JPH07124227A - Thermoplastic norbornene type resin molding - Google Patents

Abstract

PURPOSE:To provide a molding having an excellent adhesive property and a low impurity elution property by providing on the surface of a base made from a thermoplastic norbornene resin a coating layer composed of a polymer of an acrylic monomer having a hydrocarbon group of a specific number of carbon atoms and a copolymer of an acrylic monomer and a vinyl monomer. CONSTITUTION:A coating layer composed of a polymer of an acrylic monomer having a hydrocarbon group of four or more carbon atoms, a copolymer of acrylic hydrocarbon and a vinyl monomer or a copolymer of aromatic vinyl hydrocarbon and a conjugate diene monomer, or a hydrogenated product of the latter copolymer, is provided over at least part of the surface of the base of a molding which is made from a thermoplastic norbornene resin. The molding forms a container having the coating layer on its outer surface, for use as medical equipment. The molding ensures safety since its coated surface is resistant to damage, the coating layer does not loose its transparency through precipitation even when sterilized with steam, and no components harmful to humans are eluted from the coating layer and the resin.

Description

Detailed Description of the Invention

[0001]

[Industrial application] Thermoplastic norbornene resins are
It excels in transparency, heat resistance, chemical resistance, solvent resistance, moisture resistance, water resistance, and low elution of organic substances. Recently, thermoplastic norbornene-based resins are being developed for medical applications.

When attempting to seal a chemical or the like into a container made of a thermoplastic norbornene resin by an automated sealing system, the outer surface of the container may be scratched or oil-resistant due to contact with a machine or contact between containers. There is a problem of causing stains, and it has been attempted to form a resin coat layer in order to increase the hardness of the outer surface of the container and to easily remove stains caused by oil.

In order to use it as a medicine container for medical treatment, "disposable transfusion set and infusion set standard", "disposable syringe set", which are the standards based on the provisions of Article 42, Paragraph 2 of the Pharmaceutical Affairs Law, , Etc., and may be required to pass the Japanese Pharmacopoeia General Test Method Infusion Plastic Container Test Method. However, in this dissolution test,
The coating layer formed on the outer surface is used to measure the amount of additives such as oxidation stabilizers and low-molecular impurities such as residual monomers that are eluted by dipping strip-shaped fragments cut vertically from the container into distilled water. When low-molecular impurities are eluted from, the impurities will not elute from the inner surface that is in contact with the enclosed drug, and even if it does not cause hemolysis etc., it will be judged as a failure and approval cannot be obtained, It could not be used as a medical container, medicine bottle, etc.

[0004]

DISCLOSURE OF INVENTION Problems to be Solved by the Invention As a result of diligent efforts to reduce the impurity elution of the coat layer of a thermoplastic norbornene-based resin molded product, the present inventors have found that the surface of a thermoplastic norbornene-based resin is coated with a specific resin. It was found that a molded product having excellent adhesion and low elution of impurities can be obtained by forming the coating layer consisting of the above, and has completed the present invention.

[0005]

Thus, according to the present invention, the weight of an acrylic monomer having a hydrocarbon group having 4 or more carbon atoms is provided on at least a part of the surface of a base material made of a thermoplastic norbornene resin. Molding having a coat layer composed of a combination, a copolymer of the acrylic monomer and the vinyl monomer, a copolymer of the aromatic vinyl hydrocarbon and the conjugated diene monomer, or a hydrogenated product Goods are offered.

(Thermoplastic Norbornene Resin) The thermoplastic norbornene resin used in the present invention is disclosed in JP-A-51-8.
No. 0400, No. 60-26024, No. 1-168725, No. 1-190726, No. 3-14882, No. 3-122.
No. 137, JP-A-4-63807, and other known resins, and more specifically, ring-opening polymers of norbornene-based monomers, hydrogenated products thereof, addition-type polymers of norbornene-based monomers. , Addition polymers of norbornene-based monomers and olefins, 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 compounds. Substituted derivatives and halogens of these substituted or unsubstituted olefins,
Polar group substituents such as hydroxyl group, 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-norboernene, 5-octyl-2-norbornene, 5-
Octadecyl-2-norbornene, etc .; Monomers obtained by adding one or more cyclopentadiene to norbornene, derivatives or substitution products similar to the above, for example, 1,4: 5,8
-Dimethano-1,2,3,4,4a, 5,8,8a-
2,3-cyclopentadienooctahydronaphthalene,
6-methyl-1,4: 5,8-dimethano-1,4,4
a, 5,6,7,8,8a-octahydronaphthalene,
1,4: 5,10: 6,9-trimethano-1,2,3,3
4,4a, 5,5a, 6,9,9a, 10,10a-dodecahydro-2,3-cyclopentadienoanthracene, etc .; a polycyclic monomer which is a multimer of cyclopentadiene, the same as above. Derivatives and substitution products, for example, dicyclopentadiene, 2,3-dihydrodicyclopentadiene, etc .; Addition products of cyclopentadiene and tetrahydroindene, etc., derivatives and substitution products similar to the above, for example, 1,4-methano- 1, 4, 4a, 4b, 5, 8, 8
a, 9a-octahydrofluorene, 5,8-methano-
1,2,3,4,4a, 5,8,8a-octahydro-
2,3-cyclopentadienonaphthalene and the like; and the like.

The norbornene-based monomer may be polymerized by a known method, and if necessary, it may be a thermoplastic saturated norbornene-based resin by copolymerizing with another copolymerizable monomer or by hydrogenation. It can be a thermoplastic norbornene-based polymer hydrogenated product. Further, a polymer or a polymer hydrogenated product is subjected to a method known in JP-A-3-95235 or the like to obtain an α, β-unsaturated carboxylic acid and / or a derivative thereof, a styrene-based hydrocarbon, an olefin-based unsaturated bond and a hydrolyzed product. It may be modified by using an organosilicon compound having a decomposable group or an unsaturated epoxy monomer. In addition, in order to obtain a resin excellent in moisture resistance and chemical resistance, a thermoplastic norbornene-based resin containing no polar group is preferable.

In the present invention, the number average molecular weight of the thermoplastic norbornene-based resin is GPC with a toluene solvent.
The polystyrene conversion value measured by the (gel permeation chromatography) method is 10,000 to 200,
000, preferably 15,000 to 100,000, more preferably 20,000 to 50,000. When the thermoplastic norbornene-based resin has an unsaturated bond in the molecular structure, it can be made into a thermoplastic saturated norbornene-based resin by hydrogenation. In the case of hydrogenation, the hydrogenation rate is 90% or more, preferably 95%, from the viewpoint of heat deterioration resistance and light deterioration resistance.
Or more, more preferably 99% or more.

When used for medical purposes, it is preferable that the transition metal derived from the polymerization catalyst does not remain in the resin and elute. Pore volume 0.5 cm ³ /
g or more, preferably 0.7 cm ³ / g or more, preferably a specific surface area of 250 cm ² / g or more, a heterogeneous catalyst in which a hydrogenation catalyst metal such as nickel is supported on an adsorbent such as alumina. Hydrogenate the polymer using
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 transition metal atom derived from the polymerization catalyst in the resin is 1 ppm or less. It is possible to

The thermoplastic norbornene-based resin used in the present invention preferably has a higher glass transition temperature, and when used in medical applications, it is preferably 105 ° C. or higher, more preferably 120 ° C. or higher, and particularly preferably 130 ° C. or higher. belongs to. Some sterilization methods do not require heating such as γ-ray irradiation, but the simplest sterilization methods include methods that require heating, particularly boiling methods and steam sterilization methods. Glass sterilization temperature is 105 ℃ in sterilization by boiling
If the above conditions are satisfied, steam sterilization requires different heat resistance depending on the temperature setting during sterilization. The most common steam sterilization is a method performed at 121 ° C using an autoclave. In this case, a glass transition temperature of 130 ° C. or higher is preferable. Generally, the more the number of monomers having a large number of rings, the higher the glass transition temperature of the resin becomes.
The hydrogenated product of a ring-opening polymer containing only monomers having 4 or more rings is
It usually has a glass transition temperature of 130 ° C. or higher. Further, in the case of the addition type polymer, the glass transition temperature is 300 ° C. or higher even for the addition type polymer of norbornene. However, if the glass transition temperature is too high, there are adverse effects such as difficulty in injection molding. Therefore, select a monomer, comonomer, polymerization method, etc. to produce a thermoplastic norbornene resin with a glass transition temperature according to the purpose. do it.

Further, the thermoplastic norbornene-based resin includes
Various additives may be added as long as the object of the present invention is not impaired. For example, in the case of thermoplastic norbornene-based resin, phenol-based or phosphorus-based antioxidants; phenol-based thermal deterioration inhibitors; benzophenone-based UV stabilizers; amine-based antistatic agents; aliphatic alcohols Lubricants such as esters, partial esters of polyhydric alcohols and partial ethers; and the like may be added, and other resins, rubbery polymers and the like may be mixed and used. In particular, a rubber polymer having a glass transition temperature of 40 ° C. or lower is 0.01 to 10% by weight, preferably 0.02 to 5% by weight, more preferably 0.05 to 1% by weight, particularly preferably 0.1 to 0%. One having 0.5% by weight dispersed in a thermoplastic norbornene-based resin as a microdomain having a particle size of 0.3 μm or less, preferably 0.2 μm or less is excellent as a medical resin. If too much is added, transparency,
The glass transition temperature, heat resistance, etc. are reduced. If the amount added is too small, it may become cloudy due to steam sterilization and the transparency may be lost. In addition, by forming the microdomains, light rays having a wavelength equal to or larger than the particle diameter are less likely to be scattered and excellent in transparency. A rubbery polymer having a glass transition temperature of 40 ° C. or lower is difficult to elute and is difficult to modify the drug. In addition, although there are cases where the glass transition temperature of the block copolymer or the like is two or more, the lowest glass transition temperature may be 40 ° C. or lower. Such rubbery polymers include copolymers of aromatic vinyl-based monomers and conjugated diene-based monomers (hydrogenates), norbornene-based rubbers that are incompatible with the used thermoplastic norbornene-based resin. Polymers are preferred.

(Substrate) The substrate used in the present invention is formed by molding a thermoplastic norbornene resin. The molding method is
There is no particular limitation. Injection molding, melt extrusion, hot pressing, solvent casting, stretching and the like, which are general molding methods for thermoplastic resins, can be used.

The shape of the molded product is not particularly limited and may be a desired shape depending on the application. In the present invention, a drug container, particularly a drug bottle, is preferable because the elution property of low-molecular impurities is improved.

(Surface Modification Treatment) In the production of the molded article of the present invention, the surface to be formed may be subjected to a surface modification treatment prior to forming the coat layer. The surface tension of the untreated thermoplastic norbornene resin is usually 25-4.
It is about 0 dyne / cm. In one of the methods for producing a molded product of the present invention, the surface tension of the molded product made of a thermoplastic norbornene-based resin is 50 dyne / cm or more, preferably 60 dyne / cm.
You may modify | reform so that it may become cm or more, More preferably, it may be 70 dyne / cm or more. The surface modification treatment is not particularly limited, and specific examples thereof include energy ray irradiation treatment and chemical treatment. These treatments are preferably not performed from the viewpoint of production efficiency, but are preferably performed from the viewpoint of adhesion to the coat layer, and therefore, depending on the purpose,
Determines whether processing is required.

Examples of the energy ray irradiation treatment include corona discharge treatment, plasma treatment, electron beam irradiation treatment and ultraviolet ray irradiation treatment. From the viewpoint of treatment efficiency and the like, corona discharge treatment and plasma treatment, particularly corona discharge treatment are preferable. The energy beam irradiation treatment conditions are not particularly limited as long as the desired surface modification is performed, and a known method may be used. For example, in the case of corona discharge treatment, the conditions known in JP-B-58-5314 and JP-A-60-146078 may be used.
Also, in the case of plasma treatment, the conditions known in Japanese Patent Publication No. 53-794 and Japanese Patent Laid-Open No. 57-177032 may be used.

The chemical treatment may be carried out by immersing in a potassium dichromate solution, an aqueous solution of an oxidizing agent such as concentrated sulfuric acid, and thoroughly washing with water. Although it is efficient to shake in a state of being immersed, there is a problem that the surface is dissolved and the transparency decreases when treated for a long period of time, and particularly in a thermoplastic norbornene-based resin having a polar group,
It is necessary to adjust the treatment time depending on the reactivity and concentration of the chemicals used.

(Coating agent) The coating agent used in the present invention is a polymer of an acrylic monomer, a copolymer of an acrylic monomer and a vinyl monomer, or a conjugate with an aromatic vinyl hydrocarbon. It is a copolymer (hydrogenated product) with a diene monomer.

(Acrylic Monomer Polymer, Acrylic Monomer and Vinyl Monomer Copolymer) Synthesis of an acrylic monomer polymer which is a resin used as a coating agent in the present invention, Alternatively, the acrylic monomer used in the synthesis of the copolymer of the acrylic monomer and the vinyl monomer has a hydrocarbon group having 4 or more carbon atoms, and from the viewpoint of productivity, it is preferable. , General formula 1

[Chemical 1] (In the formula, R ¹ represents H or CH ³ , and R ² has 4 carbon atoms.
It represents a straight-chain or branched hydrocarbon group or an alicyclic hydrocarbon group having 5 or more carbon atoms. Particularly, R ^{2 in the} formula is preferably an alicyclic hydrocarbon group having 6 or more carbon atoms.

Further, the vinyl-based monomer copolymerizable therewith is preferably represented by the general formula 2

[Chemical 2] (In the formula, R ³ represents H or CH ₃ , and R ⁴ represents a hydrocarbon having a 5- or more-membered ring structure). Preferably, R ⁴ is a compound having a benzene ring or a cyclohexyl group.

The copolymer of the acrylic monomer and the vinyl monomer used in the present invention has a repeating structural unit derived from the acrylic monomer of 5 to 100% by weight, preferably 15 to
70% by weight, 95-0% by weight, preferably 85-30, of repeating structural units derived from a copolymer of vinyl monomers.
The content is% by weight, and may be a random copolymer, a block copolymer, or an alternative copolymer. If the acrylic monomer is too small, the adhesion to the base material will decrease,
If the amount is too large, the stability of the strength of the coat layer becomes poor.

The acrylic monomer polymer and the copolymer of acrylic monomer and vinyl monomer used in the present invention have a number average molecular weight of 5,000 to 500,000, preferably 20, 000 to 400,000.
If the molecular weight is too small, the resin becomes brittle, and if it is too large, it becomes difficult to dissolve it in the solvent. The glass transition point is preferably 120 ° C. or higher. For that purpose, the acrylic monomer may be one in which R ² in the general formula 1 has a large number of carbon atoms, preferably R ² is an alicyclic hydrocarbon group having 6 or more carbon atoms. . The hardness is preferably H or more in terms of pencil hardness, and in the case of a copolymer, a vinyl monomer having R ⁴ in the general formula 2 having a small carbon number, preferably R ⁴ being a benzene ring is used. Used more, preferably more than the acrylic monomer, that is, 50 vinyl monomer.
It is preferable to use at least wt%.

(Copolymer of Aromatic Vinyl Hydrocarbon and Conjugated Diene Monomer (Hydrogenate)) Aromatic vinyl hydrocarbon and conjugated diene monomer which are one of the resins used as the coating agent in the present invention. Copolymer of polymer (hydrogenated product)
Examples of aromatic vinyl hydrocarbons used in the synthesis of
Examples thereof include styrene, α-methylstyrene, vinyltoluene, and substitution products thereof. Further, as the conjugated diene-based monomer, butadiene, isoprene, 1,3
-Pentadiene, 2,3-dimethylbutadiene and the like are exemplified.

The copolymer of the aromatic vinyl-based monomer and the conjugated diene-based monomer used in the present invention has a repeating structural unit derived from the aromatic vinyl-based monomer of 20 to 90% by weight, preferably 30. To 75% by weight, the repeating structural unit derived from the copolymer of vinyl-based monomer is 80 to 20% by weight, preferably 70 to 25% by weight, whether it is a random copolymer or a block copolymer, It may be an alternative copolymer.

The copolymer of the aromatic vinyl monomer and the conjugated diene monomer used in the present invention preferably has a number average molecular weight of 2,000 to 500,000. If the molecular weight is too small, the resin becomes brittle, and if it is too large, it is difficult to dissolve in a solvent and it is difficult to apply.

Depending on the environment, discoloration or deterioration may occur, and it is preferable to hydrogenate this copolymer. When hydrogenated, the hydrogenation rate is preferably 70% or more, particularly preferably 80% or more, and 90%, in order to prevent discoloration or deterioration.
It is more preferable to set it as above. Further, it may be modified with a carboxylic acid or a derivative thereof.

As the copolymer (hydrogenated product) of the aromatic vinyl hydrocarbon and the conjugated diene monomer used in the present invention, commercially available Tuftec H1051 (produced by Asahi Kasei, styrene / ethylene / butadiene / styrene / block copolymer) is used. Polymer hydrogenated products), Septon 2002 (Kuraray, styrene / ethylene / propylene / styrene / block copolymer), Kraton G1701X (Shell Chemical, styrene / ethylene / propylene / block copolymer) and the like can also be used.

(Coating) It is possible to dissolve the above copolymer,
Highly volatile solvents such as halogenated hydrocarbons such as dichloromethane and chloroform; diethyl ether, T
Ethers such as HF; Ketones such as methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone;
Esters such as ethyl acetate and butyl acetate;
A resin layer can be formed on the outer surface of the molded product by applying a solution having a concentration of 0% by weight, preferably 2 to 6% by weight, to the thermoplastic norbornene-based resin molded product substrate and then drying. If the concentration is too high, the tackiness increases and the work efficiency of coating decreases. The thickness of the resin layer is 0.1
The thickness is set to 10 μm, preferably 0.5 to 5 μm. Further, if the residual solvent amount is high, it may cause foaming when performing steam sterilization and may fail the elution test. Therefore, the residual solvent amount in the formed resin layer is preferably 50 ppm or less. . Furthermore, in order to prevent scratches, a surface active agent such as polysiloxane
For example, commercially available Desparon LS009 (manufactured by Fujikura Kasei Co., Ltd., etc. may be added up to about 5.0% by weight.

The coating method is not particularly limited, and a usual coating method such as brush coating, dipping, spraying, spin coating, or roll coater may be used, and the drying method may be such that the resin or coating layer is deteriorated or scratched. There is no particular limitation as long as it is a method capable of removing the solvent.

The thus-obtained molded product was not easily scratched on the surface and was found to have good adhesiveness in a cross-cut peeling test so that it does not peel off from the substrate even after steam sterilization at 121 ° C. No change was observed, and it showed good results in the eluate test and hemolytic test based on the Japanese Pharmacopoeia 12th revised general test method “Plastic test method for infusion”, and it is safe for the human body. It can be used as medical equipment such as containers, syringes, infusion tubes, etc.

[0031]

EXAMPLES The present invention will be specifically described below with reference to Reference Examples, Examples and Comparative Examples. The scratch resistance test, cross-cut peeling test, steam sterilization treatment, eluate test and hemolytic test were carried out as follows.

(Scratch resistance test) The coated portion of the molded product was rubbed with # 0000 steel wool to check for scratches.

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

(Pencil hardness test) According to JIS K-5400, it was measured with a load of 1 kg.

(Steam sterilization treatment) 1 in an autoclave
The treatment was performed at 21 ° C. for 30 minutes.

(Eluate Test and Hemolytic Test) The eluate test and hemolytic test were carried out based on the Japanese Pharmacopoeia 12th revised general test method "Plastic Test Method for Infusion Solution". The cut pieces used in any of the tests were obtained by coating the outer surface of the container B obtained in Reference Example 1 below as described in each Example and Comparative Example,
The side surface was cut into a length of 5 cm and a width of 0.5 cm. In the eluate test, 240 cut pieces were used.
Preparation of the test solution A and blank test solution A'used in the hemolytic test
According to the acute toxicity test of "Plastic test method for infusion",
To prepare the test liquid A, 180 pieces of the above-mentioned cut pieces were used. Further, the supernatant of the liquid which was subjected to the visual hemolysis test 7-8
ml was collected, and the visible light absorption spectrum of this solution was measured under the following conditions. When the light transmittance at 540 nm was 2.0% or less in the supernatant of A and the supernatant of A ′, the hemolytic property was Not evaluated. Measuring device: JASCO Corporation spectrophotometer U-best30 type cell: 10 mm quartz cell Control solution: Test solution A, physiological saline used for hemolytic test Sample solution: A'supernatant, A'supernatant

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 weightless was continuously added 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 pressurize at a pressure of 50.
A hydrogenation reaction was carried out at a temperature of 200 ° C. for 3 hours at kg / cm ³ . 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 isopropyl alcohol with stirring to coagulate 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 torr 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 this 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 the hydrogenated product of this ring-opening polymer was calculated by gel permeation chromatography as the polystyrene equivalent number-average molecular weight of 28,000, weight-average molecular weight of 58,000, hydrogenation rate of 99.8 or more, and differential scanning. Glass transition temperature 142 ° C, molecular weight 2,0 by calorimetric analysis
Less than 0.1% of resin component less than 00, titanium atomic weight 1 pp
m (detection limit) or less, nickel atomic weight 0.1 ppm (detection limit) or less, aluminum atomic weight 0.21 ppm,
The chlorine atom weight was 0.37 ppm.

To 99.8 parts by weight of the hydrogenated product of this ring-opening polymer, 0.2 parts by weight of a rubbery polymer (Tuftec H1052, glass transition temperature 0 ° C. or lower, manufactured by Asahi Kasei), an antioxidant (Irganox 1010, Ciba Geigy). (Manufactured by Mitsui Chemicals Co., Ltd.) 0.05 part by weight, and a twin-screw kneader (TEM-35B, screw diameter 37 mm, L / D = 32, screw rotation speed 250 r)
pm, resin temperature 265 ° C., feed rate 10 kg / hour) and kneaded to obtain extruded pellets.

This pellet was blown into a container B (diameter 200 mm, height 200 mm, thickness 3 mm) having a cylindrical side surface and one bottom surface at a mold temperature of 100 ° C., a resin temperature of 290 ° C., and an air pressure of 5 kg / cm ^2. Molded.

Reference Example 2 Dicyclopentanyl methacrylate (FA513M,
40 parts by weight of Hitachi Chemical Co., Ltd.) and 78 parts by weight of cyclohexane were mixed, 0.65 parts by weight of benzoyl peroxide was added, and the mixture was refluxed at 80 ° C. and stirred for 5 hours to obtain a polymerization reaction solution. The obtained polymerization reaction liquid was diluted with 300 parts by weight of cyclohexane and gradually poured into 1500 parts by weight of isopropyl alcohol while stirring to coagulate polydicyclopentanyl methacrylate. The coagulated polymer is collected by filtration, and is then dried at 5 torr and 80 at a rotary vacuum dryer.
It was dried at ℃ for 24 hours to obtain 38 parts by weight of polydicyclopentanyl methacrylate.

The molecular weight of this polydicyclopentanyl methacrylate is a number average molecular weight of 15,0 in terms of polysterene by gel permeation chromatography.
And a weight average molecular weight of 38,000.

Example 1 4 parts by weight of the polydicyclopentanyl methacrylate obtained in Reference Example 2 was dissolved in 100 parts by weight of ethyl acetate to obtain a coating solution.

The coating liquid was applied by dipping so that the coating liquid did not enter the inside of the container B of Reference Example 1. 1 at 40 ° C
The film thickness obtained by drying for about 3 hours was about 5 μm.

The pencil hardness of the coated outer surface is 2H
Met. The outer surface was subjected to a scratch resistance test, but no scratch was observed. In the cross-cut peeling test, good adhesion was shown at 100/100. Furthermore, no change was observed in the steam sterilization treatment. As a result of the eluate test, foaming was 3
Disappears within minutes, pH difference is -0.03, UV absorption is 0.007, potassium permanganate reducing substance 0.15
It was ml. In addition, the results of the hemolytic test showed that no hemolytic property was visually observed, and the difference in light transmittance at 540 nm between the blank physiological saline and the hemolytic test solution was 0.5%.

Example 2 A compounding agent (Disparlon LS009, manufactured by Fujikura Kasei) 1 was used in place of polydicyclopentanyl metaacrylate.
The same process as in Example 1 was carried out except that a mixture of 100 parts by weight of polydicyclopentanyl methacrylate (obtained in Reference Example 2) was used. The film thickness was about 5 μm, the pencil hardness was 2H, no scratch was observed in the scratch resistance test, good cross-cut peeling test showed 100/100 good adhesion, and no change was observed even by the steam sterilization treatment. As a result of the eluate test, foaming disappeared within 3 minutes and the pH difference was 0.5.
4, ultraviolet absorption was 0.06, potassium permanganate reducing substance 0.30ml. In the hemolytic test, no hemolytic property was visually observed, and the light transmittance difference was 0.9.
%Met.

Reference Example 3 Instead of 40 parts by weight of dicyclopentanyl methacrylate, dicyclopentanyl methacrylate (FA513
M) 35 parts by weight of a dicyclopentanyl methacrylate / styrene copolymer was obtained in the same manner as in Reference Example 2 except that 10 parts by weight of M) and 30 parts by weight of styrene were used.

The molecular weight of this copolymer is a polystyrene conversion value by gel permeation chromatography,
Number average molecular weight 21,000, weight average molecular weight 400000
It was 0. Based on the residual monomer ratio, the ratio of the repeating structural unit derived from dicyclopentanyl methacrylate to the repeating structural unit derived from styrene in the polymer was about 22.5: 77.5.

Example 3 The procedure of Example 1 was repeated except that the dicyclopentanyl methacrylate / styrene copolymer obtained in Reference Example 3 was used in place of the polydicyclopentanyl methacrylate. The film thickness was about 5 μm, the pencil hardness was 3H, no scratches were observed in the scratch resistance test, good cross-cut peeling test showed 100/100 good adhesion, and no change was observed even by the steam sterilization treatment. As a result of the eluate test, foaming disappeared within 3 minutes, pH difference was 0.35, ultraviolet absorption was 0.03,
It was 0.21 ml of potassium permanganate reducing substance. Further, in the hemolytic test, no hemolytic property was visually observed, and the difference in light transmittance was 0.4%.

Example 4 Instead of polydicyclopentanyl methacrylate, a styrene / ethylene / butadiene / styrene / block copolymer hydrogenated product (Tuftec H1051, manufactured by Asahi Kasei,
Number average molecular weight 48800, weight average molecular weight 65100,
The treatment was carried out in the same manner as in Example 1 except that a mixture of 100 parts by weight of a styrene content of about 40% by weight and a hydrogenation rate of the portion other than styrene of 99% or more) and 1 part by weight of a compounding agent (Disparlon LS009) was used. The film thickness is about 5 μm and the pencil hardness is 3
H, no scratch was observed in the scratch resistance test, good adhesion was observed in the cross-cut peeling test at 100/100, and no change was observed even by the steam sterilization treatment. As a result of the eluate test, foaming disappeared within 3 minutes, pH difference was 0.30, ultraviolet absorption was 0.04, and potassium permanganate reducing substance was 0.10 ml. In the hemolytic test, no hemolytic property was visually observed, and the difference in light transmittance was 0.8%.

Comparative 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 (Irgacure 184, manufactured by Ciba Geigy), and a silicone-based surfactant (FC -430,
Sumitomo 3M) 0.1 part by weight of isopropyl alcohol 8 parts
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 the container A. The film thickness was about 5 μm. After leaving at 50 ° C. for 1 minute to volatilize isopropyl alcohol, UV irradiation was performed at 10000 mJ / cm ² for 2 minutes by a high pressure mercury lamp to cure the hard coat agent.

The pencil hardness of the hard-coated outer surface of the container A was 3H, and it was subjected to a scratch resistance test, but no scratch was observed. In the cross-cut peeling test, good adhesion of 100/100 meshes was obtained, and steam sterilization treatment was performed. But no change was observed. Further, in the hemolytic test, no hemolytic property was visually observed, but the difference in light transmittance was 2.5%.

Comparative Example 2 37 parts by weight of polymethylmethacrylate were obtained in the same manner as in Reference Example 2 except that methylmethacrylate was used instead of dicyclopentanylmethacrylate.

The molecular weight of this polymethylmethacrylate was a number average molecular weight of 14,000 and a weight average molecular weight of 35,000 in terms of polystyrene by gel permeation chromatography.

The procedure of Example 1 was repeated except that polymethylmethacrylate was used instead of polydicyclopentanylmethacrylate. The film thickness was about 5 μm, the pencil hardness was 3H, no scratch was observed in the scratch resistance test, no adhesion was observed at 0/100 in the cross-cut peeling test, and the coated surface was clouded by the steam sterilization treatment. Further, in the hemolytic test, no hemolytic property was visually observed, and the difference in light transmittance was 0.4%.

[0060]

INDUSTRIAL APPLICABILITY The molded article of the present invention is less likely to damage the coated surface, does not lose transparency due to cloudiness of the coating layer even after steam sterilization, and is harmful to the human body both from the coating layer and from the resin. The components do not easily elute and are safe when used in medical containers.

Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical display location B32B 27/28 8413-4F 27/30 A 8115-4F // C08L 45/00 LKB C09D 133/00 PFZ (72 ) Inventor Sadaji Ohara 1-2-1 Yokou, Kawasaki-ku, Kawasaki-shi, Kanagawa Nihon Zeon Co., Ltd.

Claims (3)

[Claims] 1. A polymer of an acrylic monomer having a hydrocarbon group having 4 or more carbon atoms on at least a part of the surface of a base material made of a thermoplastic norbornene resin, the acrylic monomer and a vinyl monomer. A molded article having a coat layer comprising a copolymer of monomers, a copolymer of an aromatic vinyl hydrocarbon and a conjugated diene monomer, or a hydrogenated product thereof. 2. The molded article according to claim 1, which is a container having the coat layer on the outer surface thereof. 3. The molded article according to claim 1, which is a medical device.