products thereof,
Also, the norbornene rubber polymer which is incompatible with the thermoplastic norbornene resin of the present invention has good dispersibility with the thermoplastic norbornene resin and is preferable. The copolymer of the aromatic vinyl-based monomer and the conjugated diene-based monomer may be a block copolymer or a random copolymer. From the viewpoint of weather resistance, it is more preferable that the portion other than the aromatic ring is hydrogenated. Specifically, styrene / butadiene block copolymers, styrene / butadiene / styrene / block copolymers, styrene / isoprene / block copolymers, styrene / isoprene / styrene / block copolymers, and hydrogenated products thereof. , Styrene / butadiene / random copolymer and the like.

Further, when the resin of the present invention is molded into a chemical container, it is necessary that the resin be transparent enough to confirm the amount and state of the contents. For that purpose, the compounding agent preferably has a small difference in refractive index from the thermoplastic norbornene-based resin to which it is added. When a mixture having a large difference in refractive index is mixed, it becomes opaque so that the amount of the content becomes invisible when added in a large amount. On the other hand, if the amount is too small, the turbidity cannot be sufficiently prevented by steam sterilization.

When a compounding agent is added to the thermoplastic norbornene-based resin, the transparency generally decreases, but the transparency varies depending on the resin, the compounding agent, and the compounding ratio, and when molded to a thickness of 1 mm, the wavelength range of 450 to 700 nm is obtained. The light transmittance in the range is usually 40% or more, preferably 50% or more, more preferably 60% or more. In the case where the compounding agent forms and is dispersed in microdomene, it is 0.3 μm or less, particularly, 0.
When the microdomains of 2 μm or less are formed, the compounding agent has a diameter smaller than the wavelength of visible light, and light is less likely to scatter, so that the transparency is excellent.

Further, the smaller the difference in refractive index between the compounding agent and the thermoplastic norbornene-based resin, the more excellent the transparency is. When the compounding amount is 5% by weight to 0.5% by weight, preferably 0.2 or less,
It is more preferably 0.1 or less, particularly preferably 0.05 or less, particularly preferably 0.02 or less, and the compounding amount is 0.1.
If it is less than 5% by weight, it is 0.3 or less, more preferably 0.2.
The ratio is particularly preferably 0.1 or less, particularly preferably 0.05 or less.

Different types of thermoplastic norbornene resins have different refractive indices. For example, in rubbery polymers, the ratio of monomers may be changed, or the number of unsaturated bonds in the main chain may be changed by hydrogenation or the like. With, it is possible to continuously change the refractive index. It is preferable to select a rubbery polymer having an appropriate refractive index according to the refractive index of the thermoplastic norbornene-based resin used.

(Compounding) In the present invention, the thermoplastic norbornene resin is 90 to 99.99% by weight, preferably 95.
To 99.98% by weight, more preferably 99 to 99.95.
% By weight, particularly preferably 99.5 to 99.9% by weight, and 10 to 0.01% by weight of the compounding agent, preferably 5 to 0.02% by weight, more preferably 1 to 0.05% by weight, particularly preferably 0.5 to 0.1% by weight is added and dispersed in a thermoplastic norbornene resin. If the amount added is too large, the transparency, glass transition temperature, and heat resistance of the resin will decrease. If the added amount is too small, the effect of compounding the compounding agent cannot be obtained. .

The method of addition is not particularly limited as long as the compounding agent is a method in which it is sufficiently dispersed in the thermoplastic norbornene resin. For example, when a rubbery polymer is used as a compounding agent, a method of kneading the resin temperature in a molten state with a mixer, a biaxial kneader, or the like, a coagulation method of dissolving and dispersing in a suitable solvent,
There is a method of removing the solvent by a casting method or a direct drying method.

When kneading, the resin temperature is Tg + 50.
Sufficient shearing is applied at a temperature of ℃ to Tg + 150 ℃.
If the resin temperature is too low, the viscosity will be high, and it will be difficult to knead. If it is too high, the resin and the rubbery polymer will be deteriorated, and the two cannot be kneaded well due to the difference in viscosity and melting point.

When the kind and amount of the compounding agent are adjusted, the resin becomes transparent to the extent that the amount of the content can be confirmed when the resin is molded into a chemical container. In order to improve transparency, it is preferable that the compounding agent becomes a microdomain and is dispersed in the thermoplastic norbornene-based resin. In the case of organic compounds,
If the compounding amount is large, it may not be a microdomain, but for example, in the case of a rubbery polymer, it is 0.8 to 0.01.
A micro domain can be formed by adding the composition in a weight percentage. Further, when the compounding amount is small or the compounding agent is not added, steam sterilization by an autoclave or the like may cause the resin to become cloudy and lose transparency.

For example, Labo Plastomill (made by Toyo Seiki)
When using, the number of rotations is 20
When kneading at a feed rate of about 30 rpm and a residence time of about 1 to 10 minutes, a rubbery polymer usually forms a microdomain having a diameter of 0.3 μm or less in a thermoplastic norbornene-based resin. Can be dispersed. Usually, in a twin-screw kneader, L / D is 25 or more,
It is preferably 30 or more and the residence time is about 1 to 10 minutes. The longer the residence time, the easier it is to form microdomains, but since the resin or rubbery polymer is likely to deteriorate, the resin to be used, the rubbery polymer, and the combination of the devices used for kneading, preliminary kneading, It is necessary to decide the number of rotations and the residence time that match the combination.

When the rubbery polymer is used as the compounding agent, the microdomains are substantially spherical, and the variation in particle size among particles is small. Usually, the diameter is 0.3 μm or less, preferably 0.2 μm or less. With this particle size, the decrease in the transparency of the thermoplastic norbornene-based resin composition due to the addition of the rubber-like polymer is small, as will be described later, and there is no problem. Also in the case of other compounding agents, it is preferable that the microdomains have a substantially spherical shape and that there is no variation in particle size among particles, and the diameter is 0.3 μm or less, particularly 0.2 μm.
The following is preferable. Even if the micro domain is not spherical, it is preferable that the smallest sphere capable of confining the micro domain has a diameter of 0.3 μm or less, particularly 0.2 μm or less.

(Additives) If desired, various additives may be added to the thermoplastic norbornene-based resin used in the present invention. The additives used in the resin are those that are compatible with the resin, such as phenol-based and phosphorus-based antioxidants,
Antistatic agents, UV absorbers, lubricants, etc. When the sheet is formed by the solution casting method, it is also preferable to add a leveling agent in order to reduce the surface roughness. As the leveling agent, for example, a fluorine-based nonionic surfactant, a special acrylic resin-based leveling agent, a silicone-based leveling agent such as a coating leveling agent can be used, and among them, those having good compatibility with a solvent are preferable. However, since these may be eluted from the resin, it is preferable that the additive has a large molecular weight, and the addition amount is small.

For example, an antioxidant has a relatively small molecular weight and is easily eluted, but the molecular weight is 600 or more, preferably 7
If the antioxidant is 00 or more, elution can be prevented,
3000 ppm or less, preferably 1000 ppm or less,
More preferably, if it is added at 500 ppm or less, the antioxidant hardly elutes.

As the antioxidant having a molecular weight of 600 or more,
Pentaerythrityl-tetrakis [3- (3,5-di-
t-butyl-4-hydroxyphenyl) propionate], 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl)
Benzene, tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 3,9-bis [1,1-dimethyl-2- [β- (3-t-butyl-4]
-Hydroxy-5-methylphenyl) propionyloxy] ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 1,6-hexanediol-bis [3- (3,5-di- t-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], N, N′-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamide), 1- [2- [3- (3,5-di-
t-Butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy]-
2,2,6,6-tetramethylpiperidine and the like can be mentioned.

In order to prevent the occurrence of turbidity during steam sterilization, the thermoplastic norbornene-based resin contains 5 to 0.01% by weight, preferably 2 to 0% by weight of a partially etherified product and / or partially esterified product of a polyhydric alcohol. 0.05% by weight,
Particularly preferably, 1.0 to 0.1% by weight may be added. Addition can prevent the occurrence of turbidity during steam sterilization, as in the case of adding the compounding agent.

Examples of the partially esterified product obtained by esterifying a part of the alcoholic hydroxyl group of the polyhydric alcohol include glycerin monostearate, glycerin monolaurate, glycerin monobehenate and diester known in JP-A-63-275654. Glycerin monostearate, glycerin distearate, glycerin dilaurate, pentaerythritol monostearate, pentaerythritol monolaurate, pentaerythritol monobeherate, pentaerythritol distearate, pentaerythritol dilaurate, pentaerythritol tristearate, dipentaerythritol Examples include distearate.

Examples of the partially etherified product obtained by etherifying a part of the alcoholic hydroxyl group of the polyhydric alcohol include 3- (octyloxy) -1,2-propanediol and 3- (decyloxy) -1,2-propane. Diol, 3- (lauryloxy) -1,2-propanediol, 3- (4-nonylphenyloxy) -1,2-propanediol, 1,6-dihydroxy-2,2-di (hydroxymethyl)- 7- (4-nonylphenyloxy) -4-oxoheptane, ether compound obtained by reaction of condensate of p-nonylphenol and formaldehyde and glycidol, ether compound obtained by reaction of condensate of p-octylphenol and formaldehyde and glycidol , P-octylphenol and dicyclopentadiene condensate And ether compounds obtained by the reaction of glycidol and the like. Among these, those having a molecular weight of 500 to 2000, particularly 800 to 1500 are preferable. When using additives with low molecular weight,
When the addition amount is large, it is preferable to add a small amount of one having a large molecular weight because it is easily eluted. If the amount added is small,
The effect of preventing turbidity from steam sterilization is small.

(Molding) In the present invention, a thermoplastic norbornene resin is molded into a medical device. The medical device of the present invention, for example, liquid or powder such as liquid medicine container for injection, ampoule, prefilled syringe, infusion bag, solid medicine container, eye drop container, drip drop container,
Solid drug containers; Food containers; Sampling test tubes for blood tests, blood collection tubes, sample containers such as sample containers;
Sterile containers for medical materials such as scalpels, forceps, gauze and contact lenses; medical instruments such as syringes; laboratory instruments such as beakers, petri dishes and flasks; optical parts such as plastic lenses for medical examinations; medical infusion tubes, piping, Piping materials such as joints and valves; In particular, the effect of the present invention is great in a medicine container in which a medicine is enclosed by using a machine, a sampling test tube for blood test in which a coagulant is enclosed, a blood collection tube, and the like.

The method for molding the thermoplastic norbornene-based resin is not particularly limited. Depending on the purpose, injection molding method, blow molding method, injection blow molding method, rotational molding method,
A vacuum molding method, an extrusion molding method, a calender molding method, a solution casting method and the like are possible.

The heat resistance, chemical resistance, dielectric properties and rigidity of the molded product of the thermoplastic norbornene resin when the compounding agent of the present invention is blended are substantially the same as those of the molded product of the thermoplastic norbornene resin which is not added. Is.

Further, the thermoplastic norbornene-based resin of the present invention absorbs little chemicals. In particular, there is little adsorption of compounds having polar groups such as alcohols, amines, esters, amides, ethers, carboxylic acids and amino acids, and the thermoplastic norbornene-based resin of the present invention exudes organic substances and the like. Since it does not occur, the chemicals that come into contact do not deteriorate.

(Primer) In the present invention, a chemical,
A hard coat layer is formed on a surface portion that does not come into contact with a living body or a medical device that comes into contact with the living body. When the rubbery polymer is added to the thermoplastic norbornene-based resin as described above, the adhesiveness is good. However, in the case of a thermoplastic norbornene-based resin whose adhesion is not improved by such a method, it is preferable to form a primer layer on the portion to be hard-coated.

The primer used in the present invention is composed of a halogenated hydrocarbon polymer and usually has a molecular weight of 5,000 to 2.
0,000, preferably 10,000-150,000
0, more preferably 20,000 to 100,000. Such halogenated hydrocarbon polymers include ethylene, propylene, butadiene, isoprene,
Examples thereof include halogenated hydrocarbon-based polymers obtained by polymerizing or copolymerizing hydrocarbon-based monomers such as styrene, and those obtained by polymerizing or copolymerizing halogen-containing monomers such as vinyl chloride, benylidene chloride and chloroprene. Of these, chlorinated hydrocarbon polymers are preferable, and chlorinated polypropylene is particularly preferable.

The content of halogen is 15 to 55% by weight,
Preferably 20-45% by weight, more preferably 25-3
It is 5% by weight. If the molecular weight is too small, the strength of the primer layer will be low, and if it is too large, the viscosity will be too high and the coating workability will be poor. Further, if the content of halogen is too small or too large, the adhesion between the primer layer and the hard coat-forming surface and between the primer layer and the hard coat layer deteriorates.

When the ultraviolet-curable hard coat layer is formed, a photopolymerizable monomer, a photopolymerizable oligomer, etc., which will be described later, particularly 2 to 20 monofunctional acrylate monomers are used.
Addition by weight% is preferable because the adhesion between the primer layer and the hard coat layer is improved.

In the present invention, the primer is used as a primer solution by dissolving it in a solvent. The solvent is not particularly limited as long as it is a substantially poor solvent for the thermoplastic saturated norbornene-based resin. For example, toluene is a good solvent for thermoplastic saturated norbornene-based resins, but if it is diluted to 70 wt% or less with methyl isobutyl ketone, erosion will be small even if it is applied to thermoplastic saturated norbornene-based resins. Can be used as When forming an ultraviolet-curable hard coat layer, n
Monofunctional acrylates such as butyl methacrylate and isoamyl methacrylate are also poor solvents for thermoplastic saturated norbornene-based resins, and are preferable because they are reactive diluents having an effect as a photopolymerizable monomer to be added to the aforementioned primer. Is.

The concentration of the primer solution is 1 to 30% by weight,
It is preferably 2 to 20% by weight, more preferably 3 to 10% by weight.

(Method for forming primer layer) The primer layer formed in the present invention is formed by applying it to the surface of the hard coat layer made of the thermoplastic saturated norbornene resin and sufficiently removing the volatile components in the solvent. To be done. In addition,
For example, when only the reactive diluent as described above is used as the solvent for the primer, the removing operation is unnecessary.

The method of applying the primer solution is not particularly limited, and for example, spraying, dipping, spin coating, roll coater and the like are possible. Moreover, the method for removing the volatile components in the primer solution is not particularly limited. The volatilization temperature and time required to substantially remove the solvent vary depending on the type of solvent used, the coating amount, the shape of the adhesive surface or the hard coat layer forming surface, but the molded product having the hard coat layer forming surface. So that there is no thermal deformation of the
In addition, the conditions may be determined so that they can be removed sufficiently.
Specifically, it is suitable to leave it at 60 to 120 ° C. for about 3 to 60 minutes. After removing the volatile components at a high temperature, it is preferable to perform cooling at room temperature for about 10 seconds to 10 minutes, and to cool to near room temperature.

The amount to be applied is not particularly limited, but it is preferable that the thickness is about 1 to 10 μm, particularly about 2 to 5 μm. When it is necessary to remove the volatile components after coating, it is preferable that the above thickness be obtained after sufficient removal. If the coating amount of the primer is small, the effect of the primer is small, and if it is too large, it may be difficult to dry or sufficient adhesiveness may not be obtained.

(Coating Agent) The coating agent used when forming the hard coat layer may be a silicon-based coating agent or an organic coating agent. Silicone-based coating agents are partial hydrolysates of silane compounds, and organic-based coating agents include coating agents that heat-cure melamine-based, alkyd-based, urethane-based, and acrylic-based coating materials, and polyfunctional acrylic-based coating agents. There is an ultraviolet curable coating agent that cures monomers and the like with ultraviolet light. The ultraviolet-curable coating agent is preferable because it can be cured under the condition that the thermoplastic saturated norbornene-based resin is not easily deformed by heat, and has sufficient hardness and weather resistance.

The UV-curable coating agent used in the present invention contains a reactive monomer and / or a reactive oligomer, a photopolymerization initiator and other additives, and is solvent-free or diluted with a solvent.

As the reactive monomer, acrylates are the main ones, but specifically, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-ethylhexyl methacrylate, phenoxyethyl acrylate, phenoxypropyl acrylate, Other monofunctional acrylate monomers such as higher alkyl acrylates; Other monofunctional monomers such as styrene and vinylpyrrolidone; ethylene glycol, diethylene glycol, tripropylene glycol, butylene glycol, hexanediol, trimethylolpropane, tetramethylolpropane, penta Examples thereof include polyfunctional acrylate monomers in which two or more acrylates are bonded to polyols such as erythritol.

As the reactive oligomer, polyester acrylate having an acroyl group at the terminal, epoxy acrylate or polyurethane acrylate having an epoxy group in the molecular chain and an acroyl group at the terminal, unsaturated polyester having a double bond in the molecular chain, Mention may be made of 1,2-polybutadiene and other oligomers having epoxy groups or vinyl ether groups.

As the photopolymerization initiator, acetophenones such as 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone and chlorinated acetophenone; benzophenones; benzyl, methylorthobenzoylbenzoate, benzoin alkyl ether Azo compounds such as α, α′-azobisisobutyronitrile, 2,2′-azobispropane and hydrazone; Organic peroxides such as benzoyl peroxide and ditertiary butyl peroxide; Diphenyldiene Diphenyl disulfides such as sulfide, dibenzyl disulfide, dibenzoyl disulfide; and the like. Further, commercially available Darocure 1173 (manufactured by Merck), Darocure 1116 (manufactured by Merck), Irgacure 184 (manufactured by Ciba Geigy), Irgacure 651 (manufactured by Ciba Geigy) and the like can also be used.

In the present invention, a UV-curable coating agent comprising a monofunctional acrylate monomer, a difunctional or trifunctional acrylate monomer, a tetrafunctional or higher functional acrylate monomer, and a photopolymerization initiator is preferable.

In the present invention, a photopolymerizable monomer having one acrylate group is referred to as a monofunctional acrylate monomer, and one having two acrylate groups is referred to as a bifunctional acrylate monomer.

Examples of the monofunctional acrylate monomer include n-butyl acrylate, isoamyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-ethylhexyl methacrylate, phenoxyethyl acrylate, phenoxypropyl acrylate and other higher alkyls. Examples thereof include acrylate. An acrylate having a side chain of about 4 to 6 carbon atoms is preferable in order to reduce the curing shrinkage of the ultraviolet curable coating agent.

Examples of the bifunctional or trifunctional acrylate monomer include ethylene glycol, diethylene glycol, tripropylene glycol, butylene glycol, neopentyl glycol, hexanediol, tremethylolpropane, tetramethylolpropane, pentaerythritol and dipentaerythritol. It is one in which two or three acrylates are bonded to polyols.

Examples of the tetrafunctional or higher functional acrylate monomer include polyols such as tetramethylolpropane, pentaerythritol and dipentaerythritol.
One or more acrylates are bonded.

The mixing ratio of the monofunctional acrylate monomer is usually 0 to 80% by weight, preferably 0 to 60% by weight, and the di- or trifunctional acrylate is based on the total weight of the acrylate monomer and the photopolymerization initiator. The monomer is 5 to 70% by weight, preferably 10 to 50% by weight, the tetrafunctional or higher acrylate monomer is 10 to 80% by weight, preferably 20 to 75 parts by weight, and the photopolymerization initiator is 0.5 to 10% by weight.
% By weight, preferably 1 to 5% by weight. If the amount of the tetrafunctional or higher functional acrylate monomer is too large, the curing shrinkage will increase, and if it is too small, the hardness of the hard coat layer will decrease and the curing speed will also decrease. When the amount of the monofunctional acrylate monomer is small, the viscosity becomes high and the workability becomes poor. In addition, when the amount of the monofunctional acrylate monomer is large, the curing shrinkage is reduced, and the amount of the bifunctional or trifunctional acrylate monomer is decreased, which lowers the flexibility of the hard coat layer and causes cracks. Also, in order to improve the adhesiveness, 2
Alternatively, it is preferable that the amount of the trifunctional acrylate monomer is large.

Furthermore, appropriate additives may be added as long as the adhesiveness and hardness of the hard coat layer are satisfied. For example, by adding a suitable surfactant, for example, a nonionic surfactant having good compatibility with an ultraviolet curing agent, particularly an amine surfactant or other antistatic agent, the surface chargeability can be improved. Alternatively, the addition of a fluorine-based nonionic surfactant may improve the surface smoothness after wetting with the substrate and curing. In particular, since the surface smoothness after curing is improved, slippage of the hard coat layer on the surface is improved, so that the molded product is less likely to be scratched. Further, by adding an appropriate thermoplastic resin, the viscosity can be adjusted and the adhesiveness can be improved. As the thermoplastic resin for improving the adhesiveness, in the case of a thermoplastic saturated norbornene-based resin, a thermoplastic norbornene-based resin or a resin having a structure similar to that of the thermoplastic norbornene-based resin, for example, a ring-opening polymer of a norbornene-based monomer or dicyclopentadiene is used. Examples thereof include petroleum resins such as a system, a diene system, an aliphatic system, and a water white system, or hydrogenated products thereof.

These mixtures can be used as they are as UV-curable coating agents, but depending on the operability, alcohol solvents such as methanol, ethanol, propanol, etc .; ethylene glycol, butadiol, hexanediol. Glycol solvents such as; Aromatic hydrocarbon solvents such as toluene and xylene; Alicyclic hydrocarbon solvents such as cyclohexane and methylcyclohexane; Ketone solvents such as methyl isobutyl ketone, methyl ethyl ketone, and acetone; n-butyl ether, diethyl Ether solvent such as ether; Ester solvent such as ethyl acetate and butyl acetate; Cellosolve solvent such as methyl cellosolve and ethyl cellosolve; Chlorine solvent such as chloroform and methylene chloride; Is 5 to 30 Used dissolved in a concentration of amount% may be UV-curable coating agent.

(Method for forming hard coat layer) In the present invention, to form a hard coat layer, an ultraviolet-curable coating agent is applied to the hard coat layer forming surface or the hard coat forming surface subjected to the above-mentioned primer treatment. , UV rays to cure. When the UV-curable coating agent is dissolved in a solvent and used, the volatile components are sufficiently removed after the application of the UV-curable coating agent and before the next step. If you cure the UV-curable coating agent while containing a large amount of solvent,
This tends to cause cracks in the coating film, and also causes the failure to obtain a coating film with high hardness.

The method of applying the ultraviolet curable coating agent is not particularly limited, and spraying, dipping, spin coating, roll coater and the like can be used. The method for removing the solvent is also not particularly limited. The temperature and time required to substantially remove the solvent by volatilization differ depending on the type of solvent used, the coating amount, and the shape of the hard coat layer forming surface, but there is no thermal deformation of the thermoplastic saturated norbornene resin. As described above, the conditions may be determined so that the temperature is approximately 120 ° C. or lower and the volatile components can be sufficiently removed. Specifically, 60 to 120
A removal method at 3 ° C for about 3 to 60 minutes is suitable. After removing the solvent at a high temperature, it is preferable to perform cooling at room temperature for about 10 seconds to 10 minutes, and then to cool it to near room temperature. In addition, when the solvent is not used, the removing operation by volatilization is unnecessary.

It is preferable that the coating amount be about 2 to 300 μm. When the solvent is removed, it is preferable that the above-mentioned thickness is obtained after the removal. If the coating amount of UV curable coating agent is small,
A hard coat layer having high strength cannot be obtained, and a sufficient effect of improving surface hardness cannot be obtained. When the amount is large, it takes time to remove the solvent and the curing reaction, resulting in poor productivity. Further, when the curing is insufficient and the hardness is low, the hard coat layer may lack flexibility and crack.

Then, by irradiating ultraviolet rays from a light source that efficiently generates ultraviolet rays such as a high pressure mercury lamp, curing takes place in a short time, and a hard coat layer having high hardness is formed. The irradiation intensity of ultraviolet rays is usually 1500 to 20000 mJ / c when a high pressure mercury lamp is used.
m ² , preferably 3000 to 15000 mJ / cm ² .

The hardened hard coat layer has a pencil hardness of 2H or more, preferably 3H or more, and a cross-cut peeling test of 80.
Eyes / 100 eyes or more, preferably 90 eyes / 100 eyes or more, showing adhesion, and further, in a steel wool test using # 0000 steel wool, it is not scratched and does not peel off by steam sterilization treatment. Do not dissolve or peel off with common solvents or machine oils.

[0070]

EXAMPLES The present invention will be described more specifically below with reference to Reference Examples, Examples, and Comparative Examples. The pencil hardness, cross-cut peeling test, steel wool test and steam treatment were carried out as follows.

(Pencil hardness measurement method) JIS K-5400
According to the above, the load was measured with a 1 kg load.

(Cross-cut peeling test) On the hard coat layer formed on the surface of the molded product, 11 vertical and horizontal cuts were made by a cutter at intervals of 1 mm to make 100 1-mm square grids, and cellophane was used. Adhesive tape (manufactured by Sekisui Chemical Co., Ltd.) is attached, and the outer adhesive tape is peeled off in the 90 ° direction. The test results are shown by the number of unpeeled eyes.

(Steel Wool Test) A molded article hard-coated with # 0000 steel wool was rubbed,
I checked for scratches.

(Steam treatment) 121 in an autoclave
The treatment was performed at 30 ° C. for 30 minutes.

Reference Example 1 60 parts by weight of ethyl tetracyclododecene, 600 parts by weight of cyclohexane and 6.0 parts of 1-hexene under nitrogen substitution.
Parts by weight, 45 parts by weight of triethylaluminum 15% by weight toluene solution and 15.0 parts by weight of triethylamine are added, and the mixture is kept at 20 ° C. while stirring, and 240 parts by weight of ethyl tetracyclododecene and 20% by weight titanium tetrachloride in toluene solution 27 0.0 parts by weight was added continuously over 60 minutes. Then, after reacting for 1 hour, ethyl alcohol 1
The reaction was stopped by adding 5.0 parts by weight and 6.0 parts by weight of water. After the reaction solution was heated to 40 ° C. to hydrolyze the catalyst, 9 parts by weight of calcium sulfate and 180 parts of cyclohexane were added.
Parts by weight were added to remove excess water. The precipitated metal-containing precipitate was removed by filtration to obtain 1113 parts by weight of a transparent polymer solution containing an ethyltetracyclododecene ring-opening polymer.

To 750 parts by weight of this polymer solution, Ni-
Add 15 parts by weight of diatomaceous earth catalyst (N113, manufactured by JGC Chemical Co., Ltd.), put in a pressure resistant reactor, introduce hydrogen, and apply pressure 50
A hydrogenation reaction was carried out at a temperature of 200 ° C. for 3 hours at kg / cm ² . After completion of the reaction, 700 parts by weight of cyclohexane was added for dilution, and the catalyst was removed by filtration to obtain 1350 parts by weight of hydrogenated solution of ethyltetracyclododecene ring-opening polymer.

550 parts by weight of this hydrogenated solution was poured into 1500 parts by weight of isoproyl alcohol with stirring to solidify the hydrogenated product of the ring-opening polymer. The solidified ring-opening polymer hydrogenated product was collected by filtration, washed twice with 300 parts by weight of isopropyl alcohol, and then dried in a rotary vacuum dryer at 5 toor and 120 ° C. for 48 hours to obtain ethyl tetracyclododecene. 52 parts by weight of a hydrogenated product of a ring-opening polymer was obtained.

100 parts by weight of the hydrogenated product of the ring-opening polymer was retained in a column having an inner diameter of 10 cm and a length of 100 cm filled with 900 parts by weight of a cyclohexane solution and 4.5 parts by weight of activated alumina (Neobead D manufactured by Mizusawa Chemical Co., Ltd.). It was passed for 100 seconds and circulated for 24 hours. Pour into 2500 parts by weight of isopropyl alcohol while stirring,
The ring-opened polymer hydrogenated product was solidified. The solidified ring-opening polymer hydrogenated product was collected by filtration, washed twice with 430 parts by weight of isopropyl alcohol, and then dried at 5 torr and 120 ° C. for 48 hours in a rotary vacuum drier to open ethyl tetracyclododecene. 78 parts by weight of hydrogenated ring polymer was obtained.

The molecular weight of this ring-opened polymer hydrogenated product was determined by gel permeation chromatography to have a polystyrene-equivalent number average molecular weight of 28,000, a weight average molecular weight of 58,000, a hydrogenation rate of 99.8% or more, and a differential value. Scanning calorimetric analysis, glass transition temperature 142 ℃, molecular weight 2,
0.1% less than 000 resin component, 1ppm titanium atomic weight
(Detection limit) or less, nickel atomic weight was 0.1 ppm or less, aluminum atomic weight was 0.21 ppm, and chlorine atomic weight was 0.37 ppm.

To 99.8 parts by weight of this hydrogenated ring-opening polymer, 0.2 part by weight of a rubbery polymer (Tuftec H1052, glass transition temperature 0 ° C. or lower, manufactured by Asahi Kasei Co., Ltd.), and an antioxidant (Irganox 1010, Ciba-Geigy) 0.0
5 parts by weight were added, and a twin-screw kneader (TEM-35B, screw diameter 37 mm, L / D = 32, screw rotation number 2
50 rpm, resin temperature 265 ° C., feed rate 10 k
k / g) and extruded into pellets.

A container A (diameter: 20 mm, height: 4) having a mold side temperature of 100 ° C., a resin temperature of 290 ° C., a blown air pressure of 5 kg / cm ² and a cylindrical side surface and one bottom surface was used.
0 mm, thickness 2 mm) and container B (diameter 200 mm, height 130 mm, thickness 3 mm) were blow molded.

The pellets were injection-molded (molding pressure 350t, resin temperature 280 ° C., mold temperature 100 ° C.),
About 100 test pieces of 100 mm × 50 mm × 2.0 mm were prepared. The total light transmittance of this test piece was 90.2%, the transparency was good, and the turbidity was 0.1%.

In container B, LB medium (1% by weight of bactotryptone, 0.5% by weight of yeast extract, Na
PH of an aqueous solution containing 1% by weight of Cl and 0.1% by weight of glucose
(Adjusted to 7.5) 300 ml, agar 6 g, put one piece of test piece, cap with aluminum foil, steam sterilize,
Although kept at 37 ° C. for 3 days, no fungal growth was observed, and no turbidity, cracking, deformation, etc. could be visually confirmed. The turbidity measured after removing the LB medium solidified by agar from the test piece taken out from the container was 0.2.
The total light transmittance was 7% and 89.7%.

200 g of distilled water was placed in a hard glass flask, covered with a hard glass lid, steam sterilized at 120 ° C. for 1 hour using an autoclave, cooled to room temperature, and allowed to stand for 24 hours. Distilled water was collected.

Further, the test piece was ultrasonically washed in distilled water for 20 minutes, dried at 40 ° C. for 10 hours, cut into 10 mm width, put 20 g portion in a hard glass flask, put 200 g distilled water in a hard glass. The product was capped, steam sterilized at 120 ° C. for 1 hour using an autoclave, cooled to room temperature, and allowed to stand for 24 hours to collect distilled water.

The elution amount from the test piece was obtained from the difference in the analysis results by the atomic absorption method of these two kinds of distilled water, the ion chromatography, the combustion-non-dispersion type infrared gas analysis method and the like. 0.1 ppm (detection limit) or less, nickel atom elution amount is 0.01 ppm (detection limit) or less, aluminum atom elution amount is 0.01 (detection limit) p
pm or less, chlorine atom elution amount 0.02 (detection limit) ppm
Hereinafter, the total organic carbon amount was 2 ppm (detection limit) or less.

The test piece was subjected to an eluate test according to the Japanese Pharmacopoeia 12th revision "Plastic Test Method for Infusion Solution".
The bubbling disappeared within 3 minutes, the pH difference was -0.03, the ultraviolet absorption was 0.007, and the potassium permanganate reducing substance was 0.15 ml, which had properties suitable for medical use.

Example 1 10 parts by weight of dipentaerythritol hexaacrylate, 10 parts by weight of 1,6-hexanediol diacrylate, 3 parts by weight of a photopolymerization initiator (Darocur 1173, manufactured by Merck & Co.), a fluorine-based surfactant (FC -430, manufactured by Sumitomo 3M) 0.1 part by weight of isopropyl alcohol 8
It was dissolved in 0 part by weight to obtain a hard coat agent.

This hard coating agent was applied to the inside of the container A obtained in Reference Example 1 by dipping so that the hard coating agent did not come into contact with it. The film thickness was about 5 μm. After leaving at 50 ° C. for 1 minute to volatilize isopropyl alcohol, the hard coat agent was cured by irradiating ultraviolet rays at 10,000 mJ / cm ² with a high pressure mercury lamp for 2 minutes.

The hard-coated outer surface of Container B was subjected to a steel wool test and no scratches were noted. In addition, no change was observed in the oil resistance test, and
Also in the cross-cut peeling test, good adhesion was shown at 100/100. Furthermore, no change was observed in the steam treatment. The pencil hardness of this outer surface was 3H.

Further, methanol, acetone, toluene,
Also, the solvent was immersed in gasoline so that these solvents would not enter the inside, and allowed to stand for 24 hours, but no particular abnormality was observed.

Example 2 7 parts by weight of dipentaerythritol hexaacrylate, 3 parts by weight of 1,6-hexanediol diacrylate, a photopolymerization initiator (Darocur 117
Example 3 except that 0.3 parts by weight of Merck & Co., Ltd.) and 0.1 parts by weight of a fluorosurfactant (FC-430, manufactured by Sumitomo 3M Co., Ltd.) were dissolved in 90 parts by weight of isopropyl alcohol. The same process was carried out. The film thickness was 3 μm.

The hard-coated outer surface of Container B was subjected to a steel wool test and no scratches were noted. In addition, no change was observed in the oil resistance test, and
Also in the cross-cut peeling test, good adhesion was shown at 100/100. Furthermore, no change was observed in the steam treatment. The pencil hardness of this outer surface was 3H.

Further, methanol, acetone, toluene,
Also, the solvent was immersed in gasoline so that these solvents would not enter the inside, and allowed to stand for 24 hours, but no particular abnormality was observed.

Comparative Example 1 When the outer surface of the container B obtained in Reference Example 1 was subjected to a steel wool test, it was markedly scratched. Also, cracks occurred in the oil resistance test. No change was observed with steam treatment. The pencil hardness of this external surface is HB
Met.

Further, methanol, acetone, toluene,
Further, when these solvents were immersed in gasoline and gasoline so that they would not enter the inside, and allowed to stand for 24 hours, no abnormalities were observed in methanol and acetone, but the surfaces were dissolved in toluene and gasoline.

[0097]

EFFECTS OF THE INVENTION The medical device of the present invention has a hard outer surface, is hard to be scratched, and is excellent in chemical resistance, and is hard to be damaged even in the step of filling chemicals.

─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-3-275052 (JP, A) JP-A-4-89821 (JP, A) JP-A-4-305450 (JP, A) JP-A-4- 363312 (JP, A) JP-A-1-221161 (JP, A) JP-A-3-31306 (JP, A) JP-A-3-275070 (JP, A) JP-A-5-225613 (JP, A) JP-A-4-276253 (JP, A) JP-A-1-223115 (JP, A) Special Table 4-506230 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) A61M 5/178

Claims (4)

(57) [Claims] 1. A thermoplastic norbornene-based resin having a transition metal atom content of 1 ppm or less 90 to 99.99% by weight.
To the compounding agent 10 which is incompatible with the norbornene resin
0.01 wt% was added, and the compounding ingredient was
A medical device formed by forming a hard coat layer on the outer surface of at least a part of a base material formed by being dispersed as a matrix. 2. The medical device according to claim 1, wherein the hard coat layer is obtained by curing an ultraviolet curable hard coat agent. 3. The medical device according to claim 1, which is a chemical container. 4. The medical device according to claim 3, wherein the container is sterilized after being filled with a chemical.