JP2010248425A - Molding for medical use - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a molding for medical use having well-balanced stiffness, impact resistance and transparency, and satisfying the quality of dialysis fluid supply sections and dialysis fluid circuits, and the testing method 1(2) specified in the Production Acceptance Criteria for Dialysis-type Artificial Kidney Apparatuses. <P>SOLUTION: The molding for medical use includes a propylene resin composition comprising 100 pts.wt. of a mixture containing 60-99 pts.wt. of a propylene polymer (a) and 1-40 pts.wt. of a polyethylene (b), wherein the MFR ratio of the polyethylene (b) to the propylene polymer (a) is 0.05-1.2, compounded with 0.1-0.6 pts.wt. of a nucleating agent (A) represented by a chemical structure (1), which is sterilized by radiation. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a propylene resin composition and a molded article thereof, and more particularly, has a good balance of rigidity, impact resistance, and transparency, and among dialysis-type artificial kidney device approval criteria, the dialysate supply section and the dialysate circuit. Quality and test method The present invention relates to a molded article for medical use that satisfies 1 (2).

Propylene polymers are used in various medical devices and instruments, taking advantage of their excellent safety and hygiene, molding processability, and mechanical properties. In particular, in recent years, the use as a member for artificial dialysis has been frequently seen, and materials for the use have been developed (for example, see Patent Document 1).
When kidney function declines, a device called an artificial kidney removes water and waste products from the blood and makes adjustments to keep the blood from becoming acidic. In general, this is called artificial dialysis. The concept is shown in FIG. 1, and the details of a dialyzer for cleaning blood are shown in FIG.
1 and 2, first, a needle is inserted into the blood vessel of the arm 1 of a person undergoing dialysis, and blood is continuously taken out by the blood pump 3. The blood pump 3 can feed blood in one direction by rotating while pressing the roller against the soft tube 2. The part that cleans blood is a tool called a dialyzer 5. In order to reduce the efficiency when air enters the dialyzer 5 and to protect the safety of a person undergoing dialysis, cylinders called air traps 4 are attached to the front and rear of the dialyzer so that the air does not enter. In the dialyzer 5, excess water and waste products can be discharged from the blood through the semipermeable membrane to clean the blood. At that time, the dialysate is accurately sent to the dialyzer 5 by the adjusting device called the console 6, and the dialysate mixed with the internal water and waste is carried outside. Various alarms are also attached to the console 6 so that artificial dialysis can be performed safely.

The dialyzer 5 is composed of a cylindrical plastic container having a length of about 30 cm. Among them, about 10,000 very thin threads of hollow fibers 11 that are semipermeable membranes are parallel to the container. It is stored in bundles. The hollow fiber 11 has a hole in the center like macaroni, blood flows through the hole, and dialysate flows outside the hollow fiber 11. Since the hollow fiber 11 is made so that water and waste products can be passed through the dialysate, the blood can be cleaned by continuously feeding the blood.
The dialyzer 5 includes a cylindrical outer cylinder 12 and a header 13 for covering the outer cylinder 12. The headers 13 on both sides are coupled to the hollow fiber 11, and when blood flows from the blood inlet 7 of one header 13 and flows through the hollow fiber 11, water and waste in the blood are hollow. It is discharged into the dialysate, which is outside the fiber 11, and then the blood flows out from the blood outlet 8 of the other header 13. Further, the outer cylinder 12 is provided with a dialysate inlet 9 and a dialysate outlet 10, and has a structure for extracting water and waste products by circulating the dialysate in the dialyzer 5.

Currently, the outer cylinder and header portion of such a dialyzer, which is a member for artificial dialysis, are mainly made of polycarbonate (hereinafter also referred to as PC) (for example, see Patent Documents 2 and 3). ). Since PC is excellent in transparency and impact resistance, it is an excellent material in that the inside of the dialyzer is easy to see and can be used with confidence, and it is difficult to break during transportation and use. However, on the other hand, PC requires a drying process before molding, resulting in poor working efficiency, high melting point, high molding temperature and low energy efficiency, and elution of chemical substances caused by raw materials. It included problems such as adverse effects and high prices. Therefore, it has excellent impact resistance, transparency and moldability instead of PC, and satisfies the quality and test method 1 (2) of dialysate supply part and dialysate circuit among the dialysis artificial kidney device approval standards The current situation is that a material that can be used is desired.
Unlike disposable syringes, the members for artificial dialysis are in contact with blood for a long time. Therefore, it is not preferable that components that elute such as lubricants are included, and it is necessary to satisfy the dialysis artificial kidney device approval criteria.

  In view of the above-mentioned problems, the object of the present invention is to satisfy the quality and test method 1 (2) of the dialysate supply section and dialysate circuit among the dialysis-type artificial kidney device approval criteria, and to have impact resistance and transparency. It is to provide a molded product for medical use having excellent properties and moldability.

  As a result of intensive research to solve the above problems, the present inventors have approved a dialysis artificial kidney device for a propylene resin composition based on a specific propylene polymer and using a specific nucleating agent. Among the standards, the quality of the dialysate supply section and dialysate circuit and test method 1 (2) are satisfied, and it is found to be suitable as a medical molded article having excellent impact resistance, transparency and moldability, The present invention has been completed.

That is, according to the first invention of the present invention, the MFR ratio between the propylene polymer (a) and the polyethylene (b) (the MFR of the polyethylene (b) / the MFR of the propylene polymer (a)) is 0.05. The chemical structure is represented by the following chemical structural formula (1) with respect to 100 parts by weight of a polymer mixture comprising 60 to 99 parts by weight of a propylene polymer (a) and 1 to 40 parts by weight of polyethylene (b). There is provided a medical molded article comprising a propylene-based resin composition containing 0.1 to 0.6 parts by weight of the nucleating agent (A) to be sterilized and sterilized by radiation.

[Wherein n is an integer of 0 to 2 and R1 to R5 are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an alkenyl group, an alkoxy group, a carbonyl group, a halogen group, and It is a phenyl group, R6 is a C1-C20 alkyl group. ]

According to a second invention of the present invention, there is provided a medical molded product characterized in that, in the first invention, the density of the polyethylene (b) is 0.875 to 0.920 g / cm ³ .

  According to a third invention of the present invention, in the first or second invention, the polyethylene (b) is polymerized using a metallocene catalyst, and the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) ( A medical molded article characterized in that Mw / Mn) is less than 3.5 is provided.

  According to the fourth aspect of the present invention, in any one of the first to third aspects, the lubricant is blended in the range of 0.001 to 0.5 parts by weight with respect to 100 parts by weight of the polymer mixture. The medical molded product characterized by the above is provided.

  According to a fifth invention of the present invention, there is provided a medical molded product characterized in that the medical molded product is an artificial dialysis member in any one of the first to fourth inventions.

  Further, according to a sixth invention, there is provided a medical molded product according to the fifth invention, wherein the artificial dialysis member is an outer cylinder, a header and / or a cap of a dialyzer.

The medical molded article of the present invention is preferably composed of a propylene-based resin composition using a specific polymer mixture as a base material and using a specific amount of a specific nucleating agent. Quality and test method of fluid supply section and dialysate circuit 1 (2), excellent impact resistance, transparency and moldability, and moldability compared to conventional polycarbonate (PC) And can be obtained at a low molding temperature.

It is a conceptual diagram of artificial dialysis. It is principal part sectional drawing of a dialyzer.

In the present invention, the MFR ratio between the propylene polymer (a) and the polyethylene (b) (the MFR of the polyethylene (b) / the MFR of the propylene polymer (a)) is 0.05 to 1.2. 0.1-0.6 parts by weight of a specific nucleating agent (A) with respect to 100 parts by weight of a polymer mixture composed of 60-99 parts by weight of a polymer (a) and 1-40 parts by weight of polyethylene (b) A medical molded article characterized by being blended and sterilized by radiation.
Hereinafter, the component which comprises a propylene-type resin composition, the manufacturing method of a resin composition, and a medical molded article are demonstrated in detail.

[1] Components constituting propylene-based resin composition Propylene polymer (a)
The propylene polymer (a) used in the present invention may be a propylene homopolymer, a propylene copolymer, or a mixture thereof. Random copolymers are desirable from the standpoints of physical property retention and transparency after irradiation.
The propylene-based copolymer is a copolymer of propylene and α-olefin, which may be a random copolymer or a block copolymer, but from the viewpoint of transparency, a random copolymer is used. Coalescence is desirable. Examples of the α-olefin used for copolymerization include α-olefins having 2 to 20 carbon atoms excluding propylene, and examples thereof include ethylene, butene-1, hexene-1, and octene-1. One or more α-olefins copolymerized with propylene may be used. Of these, ethylene and butene-1 are preferred. More preferably, ethylene is suitable.
Specific examples of the copolymer include propylene-ethylene copolymer, propylene-ethylene-diene copolymer, propylene-butene-1 copolymer, propylene-hexene-1 copolymer, propylene-octene- 1 copolymer etc. can be illustrated. Of these, propylene-ethylene copolymer, propylene-butene-1 copolymer, and propylene-ethylene-butene-1 copolymer are particularly preferable. The constituent ratio of the amount of α-olefin that is comonomer with propylene is preferably 70 to 99/30 to 1 in terms of weight ratio. Usually, the amount of α-olefin is 0.05 to 10.0% by weight, preferably about 0.1 to 5.0% by weight. Of course, a so-called polypropylene polymer alloy in which a rubber component such as EPR is introduced as a soft segment into a hard segment composed of a crystalline phase mainly composed of polypropylene at the polymerization stage can also be used.
As for the glass transition temperature of a propylene polymer (a) and a copolymer (a), a -100-20 degreeC thing is mentioned.
Moreover, you may use such a propylene polymer (a) in mixture of 2 or more types.

The propylene polymer (a) used in the present invention preferably has a melt flow rate (MFR) at 230 ° C. and a load of 2.16 kg of 0.3 to 100 g / 10 min. When the MFR is within this range, a resin composition suitable for a high production rate derived from the rigidity and impact resistance of the resin composition and the molding temperature is provided. When the MFR is less than 0.3 g / 10 min, molding becomes difficult. On the other hand, if it exceeds 100 g / 10 minutes, there is a possibility that good impact resistance as a medical molded product cannot be obtained.
Here, MFR at 230 ° C. is a value measured under a load of 230 ° C. and 2.16 kg in accordance with JIS K7210.

When the propylene homopolymer is used as the propylene polymer (a), the isotactic pentad fraction (mmmm) is 90% or more, preferably 94% or more, more preferably 97% or more. If the isotactic pentad fraction (mmmm) is less than 90%, the molded product may be easily deformed at the time of molding due to a decrease in rigidity and heat distortion temperature. Conversely, as the stereoregularity is improved, Rigidity and heat resistance are also improved, and deformation of the molded product can be prevented.
Here, the isotactic pentad fraction (mmmm) is a value measured by ¹³ C-NMR method.

When the propylene random copolymer (hereinafter sometimes referred to as a random copolymer) is used as the propylene polymer (a), the amount of α-olefin in the random copolymer is 0.1 to 0.1. 10.0% by weight is preferred. If it is less than 0.1% by weight, the transparency is insufficient, and the physical properties may deteriorate significantly after the radiation sterilization treatment. On the other hand, if it exceeds 10.0% by weight, the crystallinity is not exhibited, so that the rigidity is remarkably lowered and it is not suitable as a medical molded product.
Here, the α-olefin content is a value measured by the IR method using a propylene copolymer whose composition is tested by ¹³ C-NMR as a reference substance.

The random copolymer preferably used in the present invention preferably has a melting temperature (peak value) of 155 ° C. or less, more preferably 125 to 150 ° C., obtained from a differential scanning calorimeter. When the melting temperature (peak value) exceeds 155 ° C., it becomes difficult to join the members such as the outer cylinder and the header by the ultrasonic welding method.
Here, the melting temperature (peak value) obtained from the differential scanning calorimeter is a value to be measured in accordance with JIS K7121 “Plastic transition temperature measurement method”.

  When the propylene-based block copolymer (hereinafter sometimes referred to as a block copolymer) comprising a polypropylene segment and a propylene copolymer segment is used as the propylene-based polymer (a), the block copolymer contains The polypropylene segment accounts for 70 to 99% by weight, the propylene copolymer segment is preferably 1 to 30% by weight, the polypropylene segment is 86 to 98% by weight, and the propylene copolymer segment is more preferably 2 to 14% by weight. Within this range, it is suitable as a medical molded product from the viewpoint of mechanical properties and impact resistance.

At this time, the isotactic pentad fraction (mmmm) of the polypropylene segment is 90% or more, preferably 94% or more, more preferably 97% or more. If the isotactic pentad fraction (mmmm) is less than 90%, the molded product is easily deformed during molding.
Here, the isotactic pentad fraction (mmmm) is a value measured by ¹³ C-NMR method.

Further, as the propylene polymer (a), an α-olefin-propylene copolymer is polymerized in the first stage, and then an α-olefin-propylene copolymer having a different α-olefin content is polymerized in the second stage. It may be a propylene block copolymer (hereinafter also referred to as a block copolymer).
The total α-olefin content contained in the block copolymer is preferably 0.5 to 12% by weight, and more preferably 2 to 9% by weight. Moreover, as an alpha olefin, ethylene is preferable. When the α-olefin content is within this range, the resulting resin composition is suitable for impact resistance. When the total α-olefin content is less than 0.5% by weight, the impact resistance as a medical molded article is insufficient, and when it exceeds 12% by weight, the rigidity becomes insufficient.
Here, the α-olefin content is a value measured by the IR method using a propylene copolymer whose composition is tested by ¹³ C-NMR as a reference substance.

  Although it does not specifically limit as a manufacturing method of a propylene polymer, The polymerization method using a stereoregular catalyst is preferable. Examples of stereoregular catalysts include Ziegler catalysts and metallocene catalysts.

  As Ziegler catalysts, transition metal components such as titanium trichloride, titanium tetrachloride, trichloroethoxytitanium, etc., contact materials of the above-mentioned titanium halide compounds and magnesium compounds represented by magnesium halide, and alkylaluminum Compounds or their two-component catalysts with organic metal components such as halides, hydrides, alkoxides, and further, electron-donating compounds containing nitrogen, carbon, phosphorus, sulfur, oxygen, silicon, etc. are added to these components 3 Component-based catalysts can be mentioned.

  The metallocene catalyst includes (i) a transition metal compound belonging to Group 4 of the periodic table (so-called metallocene compound) containing a ligand having a cyclopentadienyl skeleton, and (ii) a stable ionic state by reacting with the metallocene compound. A catalyst comprising an activatable cocatalyst and, if necessary, (iii) an organoaluminum compound, any known catalyst can be used. The metallocene compound is preferably a bridged metallocene compound capable of stereoregular polymerization of propylene, and more preferably a bridged metallocene compound capable of isoregular polymerization of propylene.

  Examples of (i) metallocene compounds include JP-A-60-35007, JP-A-63-130314, JP-A-63-295607, JP-A-1-275609, JP-A-2-41303, and JP-A-2-41303. JP-A-2-131488, JP-A-2-76887, JP-A-3-163088, JP-A-4-300787, JP-A-4-21694, JP-A-5-43616, JP-A-5-209913, JP-A-6-6 No. 239914, JP-A-7-504934, and JP-A-8-85708.

More specifically, methylene bis (2-methylindenyl) zirconium dichloride, ethylenebis (2-methylindenyl) zirconium dichloride, ethylene 1,2- (4-phenylindenyl) (2-methyl-4-phenyl) -4H-azulenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride, isopropylidene (4-methylcyclopentadienyl) (3-t-butylindenyl) zirconium dichloride, dimethylsilylene (2- Methyl-4-t-butyl-cyclopentadienyl) (3′-t-butyl-5′-methyl-cyclopentadienyl) zirconium dichloride, dimethylsilylenebis (indenyl) zirconium dichloride, dimethylsilylenebis (4,5 , , 7-tetrahydroindenyl) zirconium dichloride, dimethylsilylenebis [1- (2-methyl-4-phenylindenyl)] zirconium dichloride, dimethylsilylenebis [1- (2-ethyl-4-phenylindenyl)] zirconium Dichloride, dimethylsilylenebis [4- (1-phenyl-3-methylindenyl)] zirconium dichloride, dimethylsilylene (fluorenyl) t-butylamidozirconium dichloride, methylphenylsilylenebis [1- (2-methyl-4, ( 1-naphthyl) -indenyl)] zirconium dichloride, dimethylsilylenebis [1- (2-methyl-4,5-benzoindenyl)] zirconium dichloride, dimethylsilylenebis [1- (2-methyl-4-phenyl-4H) -Azulenyl) ] Zirconium dichloride, dimethylsilylenebis [1- (2-ethyl-4- (4-chlorophenyl) -4H-azurenyl)] zirconium dichloride, dimethylsilylenebis [1- (2-ethyl-4-naphthyl-4H-azurenyl)] Zirconium dichloride, diphenylsilylene bis [1- (2-methyl-4- (4-chlorophenyl) -4H-azulenyl)] zirconium dichloride, dimethylsilylene bis [1- (2-ethyl-4- (3-fluorobiphenylyl) ) -4H-azurenyl)] zirconium dichloride, dimethylgermylenebis [1- (2-ethyl-4- (4-chlorophenyl) -4H-azurenyl)] zirconium dichloride, dimethylgermylenebis [1- (2-ethyl-) 4-phenylindenyl)] zirconium Zirconium compounds such as chloride can be exemplified. In the above, compounds in which zirconium is replaced with titanium or hafnium can be used in the same manner. In some cases, a mixture of a zirconium compound and a hafnium compound can be used. Further, the chloride can be replaced with other halogen compounds, hydrocarbon groups such as methyl, isobutyl and benzyl, amide groups such as dimethylamide and diethylamide, alkoxide groups such as methoxy group and phenoxy group, hydride groups and the like.
Among these, a metallocene compound in which an indenyl group or an azulenyl group is crosslinked with silicon or a germyl group is preferable.

The metallocene compound may be used by being supported on an inorganic or organic compound carrier. The carrier is preferably an inorganic or organic porous compound. Specifically, ion-exchange layered silicate, zeolite, SiO ₂ , Al ₂ O ₃ , silica alumina, MgO, ZrO ₂ , TiO ₂ , B Examples include inorganic compounds such as ₂ O ₃ , CaO, ZnO, BaO, and ThO ₂ , organic compounds composed of porous polyolefin, styrene / divinylbenzene copolymer, olefin / acrylic acid copolymer, and the like, or a mixture thereof. It is done.

  (Ii) As a co-catalyst that can be activated to a stable ionic state by reacting with a metallocene compound, an organoaluminum oxy compound (for example, an aluminoxane compound), an ion-exchange layered silicate, a Lewis acid, a boron-containing compound, an ionic compound And fluorine-containing organic compounds.

  (Iii) Examples of the organoaluminum compound include trialkylaluminum such as triethylaluminum, triisopropylaluminum, and triisobutylaluminum, dialkylaluminum halide, alkylaluminum sesquihalide, alkylaluminum dihalide, alkylaluminum hydride, and organoaluminum alkoxide. Can be mentioned.

As a method for producing the propylene polymer (a), in the presence of the above catalyst, a slurry method using an inert solvent, a solution method, a gas phase method substantially using no solvent, or a polymerization monomer as a solvent. And bulk polymerization method.
For example, in the case of slurry polymerization, it can be carried out in an inert hydrocarbon or liquid monomer such as n-butane, isobutane, n-pentane, isopentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene and the like. . The polymerization temperature is usually −80 to 150 ° C., preferably 40 to 120 ° C. The polymerization pressure is preferably 1 to 60 atmospheres, and the molecular weight of the resulting propylene polymer can be adjusted with hydrogen or other known molecular weight regulators. The polymerization is carried out by a continuous or batch reaction, and the conditions may be those usually used. Furthermore, the polymerization reaction may be performed in one stage or in multiple stages.

  In addition, when a polymer produced using a metallocene catalyst is blended with the propylene polymer (a), the propylene polymer (a) is more compatible with one produced using a metallocene catalyst. Good and more preferable.

2. Polyethylene (b)
The polyethylene (b) used in the present invention can further improve the impact resistance while maintaining the transparency, low odor, rigidity and low foreign matter appearance by changing the material morphology.
Such polyethylene (b) is desirably polyethylene having a density of 0.875 to 0.920 g / cm ³ , preferably 0.880 to 0.910 g / cm ³ , and may be an ethylene homopolymer. When (b) is used in an amount of 30 wt% or less, preferably 15 to 25 wt%, in which other α-olefin is copolymerized, the impact resistance is improved. Examples of other α-olefins include propane, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-heptene, 1-octene, 1-octene, Decene etc. can be mentioned.
Specific copolymers of polyethylene (b) are ethylene-propylene copolymer, ethylene-1-butene copolymer, ethylene-1-pentene copolymer, ethylene-1-hexene, ethylene-4-methyl- 1-pentene copolymer, ethylene-3-methyl-1-pentene copolymer, ethylene-1-heptene copolymer, ethylene-1-octene copolymer, ethylene-1-decene copolymer, etc. Can do.
Polyethylene (b) having a glass transition temperature (Tg) of −130 to 10 can be used, but generally it is considerably lower than propylene polymer (a), so this is blended into propylene polymer (a). Attempts have been made to improve the impact resistance after irradiation while maintaining transparency, but the results did not exceed expectations. However, the combined use of the nucleating agent of the present invention can be expected to have an excellent effect in promoting the blending effect.

The MFR of polyethylene (b) at 190 ° C. is 1 to 60 g / 10 minutes, preferably 2 to 40 g / 10 minutes. If it is within this range, the propylene polymer (a) and polyethylene (b) constituting the resin composition are well mixed, and a well-balanced resin composition excellent in transparency can be obtained. When the MFR of the polyethylene (b) is less than 1 g / 10 minutes or exceeds 60 g / 10 minutes, the dispersion in the propylene polymer (a) is deteriorated, and a stable composition cannot be obtained.
Here, MFR at 190 ° C. is a value measured under a load of 190 ° C. and 2.16 kg in accordance with JIS K7210.
Also, the value of (weight average molecular weight) / (number average molecular weight), which is an index of the width of the molecular weight distribution, should be less than 7.0, preferably less than 3.5, and more preferably less than 3.0. As a medical molded product, the physical property balance between rigidity and impact resistance is good.

Here, (weight average molecular weight) / (number average molecular weight) is defined by the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography (GPC). It is what is done. The measuring method of Mw / Mn is as follows.
Apparatus: Waters GPC 150C type Detector: MIRAN 1A infrared spectrophotometer (measurement wavelength, 3.42 μm)
Column: AD806M / S manufactured by Showa Denko Co., Ltd. (column calibration is performed by Tosoh monodisperse polystyrene (0.5 mg / ml solution of each of A500, A2500, F1, F2, F4, F10, F20, F40, and F288) Measurement was performed, and the logarithm of the elution volume and the molecular weight was approximated by a quadratic equation. ]
Measurement temperature: 140 ° C
Injection volume: 0.2ml
Concentration: 20 mg / 10 mL
Solvent: Orthodichlorobenzene Flow rate: 1.0 ml / min
The molecular weight of the sample was converted to polyethylene using the viscosity formula of polystyrene and polyethylene. Here, the coefficients of the viscosity formula of polystyrene are α = 0.723 and log K = −3.767, and polyethylene has α = 0.723 and log K = −3.407.

Further, when the polyethylene (b) is mixed with the propylene polymer (a), the smaller the MFR difference between the polyethylene (b) and the propylene polymer (a), the more the polyethylene (b) becomes the propylene polymer ( This is desirable because it tends to exist as a finely dispersed matrix in a) and the transparency becomes good.
Specifically, the MFR ratio of the MFR / propylene polymer (a) of polyethylene (b) is preferably 0.05 to 1.2, and more preferably 0.1 to 1.0. This range is expected to be meaningful in order to properly exhibit functions such as transparency, foreign matter mixing, and odor prevention as the medical molded article of the present invention.

The density of polyethylene (b) is 0.875 to 0.920 g / cm ³ , preferably 0.880 to 0.910 g / cm ³ . When the density is less than 0.875 g / cm ³ , the rigidity and transparency are insufficient when blended with polypropylene (a), whereas when it exceeds 0.920 g / cm ³ , the transparency may be remarkably deteriorated. is there. When the polyethylene (b) is blended with the propylene polymer (a), the transparency tends to deteriorate, but the density difference from the propylene polymer (a) is small, and the polyethylene (b) and the propylene polymer. When polyethylene (b) having an MFR ratio of polymer (a) (MFR of polyethylene (b) / MFR of propylene-based polymer (a)) close to 0.5 can be used, the tendency of deterioration of transparency can be reduced. , Impact resistance can be improved.
Here, the density is a value measured according to JIS K7112.

  Such polyethylene (b) can be produced by using an olefin stereoregular polymerization catalyst and polymerizing in the presence of ethylene and, if necessary, other α-olefins while adjusting the molecular weight. . Specifically, polyethylene (b) uses a catalyst such as a Ziegler catalyst, a Phillips catalyst, or a metallocene catalyst as a stereoregular polymerization catalyst for olefins, such as a gas phase method, a solution method, a high pressure method, and a slurry method. In the process, ethylene can be produced by copolymerizing with an α-olefin such as propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, if necessary. In particular, in order to reduce (weight average molecular weight) / (number average molecular weight) and to reduce density, a metallocene catalyst is used as a stereoregular polymerization catalyst for olefin, and it may be produced by a high pressure method or a solution method. desirable.

In addition, the polyethylene (b) used in the present invention can be used singly or in combination of two or more, as long as the effects of the present invention are not impaired.
Such polyethylene (b) is commercially available, such as Novatec LL series, Harmolex series, Kernel series, Mitsui Chemicals Tuffmer P series, Tuffmer A series, Prime Co., Ltd. Examples include the polymer Evolue series, Sumitomo Chemical Co., Ltd. Sumikasen E, EP series, and Excellen GMH series.
Moreover, as polyethylene (b) polymerized using a metallocene catalyst, Harmolex series, Kernel series, Evolue series made by Prime Polymer, Exelen FX series made by Sumitomo Chemical Co., Ltd., etc. are available. Can be illustrated.

3. Proportion of Propylene Polymer (a) and Polyethylene (b) In the polymer mixture used in the present invention, the proportion of propylene polymer (a) and polyethylene (b) is determined based on the propylene polymer (a ) Is 60 to 99 parts by weight, polyethylene (b) is 40 to 1 part by weight, preferably 60 to 99 parts by weight of propylene polymer (a), preferably 80 to 95 parts by weight, polyethylene (b) Is 40 to 1 part by weight, preferably 20 to 5 parts by weight. Within this range, a resin composition having excellent impact resistance after radiation irradiation is obtained. In general, when a polypropylene-based polymer (a) is blended with 20% by weight of polyethylene (b), for example, when the mixture is melt-cooled, the polypropylene polymer (a) having a high melting point is first crystallized. Then, polyethylene (b) having a low melting point crystallizes. Then, it is considered that a so-called sea-island structure in which polyethylene (b) is separated and precipitated in the polypropylene polymer (a) phase is considered. If it does so, it will become a phase-separation structure, On the other hand, development of a polypropylene-type polymer (a) spherulite will also be permitted. Although it is feared that it becomes opaque due to scattering and refraction, it is also predicted that it will cause the presence of foreign substances and odor generation, but the nucleating agent of the present invention is very sensitive to cooling conditions. In contrast, since crystallization starts at a relatively high temperature range and there are many crystal nuclei, rather than extremely large spherulites growing irregularly, many spherulites become smaller, and Although it can be estimated to be uniform, the mechanism is not fully understood. As described above, the nucleating agent of the present invention effectively functions not only in the polypropylene polymer (a) but also in the blend system and polymer alloy in which the polyethylene polymer (a) is blended with the polyethylene (b). It can be said that.

Although it is difficult to explain with a quantitative display, the MFR ratio of the MFR / propylene polymer (a) of polyethylene (b) can be set in a wide range of 0.01 to 3.0, but preferably The MFR of the polyethylene (b) and the propylene-based polymer (a) are very close by setting in the range of 0.05 to 1.2, more preferably 0.1 to 1.0. And is expected to be advantageous because the processability of the composition is in the same state. For example, the tendency of the magnitude of the MFR of the polymer tends to be linked to the magnitude of the molecular weight of the polymer, and is also expected to be slightly linked to the level of the melting point of the polymer.
For example, (1) MFR: 80 parts by weight of a propylene polymer (a) (PP) of 6 g / 10 min and MFR: 20 g by weight of a polymer mixture of polyethylene (b) (PE) of 4 g / 10 min Specification and (2) MFR: 6 g / 10 min propylene polymer (a) 80 parts by weight and MFR: 15 g / 10 min polyethylene (b) 20 parts by weight polymer mixture specification Therefore, the former (1) polymer mixture is a measure of processability in which MFR replaces molecular weight, so that MFR is not only close in terms of 4 and 6, but also has a molecular weight and melting point slightly linked to MFR. Is close to the specification of (1), so that the crystallization temperature of PP and PE which are both polymers (a) and (b) is closer as well as processability. First, due to the difference in PP is placed in the PP matrix in a phase-separated state in order to start after the crystallization of high PP starts and then the matrix system goes down to the crystallization temperature of PE. Therefore, it is expected that many fine crystals are generated stably.

Because it is such a propylene resin composition of the best specification, it is excellent only by blending 0.1 to 0.6 parts by weight of the nucleating agent (A) represented by the chemical structural formula (1). Transparency (haze) is expected to be achieved.
From the viewpoint of transparency (haze), it is advantageous to add 0.4 part by weight of the nucleating agent (A) more than 0.2 part by weight. 0.15, 0.2, 0.31, 0.4, 0.5, 0.65, 0.8, 1.0, and 1.5 parts by weight, and it is desired to increase the blending amount monotonously. However, if no consideration is given from the viewpoint of processability, odor is generated due to decomposition of the nucleating agent (A) during processing, volatilization, modified products such as aldehyde, and the like. However, the MFR ratio of the MFR / propylene polymer (a) of the polyethylene (b) of the present invention can be set in a wide range of 0.01 to 3.0, preferably 0.05 to 1.2. It is significant because it is also considered from the viewpoint of processability of the polymer mixture, such as being in the range of 0.1 to 1.0, more preferably, in the polymer mixture of a specific specification. Therefore, it is possible to achieve transparency with a relatively small blending amount, such as 0.1 to 0.6 parts by weight of the nucleating agent (A). Can be predicted.

  Although the polymer mixture of the specific specification of the present invention, particularly 0.1 to 0.6 parts by weight of the nucleating agent (A), is blended in a relatively small amount, the specific polymer mixture of the present invention In order to increase the crystallization temperature, it may be possible to increase the molding cycle, but not only can a transparent molded product be easily molded at the normal molding stage, but this can also be used as a medical molded product. This is because, when used, for example, it is possible to cope with sanitary and health damage due to blooming of the nucleating agent (A). In addition, there is a possibility that unforeseen problems may occur in the long-term use in the medical field as a medical molding, but the normal usage method in the medical field is that of a medical molded product in the medical field, especially an artificial one. Because molded products such as dialysis modules may be left in extremely harsh environments such as radiation sterilization, boiling sterilization of medical molding, and microwave sterilization, consideration must be given to environmental contamination in the medical field. become. Normal medical molded products are also required to have low-temperature impact resistance corresponding to thermal deformation of medical molded products, drops in cold regions, etc., but the medical molded products of the present invention have sufficient properties. Yes.

  The medical molded article of the present invention, for example, if the nucleating agent (A) is blended in the polymer mixture by about 0.2 parts by weight, the heat deformation temperature is 110 to 120 ° C. when no additive is added. It is expected to improve to 120-130 ° C. Also about a bending elastic modulus, about 1000 (MPa) thing without nucleating agent (A) addition improves about 20 to 50%. Further, since the rigidity is also improved, the medical molded product is improved in mechanical characteristics. Therefore, even a thin molded product is advantageous because it has predetermined performance and characteristics. The specification based on the polymer mixture may be due to irregular reflection due to the difference in refractive index between the crystal part and the non-crystal part, but it is more preferable to use polyethylene (b) using a metallocene catalyst. Can respond.

In particular, even when a medical molded product is subjected to radiation sterilization, and in some cases, microwaves, boiling, etc., some deterioration of the polymer mixture, crosslinking, modification, malodor, etc. are expected, but the product of the present invention Also has performance as a medical material from the standpoint of maintaining transparency, mechanical properties, and hygiene such as blooming resistance of nucleating agents and anti-aldehyde degradation.
Even if the change in the molded product for medical use after radiation sterilization is observed, there is almost no change in transparency (haze t = 2 mm), and it is only slightly reduced in IZOD impact (23 ° C. KJ / m ² ). . Similarly, even at the heat distortion temperature (HDT 0.45 MPa), there is no extreme decrease before and after radiation sterilization. However, importantly, the decomposition of the nucleating agent and the absence of blooming from a medical molded product stored for a long time make the application of the present invention more reliable.

  Thus, in the polymer mixture of the propylene polymer (a) and the polyethylene (b), the expression of the function and effect by adding the nucleating agent (A) described later is the propylene polymer. The MFR ratio of the MFR / propylene polymer (a) of the polyethylene (b) is 0.05-1. 2 is preferable, and it is expected to be advantageously expressed by a specific amount ratio of 0.1 to 1.0. Similarly, as a relationship between the two constituting the polymer mixture, the ratio of the mixing amount is within a specific range of 60 to 99 parts by weight of the propylene polymer (a) and 40 to 1 part by weight of the polyethylene (b). Since the MFR ratio of the coalesced (a) and polyethylene (d) is selected within a specific range, it is expected to be properly expressed. The fact that the MFR ratio is in a specific range is not only expected to have almost the same advantageous conditions in terms of melt mixing property and workability, but there are two types of MFR ratios having different melting points. It is also predicted that the change in behavior that occurs based on the difference in crystallization temperature that occurs due to the resin mixture is corrected. In any case, in the present invention, in order to most effectively express the transparency of the nucleating agent (A), which will be described later, and the nucleating agent function, the above-mentioned MFR is used in two kinds of specific polymer mixtures. The range of the ratio functions most effectively, and such a secondary effect of the combined cause cannot be predicted centrally, but is based on the knowledge of the present inventors.

Furthermore, when the molecular weight distribution (Mw / Mn) of polyethylene (b) is less than 3.5, the oligomer, low molecular weight content is small, there is no stickiness, odor generation is prevented during molding, and the molded product has a bad odor, Not only for the publicly known reason that the amount of the leaching substance affecting the taste is small, but also for expressing the functions such as transparency, rigidity and impact resistance of the nucleating agent (A) described later. It works very advantageously.
When the nucleating agent (A) described later is added to the propylene polymer (a), the polymer mixture of the propylene polymer (a) and the polyethylene (b), This means that the nucleating agent does not volatilize, decompose, or bias at high temperatures, and has an affinity for uniform dispersion, and is a very effective nucleating agent having a close relationship with the resin.
In addition to the propylene polymer (a) and the polyethylene (b), other polymers may be blended in the polymer mixture used in the present invention as long as the effects of the present application are not impaired.

4). Nucleator (A)
Although there is no limitation in particular in the nucleating agent (A) used for this invention, it is a compound shown by General formula (1), Among these, the compound shown by General formula (2) is preferable, Chemical structural formula ( The compound represented by 3) is more preferable.

[Wherein n is an integer of 0 to 2 and R1 to R5 are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an alkenyl group, an alkoxy group, a carbonyl group, a halogen group, and It is a phenyl group, R6 is a C1-C20 alkyl group. ]

[However, n is an integer of 0-2, R1, R2, R4, R5 are hydrogen atoms, R3 is a hydrogen atom or an alkyl group, alkenyl group, alkoxy group, carbonyl having 1-20 carbon atoms] A group, a halogen group, and a phenyl group, and R 6 is an alkyl group having 1 to 20 carbon atoms. ]

  A commercially available product can be used as such a nucleating agent. Specific examples include NX8000J manufactured by Milliken Corporation.

  The nucleating agent (A) used in the present invention is a nucleating agent having the properties of giving excellent transparency to the obtained molded product and extremely low elution.

  The compounding quantity of the nucleating agent (A) used for this invention is 0.1-0.6 weight part with respect to 100 weight part of polymer mixtures, Preferably it is 0.2-0.5 weight part. . When the amount is less than 0.1 parts by weight, it is difficult to obtain a sufficient effect. When the amount is 0.6 parts by weight or more, further improvement in performance cannot be expected and elution tends to occur.

  In the present invention, in addition to the nucleating agent (A), known nucleating agents such as sorbitol nucleating agents, organic phosphate nucleating agents, aromatic phosphate esters, and talc are used as other nucleating agents. In some cases, a synergistic effect can be expected depending on the combination of nucleating agents.

5). Neutralizing agent In the present invention, it is desirable to add a neutralizing agent. Specific examples of the neutralizing agent include metal fatty acid salts such as calcium stearate, zinc stearate and magnesium stearate, hydrotalcite (trade name: magnesium represented by the following general formula (9) of Kyowa Chemical Industry Co., Ltd.) Aluminum complex hydroxide salt), Mizukarak (lithium aluminum composite hydroxide salt represented by the following general formula (10)), and the like. In particular, when used as a member that is in contact with the liquid for a long period of time, such as a prefilled syringe, a kit preparation, or an infusion bag, hydrotalcite or Mizukarak that does not elute into the liquid to be contacted is advantageous.

Mg _1-x Al _x (OH) ₂ (CO ₃ ) _{x / 2} · mH ₂ O (9)
[Wherein x is 0 <x ≦ 0.5, and m is a number of 3 or less. ]

[Al ₂ Li (OH) ₆ ] _n X · mH ₂ O (10)
[Wherein, X is an inorganic or organic anion, n is the valence of the anion (X), and m is 3 or less. ]

  The blending amount of the neutralizing agent is preferably in the range of 0.005 to 0.2 parts by weight and more preferably in the range of 0.01 to 0.05 parts by weight with respect to 100 parts by weight of the polymer mixture.

6). Lubricant In the present invention, it is desirable to blend a lubricant. Examples of the lubricant include known lubricants, but butyl stearate and silicone oil are preferable. Specific silicone oils include dimethylpolysiloxane, methylphenylpolysiloxane, methylhydrodienepolysiloxane, α-ωbis (3-hydroxypropyl) polydimethylsiloxane, polyoxyalkylene (C ₂ -C ₄ ) dimethylpolysiloxane. And a polyorgano (C ₁ -C ₂ alkyl group and / or phenyl group) siloxane and polyalkylene (C ₂ -C ₃ ) glycol condensate. Of these, dimethylpolysiloxane and methylphenylpolysiloxane are preferred. A single lubricant or a plurality of lubricants may be used.
When silicone such as dimethylpolysiloxane is added, not only can scratches that occur during molding be prevented, but also burns that can occur in cylinders and hot runners can be prevented.

  The blending amount of the lubricant is preferably 0.001 to 0.5 parts by weight, more preferably 0.01 to 0.15 parts by weight, and 0.03 to 0.1 parts by weight with respect to 100 parts by weight of the polymer mixture. Particularly preferred. If the amount is less than 0.001 part by weight, the effect cannot be expected. On the other hand, if the amount exceeds 0.5 part by weight, not only a further effect cannot be expected, but also economically undesirable.

7). Other Additives In the present invention, in addition to the components described above, additives such as various antioxidants, ultraviolet absorbers, light stabilizers and the like used as stabilizers for propylene polymers may be blended. it can.

  Specifically, as the antioxidant, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-di-phosphite, di-stearyl-pentaerythritol-di-phosphite, bis ( 2,4-di-t-butylphenyl) pentaerythritol-diphosphite, tris (2,4-di-t-butylphenyl) phosphite, tetrakis (2,4-di-t-butylphenyl) -4 Phosphorous antioxidants such as 4,4'-biphenylene-diphosphonite, tetrakis (2,4-di-t-butyl-5-methylphenyl) -4,4'-biphenylene-diphosphonite, 2,6-di-t-butyl-p-cresol, tetrakis [methylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate)] methane, 1 3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate Phenolic antioxidants such as di-stearyl-β, β'-thio-di-propionate, di-myristyl-β, β'-thio-di-propionate, di-lauryl-β, β'-thio-di -Thio antioxidants such as propionate.

  Examples of the ultraviolet absorber include 2-hydroxy-4-n-octoxybenzophenone, 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2 And ultraviolet absorbers such as' -hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole.

  Examples of the light stabilizer include n-hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate, 2,4-di-t-butylphenyl-3 ′, 5′-di-t-butyl-4 ′. -Hydroxybenzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, dimethyl-2- (4-hydroxy-2,2,6,6-tetramethyl-1-piperidyl) succinate ) Ethanol condensate, poly {[6-[(1,1,3,3-tetramethylbutyl) amino] -1,3,5-triazine-2,4diyl] [(2,2,6,6- Tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]}, N, N′-bis (3-aminopropyl) ethylenediamine-2,4- Bis [N-butyl-N- ( , Mention may be made of a light stabilizer such as 2,2,6,6-pentamethyl-4-piperidyl) amino] -6-chloro-1,3,5-triazine condensate.

  Furthermore, amine-based antioxidants represented by the following general formula (5) and the following general formula (6), which have no discoloration and are excellent in resistance to NOx gas discoloration by radiation treatment, 5,7-di-t-butyl-3 Examples include lactone antioxidants such as-(3,4-di-methyl-phenyl) -3H-benzofuran-2-one and vitamin E antioxidants such as the following general formula (7).

  However, in performing radiation sterilization, from the viewpoint of coloring after radiation sterilization, it is generally preferable not to add a phenolic antioxidant, and usually 0.01 to 0.2% by weight of a phosphorus antioxidant (for example, Asahi Denka Kogyo Co., Ltd. Adegas Tab 2112) and a hindered amine UV stabilizer (abbreviation is HALS, for example, TINUVIN 622LD manufactured by Ciba Specialty Chemicals Co., Ltd.) 0.01 to 0.2% by weight, combined with radiation irradiation. Make it correspond.

In addition, when joining the outer cylinder of the dialyzer, which is one of the members for artificial dialysis, and the header by the laser welding method, a UV absorber, an infrared absorber, a pigment, and an organic dye are blended to facilitate welding. You may do it.
Of these, organic dyes (quartalimide) are suitable for laser welding, and are desirably used in the range of 0.0001 to 0.05 parts by weight with respect to 100 parts by weight of the polymer mixture. As such organic dyes, commercially available ones can be used. Specific examples include Lumogen IR 788 manufactured by BASF.

  In addition, antistatic agents, slip agents, dispersants such as fatty acid metal salts, high density polyethylene, olefinic elastomers, non-olefinic elastomers, and the like can be blended within a range that does not impair the object of the present invention.

[2] Propylene-based resin composition production method The propylene-based resin composition used in the present invention comprises a propylene-based polymer (a), polyethylene (b) and a nucleating agent (A), or polyethylene as necessary. (B) and other additives are added to a Henschel mixer, a super mixer, a ribbon blender, etc. and mixed, and then mixed with a normal single screw extruder, twin screw extruder, Banbury mixer, plastic bender, roll, etc. It can be obtained by melt-kneading in a temperature range of ˜260 ° C.

[3] Medical molded article The medical molded article of the present invention is obtained by molding the propylene resin composition by various molding methods such as injection molding, extrusion molding, and blow molding, which are known methods. can get.
The medical molded article of the present invention includes disposable syringes and parts thereof, catheters / tubes, infusion bags, blood bags, vacuum blood collection tubes, surgical nonwoven fabrics, blood filters, blood circuits, and other disposable instruments, artificial lungs, artificial Parts of artificial organs such as anus, prefilled syringe, kit preparation, drug container, test tube, suture, base material of dental material, part of orthopedic material, case of contact lens, PTP (PRESS THROUGH PACKAGE), SP (STRIP PACKAGE) / packaging, P vial (plastic vial), eye drop container, drug solution container, liquid long-term storage container, cap and the like. In addition, in order to satisfy the quality and test method 1 (2) of the dialysate supply section and dialysate circuit among the dialysis-type artificial kidney device approval standards, in particular, the members for artificial dialysis, specifically dialyzer outer cylinder and header, and its Suitable for related members.
The medical molded article of the present invention has been subjected to radiation sterilization. Examples of the radiation include γ-rays and electron beams. The medical molded article of the present invention is preferably irradiated with 1 to 50 KGy, and is preferably irradiated with 5 to 30 KGy. More preferred. Depending on the degree of sterilization required and the environment at the time of molding, it is difficult to obtain a sufficient effect when the irradiation dose is less than 1 KGy. On the other hand, when it exceeds 50 KGy, the physical properties are significantly lowered after irradiation, which is good. You might not be able to get a good product.

In particular, since a medical molded article has a risk of having a great adverse effect on the human body when it is damaged during use, it is desired that the medical molded article has excellent impact resistance. Of JIS K7110 - it is preferred that the Izod impact value measured at to 23 ° C. in accordance with "plastic Izod impact strength test method" is a front irradiation 2.0 kgf / cm ² or more, 2.5 kgf / cm ² or more It is more preferable that If the Izod impact value is less than 2.0 kgf / cm ² , the possibility of breakage during use or transportation of the product increases, which is not preferable.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to a following example, unless the summary is exceeded. In addition, the measurement method of physical property values, evaluation methods, resins, and additives used in Examples and Comparative Examples are as follows.

1. Measurement method and evaluation method of physical properties (1) Flexural modulus:
The measurement was performed at 23 ° C. in accordance with “a hard plastic bending test method” of JIS K7203 (unit: MPa). The higher this value, the better the resulting molded product. The flexural modulus is desirably 700 or more, and if it is 700 or more, the product has sufficient practical strength as a product.
(2) Izod impact strength (IZOD impact):
Using a test piece with a notch, measurement was performed at 23 ° C. according to JIS K7203 (unit: KJ / m ² ). The higher this value is, the better the resulting molded article is in impact resistance. The Izod impact strength is preferably 3 or more, and more preferably 5 or more. When the Izod impact strength is 5 or more, the product has extremely excellent impact resistance.
(3) Haze value:
It measured based on JISK7105 using the sheet piece of thickness 1mm. The smaller this value, the better the resulting molded product. The haze value is preferably 15 or less, and more preferably 10 or less. When the haze value is 10 or less, the product is extremely excellent in transparency.
(4) Deflection temperature under load (thermal deformation temperature: HDT):
Measurement was performed at a load of 0.45 MPa in accordance with JIS K7207. The higher this temperature, the better the molded product obtained.
(5) Odor evaluation The molded product is put in the odor bag used in the odor test based on the Odor Prevention Law, the air inside the odor bag is replaced with odorless air through activated carbon, and then sealed, and the room temperature is 23 ± 2 ° C. It was stored for 1 week under the condition of humidity 50 ± 5%. Thereafter, the odor intensity was evaluated on the basis of JIS Z9080 according to the following five-stage scale.
1: No smell at all.
2: A slight odor is felt.
3: I usually feel a smell.
4: I feel quite smelly.
5: A very strong smell is felt.
(6) Compatibility with dialysis artificial kidney device:
The measurement was performed according to the quality and test method 1 (2) of the dialysate supply section and dialysate circuit among the dialysis artificial kidney device approval criteria. In addition, the standard of the dissolution test result is as follows.
(I) Appearance: Colorless, no foreign matter (ii) Abalone: Disappears within 3 minutes (iii) pH: Difference from blank is 1.5 or less (iv) Zinc: Standard solution or less (v) Potassium permanganate reduction Substance: Difference in consumption of potassium permanganate from the standard solution: 1.0 ml or less (vi) Evaporation residue: 1.0 mg or less (vii) Ultraviolet absorption spectrum: 0.1 or less Artificial radiation-sterilized treatment The dialysis member was subjected to a dissolution test at a temperature of 70 ° C.

2. Resin, additive propylene polymer (a)
(A-1) Ethylene-propylene random copolymer: MFR (JIS K7210, 230 ° C., 2.16 kg load) 30 g / 10 minutes, ethylene content 3.4 wt% (Novatech MX03EQ manufactured by Nippon Polypro Co., Ltd.)
(A-2) Propylene homopolymer: MFR (JIS K7210, 230 ° C., 2.16 kg load) 11 g / 10 min, stereoregularity 97% (Novatech MA3 manufactured by Nippon Polypro Co., Ltd.)
(A-3) Metallocene-based ethylene-propylene random copolymer: MFR (JIS K7210, 230 ° C., 2.16 kg load) 30 g / 10 min, ethylene content 0.7 wt% (Wintech manufactured by Nippon Polypro Co., Ltd.) WMG03P)

Polyethylene (b)
(B-1) Metallocene polyethylene: Density (JIS K7112) 0.898 g / cm ³ , MFR (JIS K7210, 190 ° C., 2.16 kg load) 2.2 g / 10 min, (Mw / Mn) 2.2. (Nippon Polyethylene Corporation Kernel KF262)
(B-2) Metallocene polyethylene: Density (JIS K7112) 0.905 g / cm ³ , MFR (JIS K7210, 190 ° C., 2.16 kg load) 12 g / 10 min, (Mw / Mn) 2.2. (Kernel KS571 manufactured by Nippon Polyethylene Co., Ltd.)
(B-3) metallocene-based polyethylene: Density ^{(JIS K7112) 0.885g / cm 3} , MFR (JIS K7210,190 ℃, 2.16kg load) 32 g / 10 min, (Mw / Mn) 2.2. (Nippon Polyethylene Corporation Kernel KJ650T)
(B-4) Metallocene-based polyethylene: Density (JIS K7112) 0.913 g / cm ³ , MFR (JIS K7210, 190 ° C., 2.16 kg load) 2.4 g / 10 min, (Mw / Mn) 2.2. (Kernel KF271 manufactured by Japan Polyethylene Corporation)
(B-5) Metallocene polyethylene: density (JIS K7112) 0.877 g / cm ³ , MFR (JIS K7210, 190 ° C., 2.16 kg load) 3.7 g / 10 min, (Mw / Mn) 2.2. (Nippon Polyethylene Corporation Kernel KS341T)
(B-6) Metallocene polyethylene: Density (JIS K7112) 0.906 g / cm ³ , MFR (JIS K7210, 190 ° C., 2.16 kg load) 1 g / 10 min, (Mw / Mn) 2.2. (Harmolex NF324 manufactured by Nippon Polyethylene Co., Ltd.)
(B-7) Metallocene polyethylene: density (JIS K7112) 0.880 g / cm ³ , MFR (JIS K7210, 190 ° C., 2.16 kg load) 50 g / 10 min, (Mw / Mn) 2.2. (Nippon Polyethylene Corporation Kernel KJ740T)
(B-8) Metallocene polyethylene: density (JIS K7112) 0.921 g / cm ³ , MFR (JIS K7210, 190 ° C., 2.16 kg load) 2.5 g / 10 min, (Mw / Mn) 2.2. (Nippon Polyethylene Co., Ltd. Kernel KF283)
(B-9) Metallocene polyethylene: density (JIS K7112) 0.870 g / cm ³ , MFR (JIS K7210, 190 ° C., 2.16 kg load) 2.2 g / 10 min, (Mw / Mn) 2.2. (Nippon Polyethylene Corporation Kernel KS330T)

(A-1) Mirad NX8000: (NX8000; manufactured by Milliken & Company): Nucleator (A) Equivalent: The following chemical structural formula (3)

(A-2) ADK STAB NA21 (manufactured by ADEKA Corporation): Organophosphate metal salt compound-based clearing nucleating agent: Clearing nucleating agent outside the scope of the present invention (A-3) Gelol MD (New Nippon Rika ( Co., Ltd.): Dimethylbenzylidenesorbitol-based clearing nucleating agent: Clearing nucleating agent outside the scope of the present invention

(B-1) Hindered phenol antioxidant: Irganox 1010 (IR1010; manufactured by Ciba). Tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxylphenyl) propionate] methane.
(B-2) Phosphorus antioxidant: Irgaphos 168 (IF168; manufactured by Ciba). Tris (2,4-di-tert-butylphenol) phosphite.
(B-3) Hindered amine antioxidant: dimethyl succinate 1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate (B-4) hydroxylamine Antioxidant: Irgastab FS042 (FS042; manufactured by Ciba): N, N-dioctadecylhydroxyamine.
(B-5) Calcium stearate (CAST; manufactured by NOF Corporation)
(B-6) Silicone oil: Dowcorning 360 Medical Fluid (silicone) -100 (manufactured by Toray Dow Corning Co., Ltd.)

[Examples 1 to 11, Comparative Examples 1 to 8, Reference Examples 1 to 4]
Polymers and additives were prepared at the blending ratios (parts by weight) shown in Table 1, and after dry blending with a super mixer, they were melt-kneaded using a 35 mm diameter twin screw extruder. Extrusion pelletization was performed from the die at a die outlet temperature of 220 ° C. The obtained pellets were injection molded by an injection molding machine at a resin temperature of 250 ° C., an injection pressure of 900 kg / cm ² and a mold temperature of 40 ° C. to prepare test pieces. The physical properties were measured using the obtained test pieces. The evaluation results are shown in Table 1.

As is apparent from Table 1, Example 1 is a propylene-based resin composition within the scope of the present invention in which polyethylene (b-1) is blended with an ethylene-propylene random copolymer (a-1) and is transparent. It can be seen that the balance of low odor and mechanical properties is excellent, and that the dialysis artificial kidney device is compatible with related members.
Example 2 is a propylene resin composition within the scope of the present invention in which polyethylene (b-1) is blended with a propylene homopolymer (a-2), the rigidity and heat resistance are extremely improved, and the dialysis type. It turns out that it has the compatibility to the related member of an artificial kidney apparatus.
Example 3 is a propylene resin composition within the scope of the present invention in which a large amount of polyethylene (b-1) is blended with the ethylene-propylene random copolymer (a-1) used in Example 1. It can be seen that a molded article having extremely excellent impact resistance can be obtained.
Example 4 is a propylene system within the scope of the present invention in which the MFR ratio in which polyethylene (b-2) is blended with respect to the ethylene-propylene random copolymer (a-1) used in Example 1 is 0.55. It is a resin composition, and it can be seen that a molded article with extremely good transparency can be obtained.
Example 5 is a propylene-based resin within the scope of the present invention in which the MFR ratio in which polyethylene (b-3) is blended with respect to the ethylene-propylene random copolymer (a-1) used in Example 1 is 1.07. It turns out that it is a resin composition and the molded article which has the outstanding impact resistance is obtained.
Example 6 is a propylene within the range of the present invention in which polyethylene (b-4) having a density of 0.913 g / cm ³ was blended with the ethylene-propylene random copolymer (a-1) used in Example 1. It can be seen that a molded product having an excellent impact resistance is obtained.
Example 7 is a propylene within the range of the present invention in which polyethylene (b-5) having a density of 0.877 g / cm ³ is blended with the ethylene-propylene random copolymer (a-1) used in Example 1. It can be seen that a molded product having an excellent impact resistance is obtained.
Examples 8 and 9 are propylene resin compositions within the scope of the present invention in which the hindered phenol is not blended as an antioxidant in the propylene resin composition used in Example 4.
Example 8 is a formulation in which the antioxidant is changed from hindered phenol to hindered amine, and it can be seen that even if the antioxidant is hindered amine, a product having excellent transparency and mechanical properties is obtained. .
In addition, Example 9 is a combination in which hydroxylamine is added to the combination of antioxidants of Example 8, and even when hydroxylamine is combined with the antioxidant, a product having excellent transparency and mechanical properties is obtained. I understand that.
Example 10 is a composition in which silicone oil as a lubricant is added to the propylene-based resin composition used in Example 4, and if silicone oil of this amount is added, transparency and mechanical properties are not impaired, It turns out that an excellent thing is obtained.
Example 11 is a propylene resin composition within the scope of the present invention in which the MFR ratio in which polyethylene (b-2) is blended is 0.55 with respect to the metallocene ethylene-propylene random copolymer (a-3). In addition, it can be seen that a molded product having an excellent balance between mechanical properties and impact resistance and having compatibility with related members of a dialysis artificial kidney device having extremely good heat resistance and transparency can be obtained.

On the other hand, Comparative Example 1 is outside the scope of the present invention in which polyethylene (b-6) having an MFR ratio of 0.03 is blended with the ethylene-propylene random copolymer (a-1) used in Example 4. It is a propylene-based resin composition, and Comparative Example 2 is a blend of polyethylene (b-7) with an MFR ratio of 1.67 to the ethylene-propylene random copolymer (a-1) used in Example 4. The propylene-based resin composition outside the scope of the present invention. It can be seen that the deterioration in transparency becomes more severe as the MFR ratio of the propylene-based polymer (a) and polyethylene (b) used falls outside the scope of the present invention.
Comparative Examples 3 to 5 are propylene resin compositions outside the scope of the present invention in which polyethylene is not blended with the propylene polymer.
Comparative Example 3 is a blend of the ethylene-propylene random copolymer (a-1) and the modifier (A-1), which is excellent in transparency but significantly reduced the impact resistance after irradiation. I understand that.
The comparative example 4 mix | blends the modifier (A-1) with the propylene homopolymer (a-2), and it turns out that the impact resistance after radiation irradiation has fallen remarkably.
In Comparative Example 5, the metallocene-based ethylene-propylene random copolymer (a-3) is blended with the modifier (A-1), and it can be seen that the impact resistance after irradiation is significantly reduced. .
Comparative Examples 6 to 8 are propylene-based resin compositions outside the scope of the present invention in which the nucleating agent (A) used in the present invention is not blended. Comparative Example 6 is a propylene-based resin composition in which no nucleating agent (A) is blended, and it can be seen that the transparency is extremely poor unless the nucleating agent (A) is blended. In Comparative Example 7, instead of the nucleating agent (A), Gelol MD, which is a generally preferred nucleating agent, was used, but the odor was bad and compared with Example 1. It turns out that transparency is inferior. Comparative Example 8 uses Adeka Stub NA21, which is a generally preferred nucleating agent in the same manner as Gerol MD, instead of the nucleating agent (A), and is inferior in transparency as compared with Example 1. I understand.
Comparative Example 9 is a propylene-based resin composition in which polyethylene (b-1) is excessively blended with respect to the ethylene-propylene random copolymer (a-1) used in Example 1, and the polyethylene (b ) Is added, the impact resistance is improved. However, on the other hand, Reference Example 1, which shows that the flexural modulus is less than 700 and the rigidity is extremely lowered and sufficient mechanical strength cannot be obtained, is the ethylene-propylene random copolymer used in Example 1 ( A propylene-based resin composition in which polyethylene (b-8) having a density of 0.921 g / cm ³ is blended with respect to a-1), and Reference Example 2 is an ethylene-propylene random copolymer used in Example 1. A propylene-based resin composition in which polyethylene (b-9) having a density of 0.870 g / cm ³ is blended with the coalescence (a-1). It can be seen that as the density difference from the propylene-based polymer (a) used increases, the deterioration in transparency becomes more severe.

  The medical molded product of the present invention satisfies the quality and test method 1 (2) of the dialysate supply section and dialysate circuit among the dialysis-type artificial kidney device approval criteria, and has impact resistance, transparency, and molding. It turns out that it is excellent in property. In addition, the medical molded article of the present invention has been subjected to radiation sterilization treatment, but there is little decrease in physical properties due to sterilization treatment. Furthermore, the outer cylinder and header of the dialyzer can be clearly observed from the outside due to its excellent transparency, and the elution characteristics are also excellent. It can be put to practical use.

1 Arm of person undergoing dialysis 2 Tube 3 Blood pump 4 Air trap 5 Dializer 6 Console 7 Blood inlet (with cap)
8 Blood outlet (with cap)
9 Dialysate inlet (with cap)
10 Dialysate outlet (with cap)
11 Hollow fiber 12 Outer cylinder of dialyzer 13 Header of dialyzer

JP 2008-255325 A JP 2002-219169 A WO99 / 64506 pamphlet

Claims (6)

The MFR ratio between the propylene polymer (a) and the polyethylene (b) (the MFR of the polyethylene (b) / the MFR of the propylene polymer (a)) is 0.05 to 1.2, and the propylene polymer ( a) The nucleating agent (A) represented by the following chemical structural formula (1) is 0.1 to 100 parts by weight of a polymer mixture comprising 60 to 99 parts by weight and polyethylene (b) 1 to 40 parts by weight. A medical molded article comprising a propylene-based resin composition blended with 0.6 parts by weight and sterilized by radiation.

[Wherein n is an integer of 0 to 2 and R1 to R5 are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an alkenyl group, an alkoxy group, a carbonyl group, a halogen group, and It is a phenyl group, R6 is a C1-C20 alkyl group. ] The medical molded article according to claim 1, wherein the density of the polyethylene (b) is 0.875 to 0.920 g / cm ³ .   The polyethylene (b) is polymerized using a metallocene catalyst, and the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is less than 3.5. Or the medical molded article of Claim 2.   The medical molding according to any one of claims 1 to 3, wherein the lubricant is blended in an amount of 0.001 to 0.5 parts by weight with respect to 100 parts by weight of the polymer mixture. Goods.   The medical molded article according to any one of claims 1 to 4, wherein the medical molded article is an artificial dialysis member. The medical molded article according to claim 5, wherein the artificial dialysis member is an outer cylinder, a header and / or a cap of a dialyzer.