JP2003138074A - Medical stretch blow molded container - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a medical stretch blow molded container made of a propylene-α-olefin copolymer which is superior in transparency, stretch blow molding properties, and hygienic qualities to the conventional propylene-α-olefin copolymer. SOLUTION: The medical stretch blow molded container is a container which is molded by subjecting a propylene-α-olefin copolymer resin composition comprising 100 pts.wt. propylene-α-olefin copolymer to be obtained with the use of a metallocene catalyst and 0.005-0.5 pt.wt. phenolic antioxidant and having a Q value of 1.5-3.5, a melting point of 110-150 deg.C, and preferably a content of 6-10C volatile hydrocarbons of <=300 ppm to stretch blow molding at a draw ratio in both longitudinal and crosswise directions of the container of >=1.5 times.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a stretch blow container for medical use, and more particularly to a stretch blow container for medical use made of a propylene / α-olefin copolymer, which is excellent in transparency, stretch blow moldability, hygiene and impact resistance. Regarding the container.

[0002]

2. Description of the Related Art Vinyl chloride resins and polyolefin resins such as polyethylene and polypropylene have been widely used as materials for medical containers such as infusion containers, medication containers, and eyewash containers. A lot of hygienic polyolefin resins have been used. These medical containers are required to be transparent so that the amount of content liquid and the presence or absence of foreign matter can be confirmed from the outside, and heat resistance to withstand heat sterilization such as steam heating for the purpose of sterilizing the container and content liquid. . Therefore, among the polyolefin resins, the propylene / α-olefin copolymer has been used mainly because it has excellent transparency and heat resistance. In particular, in an infusion container or the like that requires heat sterilization, a container by a so-called stretch blow molding method is used in which blow molding is performed while stretching in order to improve transparency and heat resistance. As a molding resin, propylene / α is used. -Olefin copolymers have been used.

Further, the medical container needs hygiene,
Specifically, it is necessary to suppress as much as possible the amount of insoluble fine particles that elutes from the container into the drug solution and the amount of low molecular weight substances that volatilize in the gas phase of the container. However, the conventional techniques are insufficient, and further improvement has been strongly demanded particularly for containers that require heat sterilization. On the other hand, in the case of an infusion container, it is necessary to integrate a rubber stopper with a resin cap to heat seal the bottle body so that an injection needle can be inserted into the mouth. However, there is also a problem in that the decomposition gas of the resin is mixed into the inside of the bottle and contaminated by heating for a long time or conversely, by heat sealing for a long time.

[0004]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems and is more excellent in transparency, stretch blow moldability and hygiene than conventional propylene / α-olefin copolymers. An object of the present invention is to provide a medical stretch blow container made of a copolymer.

[0005]

Means for Solving the Problems As a result of studying the improvement of the above problems, the present inventors have drawn a specific propylene / α-olefin copolymer resin composition so that it has a specific draw ratio. The inventors have found that the blow molding for medical use is excellent in transparency, stretch blow moldability, hygiene, and impact resistance, and have completed the present invention.

That is, according to the first aspect of the present invention,
MFR of 0.5 to 50 g, obtained by blending 0.005 to 0.5 parts by weight of a phenolic antioxidant with 100 parts by weight of a propylene / α-olefin copolymer obtained by using a metallocene catalyst. / 10 minutes, Q value is 1.5 ~
Propylene / α having a melting point of 3.5 to 110 ° C to 150 ° C
-A container formed by stretch-blow molding of an olefin copolymer resin composition, wherein the stretch ratio in the machine direction and the transverse direction of the container is 1.5 times or more. Provided.

According to the second aspect of the present invention, the first aspect
M of the propylene / α-olefin copolymerization described in the invention of
Provided is a stretch blow container for medical use, which has an FR of 0.5 to 20 g / 10 min and the stretch blow molding is hot stretch blow molding.

According to the third aspect of the present invention, the first aspect
The invention provides a stretch blow container for medical use, wherein the propylene / α-olefin copolymer has an MFR of 10 to 50 g / 10 minutes and the stretch blow molding is cold stretch blow molding. .

According to a fourth aspect of the present invention, the content of the volatile hydrocarbon having 6 to 10 carbon atoms in the medical stretch blow container is 300 ppm or less. A stretched blow container for medical treatment according to any one of the inventions is provided.

According to a fifth aspect of the present invention, a propylene / α-olefin copolymer resin composition obtained by using a metallocene catalyst is further prepared from hydrotalcite or a metal hydroxide salt as a neutralizing agent. A medical stretch blow container according to any one of the first to fourth inventions, characterized in that at least one selected from the above is blended in an amount of 0.005 to 0.5 part by weight.

According to a sixth aspect of the present invention, the first aspect
A stretch blow container for infusion is provided, which is characterized in that the stretch blow container for medical use according to any one of the inventions 1 to 5 is heat-sterilized at a temperature of 110 ° C. or higher.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The contents of the present invention will be described below. 1. Method for producing propylene / α-olefin copolymer The propylene / α-olefin random copolymer used in the stretching blow container of the present invention is a copolymer polymerized using a metallocene catalyst. The metallocene catalyst is titanium,
It is a catalyst using a complex of a transition metal of Groups 4 to 6 such as zirconium and hafnium with a cyclopentadienyl group or a cyclopentadienyl derivative group.

In the metallocene catalyst, as the cyclopentadienyl derivative group, an alkyl substituent such as pentamethylcyclopentadienyl, or two or more substituents are bonded to form a saturated or unsaturated cyclic substituent. A group can be used, and typical examples thereof include an indenyl group, a fluorenyl group, an azulenyl group, and partial hydrogenated products thereof. Further, those in which a plurality of cyclopentadienyl groups are bound by an alkylene group, a silylene group, a germylene group or the like are also preferably used.

Specific examples of the metallocene complex preferably include the following compounds. (1) methylenebis (cyclopentadienyl) zirconium dichloride,
(2) Methylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) zirconium dichloride, (3) Isopropylidene (cyclopentadienyl)
(3,4-dimethylcyclopentadienyl) zirconium dichloride, (4) ethylene (cyclopentadienyl) (3,5-dimethylpentadienyl) zirconium dichloride, (5) methylenebis (indenyl) zirconium dichloride, (6) Ethylene bis (2-methylindenyl) zirconium dichloride, (7) ethylene 1,2-bis (4-phenylindenyl) zirconium dichloride, (8) ethylene (cyclopentadienyl)
(Fluorenyl) zirconium dichloride, (9) dimethylsilylene (cyclopentadienyl) (tetramethylcyclopentadienyl) zirconium dichloride, (1
0) dimethylsilylenebis (indenyl) zirconium dichloride, (11) dimethylsilylenebis (4,5,5
6,7-Tetrahydroindenyl) zirconium dichloride, (12) dimethylsilylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, (1)
3) Dimethylsilylene (cyclopentadienyl) (octahydrofluorenyl) zirconium dichloride, (1
4) Methylphenylsilylenebis [1- (2-methyl-
4,5-Benzo (indenyl)] zirconium dichloride, (15) Dimethylsilylenebis [1- (2-methyl-4,5-benzoindenyl)] zirconium dichloride, (16) Dimethylsilylenebis [1- (2- Methyl-4H-azulenyl)] zirconium dichloride, (1
7) Dimethylsilylenebis [1- (2-methyl-4-
(4-Chlorophenyl) -4H-azurenyl)] zirconium dichloride, (18) dimethylsilylene bis [1
-(2-Ethyl-4- (4-chlorophenyl) -4H-
Azulenyl)] zirconium dichloride, (19) dimethylsilylenebis [1- (2-ethyl-4-naphthyl-
4H-azurenyl)] zirconium dichloride, (2
0) diphenylsilylene bis [1- (2-methyl-4-
(4-Chlorophenyl) -4H-azurenyl)] zirconium dichloride, (21) dimethylsilylene bis [1
-(2-Methyl-4- (phenylindenyl))] zirconium dichloride, (22) dimethylsilylene bis [1- (2-ethyl-4- (phenylindenyl))]]
Zirconium dichloride, (23) dimethylsilylene bis [1- (2-ethyl-4-naphthyl-4H-azulenyl)] zirconium dichloride, (24) dimethylgermylene bis (indenyl) zirconium dichloride,
(25) Dimethylgermylene (cyclopentadienyl)
(Fluorenyl) zirconium dichloride.

The same compounds as described above can be used for other Group 4, 5 and 6 transition metal compounds such as titanium compounds and hafnium compounds. These compounds may be used in combination with the catalyst component and catalyst of the present invention.

Further, compounds in which one or both of the chlorides of these compounds are replaced by bromine, iodine, hydrogen, methylphenyl, benzyl, alkoxy, dimethylamide, diethylamide and the like can be exemplified. further,
Instead of the above zirconium, compounds in which titanium, hafnium, etc. are replaced can be exemplified.

The cocatalyst is composed of an ionic compound or Lewis acid capable of converting a metallocene compound component into a cation by reacting with an aluminumoxy compound or a metallocene compound, a solid acid, or an ion-exchange layered silicate. At least one compound selected from the group is used. Moreover, an organoaluminum compound can be added together with these compounds as needed.

Examples of the aluminum oxy compound include methyl alumoxane, ethyl alumoxane, propyl alumoxane, butyl alumoxane, isobutyl alumoxane, methyl ethyl alumoxane, methyl butyl alumoxane and methyl isobutyl alumoxane.
It is also possible to use a reaction product of a trialkylaluminum and an alkylboronic acid. For example, a 2: 1 reaction product of trimethylaluminum and methylboronic acid, a 2: 1 reaction product of triisobutylaluminum and methylboronic acid, a 1: 1: 1 reaction product of trimethylaluminum and triisobutylaluminum and methylboronic acid, triethylaluminum and butylboron. 2: 1 reaction of acid and the like.

As the ion-exchange layered silicate, montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite, stevensite,
A silicate such as a smectite group such as bentonite or teniolite, a vermiculite group, or a mica group is used.
It is preferable that these silicates have been chemically treated. Here, as the chemical treatment, both surface treatment for removing impurities adhering to the surface and treatment for affecting the crystal structure and chemical composition of the layered silicate can be used. Specifically, (a) acid treatment, (b) alkali treatment, (c) salt treatment, (d) organic substance treatment and the like can be mentioned. These treatments remove impurities on the surface, exchange cations between layers, and elute cations such as Al, Fe, and Mg in the crystal structure, resulting in ionic complexes, molecular complexes, organic derivatives, etc. Can be formed to change the surface area, interlayer distance, solid acidity, and the like. These treatments may be performed alone or two or more treatments may be combined.

If desired, triethylaluminum, triisobutylaluminum,
Organoaluminum compounds such as diethyl aluminum chloride may also be used.

In the present invention, a propylene / α-olefin random copolymer is obtained by using the above metallocene catalyst. Examples of the α-olefin include α-olefins having 2 to 20 carbon atoms excluding propylene, and examples thereof include ethylene, butene-1, pentene-1,3-methyl-1-butene, hexene-1,3-methyl-1. -Penten, 4-
Methyl-1-pentene, heptene-1, octene-1,
Examples include nonene-1, decene-1, dodecene-1, tetradecene-1, hexadecene-1, octadecene-1, eicosene-1. Α-copolymerized with propylene
The olefins may be used alone or in combination of two or more.
Of these, ethylene and butene-1 are preferable, and ethylene is particularly preferable. In the propylene / α-olefin copolymer, a structural unit derived from propylene (hereinafter,
A preferable ratio of “propylene unit” is 90 to 99% by weight based on all the constituent units, and a constituent unit derived from α-olefin (hereinafter, referred to as “comonomer unit”).
Is 1 to 10% by weight. Of these, particularly preferred as the propylene / α-olefin copolymer used in the present invention are propylene, ethylene and / or butene-
It is a random copolymer with 1 or a ternary random copolymer with propylene, ethylene and butene-1.

As the polymerization method, in the presence of these catalysts,
Examples thereof include a slurry method using an inert solvent, a gas phase method or a solution method substantially using no solvent, and a bulk polymerization method using a polymerization monomer as a solvent.

2. Propylene / α-olefin Copolymer Composition (1) Additive Blending Component Examples of additives to be blended with the propylene / α-olefin copolymer used in the present invention include a phenolic antioxidant and a neutralizing agent. In the case of a polypropylene resin such as a propylene / α-olefin copolymer used in the present invention, without a phenolic antioxidant, not only deterioration during kneading granulation and blow molding, but also heat and heat during raw material storage and product storage Air causes molecular breakage to cause remarkable deterioration of physical properties and deterioration of odor due to generation of volatile components, so that it is practically difficult to use. Other than the phenol-based antioxidant used in the present invention or a small amount thereof may be added, but phosphorus-based antioxidants and sulfur-based antioxidants which are generally used are not preferable because they are easily hydrolyzed.

As the neutralizing agent to be added to the propylene / α-olefin copolymer used in the present invention, at least one neutralizing agent selected from hydrotalcite and metal hydroxide salts is preferable. Other neutralizing agents generally include neutralizing agents such as fatty acid metal salts such as calcium stearate, and it is possible to use a very small amount, but these are used during molding and heat sterilization. Is decomposed into free fatty acid and metal by the heat of, and this fatty acid is eluted into the drug to become insoluble fine particles, or the odor inside the container is deteriorated, which is not preferable.

Further, other optional compounding ingredients may be compounded according to various purposes within a range that does not significantly impair the effects of the present invention. As additional components thereof, phosphorus-based antioxidants, sulfur-based antioxidants, light stabilizers, crystallization nucleating agents, ultraviolet absorbers, antistatic agents that are commonly used as additives and compounding materials for polyolefins, etc. , Lubricant, lubricant, anti-fog agent, anti-blocking agent, flame retardant, conductivity-imparting agent, cross-linking agent, cross-linking aid, metal deactivator, anti-bacterial agent,
Examples include various auxiliaries such as optical brighteners, other various resins and elastomers, fillers, colorants and the like. Since these additives have a high possibility of contaminating the contents, it is preferable not to add them or to avoid excessive addition even if they are added. However, when the stretch ratio of stretch blow molding is low, it is preferable to add a crystallization nucleating agent from the viewpoint of imparting transparency.
The preferred additives will be specifically described below.

(I) Phenolic Antioxidant The phenolic antioxidant is preferable as the antioxidant to be added to the propylene / α-olefin copolymer used in the present invention. Specific phenolic antioxidants include tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate and 1,1,3-tris (2-methyl-4-hydroxy-). 5-t-butylphenyl) butane, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 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, 3,9-bis [2- [3- (3-t-butyl-4-
Hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4,8,10 tetraoxaspiro [5,5] undecane, 1,3,5-
Examples include tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanuric acid. Among them, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, which has a high molecular weight and a low volatility from the viewpoints of volatilization into a drug and extraction and is excellent in extraction resistance. ], 1,3,5-trimethyl-
More preferred is 2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene.

The compounding amount of the phenolic antioxidant is
0.005-0.5 parts by weight, preferably 0.01-, per 100 parts by weight of propylene / α-olefin copolymer
0.3 parts by weight. If the amount is less than 0.005 part by weight, the oxidation resistance of the product is not sufficient. On the other hand, if the amount exceeds 0.5 part by weight, not only is it uneconomical, but there are problems such as contamination with chemicals, discoloration and bleeding. Not preferable.

(Ii) Neutralizer For the propylene / α-olefin copolymer used in the present invention
As the neutralizing agent to be blended, hydrotalcite, hydroxylation
At least one neutralizing agent selected from metal salts is preferred.
May be used alone or in combination of two or more.
Yes. As a concrete hydrotalcite, Magnesium
Content of calcium, calcium, zinc, aluminum, bismuth, etc.
Contains no water-based carbonates or water of crystallization.
And synthetic products are included. As a natural product, Mg₆Al
_Two(OH)₁₆CO_Three・ 4H_TwoO structure
Be done. In addition, as a synthetic product, Mg_0.7Al
_0.3(OH)_Two(CO_Three)_0.15・ 0.54H
_TwoO, Mg_4.5Al_Two(OH)_ThirteenCO_Three・ 3.5H
_TwoO, Mg_4.2Al_Two(OH)₁₂． 4CO_Three, Zn
₆Al_Two(OH) ₁₆CO_Three・ 4H_TwoO, Ca₆Al_Two
(OH)₁₆CO_Three・ 4H_TwoO, Mg₁₄Bi_Two(O
H)_29.6・ 4.2H_TwoO etc. are mentioned. Also, ingredients
Physical metal hydroxide salts include magnesium hydroxide and water
Aluminum oxide, lithium aluminum composite hydroxide
Mention may be made of salt.

The content of these neutralizing agents is propylene / α
0.005 per 100 parts by weight of olefin copolymer
To 0.5 parts by weight, preferably 0.01 to 0.2 parts by weight. If it is less than 0.005 parts by weight, the effect of preventing corrosion of the mold, molding machine, etc. is not sufficient, while if it exceeds 0.5 parts by weight, not only is it uneconomical, but problems such as bleeding occur. To do.

(2) Method of compounding additives As a method of compounding the above-mentioned additive components, the powder of the propylene / α-olefin copolymer obtained by polymerization is directly premixed with the additive and melt-kneaded and mixed. Further, the blend can be obtained by a method of blending a masterbatch in which the additive is highly concentrated in advance. Examples of the mixer or kneader used for the mechanical mixing or melt kneading include Henschel mixer, super mixer, V blender, tumbler mixer, ribbon blender, Banbury mixer, kneader blender, Brabender plastograph, roll, single screw. Examples thereof include an extrusion granulator and a twin-screw extrusion granulator. The melt-kneading temperature is generally 100 to 300 ° C.

(3) Physical Properties of Composition The resin composition obtained by blending the propylene / α-olefin copolymer of the present invention with a funol-type antioxidant has the following physical properties. (I) Q value The Q value is the gel permeation chromatograph (GP
C: Gel Permeation Chromato
weight average molecular weight (Mw) measured by
And the number average molecular weight (Mn). The smaller this value, the more uniform the molecular weight and the narrower the molecular weight distribution. The Q value of the propylene / α-olefin copolymer used in the present invention is 1.5 to
It is 3.5, preferably 2.0 to 3.0. When the Q value is less than 1.5, the melt viscosity becomes high when injection molding a stretch blow preform, the resin is not sufficiently filled, and short shots easily occur. On the other hand, when the Q value exceeds 3.5, the impact strength decreases and the odor in the container deteriorates with an increase in low molecular weight components. The method for adjusting the Q value of the propylene / α-olefin random copolymer is preferably carried out by using a catalyst system in which two or more metallocene catalyst components are used in combination or a catalyst system in which two or more metallocene complexes are used in combination. Alternatively, the Q value can be widely controlled by carrying out multi-stage polymerization of two or more stages during the polymerization.
On the contrary, in order to adjust the Q value narrowly, it can be adjusted by polymerizing the propylene / α-olefin random copolymer and then melt-kneading it with an organic peroxide.

The Q value is specifically measured by measuring the ratio of the weight average molecular weight to the number average molecular weight under the following conditions. GPC device: Waters ISOC-ALC / GP
C solvent: O-dichlorobenzene Measurement temperature: 140 ° C. Flow rate: 1 m / min Standard material: Tosoh monodisperse polystyrene

(Ii) Melting point Differential scanning calorimeter (DSC: Differential) of the propylene / α-olefin copolymer used in the present invention
The melting point, which is the melting peak temperature measured by Scanning Calorimeter), is 110 to 150 ° C.
And preferably 115 to 145 ° C, more preferably 120 to 140 ° C. When the melting point is less than 110 ° C, the heat resistance is deteriorated although the transparency and the heat sealing property are excellent. On the other hand, when the melting point is higher than 150 ° C., the transparency and heat sealability are deteriorated. In particular, in the case of a stretched blow container for infusion, this heat-sealing property is important because a rubber plug for inserting an injection needle is capped by injection molding and heat-bonded to the bottle. The melting point can be easily adjusted by controlling the amount of α-olefin supplied to the polymerization reaction system.

The melting point was specifically measured using a differential scanning calorimeter (DSC-7 type) manufactured by Perkin Elmer Co., Ltd., a sample weight of 5 mg was taken, and the scanning speed was from 200 ° C to 40 ° C.
20 ℃ at 10 ℃ / min after cooling to 10 ℃ / min
The peak position of the curve drawn by reheating to 0 ° C. is the melting peak temperature (melting point).

(Iii) Volatile Hydrocarbons 6 to 10 carbon atoms in the medical stretch blow container of the present invention.
The content of volatile hydrocarbons is a value obtained by measuring a gas obtained by thermally decomposing a resin with a gas chromatograph, and is 300 ppm or less, preferably 200 ppm.
Or less, more preferably 100 ppm or less. The content of volatile hydrocarbons having 6 to 10 carbon atoms is 300 ppm
If it exceeds, the volatile components accumulate in the container due to heat during molding or heat during heat sterilization, which causes odor. It is also considered to cause an increase in insoluble fine particles in the chemical solution.

The volatile hydrocarbon is a value measured by using a gas chromatograph under the following conditions. Pyrolysis conditions Sample weight: 5 mg Pyrolysis device; PYR-1A pyrolysis temperature manufactured by Shimadzu; 210 ° C Pipe temperature; 100 ° C Gas chromatograph condition device; GC-14B column manufactured by Shimadzu; G-100 manufactured by Chemicals Inspection Association (40m, composition;
(Methyl Silicone, polarity; non-polarity, film thickness; 1 μm) Column temperature; 60 ° C. → 150 ° C. Calibration curve; n-heptane conversion is performed.

As a method for reducing the content of volatile hydrocarbons in the medical stretch blow container of the present invention, a propylene / α-olefin random copolymer polymerized by using a metallocene catalyst having a small amount of low molecular weight components is used. It can be reduced, but (A) ~ below
A method of volatilizing the low molecular weight component by the method (c) is preferable. (A) A method in which low molecular weight components are removed by slurry polymerization, and drying is enhanced by a dryer to reduce the solvent and volatile hydrocarbons. (A) A method in which the residence time of polymerization is shortened to suppress the production of low molecular weight components, and the drying is enhanced by a dryer to reduce volatile hydrocarbons. (C) A method of providing a washing step with a low boiling point solvent such as propylene to reduce low molecular weight components, and enhancing drying with a dryer to reduce volatile hydrocarbons.

(Iv) MFR The MFR (melt flow rate) of the propylene / α-olefin copolymer used in the present invention is JIS-K7210.
It is a value measured in accordance with (230 ° C., 2.16 kg load). The preferred range varies depending on the molding method.
To adjust the MFR of a polymer, for example, the polymerization temperature,
There is a method of appropriately adjusting the amount of catalyst, the amount of hydrogen supplied as a molecular weight modifier, or a method of adjusting by adding a peroxide after completion of the polymerization.

(Iv-1) MFR for hot method stretch blow molding The MFR for hot method stretch blow molding used in the present invention is
0.5 to 20 g / 10 minutes, preferably 1 to 10 g / 10
Min, more preferably 1.5 to 5 g / 10 min. MF
When R is less than 0.5 g / 10 minutes, the melt viscosity becomes high when an injection preform is molded by injection molding, so that the resin is forced to be injected. In this case, the injection preform is apt to have a temperature distribution and molding distortion, which causes uneven thickness in the stretch-blowing step, resulting in poor moldability and poor transparency after stretch molding. On the other hand, MFR is 20g / 1
If it exceeds 0 minutes, in the case of hot method stretch blow molding,
Since the injection preform is taken out in the molten state, molding cannot be performed due to insufficient mold release on the cavity side of the injection mold or clinging to the core side. Also, the impact strength is reduced.

(Iv-2) Cold method stretch blow molding MFR used in the present invention Cold method stretch blow molding MFR
Is 10 to 50 g / 10 minutes, preferably 20 to 4
It is 0 g / 10 minutes. When the MFR is less than 10 g / 10 minutes, the melt viscosity becomes high when injection molding is performed as in the hot method stretch blow molding method, though not so much as in the hot method stretch blow molding method, so that the resin is forcibly injected. . In this case, the injection preform is apt to have a temperature distribution and molding distortion, which causes uneven thickness in the stretch-blowing step, resulting in poor moldability and poor transparency after stretch molding. On the other hand, MFR
If it exceeds 50 g / 10 minutes, the impact strength will decrease. Since the injection molding and the blow molding are completely separated in the cold method stretch blow molding, the temperature of the preform can be easily adjusted and the draw ratio can be increased. Therefore, the cold method stretch blow molding is more preferable because a stretch blow container having a high draw ratio can be easily formed, and as a result, physical properties of the high MFR product are less likely to deteriorate.

3. Production of Container by Stretch Blow Molding (1) Stretch Blow Molding Method What is the propylene / α-olefin copolymer medical stretch blow container used in the present invention as long as it can be stretched in the machine direction and the transverse direction? Any stretching method may be used. The propylene / α-olefin copolymer medical stretch blow container used in the present invention has a stretching ratio in the longitudinal direction and the transverse direction of 1.5 times or more, preferably 2.0 times or more, more preferably 2 times. It is 0.5 times or more, more preferably 3.0 times or more. When the draw ratio is less than 1.5 times, transparency,
It is also inferior in strength such as heat resistance, impact resistance, glossiness and rigidity.
On the other hand, the higher the draw ratio, the better the container performance. However, when the draw ratio is high, the blow container is broken during shaping and the thickness of the blow container becomes uneven, which makes molding difficult.

As the stretch blow molding method, a hot parison method in which a preform obtained by injection molding a bottomed parison by an injection stretch blow molding machine is not completely cooled but preliminarily blown and then stretch blow molding is continuously performed is performed. (Hot method stretch blow molding method), and cold parison method (cold method stretch blow molding method) in which what is once injection molded or extruded pipe molded is completely cooled and heated in a separate step to perform stretch blow molding. .

(2) Hot Method Stretch Blow Molding Method As a specific example of a preferable hot method stretch blow molding method for the medical propylene / α-olefin copolymer medical stretch blow molding container used in the present invention, Nissei AS・ Injection stretch biaxial stretch blow molding machine ASB-50 manufactured by B Co., Ltd.
Type, ASB-250 type, ASB-650 type, etc.
Injection stretch blow molding machine SBII manufactured by Aoki Koken Co., Ltd.
Examples thereof include I-100 type and SBIII-150P type. The preferable condition in this case is that the injection molding temperature is 1
80-250 ° C, preliminary blow air pressure 3-8kg / cm
² , the mold temperature before stretch blow is 70 to 130 ° C., and the stretch blow pressure is 5 to 20 kg / cm ² .

(3) Cold Method Stretch Blow Molding Method As a concrete example of a preferable cold method stretch blow molding method for the medical propylene / α-olefin copolymer medical stretch blow molding container used in the present invention, Frontier Co., Ltd. Biaxial stretch blow molding machine EFB2000 type, etc., Tahara Co.'s biaxial stretch blow molding machine CSB102
/ 15M type and the like. In this case, the preferable conditions include a bottle surface temperature of 90 to 160 before stretching and blowing.
The stretching blow pressure is 5 to 20 kg / cm ² .

4. Post-treatment of container (1) heat sterilization For heat sterilization of the propylene / α-olefin copolymer medical stretch blow container used in the present invention, a steam sterilizer under general pressure can be used. Any method such as a batch method, a continuous method, or a shower method may be used. The heating temperature is preferably 110 ° C or higher, and particularly preferably 115 to 125 ° C. When the temperature is low, the sterilization effect is poor, and when the temperature is too high, the container is deformed during heat sterilization, and it is practically impossible to raise the temperature above the melting point. Generally, if the heating temperature can be increased, the heating time can be reduced, so that the efficiency of the heat sterilization step can be increased and the production efficiency can be increased.

(2) Heat-sealing Heat-sealing at the mouth of the propylene / α-olefin copolymer medical stretch-blow container used in the present invention may be carried out by a method such as direct contact welding with a heating element, heat-ray radiation welding or ultrasonic welding. Can be used.

5. Uses of container (1) Medical container The use of the propylene / α-olefin copolymer medical stretch blow container used in the present invention can be used in general medical fields, for example, an intravenous infusion container, a liquid cold. Examples include medication containers such as medicines, eye drops containers, eye wash containers, nutrient containers, liquid food containers, sports drink containers, diagnostic drug containers, etc., as well as liquids, solid containers such as tablets and powders, and further reagents. It can also be used in food products. Among them, it is effective for an infusion container that requires high heat sterilization and has high performance requirements for transparency, hygiene, and heat sealability.

(2) Container for infusion As a liquid infusing agent for the medical stretch blow container made of the propylene / α-olefin copolymer used in the present invention, a blood container for humans and animals, a Ringer's liquid container containing sugar such as glucose. , A saline solution container containing an electrolyte such as sodium chloride, an intravenous infusion container such as a purified water container, and the like. Since an infusion container requires a high sterilization level, it is usually heat-sterilized, and a heat seal cap is used from the viewpoint of preventing foreign matter from entering.

[0049]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded. The methods of evaluating the physical properties of the polymer composition and the quality of the container are as follows.

1. Evaluation of physical properties (1) Ethylene content: Pellets are hot-pressed at 230 ° C. to form a sheet having a thickness of about 0.5 mmt. The wavelength sheet at infrared spectrophotometer 730 cm ^- measuring the absorbance at ^1, is converted to the absorbance of the sample sheet thickness commensurate (absorbance / thickness of the sheet). Next, the ethylene content was calculated from this relationship using samples having different ethylene contents previously measured by NMR as standard samples. (2) MFR: Temperature 23 according to JIS-K7210
The MFR of the pellet was measured under the conditions of 0 ° C. and a load of 2.16 kg. (3) Q value: measured by the above-mentioned measuring method. (4) Melting point: Measured by the above-mentioned measuring method. (5) Volatile hydrocarbon: Using a gas chromatograph, the amount of volatile hydrocarbon was measured by the above-mentioned measuring method.

2. Quality Evaluation (1) Transparency (Haze): A portion having a wall thickness of 0.6 mm was cut out from the body of the container, and the haze was measured by a haze meter according to JIS-K7105. When a portion having a wall thickness of 0.6 mm could not be obtained, the haze of three or more portions having different thicknesses was measured, and the haze was determined from the relationship between the thickness and the haze by the least square method. (2) Fine particles: The sample container was washed 5 times with ultrapure water in a clean room, and then 450 cc of ultrapure water was added. This sample container and a 0.5 mm thick sheet preliminarily heat-compressed with the same material were heat-sealed at a pressure of 2 kg for 30 seconds by a bat welding machine heated to about 200 ° C. continue. The sample container filled with this ultrapure water was placed in a stainless steel autoclave type steam sterilizer having an internal volume of 100 L, heated at 115 ° C. for 30 minutes, cooled to room temperature so as not to deform under reduced pressure, and taken out. Remove ultrapure water from the sample container in a clean room and use a particle counter to measure 25
The number of fine particles in cc was measured. Main unit: Rion Co., Ltd. particle counter KL-1
Type 0 sensor: Particle counter KS-6 manufactured by Rion Co., Ltd.
0 type fine particle size: counting 2 μm or more (3) odor: after washing the sample container 5 times with ultrapure water in a clean room, 450 cc of ultrapure water was added. This sample container and a 0.5 mm-thick sheet preliminarily heat-compressed with the same material were heated for 30 seconds at a butt welding machine heated to about 200 ° C.,
It was heat-sealed at a pressure of 2 kg. Subsequently, the sample container filled with this ultrapure water was placed in a stainless steel autoclave-type steam sterilizer having an internal volume of 100 L, heated at 115 ° C. for 30 minutes, cooled to room temperature so as not to deform under reduced pressure, and taken out. Next, this heat-sterilized filling container was put in a gear oven manufactured by Toyo Seiki Co., Ltd., which was heated to 80 ° C., for 2 hours, heated and taken out, and the mouth was quickly cut with scissors and evaluated according to the following odor criteria within 10 minutes. ◎: Not felt ○: Feeling bare △: Feeling ×: Feeling comfortable × ×: Smelling strongly (4) Drop strength: After washing the sample container 5 times with ultrapure water in a clean room, 450 cc of ultrapure water was added . This sample container and a 0.5 mm thick sheet preliminarily heat-compressed with the same material were heat-sealed at a pressure of 2 kg for 30 seconds by a bat welding machine heated to about 200 ° C. Subsequently, the sample container filled with this ultrapure water was placed in a stainless steel autoclave-type steam sterilizer having an internal volume of 100 L, heated at 115 ° C. for 30 minutes, cooled to room temperature so as not to deform under reduced pressure, and taken out. Next, this heat-sterilized filled container was cooled to 5 ° C., and 5 containers were vertically dropped at a height of 1 m from the concrete surface, and evaluation was performed according to the following criteria of drop strength. ⊚: Does not break at all. ◯: Does not break more than once, but breaks if dropped many times. B: Some of them are broken by one drop. X: All are broken by one drop.

Example 1 1. Synthesis of metallocene catalyst (1) Chemical treatment of silicate In a 3 L glass flask equipped with a stirring blade, distilled water 11
Slowly add 30 mL, followed by 750 g concentrated sulfuric acid,
Furthermore, montmorillonite (Ben clay S manufactured by Mizusawa Chemical Co., Ltd.
L; average particle size = 25 μm, particle size distribution = 10 to 60 μm)
Was dispersed in 300 g and the temperature was raised to 90 ° C. over 1 hour.
After maintaining that temperature for an hour, it was cooled to 50 ° C. in 1 hour. This slurry was filtered under reduced pressure to collect the cake. Distilled water (4 L) was added to this cake to form a reslurry, which was then filtered. This washing operation was repeated 4 times. The pH of the final washing liquid (filtrate) was 3.42. The collected cake was dried overnight at 110 ° C. under a nitrogen atmosphere. Weight after drying is 2
It was 27 g. The composition of this chemically treated montmorillonite is 5.0% Al, 0.8% Mg, and Fe 1.
6% and 37.7% of Si were contained. (2) Preparation of catalyst The following operation was carried out under an inert gas using a deoxidized and dehydrated solvent and a monomer. The previously chemically treated montmorillonite was dried under reduced pressure at 200 ° C. for 2 hours. 200 g of the dried montmorillonite obtained above was introduced into a glass reactor equipped with a stirring blade having an internal volume of 3 L,
Heptane and a heptane solution of triethylaluminum (500 mmol) were added, and the mixture was stirred at room temperature. After 1 hour, the slurry was washed with heptane to prepare a slurry of 2000 mL. Next, in advance, (r) -dimethylsilylenebis [2-methyl-4- (4-chlorophenyl) -4H-
A mixture of 870 mL of a toluene slurry of 3 mmol of azulenyl] zirconium dichloride and 42.6 mL of a heptane solution of triisobutylaluminum (30 mmol) reacted at room temperature for 1 hour was added to the montmorillonite slurry and stirred for 1 hour. Subsequently, 2.1 L of heptane was introduced into a stirring type autoclave having an internal volume of 10 L that was sufficiently replaced with nitrogen, and the temperature was maintained at 40 ° C. The montmorillonite / complex slurry prepared above was introduced therein. When the temperature stabilizes at 40 ° C, propylene is added to 10
The temperature was maintained by feeding at a rate of 0 g / hour. After 4 hours, the propylene feed was stopped and maintained for another 2 hours. From the recovered prepolymerized catalyst slurry, about 3
Except L, triisobutylaluminum (120mmo
170 mL of the heptane solution of 1) was added, and the mixture was stirred for 10 minutes and then dried at 50 ° C. under reduced pressure. By this operation, a prepolymerized catalyst containing 2.25 g of polypropylene per 1 g of the catalyst was obtained.

2. The inside of the stirring autoclave having an internal volume of 200 liters was sufficiently replaced with propylene, and then 45 kg of sufficiently dehydrated liquefied propylene was introduced. To this, 500 ml of triisobutylaluminum / n-heptane solution (0.12 mo
1), 2.1 kg of ethylene and 2.7 NL of hydrogen were added to maintain the internal temperature at 30 ° C. Then, the solid catalyst component 1.
2 g (by weight excluding polypropylene) was press-fitted with argon to initiate polymerization, the temperature was raised to 60 ° C. over 30 minutes, and the temperature was maintained for 1 hour. Ethanol 10 here
The reaction was stopped by adding 0 ml. The residual gas was purged to obtain a propylene-ethylene copolymer powder.
The obtained propylene / ethylene random copolymer is M
FR = 1.8 g / 10 minutes, ethylene content = 3.3 wt
%, Tm = 125 ° C., and Q value = 3.0.

3. Additive Additions Pentaerythyl-tetrakis [3-
(3,5-t-butyl-4-hydroxyphenyl) propionate] (manufactured by Ciba Specialty Chemicals Co., Ltd .; hereinafter abbreviated as IR1010) 0.02 parts by weight, and hydrotalcite (Kyowa Chemical Industry Co., Ltd.) as a neutralizing agent. Co., Ltd .; hereinafter abbreviated as DHT-4A.) 0.02 parts by weight was added, and the mixture was sealed with nitrogen using a super mixer and mixed for 3 minutes.
Then, using a screw type single screw extruder of 40 mmD, the hopper was melted and kneaded at 230 ° C. while being sealed with nitrogen and granulated (pelletized). The pellet was circulated in the air circulation dryer and dried at 80 ° C. for 2 hours. The results are shown in Table 1.

4. Blow Molding The pellets obtained above were molded by a hot parison method biaxial stretching blow molding machine. Specifically, Nissei AS
By using ASB-50 type injection stretch biaxial stretch blow molding machine manufactured by B Co., Ltd., resin temperature 230 ° C., pressure 90 kg / cm.
² , the bottomed parison with an outer diameter of 20 mm and a height of 100 mm was injection molded, transferred to a preliminary blow mold, and the air pressure was 5 kg / cm ^2.
Pre-blow to 1.2 times the draw ratio with this heating pot, and after heating the body temperature of the bottomed parison to 130 ° C, put it in a blow mold and draw the rod 2.0 times in the longitudinal direction with air pressure. It was stretched 2.0 times in the transverse direction at 15 kg / cm ² to form a cylindrical bottle having a capacity of 500 cc and a weight of 30 g.

5. After-treatment of container The sample container obtained above was washed 5 times with ultrapure water in a clean room, and then 450 cc of ultrapure water was added. This sample container and a 0.5 mm thick sheet preliminarily heat-compressed with the same material are heated at about 200 ° C. for 30 seconds with a butt welding machine.
It was heat-sealed at a pressure of 2 kg. Then, the ultrapure water filling container was placed in a stainless steel autoclave type steam sterilizer having an internal volume of 100 L, heated at 115 ° C. for 30 minutes, cooled to room temperature so as not to deform under reduced pressure, and taken out. The quality of this heat-sterilized filled container was evaluated. The results are shown in Table 1.

Comparative Example 1 Example 1 was repeated except that the polymerization temperature in Example 1 was 75 ° C., the comonomer and hydrogen were not fed during the polymerization, and the solid catalyst component was changed to 6 g (as a weight excluding polypropylene).
A polymer was obtained in the same manner as in. The obtained polypropylene homopolymer had MFR = 7.3 g / 10 minutes and Tm = 15.
It was 0.5 ° C. and the Q value was 3.4. A container was formed from this polymer in the same manner as in Example 1 and evaluated. The results are shown in Table 1.

Comparative Example 2 The antioxidant of Example 1 was replaced by tetrakis (2,4-di-t-butylphenyl) [1,1-biphenyl] -4,4'-diylbisphos which is a phosphorus-based antioxidant. Phonite (Ciba Specialty Chemicals Co., Ltd .; P- below)
Abbreviated as EPQ. The container was molded and evaluated in the same manner as in Example 1 except that the content was changed to (1). The results are shown in Table 1.

Comparative Example 3 Example 1 was repeated except that the antioxidant of Example 1 was not added.
A container was molded and evaluated in the same manner as in. The results are shown in Table 1.
Shown in.

[0060]

[Table 1]

Example 2 Example 2 was carried out except that the neutralizing agent of Example 1 was replaced with magnesium hydroxide which was a metal hydroxide salt (manufactured by Nitto Kasei Kogyo KK; hereinafter abbreviated as Mg (OH) ₂ ). A container was molded and evaluated in the same manner as in Example 1. The results are shown in Table 2.

Example 3 A container was molded and evaluated in the same manner as in Example 1 except that the neutralizing agent of Example 1 was not added. The results are shown in Table 2.

Example 4 A polymer was prepared in the same manner as in Example 1 except that the amount of hydrogen fed during the polymerization in Example 1 was changed to 12 NL and the solid catalyst component was changed to 1.2 g (by weight excluding polypropylene). Obtained. The obtained propylene / ethylene random copolymer had an MFR of 19 g / 10 minutes and an ethylene content of 3.2 w.
t%, Tm = 127 ° C., and Q value = 3.4. A container was formed from this polymer in the same manner as in Example 1 and evaluated. The results are shown in Table 2.

Example 5 The hydrogen feed amount in the polymerization of Example 1 was 5 NL, and the solid catalyst component was 1.0 g (by weight excluding polypropylene).
A polymer was obtained in the same manner as in Example 1 except that the above was changed. The obtained propylene / ethylene random copolymer had an MFR of 5.2 g / 10 minutes and an ethylene content of 3.0.
wt%, Tm = 125 ° C., and Q value = 3.3. A container was formed from this polymer in the same manner as in Example 1 and evaluated. The results are shown in Table 2.

[0065]

[Table 2]

Comparative Example 4 (r) -Dimethylsilylenebis [2-] was added to the metallocene complex.
A catalyst was synthesized using methyl-4- (4-chlorophenyl) -4H-azurenyl] hafnium dichloride, the ethylene gas amount was 2.6 kg, the hydrogen feed amount was 2 NL,
A polymer was obtained in the same manner as in Example 1 except that the solid catalyst component was 2.0 g (by weight excluding polypropylene). The obtained propylene / ethylene random copolymer had an MFR of 0.4 g / 10 minutes and an ethylene content of 4.3.
% by weight, Tm = 125 ° C., and Q value = 3.4. A container was formed from this polymer in the same manner as in Example 1 and evaluated. The results are shown in Table 3.

Comparative Example 5 Example 5 was repeated except that the ethylene gas amount was changed to 2.6 kg, the hydrogen feed amount was changed to 20 NL, and the solid catalyst component was changed to 0.5 g (as a weight excluding polypropylene) during the polymerization of Example 1. A polymer was obtained in the same manner as in 1. The obtained propylene / ethylene random copolymer had an MFR of 55 g / 10.
Min, ethylene content = 3.3 wt%, Tm = 125 ° C., Q
The value was 3.0. A container was formed from this polymer in the same manner as in Example 1 and evaluated. The results are shown in Table 3.

Example 6 Example 1 was repeated except that the pellet drying of Example 1 was not performed.
A container was molded and evaluated in the same manner as in. The results are shown in Table 3.
Shown in.

Comparative Example 6 The procedure of Example 1 was repeated, except that the polymerization catalyst of Example 1 was replaced by a Ziegler Natta-type catalyst (hereinafter abbreviated as Z / N) synthesized by the following method, and the amount of hydrogen and ethylene feed was adjusted. Example 1
A container was molded and evaluated in the same manner as in. The results are shown in Table 3.
Shown in.

Synthesis of catalyst Dehydrate and deoxygenate n- in a flask with sufficient nitrogen substitution.
Introduce 4000 ml of heptane, then Mg
Cl_Two8 mol, Ti (O-n-C_FourH₉)_Four16 mo
And introduced into the reaction chamber at 95 ° C. for 2 hours. 4 after reaction
Lower the temperature to 0 ° C, then methylhydropolysiloxa
960 milliliters of 20 centistokes
And introduced for 3 hours. N-
Wash with heptane. Next, the furass that has been thoroughly replaced with nitrogen.
1000 ml of n-heptane purified in the same manner as above
Introduce 1 liter of the solid component synthesized above to Mg atom
4.8 mol was introduced in terms of conversion. Then n-heptane 50
SiCl to 0 ml_FourMixed at 8 ° C at 30 ° C,
Introduce into the flask in 30 minutes and react at 70 ° C for 3 hours
It was After completion of the reaction, it was washed with n-heptane. Then n
-500 ml of heptane with phthalic chloride
Mix 0.48 mole and transfer to flask at 70 ℃ for 30 minutes.
It was introduced and reacted at 90 ° C. for 1 hour. After completion of the reaction, n-
Wash with heptane. Then SiCl_Four200 mm
Introduce the bottle into the flask at 30 ° C for 30 minutes, and
And reacted for 6 hours. After the reaction is complete, n-heptane is sufficient
After washing, a solid component was obtained. Then, thoroughly replace with nitrogen
N-heptane 10 purified in the same manner as above
Introduce 00 ml and add the solid component synthesized above.
Introduce 100g, (t-C_FourH₉) Si (CH_Three) (O
CH_Three)_Two24 ml, Al (C_TwoH ₅)_Three34
g was contacted at 30 ° C. for 2 hours. After contact, n-hep
Thoroughly rinse with_Two-Based solid catalyst
The ingredients are obtained. The titanium content of this solid catalyst component is 1.1.
% By weight.

[0071]

[Table 3]

Comparative Example 7 Comparative Example 6 except that the pellet drying of Comparative Example 6 was not performed.
A container was molded and evaluated in the same manner as in. The results are shown in Table 4.
Shown in.

Comparative Example 8 A container was molded and evaluated in the same manner as in Comparative Example 6 except that the hydrogen feed amount during polymerization in Comparative Example 6 was increased and the MFR was increased. The results are shown in Table 4.

Example 7 A container was molded and evaluated in the same manner as in Example 1 except that the heat sterilization in Example 1 was not carried out. The results are shown in Table 4.

Comparative Example 9 Polymerization was carried out in the same manner as in Comparative Example 6 except that the ethylene feed amount at the time of polymerization in Comparative Example 6 was increased, but the polymer was fused during the polymerization, resulting in insufficient heat removal and agglomeration. . Therefore, only the ethylene content was evaluated. The results are shown in Table 4.

[0076]

[Table 4]

Example 8 Example 1 was repeated except that the propylene / ethylene random copolymer polymerized in Example 4 was used and the blow molding method of Example 1 was replaced by the following cold stretch blow molding method. Similarly, a container was molded and evaluated. The results are shown in Table 5.

Cold Method Stretch Blow Molding Method These pellets were subjected to injection pressure 100 kg / cm ² , injection resin temperature 210 ° C., mold cooling water temperature 25 ° C. using an IS-150E type injection molding machine manufactured by Toshiba Machine Co., Ltd. Under the conditions, a test tubular bottomed preform having a basis weight of 30 g, an outer diameter of 2.8 mm, a height of 90 mm and a body maximum wall thickness of 5 mm was formed. Next, this preform was used with a frontier biaxial stretch blow molding machine EFB1000 type biaxial stretch blow molding machine,
The preform was heated while being rotated by an electric near-infrared lamp having a peak wavelength of 1 to 2 μm, and when the surface temperature of the preform reached 120 ° C. with a non-contact surface thermometer, the longitudinal stretching ratio was 2.5 times, A 500 cc cylindrical bottle container was obtained by biaxial stretching blow molding at an air pressure of primary pressure of 40 kg / cm ² and secondary pressure of 25 kg / cm ² as the longitudinal stretching rod was raised so that the lateral stretching ratio was 2.5 times.

Example 9 Example 8 was repeated except that the draw ratio of the cold stretch blow molding of Example 8 was changed to 3.0 times in the longitudinal direction and 3.0 times in the transverse direction.
A container was molded and evaluated in the same manner as in. The results are shown in Table 5.
Shown in.

Comparative Example 10 A container was molded and evaluated in the same manner as in Example 8 except that the composition of Example 5 was used. The results are shown in Table 5.

Comparative Example 11 A container was molded and evaluated in the same manner as in Example 8 except that the propylene / ethylene random copolymer polymerized in Comparative Example 5 was used. The results are shown in Table 5.

[0082]

[Table 5]

Comparative Example 12 A container was molded and evaluated in the same manner as in Example 1 except that the blow molding method in Example 1 was changed to the following direct blow molding method. The results are shown in Table 6.

Direct Blow Molding Method (1) Using a Dalmaged kneading section at the tip of the molding machine used, diameter 50 mm, L / D2
Small direct blow molding machine JB manufactured by Japan Steel Works, Ltd., which has a crosshead structure with screw 2 and die.
Type 105 was used. (2) Molding conditions Molding temperature of 200 ° C., blow mold cooling temperature of 15 ° C., cooling time of 24 seconds, bottle weight of 30 g, internal capacity of 500 c
c A cylindrical bottle was molded.

[0085]

[Table 6]

[0086]

EFFECTS OF THE INVENTION The blow container of the present invention is formed by molding a blow container using a specific propylene / α-olefin copolymer composition under specific conditions. , Stretch blow moldability, hygiene,
It is a blow container having impact resistance and the like superior to that of conventional materials, and is a useful stretch blow container for medical use which is extremely useful in industry.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08J 5/00 CES C08K 5/13 C08K 3/26 B29K 23:00 5/13 B29L 22:00 // B29K 23:00 B65D 1/00 A B29L 22:00 A61J 1/00 311 (72) Inventor Tadayoshi Akase 3-1, Chidoricho, Kawasaki-ku, Kawasaki-shi, Kanagawa Nihon Polychem Corporation F-term (reference) 3E033 AA02 BA30 BB04 CA03 CA18 FA03 4F071 AA14X AA20X AB17 AB21 AC11 AF23 AF30 AH05 BA01 BB06 BB07 BC04 4F208 AA11E AB01 AB06 AB16 AG07 AH63 LA02 A04 AQ AQAQ AQAQA 407AQADE A4QA4A07A04AQA4A04BQA AA15Q AA16Q AA17Q AA18Q AA19Q AA21Q CA03 CA04 CA11 DA04 DA42 DA43 DA52 DA62 FA10 FA19 JA50 JA58

Claims (6)

[Claims] 1. To 100 parts by weight of a propylene / α-olefin copolymer obtained by using a metallocene catalyst,
Obtained by blending 0.005 to 0.5 part by weight of phenolic antioxidant, MFR is 0.5 to 50 g / 10 minutes, Q
A container formed by stretch blow molding of a propylene / α-olefin copolymer resin composition having a value of 1.5 to 3.5 and a melting point of 110 to 150 ° C., which has a longitudinal direction and a transverse direction of the container. A stretchable blow container for medical use, which has a stretch ratio of 1.5 times or more. 2. The propylene / α-olefin copolymerized MFR is 0.5 to 20 g / 10 min, and the stretch blow molding is hot method stretch blow molding. Medical stretch blow container. 3. The medical treatment according to claim 1, wherein the propylene / α-olefin copolymer has an MFR of 10 to 50 g / 10 minutes, and the stretch blow molding is cold stretch blow molding. Stretch blow container. 4. The medical use according to any one of claims 1 to 3, wherein the content of the volatile hydrocarbon having 6 to 10 carbon atoms in the medical stretch blow container is 300 ppm or less. Stretch blow container. 5. A propylene / α-olefin copolymer resin composition obtained by using a metallocene catalyst, and 0.005 to 0.50% of at least one selected from hydrotalcite and metal hydroxide salts as a neutralizing agent. The medical stretch blow container according to any one of claims 1 to 4, wherein 5 parts by weight are blended. 6. A stretch blow container for infusion, wherein the stretch blow container for medical treatment according to claim 1 is heat-sterilized at a temperature of 110 ° C. or higher.