JPH10152566A - Thermoplastic norbornene-based resin molded form - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject molded form excellent in molding precision and reduced in residual stress by using a norbornene-based resin as the material and by including a joint of Luer-Lok structure made of the resin. SOLUTION: This molded form is made of a thermoplastic norbornene-based resin, preferably a hydrogenated ring-opening polymerization product of a norbornenebased monomer or an addition polymerization product of the monomer, wherein a joint having Luer-Lok structure made of the resin is molded integrally with the main molded form body; e.g. a syringe having the tip molded integrally with the-joint, wherein the main molded form boby is the syringe and the joint having Luer-Lok structure is connecting with a needle or a cock. The subject molded form is also preferably provided with corners in the Luer- Lok structure so as to have a radius (R) of a size of preferably 0.02-2mm in order to reduce the residual stress of the molded form.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic norbornene resin molded article in which a connecting portion having a luer lock structure is integrally molded. The molded article of the present invention is particularly suitable as an injection cylinder and the like.

[0002]

2. Description of the Related Art In recent years, as a structure of a syringe, a syringe having a luer lock structure for connecting a syringe needle or a stopcock at a distal end thereof which is easy to handle without liquid leakage or the like has been desired. I have. As an injection cylinder having a luer lock structure made of a plastic material, for example, an injection molded article molded from polypropylene, propylene-ethylene copolymer, or the like has been reported (Japanese Patent Publication No. 6-34827). However, polypropylene resin molded products are
Due to severe heat shrinkage and insufficient molding accuracy of the luer lock structure, problems such as liquid leakage occur. Also, since residual stress remains in the polypropylene resin molded product,
A container that is brought into contact with a drug solution for a long time, such as a pre-filled syringe (a pre-filled syringe), has problems such as being easily cracked and unsuitable.

[0003] JP-A-5-317411 and JP-A-8-155007 disclose that a thermoplastic norbornene-based resin is excellent in heat resistance, chemical resistance and transparency, and that a chemical solution is placed in a container made of the resin. It has been reported that it is an excellent material as a medical material for syringes and the like because it has excellent properties such that various compounding agents in the resin do not elute into the drug solution even after long-term storage. However, these publications do not show anything having a luer lock structure.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a molded article having a luer-lock structure having excellent molding accuracy and low residual stress. The present inventors have conducted intensive studies in view of the above-described problems of the prior art, and as a result, using a thermoplastic norbornene-based resin as a material,
It has been found that when a molded article such as an injection cylinder having a luer-lock structure connection is manufactured, a molded article having excellent molding accuracy and small residual stress can be obtained. In addition, it has been found that the provision of R at the corner of the luer lock structure can further reduce the residual stress. Furthermore, it has been found that the residual stress can be reduced and the tightening fracture torque of the connection part of the luer lock structure can be increased. The present invention has been completed based on these findings.

[0005]

Thus, according to the present invention, there is provided a molded article made of a thermoplastic norbornene-based resin, wherein a connecting portion having a luer lock structure made of the resin is formed integrally with the molded article body. The present invention provides a thermoplastic norbornene-based resin molded product characterized in that:

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Thermoplastic norbornene-based resin The thermoplastic norbornene-based resin used in the present invention is a known resin disclosed in JP-A-3-14882 and JP-A-3-122137. . Specifically, hydrogenated products of ring-opening polymers of norbornene monomers, addition polymers of norbornene monomers, addition copolymers of norbornene monomers and olefins, and modified products of these polymers, etc. No. Among these, hydrogenated ring-opening polymer of norbornene-based monomer, addition-type polymer of norbornene-based monomer, addition-type copolymer of norbornene-based monomer and olefin, and the like are preferable, and hydrogenation of ring-opened polymer of norbornene-based monomer is preferable. Are particularly preferred.

The norbornene monomers are disclosed in the above publications, JP-A-2-227424 and JP-A-2-27684.
It is a known monomer disclosed in, for example, JP-A No. 2 (Kokai) Publication.
Specifically, for example, polycyclic hydrocarbons having a norbornene structure; substituted derivatives thereof such as alkyl, alkenyl, alkylidene, and aromatic; halogens, hydroxyl groups, ester groups,
Polar group-substituted derivatives such as alkoxy group, cyano group, amide group, imide group and silyl group; substituted derivatives of these polar groups such as alkyl, alkenyl, alkylidene and aromatic. Among them, polycyclic hydrocarbons having a norbornene structure and substituted derivatives thereof such as alkyl, alkenyl, alkylidene, and aromatic are particularly excellent in chemical resistance and moisture resistance and are suitable. Specifically, the following norbornene-based monomers can be exemplified.

Specific examples of norbornene monomers include, for example, 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 and the like; dicyclopentadiene, substituted derivatives thereof and the like, for example, 2,3-dihydrodiene Cyclopentadiene and the like; dimethanooctahydronaphthalene, substituted derivatives thereof as described above, and the like, for example, 6-methyl-1,4: 5,8-dimethano-1,4,4a, 5
6,7,8,8a-octahydronaphthalene, 6-ethyl-1,4: 5,8, dimethano-1,4,4a, 5
6,7,8,8a-octahydronaphthalene, 6-ethylidene-1,4: 5,8, dimethano-1,4,4a,
5,6,7,8,8a-octahydronaphthalene, 6-
Chloro-1,4: 5,8, dimethano-1,4,4a,
5,6,7,8,8a-octahydronaphthalene, 6-
Cyano-1,4: 5,8-dimetano-1,4,4a,
5,6,7,8,8a-octahydronaphthalene, 6-
Pyridyl-1,4: 5,8-dimetano-1,4,4a,
5,6,7,8,8a-octahydronaphthalene, 6-
Methoxycarbonyl-1,4: 5,8-dimetano-1,
4,4a, 5,6,7,8,8a-octahydronaphthalene and the like; adducts of cyclopentadiene and tetrahydroindene and the like, substituted derivatives thereof as described above, and the like,
1,4-dimethano-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; multimers of cyclopentadiene, substituted derivatives thereof and the like, such as 4,9: 5,8-dimethano-3a, 4,4a,
5,8,8a, 9,9a-octahydro-1H-benzoindene, 4,11: 5,10: 6,9-trimethano-
3a, 4,4a, 5,5a, 6,9,9a, 10,10
a, 11,11a-dodecahydro-1H-cyclopentaanthracene; and the like. These norbornene-based monomers can be used alone or in combination of two or more. The proportion of the norbornene-based monomer in the thermoplastic norbornene-based resin is appropriately selected depending on the purpose of use, but is usually 30% by weight or more, preferably 50% by weight or more, and more preferably 7% by weight or more.
When the content is 0% by weight or more, the heat resistance is high, which is preferable.

Examples of copolymerizable vinyl compounds include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, and 3-ethyl- 1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,
4-dimethyl-1-hexene, 4,4-dimethyl-1-
Pentene, 4-ethyl-1-hexene, 3-ethyl-1
-Hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like, ethylene or α-olefin having 2 to 20 carbon atoms; cyclobutene, cyclopentene, cyclohexene, 3,4-dimethylcyclopentene, 3-methylcyclohexene, 2- (2-methylbutyl) -1-cyclohexene, cyclooctene, 3a,
5,6,7a-tetrahydro-4,7-methano-1H-
Cycloolefins such as indene; 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-
Non-conjugated dienes such as 1,4-hexadiene and 1,7-octadiene; These vinyl compounds can be used alone or in combination of two or more.

[0010] The polymerization method and hydrogenation method of the norbornene monomer or the vinyl compound copolymerizable with the norbornene monomer are not particularly limited, and can be carried out according to known methods. Further, the obtained polymer or polymer hydrogenated product is subjected to a known method disclosed 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, It may be modified using an organosilicon compound having an olefinically unsaturated bond and a hydrolyzable group, an unsaturated epoxy monomer, or the like.

The molecular weight of the thermoplastic norbornene resin is as follows:
Although it is appropriately selected according to the purpose of use, the intrinsic viscosity [η] measured in decalin at 80 ° C. is usually 0.01 to 20 dl /
g, preferably 0.1 to 10 dl / g, more preferably 0.2 to 5 dl / g, most preferably 0.3 to 1 dl / g.
g. If the intrinsic viscosity [η] of the thermoplastic norbornene-based resin is too small, the mechanical strength is not sufficient, and if it is too large, the molding processability is not sufficient, and neither is preferable. Although the molecular weight distribution of the thermoplastic norbornene resin is not particularly limited, the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) in terms of polystyrene by gel permeation chromatography (GPC) using toluene as a solvent (Mn) Mw / Mn) is usually 4.0 or less,
When the value is preferably 3.0 or less, more preferably 2.5 or less, the mechanical strength is highly enhanced, which is suitable.

The glass transition temperature (Tg) of the thermoplastic norbornene resin may be appropriately selected according to the purpose of use, but is usually 50 to 300 ° C., preferably 80 to 280.
C., more preferably from 100 to 250 C., most preferably from 120 to 200 C., because heat resistance and moldability are highly balanced. These thermoplastic norbornene resins can be used alone or in combination of two or more.

Optional Components In the present invention, a rubber-like polymer or other thermoplastic resin may be added to the thermoplastic norbornene-based resin, if necessary. The rubbery polymer has a glass transition temperature (T
g) is a polymer having a temperature of 0 ° C. or less, and includes a usual rubbery polymer and a thermoplastic elastomer. The Mooney viscosity (ML _{1 + 4} , 100 ° C.) of the rubbery polymer is appropriately selected depending on the purpose of use, but is usually in the range of ₅ to 200.

Examples of the rubbery polymer include ethylene-α-olefin-based rubbery polymers; ethylene-α-olefin-polyene copolymer rubbers; and ethylene and unsaturated monomers such as ethylene-methyl methacrylate and ethylene-butyl acrylate. Copolymer with carboxylic acid ester; Copolymer of ethylene and fatty acid vinyl such as ethylene-vinyl acetate; Acrylic acid such as ethyl acrylate, butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate Alkyl ester polymer; polybutadiene, polyisoprene, styrene-butadiene or styrene-isoprene random copolymer, acrylonitrile-butadiene copolymer, butadiene-isoprene copolymer, butadiene- (meth) acrylic acid alkyl ester copolymer Polymer, butadiene- (meth)
Diene rubbers such as alkyl acrylate-acrylonitrile copolymer, butadiene-alkyl (meth) acrylate-acrylonitrile-styrene copolymer; and butylene-isoprene copolymer.

As the thermoplastic elastomer, for example,
Aromatic vinyl-conjugated diene block copolymers such as styrene-butadiene block copolymer, hydrogenated styrene-butadiene block copolymer, styrene-isoprene block copolymer, hydrogenated styrene-isoprene block copolymer, low Crystalline polybutadiene resin, ethylene-
Propylene elastomer, styrene grafted ethylene
Propylene elastomer, thermoplastic polyester elastomer, ethylene ionomer resin and the like can be mentioned. Among these thermoplastic elastomers, a hydrogenated styrene-butadiene block copolymer, a hydrogenated styrene-isoprene block copolymer, and the like are preferable. Specifically, JP-A-2-133406 and JP-A-2-133406
No. 3,051,814, JP-A-3-72512, JP-A-3-74409, and the like.

As other thermoplastic resins, for example,
Low density polyethylene, high density polyethylene, linear low density polyethylene, ultra low density polyethylene, polypropylene, ethylene-ethyl acrylate copolymer, ethylene-vinyl acetate copolymer, polystyrene, polyphenylene sulfide, polyphenylene ether, polyamide, polyester, Polycarbonate and the like. These rubbery polymers and other thermoplastic resins can be used alone or in combination of two or more, and the compounding amount is appropriately selected within a range that does not impair the object of the present invention.

In the present invention, if necessary, a compounding agent usually used in the resin industry can be added. As a compounding agent, for example, a stabilizer, an ultraviolet absorber,
Pigments, dyes, lubricants, antiblocking agents, nucleating agents, hydrochloric acid absorbents, lubricants such as natural oils, synthetic oils, waxes, flame retardants, antistatic agents, fillers; zinc stearate, calcium stearate, 1,2- Fatty acid metal salts such as calcium hydroxystearate; polyhydric alcohol fatty acid esters such as glycerin monostearate, glycerin distearate, pentaerythritol distearate and pentaerythritol tristearate; and the like. Examples of the stabilizer include phenol-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants. Among these, phenol-based antioxidants are preferable, and alkyl-substituted phenol-based antioxidants are particularly preferable. preferable.

As the phenolic antioxidant, conventionally known ones can be used. For example, 2-t-butyl-6-
(3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2,4-di-
t-Amyl-6- (1- (3,5-di-t-amyl-2)
-Hydroxyphenyl) ethyl) phenyl acrylate and the like.
Acrylate compounds described in JP-B-168643; 2,6-di-t-butyl-4-methylphenol;
2,6-di-t-butyl-4-ethylphenol, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,2'-methylene-
Bis (4-methyl-6-t-butylphenol), 4,
4'-butylidene-bis (6-t-butyl-m-cresol), 4,4'-thiobis (3-methyl-6-t-butylphenol), bis (3-cyclohexyl-2-hydroxy-5-methylphenyl) ) Methane, 3,9-bis [2- [3- (3-t-butyl-4-hydroxy-5-
Methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, 1,1,3-tris (2-methyl-4-hydroxy-5 -T-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl)
Benzene, tetrakis [methylene-3- (3 ', 5'-
Di-tert-butyl-4'-hydroxyphenyl) propionate] methane [that is, pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]], triethylene glycol bis [3- (3-t-butyl-4-hydroxy-5
-Methylphenyl) propionate], alkyl-substituted phenolic compounds such as tocopherol; 6- (4-hydroxy-3,5-di-t-butylanilino) -2,4
-Bis-octylthio-1,3,5-triazine, 6-
(4-hydroxy-3,5-dimethylanilino) -2,
4-bis-octylthio-1,3,5-triazine, 6
-(4-hydroxy-3-methyl-5-tert-butylanilino) -2,4-bis-octylthio-1,3,5-triazine, 2-octylthio-4,6-bis- (3,5
-Di-t-butyl-4-oxyanilino) -1,3,5
A phenolic compound containing a triazine group such as triazine;

The phosphorus-based antioxidant is not particularly limited as long as it is commonly used in the general resin industry. Examples thereof include triphenyl phosphite, diphenyl isodecyl phosphite, phenyl diisodecyl phosphite, and tris (Nonylphenyl) phosphite, tris (dinonylphenyl) phosphite, tris (2,4-
Di-t-butylphenyl) phosphite, tris (2-
t-butyl-4-methylphenyl) phosphite, tris (cyclohexylphenyl) phosphite, 2,2-
Methylenebis (4,6-di-t-butylphenyl) octyl phosphite, 9,10-dihydro-9-oxa-
10-phosphaphenanthrene-10-oxide, 1
0- (3,5-di-tert-butyl-4-hydroxybenzyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-decyloxy-9,10-dihydro-9 Monophosphite compounds such as -oxa-10-phosphaphenanthrene;
4'-butylidene-bis (3-methyl-6-t-butylphenyl-di-tridecyl phosphite), 4,4'-
Isopropylidene-bis (phenyl-di-alkyl (C
₁₂ -C ₁₅₎ phosphite), 4,4'-isopropylidene - bis [diphenyl monoalkyl (C ₁₂ -C ₁₅₎ phosphite], 1,1,3-tris (2-methyl-4-di - tri Decyl phosphite-5-t-butylphenyl)
Butane, tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylenediphosphite, cyclic neopentanetetraylbis (octadecylphosphite), cyclic neopentanetetraylbis (isodecylphosphite) Phyto), cyclic neopentanetetraylbis (nonylphenylphosphite), cyclic neopentanetetraylbis (2,4-di-
diphosphites such as t-butylphenylphosphite), cyclic neopentanetetraylbis (2,4-dimethylphenylphosphite), and cyclic neopentanetetraylbis (2,6-di-t-butylphenylphosphite) And the like. Among these, monophosphite compounds are preferred, and tris (nonylphenyl) phosphite, tris (dinonylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite and the like are particularly preferred.

Examples of the sulfur-based antioxidants include dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, Laurylstearyl-3,3'-thiodipropionate, pentaerythritol-tetrakis- (β-lauryl-thio-propionate), 3,9-bis (2-dodecylthioethyl)-
2,4,8,10-tetraoxaspiro [5,5] undecane and the like. These antioxidants can be used alone or in combination of two or more. The compounding amount of the antioxidant is usually 0.001 to 5 with respect to 100 parts by weight of the thermoplastic norbornene resin.
Parts by weight, preferably in the range of 0.01 to 1 part by weight.

As the ultraviolet absorber, for example, 2, 2,
6,6-tetramethyl-4-piperidyl benzoate,
Bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2- (3,5-di-t-butyl) -4-hydroxybenzyl) -2-n-butylmalonate, 4- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] -1- [2-
[3- (3,5-Di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -2,2,6,6
A hindered amine-based ultraviolet absorber such as tetramethylpiperidine; 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (3-t-butyl-2-
(Hydroxy-5-methylphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole,
Benzotriazole ultraviolet absorbers such as 2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole; 2,4-di-t-butylphenyl-3,5
Bezoate ultraviolet absorbers such as -di-t-butyl-4-hydroxybenzoate and hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate; Each of these UV absorbers, alone,
Alternatively, two or more kinds can be used in combination.
The compounding amount of the ultraviolet absorber is usually in the range of 0.001 to 5 parts by weight, preferably 0.01 to 1 part by weight, based on 100 parts by weight of the thermoplastic norbornene resin.

Examples of the crystal nucleating agent include salts of benzoic acid, dibenzylidene sorbitols, salts of phosphoric esters, and polymers having a high melting point such as polyvinylcyclohexane, poly-3-methylbutene, crystalline polystyrene, and trimethylvinylsilane. Is preferred, and
Inorganic compounds such as talc, kaolin and mica can also be preferably used. These nucleating agents can be used alone or in combination of two or more. The use amount of the crystal nucleating agent is usually in the range of 0.0001 to 1 part by weight based on 100 parts by weight of the norbornene resin.

Examples of the hydrochloric acid absorbent include sodium stearate, magnesium stearate, calcium stearate, zinc stearate, lithium stearate, sodium 12-hydroxystearate and 12-hydroxystearate.
Fatty acid metal salts such as calcium hydroxystearate, magnesium 12-hydroxystearate and zinc 12-hydroxystearate; epoxy compounds such as epoxidized octyl stearate and epoxidized soybean oil; magnesium hydroxide, calcium hydroxide, hydrotalnite and the like And the like. These hydrochloric acid absorbents are used alone or in combination of two or more. The compounding amount of the hydrochloric acid absorbent is usually 0.001 to 100 parts by weight of the thermoplastic norbornene resin.
To 5 parts by weight, preferably 0.01 to 1 part by weight.

Examples of the antistatic agent include sodium alkyl sulfonate, phosphonium alkyl sulfonate, and fatty acid ester hydroxyamine compounds such as glycerin ester of stearic acid. These antistatic agents can be used alone or in combination of two or more. The compounding amount of the antistatic agent is 100% of the thermoplastic norbornene resin.
It is usually in the range of 0 to 5 parts by weight with respect to parts by weight.

Examples of the filler include silica, diatomaceous earth, alumina, titanium oxide, magnesium oxide, pumice powder, pumice balloon, basic magnesium carbonate, dolomite, calcium sulfate, potassium titanate, barium sulfate, calcium sulfite, Talc, clay, mica, asbestos, glass fiber, glass flake, glass beads,
Calcium silicate, montmorillonite, bentonite,
Examples thereof include graphite, aluminum powder, molybdenum sulfide, boron fiber, silicon carbide fiber, polyethylene fiber, polypropylene fiber, polyester fiber, and polyamide fiber.

Molded article The thermoplastic norbornene-based resin molded article of the present invention comprises the above-mentioned thermoplastic norbornene-based resin and, if necessary, various components.
Various molded articles can be formed by a usual molding method such as injection molding, press molding, extrusion molding, and rotational molding. The thermoplastic norbornene-based resin molded article of the present invention is characterized in that a connecting portion having a Luer lock structure is formed integrally with a molded article body. The luer lock structure is used to connect an injection needle, a stopcock, and the like. For example, FIG. 1 shows an example of a connection portion 1 having a luer lock structure. This luer lock structure has a female screw portion 2 formed therein. The external taper of the liquid feed pipe 3 of the connection part having the luer lock structure is 6/100, and the outermost diameter of the liquid feed pipe is 4.00 ± 0.10 mm and the inner diameter of the outer circumference is 7.0.
80 ± 0.10 mm. FIG. 2 shows an example of an injection cylinder in which a connecting portion having the luer lock structure is integrally formed at a distal end portion.

In the thermoplastic norbornene resin molded article of the present invention, in order to reduce the residual stress of the molded article,
It is preferable to provide a radius (R) at a corner of the luer lock structure (such as the portions indicated by 6 and 4 in FIG. 1). The size of R is appropriately selected according to the purpose of use, but is usually in the range of 0.01 to 5 mm, preferably 0.02 to 2 mm, and more preferably 0.05 to 1 mm, so that the residual stress is sufficient. This is preferable because cracks due to contact with the chemical solution for a long period of time and cracks due to external impact can be reduced.

Tightening of connection part having luer lock structure
The breaking torque is 7kgf · cm More preferably, more
Preferably 9 kgf · cm Above, particularly preferably 11k
gf · cm That is all. This tightening breaking torque is small
Too much damage will occur when you turn the mating connection by hand.
And the commercial value of the molded article may be lost. Departure
Connections with bright luer lock construction are integrally molded
The molded thermoplastic norbornene resin is transparent,
Excellent mechanical strength in addition to properties such as heat resistance and chemical resistance
Therefore, medical containers such as syringes, especially prefilled
It is suitable as a syringe or container for a syringe.

The pre-filled syringe is manufactured by (1) molding a thermoplastic norborn-based resin by injection molding, injection blow molding, direct blow molding, inflation molding or the like to produce a syringe or a container.
(2) Sterilize the manufactured syringe or container by wet heat sterilization or ethylene oxide gas sterilization, and then plug the tip of the syringe or container. (3) Aseptically remove the sterilized drug solution with a filling machine. Pressure-controlled wet sterilization in which the pressure of the container to be sterilized after filling with the appropriate operation, environment, or after filling the chemical solution (in an autoclave) is made substantially equal to the pressure of the container.
Or perform steam sterilization using a normal autoclave,
It can be manufactured by such a method.

[0030]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Reference Examples, Examples, and Comparative Examples.
It is not limited only to these examples. Also,
In the following examples, unless otherwise specified, parts and% are
Based on weight.

Reference Example 1 6-methyl-1,4: 5,8
20 parts of dimethano-1,4,4a, 5,6,7,8,8a-octahydronaphthalene (hereinafter referred to as MTD) are dissolved in 200 parts of cyclohexane, and 2 parts of 1-hexene and 2 parts of triethyl are used as a molecular weight regulator. 15% of aluminum
15 parts of a cyclohexane solution and 5 parts of triethylamine were added. While maintaining this solution at 20 ° C., MTD8
0 parts and 9 parts of a 20% solution of titanium tetrachloride in cyclohexane were continuously added to the reaction system over 60 minutes to carry out ring-opening polymerization. After reacting for 1 hour, the reaction was stopped by adding 5 parts of ethyl alcohol and 2 parts of water. After heating the reaction solution to 40 ° C., the catalyst was hydrolyzed, and then 3 parts of calcium sulfate and 60 parts of cyclohexane were added to remove excess water. The precipitate containing the deposited metal was removed by filtration to obtain 371 parts of a polymer solution containing a transparent MTD ring-opening polymer.

The above reaction was repeated and the resulting M
To 750 parts of the TD ring-opening polymer-containing polymer solution, 15 parts of a Ni-diatomaceous earth catalyst (N113; manufactured by JGC Chemicals, Inc.) was added, and the mixture was placed in a pressure-resistant reactor.
A hydrogenation reaction was performed at 200 ° C./cm ² and a temperature of 200 ° C. for 3 hours. After completion of the reaction, 700 parts of cyclohexane was added for dilution, and the catalyst was removed by filtration to obtain 1350 parts of a polymer solution containing a hydrogenated MTD ring-opening polymer. This solution 550
The mixture was poured into 1500 parts of isopropanol with stirring to coagulate the hydrogenated MTD ring-opened polymer. The coagulated MTD ring-opened polymer hydrogenated product was recovered by filtration, washed twice with 300 parts of isopropanol, and then dried in a rotary vacuum dryer at 5 torr and 120 ° C. for 48 hours to obtain M
52 parts of a hydrogenated TD ring-opened polymer were obtained. The hydrogenated MTD ring-opening polymer (hereinafter referred to as polymer A)
The intrinsic viscosity [η] measured in a decalin solution at 85 ° C. is 0.4 dl / g, and the ratio of Mw / Mn measured in terms of polystyrene by GPC using toluene as a solvent is 2.1;
Hydrogenation rate 99.8% or more, T by differential scanning calorimetry
g was 140 ° C.

Example 1 Polymer A obtained in Reference Example 1
With a FE210 type injection molding machine manufactured by Nissei Plastic Industry Co., Ltd.
Injection molding is performed under the conditions of a resin temperature of 300 ° C. and a mold temperature of 120 ° C. at the time of molding, and has a luer lock structure connection portion (hereinafter, sometimes referred to as a luer lock portion) shown in FIG. An injection cylinder a (FIG. 2) having a body part having a thickness of 2 mm and a length of 150 mm, a flange having a diameter of 50 mm and a thickness of 3 mm was formed. For the molded syringe a, the following B
When the residual stress was measured according to the Ergen method, it was 100 k
g / cm ² or less. Measurement method of residual stress (kg / cm ² ) (1) Measurement of rupture stress in each test solution Measurement of flexural modulus E (kg / cm ² ) 127 mm × 6.3 mmφ of polymer A by injection molding
And the flexural modulus E was measured.
= 22000 kgf / cm ² . Measurement of strain e of test piece Polymer A was pressed by electro-heating (mold temperature 200 ° C, gauge pressure 2
1kg × 10mm by press molding at 00kg / cm ² )
50 test pieces of × 130 mm were prepared. As shown in FIG. 3, the obtained test piece 31 was (y / 4) ² + (x / 1
0) An elliptical jig having an elliptical shape of ² = 1 (length 100 m)
m, height 40 mm, width 20 mm) 32, immersed in a test solution at 25 ° C. for 2 hours, and measured the breaking distance Xcm in the x-axis coordinate direction shown in FIG. When the test liquid was methyl ethyl ketone, methyl acrylate, and ethyl alcohol, the breaking distances were 7.1 cm and 7.6 c, respectively.
m, and 8.7 cm. The strain e of the test piece at a distance (break distance) Xcm in the x-axis coordinate direction of the ellipse in the above relational expression can be obtained from the following equation (1). In this case, t is the thickness of the test piece.

[0034]

(Equation 1) Measurement of rupture stress Y (kgf / cm ² ) in each test solution The rupture stress Y in each test solution was determined by the flexural modulus E obtained above.
From the (kgf / cm ² ) value and the strain e value, it was calculated by the following equation (2).

[0035] Y = E · e (kgf / cm 2) (2) [ Results] Ethyl alcohol = 210 kgf / cm ² · methyl acrylate = 120 kgf / cm ² · Methyl ethyl ketone = 100 kgf / cm ² Accordingly, the molded body above at break The residual stress is measured based on the result of the fracture when immersed in the test liquid for which the stress has been measured. (I) Residual stress of a molded body broken by the ethyl alcohol test liquid is 210 kgf / cm ² or more. (Ii) Residual stress of a molded body not broken by the ethyl alcohol test liquid is less than 210 kgf / cm ² (iii) methyl The residual stress of the molded body that was broken by the acrylate test liquid was 120 kgf / cm ² or more. (Iv) The residual stress of the molded body that was not broken by the methyl acrylate test liquid was less than 120 kgf / cm ^2. the residual stress of the molded article, 100 kgf / cm ² or more (vi) the residual stress of the molded article was not fractured in methyl ethyl ketone test solution, 100 kgf / cm less than ² (2) measurement syringe a residual stress of the syringe barrel a The methyl ethyl ketone, methyl acrylate,
And immersed in ethyl alcohol, left at 25 ° C. for 2 hours, and taken out. As a result, no change in appearance (crack) or weight change was observed in any of the test solutions. Therefore, the residual stress of the syringe barrel a is 10
It can be evaluated that it is less than 0 kgf / cm ² .

Example 2 Injection molding was carried out in the same manner as in Example 1 to obtain an injection cylinder b having a connection part having a luer lock structure without R. The residual stress of the syringe b was measured in the same manner as in Example 1. Although the appearance and weight of the injection cylinder b did not matter even when immersed in ethyl alcohol, cracks occurred in the syringe immersed in methyl acrylate and methyl ethyl ketone. Therefore, the residual stress of the syringe barrel b is
It can be evaluated that it is in the range of 120 kgf / cm ² or more and less than 210 kgf / cm ² .

[Comparative Example 1] The polymer A obtained in Reference Example 1 was the same as the mold used in Example 1, but had the same body structure, and had a simple taper nozzle without a luer-locked tip. Using a structure having the same structure as that of Example 1, injection cylinder c was obtained. The residual stress of the syringe c was measured in the same manner as in Example 1. Although the appearance and weight of the injection cylinder c were not problematic when immersed in ethyl alcohol and methyl acrylate, cracks occurred in the injection cylinder c immersed in methyl ethyl ketone. Therefore, the residual stress of the injection cylinder c is 100 kgf / cm ² or more and 120 kgf / cm ²
It can be evaluated that it is within the range of less than.

[Example 3] With respect to the injection cylinder a obtained in Example 1, an eluate test was carried out according to the Japanese Pharmacopoeia "Testing Method for Plastic Containers for Infusion (Containers Made of Polyethylene and Polypropylene)". The foaming of the test solution disappears within 1 minute, the pH difference from the blank test solution is -0.05, the ultraviolet absorption is 0.006, and the potassium permanganate reducing substance is 0.0
2 ml and the evaporation residue was 0.0 g, which proved to be a suitable material for a medical container material.

Example 4 Syringe a10 obtained in Example 1
Three days after forming the book, a rubber stopper was attached to the luer lock part at the tip of the syringe, 100 ml of distilled water was sealed inside the syringe with a rubber stopper at the inner diameter, and the tip and the stopper of the inner cylinder were held. After sterilization in an autoclave (121 ° C. × 20 minutes steam), the mixture was cooled to room temperature. Next, when a three-way cock (manufactured by Nippon Medical Supply Co., Ltd.) was strongly hand-tightened to the luer lock portion of the syringe immediately after sterilization instead of the rubber stopper, no change in appearance was observed in all of the ten syringes.
Further, when the tightening breaking torque of the luer lock portion was measured by the following measuring method, the average was 11.2 kgf · c.
m. 20ml of distilled water inside the syringe with a rubber stopper
When extruded at a speed of sec, no change was observed in the luer lock portion. Measurement method of tightening fracture torque 1) Lightly turn a three-way cock (manufactured by Nippon Medical Supply) into the luer lock part of the molded product by hand. 2) Fix the molded body with a vise. 3) A torque meter in which a metal jig capable of rotating the three-way cock is fitted is connected to the three-way cock, and it is screwed until the luer lock or the three-way cock is broken, and the torque at the time of breaking is measured.

Example 5 Injection cylinder a10 obtained in Example 1
After leaving the book at 40 ° C. for half a year, the same three-way cock used in Example 3 was strongly tightened by hand, and the distilled water inside the syringe was extruded with a rubber stopper at a rate of 20 ml / sec. No change was observed in all the luer locks in the book, and there was no liquid leakage. When the tightening breaking torque of the luer lock was measured, the average was 8.9 kgf · c.
m.

[Comparative Example 2] Syringe b10 obtained in Example 2
After leaving the book at 40 ° C. for half a year, the same three-way cock used in Example 4 was strongly tightened by hand. As a result, seven out of ten lure locks were broken. When the tightening breaking torque of the luer lock was measured, the average was 6.5 kgf.
Cm.

[Comparative Example 3] Syringe c10 obtained in Comparative Example 1
After the book was left at 40 ° C. for half a year, the same three-way cock used in Example 4 was strongly tightened by hand, and no change in appearance was observed in all of the 10 cocks. When distilled water was extruded at a rate of 20 ml / sec, 9 out of 10 plugs came off the stopcock and the internal distilled water leaked out.

[0043]

According to the present invention, there is provided a molded article having a luer-lock structure having excellent molding accuracy and a small residual stress.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view illustrating an example of a connecting portion having a luer lock structure.

FIG. 2 is a cross-sectional view showing an example of an injection cylinder in which a connecting portion having a Luer lock structure at a tip is integrally formed.

FIG. 3 is a schematic diagram showing an elliptical jig for measuring the strain of a test piece and its use.

[Brief description of reference numerals]

 1: Connection part having a luer lock structure 2: Female screw 3: Liquid feed pipe 4: R part 5: Outer cylinder 6: R part 7: Molded body 31: Test piece 32: Oval jig 33: Break of test piece Status

Claims (4)

[Claims] 1. A molded article made of a thermoplastic norbornene-based resin, wherein a connecting portion having a Luer lock structure made of the resin is molded integrally with a molded article body. Resin molding. 2. The thermoplastic norbornene-based resin molded product according to claim 1, wherein the connecting portion having a luer lock structure has a corner. 3. The thermoplastic norbornene-based resin molded product according to claim 1, wherein the molded product main body is an injection cylinder, and the connection portion having a luer lock structure is a connection portion with a syringe needle or a stopcock. 4. Fastening of a connection part having a luer lock structure
7kgf ・ cm Claim 1
4. The thermoplastic norbornene-based resin according to any one of items 3
Resin molding.