JP7043747B2 - Propylene resin composition for artificial dialysis member and its molded product - Google Patents

Description

The present invention relates to a member for artificial dialysis, and more specifically, among the criteria for approval of a dialysis-type artificial kidney device, the quality and test method 1 (2) of a dialysate supply unit and a dialysate circuit are satisfied, and rigidity and moldability are satisfied. The present invention relates to an artificial dialysis member having excellent heat resistance, impact resistance, transparency, mold stain resistance, and product appearance.

When the function of the kidney deteriorates, a device called an artificial kidney removes water and waste products from the blood and regulates the blood so that it does not become acidic. Generally, this is called dialysis. The concept is shown in FIG. 1 and the details of the dialyzer for cleaning blood are shown in FIG.
In FIGS. 1 and 2, first, a needle is pierced into a blood vessel of the arm 1 of a person undergoing dialysis, and blood is continuously taken out by a blood pump 3. The blood pump 3 can send blood in one direction by rotating while pressing the roller against the soft tube 2. Further, the part that cleans the blood is a tool called a dialyzer 5. If air enters the dialyzer 5, the efficiency will deteriorate, and in order to protect the safety of the person undergoing dialysis, cylinders called air traps 4 are attached to the front and back of the dialyzer to prevent air from entering. The dialyzer 5 can clean the blood by draining excess water and waste products from the blood through the semipermeable membrane. 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 water and waste products inside is carried out. The console 6 is also equipped with various alarms 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, in which about 10,000 extremely fine threads called hollow fibers 11 which are semipermeable membranes are parallel to the container. It is bundled and stored. 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 to pass water and waste products through the dialysate, the blood can be cleaned by continuously sending blood.
Further, the dialyzer 5 is composed of a cylindrical outer cylinder 12 and a header 13 for covering the outer cylinder 12. The headers 13 on both sides are connected to the hollow fiber 11, and when blood flows from the blood inlet 7 of one header 13 and the blood flows through the hollow fiber 11, water and waste products in the blood are hollow. The structure is such that the blood is discharged to the dialysate 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 an inlet 9 for dialysate and an outlet 10 for dialysate, and has a structure in which water and waste products are taken out by circulating the dialysate in the dialyzer 5.

Currently, the outer cylinder and header of such a dialyzer, which is a member for artificial dialysis, are made of polycarbonate (hereinafter, may be referred to as PC) or polypropylene (hereinafter, may be referred to as PP). (See, for example, Patent Document 1). Conventionally, the mainstream is made of PC, and since PC made is excellent in transparency and impact resistance, it is said that the internal state is easy to see while the dialyzer is in operation and it can be used with confidence, and it is hard to break during transportation and use. It was an advantageous product in terms of points. However, on the other hand, PC requires a drying process before molding, resulting in poor work efficiency, high melting point, high molding temperature, and poor energy efficiency, and elution of chemical substances caused by raw materials. It also included concerns about adverse effects and the high price. Therefore, it has excellent impact resistance, transparency, and moldability in place of PC, and satisfies the quality and test method 1 (2) of the dialysate supply unit and dialysate circuit among the approval criteria for dialysis-type artificial kidney devices. Currently, there is a demand for a material that can be used, and recently, PP products have been distributed as dialyzer for alternative materials.
However, PP products are resistant to mold release problems and moldability due to their large shrinkage, deformation during the hot air drying process required for dry type dialyzer, and contamination in this application where cleanliness is required. There are problems such as reduction of connected components and impact resistance to prevent cracking, and an excellent PP material is required.

Japanese Unexamined Patent Publication No. 2002-219169

In view of the above problems, an object of the present invention is to satisfy the quality and test method 1 (2) of the dialysate supply unit and the dialysate circuit among the criteria for approval of the dialysis-type artificial kidney device, and to provide rigidity and moldability. It is an object of the present invention to provide a member for artificial dialysis which is excellent in heat resistance, impact resistance, transparency, mold stain resistance, and product appearance.

As a result of diligent research to solve the above problems, the present inventor has made a propylene-based resin composition using a specific propylene-based polymer as a base material, containing a specific amount of a specific nucleating agent, and within a specific range. Satisfies the quality of the dialysate supply unit and the dialysate circuit and the test method 1 (2) among the approval criteria for the dialysate type artificial kidney device, and has rigidity, moldability, heat resistance, impact resistance, transparency, and a mold. We have found that it is suitable as a member for artificial dialysis having stain resistance and excellent product appearance, and have completed the present invention.

That is, the present invention provides the following propylene-based resin composition and molded product, and particularly provides a molded product for artificial dialysis member as a propylene-based resin composition and molded product suitable for a member for artificial dialysis. It is a thing.

[1] To 100 parts by weight of the Ziegler-based propylene-ethylene copolymer having an ethylene content of 1.5 to 2.4% by weight, the nucleating agent (A) represented by the following formula (1) is 0. .Propylene for artificial dialysis members, which is a composition containing 1 to 0.3 parts by weight and having the following characteristics (i) to (ix) and is used by treating with an electron beam or gamma ray of 10 to 60 kGy. Based resin composition.
(I) The tensile yield stress according to JIS K7161 is 30 to 40 MPa.
(Ii) The crystallization temperature (peak value) obtained by a differential scanning calorimeter based on JIS K7121 is 110 to 130 ° C.
(Iii) Flexural strength according to JIS K7171 is 35 to 50 MPa
(Iv) Deflection temperature under load (0.45 MPa) according to JIS K7191 is 90 to 110 ° C.
(V) Charpy impact strength (23 ° C.) conforming to JIS K7111 is 3.0 to 5.5 kJ / m ²
(Vi) Haze (thickness 1 mm) conforming to JIS K7136 is 8 to 25%.
(Vii) Volatile component content is 60 ppm by weight or less (viii) In the measurement of temperature elution fractionation (TREF) using orthodichlorobenzene as a solvent, 3.5% by weight of the component elutes at a temperature of 40 ° C. or lower. Below (ix), the ultimate viscosity [η] measured in decalin at 135 ° C. is 1.3 to 1.8 dl / g.

（式中、Ｒ^１は、水素原子又は炭素数１～４のアルキル基であり、Ｒ^２及びＲ^３は、同一又は異なって、それぞれ水素原子又は炭素数１～１２のアルキル基であり、Ｍは、周期表第３族又は第４族の金属原子であり、Ｘは、Ｍが周期表第３族の金属原子である場合には、ＨＯ－であり、Ｍが周期表第４族の金属原子である場合には、Ｏ＝又は（ＨＯ）_２－である。）

(In the formula, R ¹ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ² and R ³ are the same or different alkyl groups having a hydrogen atom or 1 to 12 carbon atoms, respectively, and M. Is a metal atom of Group 3 or 4 of the Periodic Table, X is HO- when M is a metal atom of Group 3 of the Periodic Table, and M is a metal of Group 4 of the Periodic Table. In the case of an atom, O = or (HO) _2- ).

[2] The artificial dialysis member according to claim 1, wherein the injection-molded product having a diameter of 0.1 mm or more and having 3 or less white foreign substances in a 10 cm × 10 cm × 1 mm injection molded product using a propylene resin composition for an artificial dialysis member. Propylene resin composition for.

[3] A molded product for an artificial dialysis member using the propylene-based resin composition for an artificial dialysis member according to [1] or [2].

[4] A molded product for an artificial dialysis member according to [3], wherein the molded product for an artificial dialysis member is an outer cylinder and / or a header of a dialyzer.

The molded product manufactured by using the propylene-based resin composition of the present invention, particularly the molded product for an artificial dialysis member, has the characteristics required for the molded product for an artificial dialysis member, that is, it is set in a dialysis device to prevent defects in the manufacturing process. Rigidity that can be used for dialysis, more efficient moldability, heat resistance required for the drying process of hollow yarn, impact resistance that prevents cracking during transportation and use, transparency that can confirm defects in hollow yarn, and cleanerness. It is useful as a member for artificial dialysis having low mold contamination for the required application and high appearance without foreign matter derived from additives that cause foreign matter contamination and misjudgment. In particular, it is very useful as a molded product for an artificial dialysis member which is an outer cylinder and / or a header of a dialyzer.

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

The propylene-based resin composition of the present invention is a propylene-based resin composition using a specific propylene-based polymer as a base material, using a specific amount of a specific nucleating agent, and within a specific range, and is a dialysis-type artificial kidney apparatus. Among the approval criteria, the quality of the dialysate supply unit and the dialysate circuit and the test method 1 (2) are satisfied, and the rigidity, moldability, heat resistance, impact resistance, transparency, mold stain resistance, and the product It is characterized by its excellent appearance.
Hereinafter, the propylene-based resin composition and the molded product of the present invention will be described in detail.

[1] Propylene-based resin composition (1) Cheegler-based propylene-ethylene copolymer (i) Ethylene content of Cheegler-based propylene-ethylene copolymer The Cheegler-based propylene-ethylene used in the propylene-based resin composition of the present invention. The copolymer is preferably a copolymer with ethylene, and for example, a copolymer with butene-1 which is another α-olefin is not preferable for this application because the heat resistance of the rigidity is lowered. The ethylene content is 1.5 to 2.4% by weight, preferably 1.7 to 2.2% by weight, and in this range, rigidity, moldability, heat resistance, impact resistance, and transparency. , A propylene-based resin composition having an excellent balance of mold contamination and the like can be obtained.
Here, the contents of propylene and ethylene are red based on the calibration curve prepared by infrared spectroscopy using the measuring method described in Examples described later, that is, the reference material whose composition has been verified by the ¹³ C-NMR method. It is a value measured by external spectroscopy.

(Ii) Tensile yield stress according to JIS K7161 The propylene-based resin composition used in the present invention has a tensile yield stress in the range of 30 to 40 MPa, preferably 30 to 38 MPa, and 30 to 38 MPa. 35 MPa is more preferable. If the tensile yield stress is 40 MPa or more, there is a concern that the impact resistance will not be sufficient, and if it is 30 MPa or less, there is a concern that problems such as tearing will occur during molding in the manufacturing process, and when used in a dialysis machine. There is a concern that problems will occur.
The tensile yield stress can be adjusted by adjusting the ethylene content of the Ziegler-based propylene-ethylene copolymer and the amount of the nucleating agent (A) added.

(Iii) Crystallization temperature (peak value) obtained by a differential scanning calorimeter based on JIS K7121.
The propylene-based resin composition used in the present invention has a crystallization temperature (peak value) in the range of 110 to 130 ° C., preferably 115 to 130 ° C., obtained by a differential scanning calorimeter based on JIS K7121. , 115-125 ° C. is more preferable. If the crystallization temperature is 130 ° C or higher, there is a concern that the impact resistance will not be sufficient, and if it is 110 ° C or lower, the molding cycle during molding of the molded product for dialysis members will deteriorate, resulting in poor productivity. Concerns arise.
The crystallization temperature can be adjusted by adjusting the ethylene content of the Ziegler-based propylene-ethylene copolymer and the amount of the nucleating agent (A) added.

(Iv) Flexural strength according to JIS K7171 The propylene-based resin composition used in the present invention has a bending strength in the range of 35 to 50 MPa, preferably 38 to 48 MPa, preferably 40 to 40 MPa, according to JIS K7171. 45 MPa is more preferable. If the bending strength is 50 MPa or more, there is a concern that the impact resistance will not be sufficient, and if it is 35 MPa or less, there is a concern that problems will occur when the product is used by incorporating it into a dialysis machine, and the heat resistance and deformation will be poor, resulting in a production process. There is a concern that it will sometimes be deformed.
The bending strength can be adjusted by adjusting the ethylene content of the Ziegler-based propylene-ethylene copolymer and the amount of the nucleating agent (A) added.

(V) Deflection temperature under load (0.45 MPa) in accordance with JIS K7191
The propylene-based resin composition used in the present invention has a deflection temperature under load in the range of 90 to 110 ° C., preferably 90 to 105 ° C., more preferably 90 to 100 ° C., in accordance with JIS K7191. If the deflection temperature under load is 110 ° C or higher, there is a concern that the impact resistance will not be sufficient, and if it is 90 ° C or lower, there is a concern that the hollow fiber will be deformed during hot air drying during manufacturing.
The deflection temperature under load can be adjusted by adjusting the ethylene content of the Ziegler-based propylene-ethylene copolymer and the amount of the nucleating agent (A) added.

(Vi) Charpy impact strength (23 ° C) conforming to JIS K7111
The propylene-based resin composition used in the present invention has a Charpy impact strength (23 ° C.) in the range of 3.0 to 5.5 kJ / m 2 and 3.5 to 5.0 kJ / m ² in accordance with JIS K7111. m ² is preferable, and 4.0 to 4.5 kJ / m ² is more preferable. If the Charpy impact strength (23 ° C) is 5.5 kJ / m ² or more, there is a concern that heat resistance and moldability will not be sufficient, and if it is 3.0 kJ / m ² or less, there is a concern that the product will be transported or used. There is a concern that it will crack.
The shearpy impact strength (23 ° C.) can be adjusted by adjusting the ethylene content of the Ziegler-based propylene-ethylene copolymer and the amount of the nucleating agent (A) added.

(Vii) Haze (thickness 1 mm) conforming to JIS K7136
The propylene-based resin composition used in the present invention has a haze (thickness of 1 mm) in the range of 8 to 25% according to JIS K7136, preferably 8 to 20%, and more preferably 8 to 15%. If the haze (thickness 1 mm) is 25% or more, there is a concern that the hollow fiber and the state inside may not be sufficiently confirmed, and if it is 8% or less, there is a concern that heat resistance deformability may occur.
The haze (thickness 1 mm) can be adjusted by adjusting the ethylene content of the Ziegler-based propylene-ethylene copolymer and the amount of the nucleating agent (A) added.

(Viii) Volatile component content The propylene-based resin composition used in the present invention has a volatile component content in the range of 60 wt ppm or less, preferably 50 wt ppm or less, and further 40 wt ppm or less. preferable. When the volatile component content is not more than the above upper limit, when the propylene-based resin composition is molded into a molded product for a highly clean artificial dialysis member, the volatile component adheres to the molded product for the artificial dialysis member. It is possible to suppress pollution caused by dialysis and reduce the frequency of performance defects. In addition to contamination, there are concerns about a decrease in productivity due to the increased frequency of mold cleaning.
The content of the volatile component can be adjusted by adjusting the catalyst and devising the production method of the Ziegler-based propylene-ethylene copolymer.

(Ix) Heat-temperature elution fractionation (TREF) using orthodichlorobenzene as a solvent
In the elution curve obtained by the temperature elution fractionation (TREF) measurement, the component elution at a temperature of 40 ° C. or lower is 3.5% by weight or less.
The component that elutes at a temperature of 40 ° C. or lower is a low crystallinity component, and if the amount of this component is large, the crystallinity of the entire product is lowered, and the mechanical strength such as the rigidity of the product is lowered. In addition, there is a concern that the surface of the molded product may bleed, which is not preferable for products that require cleanliness.
Therefore, this amount needs to be 3.5% by weight or less, preferably 3.0% by weight or less, more preferably 2.5% by weight or less, and very preferably 2.3% by weight or less. be.

Here, the details of the method for measuring the elution component by the temperature-increasing elution separation (TREF) are as follows.
The sample is dissolved in orthodichlorobenzene at 140 ° C. to prepare a solution. After introducing this into a TREF column at 140 ° C., the mixture is cooled to 100 ° C. at a temperature lowering rate of 8 ° C./min, subsequently cooled to 40 ° C. at a temperature lowering rate of 4 ° C./min, and then held for 10 minutes. Then, the solvent orthodichlorobenzene was flowed through the column at a flow rate of 1 mL / min, and the components dissolved in orthodichlorobenzene at 40 ° C. were eluted in the TREF column for 10 minutes, and then the temperature rise rate was 100 ° C./hour. The column is linearly heated to 140 ° C. to obtain an elution curve.

Column size: 4.3 mm φ x 150 mm
Column filler: 100 μm Surface-inert treated glass beads Solvent: Ortodichlorobenzene Sample concentration: 5 mg / mL
Sample injection volume: 0.1 mL
Solvent flow rate: 1 mL / min Detector: Fixed wavelength infrared detector, FOXBORO, MIRAN, 1A
Measurement wavelength: 3.42 μm

(X) Extreme viscosity measured in decalin at 135 ° C. [η]
Considering the filling of the resin in the mold at the time of injection molding, it is desired from the viewpoint of molding processing to reduce the molecular weight (that is, the ultimate viscosity is small) within a range that does not impair the physical characteristics. On the other hand, if the molecular weight is extremely reduced, the mechanical properties may be adversely affected or the problem of stickiness may occur. From the above viewpoint, the ultimate viscosity ([η]) of the Ziegler-based propylene-ethylene copolymer is preferably in the range of 1.3 to 1.8 dl / g. Here, the ultimate viscosity ([η]) is a value measured at 135 ° C. in decalin.

(Xi) Catalyst of Cheegler-based propylene-ethylene copolymer The Cheegler-based propylene-ethylene copolymer used in the present invention is not particularly limited as a catalyst, but it is preferable to use a stereoregular catalyst. As an example, a transition metal component such as a titanium halide compound such as titanium trichloride, titanium tetrachloride, or trichloroethoxytitanium, a contact material between the titanium halide compound and a magnesium compound typified by magnesium halide, and an alkylaluminum compound. Alternatively, a two-component catalyst with organic metal components such as halogenated substances, hydrides, and alkoxides, and three components obtained by adding an electron-donating compound containing nitrogen, carbon, phosphorus, sulfur, oxygen, silicon, etc. to those components. A system catalyst can be mentioned.

(2) Nucleating Agent The propylene-based resin composition of the present invention contains 0.1 to 0.3 parts by weight of the nucleating agent (A) with respect to 100 parts by weight of the Ziegler-based propylene-ethylene copolymer. When the content of the nucleating agent is 0.1 parts by weight or more, transparency can be expected, and when it is 0.3 parts by weight or less, there is less concern about bleeding on the surface of the molded product.
By using a nucleating agent, transparency can be improved, crystals of propylene resin are densely generated, and volatile components contained in the molded product for artificial dialysis members can be suppressed from leaking to the outside of the molded product. , Productivity can be improved by promoting the crystallization of the propylene resin. Furthermore, the molded product for artificial dialysis members has a thicker part such as a rib part than other parts, and cooling is delayed compared to the thin part, and voids are likely to occur inside the molded product. The inclusion of the nucleating agent can greatly suppress the generation of voids.
Nucleating agent (A)

（式中、Ｒ^１は、水素原子又は炭素数１～４のアルキル基であり、Ｒ^２及びＲ^３は、同一又は異なって、それぞれ水素原子又は炭素数１～１２のアルキル基であり、Ｍは、周期表第３族又は第４族の金属原子であり、Ｘは、Ｍが周期表第３族の金属原子である場合には、ＨＯ－であり、Ｍが周期表第４族の金属原子である場合には、Ｏ＝又は（ＨＯ）_２－である。）

(In the formula, R ¹ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ² and R ³ are the same or different alkyl groups having a hydrogen atom or 1 to 12 carbon atoms, respectively, and M. Is a metal atom of Group 3 or 4 of the Periodic Table, X is HO- when M is a metal atom of Group 3 of the Periodic Table, and M is a metal of Group 4 of the Periodic Table. In the case of an atom, O = or (HO) _2- ).

Some nucleating agents other than the nucleating agent (A) are unfavorable because white foreign matter due to unmelting is generated in the molded product for dialysis, and some have insufficient performance such as transparency. (A) is suitable.
As such a nucleating agent (A), a commercially available one can be used. Specifically, the product name "ADEKA STAB NA-21" manufactured by ADEKA CORPORATION can be mentioned.

(3) Other Additives In the propylene-based resin composition of the present invention, in addition to the above-mentioned components, various antioxidants used as stabilizers for propylene-based polymers, ultraviolet absorbers, and light stabilizers are used. , Additives such as neutralizers can be added.
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-di-phosphite, tris (2,4-di-t-butylphenyl) phosphite, tetrakis (2,4-di-t-butylphenyl) -4 , 4'-biphenylene-di-phosphonite, tetrakis (2,4-di-t-butyl-5-methylphenyl) -4,4'-biphenylene-di-phosphonite and other phosphorus antioxidants, 2,6-di-t-butyl-p-cresol, tetrakis [methylene (3,5-di-t-butyl-4-hydroxyhydrocin namemate)] methane, 1,3,5-trimethyl-2,4 Penyl antioxidants such as 6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, di- Thio-based antioxidants such as stearyl-β, β'-thio-di-propionate, di-myristyl-β, β'-thio-di-propionate, di-lauryl-β, β'-thio-di-propionate, etc. Can be mentioned.

Examples of the UV absorber include 2-hydroxy-4-n-octoxybenzophenone, 2- (2'-hydroxy-3', 5'-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2). Examples thereof include an ultraviolet absorber 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-succinate (4-hydroxy-2,2,6,6-tetramethyl-1-piperidyl) ) 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- (1,2,2,6,6-pentamethyl-4-piperidyl) amino] -6-chloro-1,3,5-triazine condensate and other photostabilizers can be mentioned. can.

Further, an amine-based antioxidant represented by the following formula (2) and the following formula (3), which has good NOx gas discoloration resistance, 5,7-di-t-butyl-3- (3,4-di-) Examples thereof include a lactone-based antioxidant such as methyl-phenyl) -3H-benzofuran-2-one, and a vitamin E-based antioxidant such as the following formula (4).

As the neutralizing agent, metal fatty acid salts such as calcium stearate, zinc stearate, magnesium stearate, hydrotalcite (trade name: DHT-4A, magnesium aluminum composite hydroxide salt manufactured by Kyowa Chemical Industry Co., Ltd.), Mizukarak (trade name, lithium-aluminum composite hydroxide salt manufactured by Mizusawa Chemical Industry Co., Ltd.) can be mentioned, but calcium stearate is economical and contributes to the improvement of moldability, and is most preferable.

Furthermore, various known additives such as lubricants, dispersants such as fatty acid metal salts, dyes, pigments and the like can be blended within a range that does not impair the object of the present invention.
It should be noted that, as long as the properties, functions, transparency and other properties of the propylene-based resin composition of the present invention are not impaired, polymers other than the Cheegler-based propylene-ethylene copolymer, for example, polyethylene and ethylene-propylene co-weight. Couplings, homopolymers such as ethylene-propylene-diene copolymers, ethylene-butene-1 copolymers, ethylene-vinyl acetate copolymers, ethylene-acrylate copolymers, acrylate polymers, or binary or The ternary copolymer may be optionally added in an amount of 0 to 30 parts by weight with respect to 100 parts by weight of the Cheegler-based propylene-ethylene copolymer. Similarly, elastomers such as natural rubber, butyl rubber, diene rubber, EPR and EPDM can be blended. Furthermore, general-purpose inorganic fillers such as talc, calcium carbonate, silica, alumina, gypsum, and mica can be used in combination.

[2] Method for producing Ziegler-based propylene-ethylene copolymer As a method for producing the Ziegler-based propylene-ethylene copolymer, a slurry polymerization method using an inert solvent, a solution polymerization method, and a substance in the presence of the above catalyst. Examples thereof include a vapor phase polymerization method that does not use a solvent, and a bulk polymerization method that uses a polymerization monomer as a solvent.
For example, in the case of the slurry polymerization method, it can be carried out in an inert hydrocarbon such as n-butane, isobutane, n-pentane, isopentane, hexane, heptane, octane, cyclohexane, benzene, toluene and xylene. In the case of the bulk polymerization method, it can be carried out in a liquid polymerization monomer. The polymerization temperature is usually −80 to 150 ° C., preferably 40 to 120 ° C. The polymerization pressure is preferably 1 to 60 atm (0.10 to 6.08 MPa), and the molecular weight of the obtained Ziegler-based propylene-ethylene copolymer can be adjusted with hydrogen or another known molecular weight adjusting agent. can. The polymerization is carried out by a continuous reaction or a batch reaction, and the conditions may be the conditions usually used. Further, the polymerization reaction may be carried out in one stage or in multiple stages.

[3] Method for Producing Propylene-based Resin Composition The propylene-based resin composition of the present invention contains a Cheegler-based propylene-ethylene copolymer, a nucleating agent (A), and other additives as necessary. After the fixed amount is put into a Henshell mixer (trade name), a super mixer, a ribbon blender, etc. and mixed, the temperature is 190 to 260 ° C. using a normal single-screw extruder, twin-screw extruder, vanbury mixer, plastic bender, roll, etc. It can be obtained by melt-kneading in a temperature range.

[4] Molded Product for Artificial Dialysis Member The molded product for artificial dialysis member of the present invention is obtained by molding the propylene-based resin composition by an injection molding method, which is a known method.
Examples of the molded product for an artificial dialysis member of the present invention include an outer cylinder and a header of a dialyzer, and related members thereof.
The molded article for an artificial dialysis member of the present invention has been subjected to radiation sterilization. Examples of the radiation include gamma rays and electron beams, and the molded product for an artificial dialysis member of the present invention is preferably irradiated with 10 to 60 kGy, and is irradiated with 15 to 30 kGy. Is more preferable. When the irradiation amount is 10 kGy or more, a sufficient effect can be obtained, while when it is 60 kGy or less, the deterioration of physical properties after irradiation is small and a good product can be obtained.

Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.
The physical characteristic measurement methods used in each Example and Comparative Example, as well as propylene-based polymers, nucleating agents, calcium stearate, and known compounding agents for resins are as follows.

<1. Measurement method>
(1) Ethylene content
¹³ The ethylene content in the random copolymer was measured by infrared spectroscopy using the characteristic absorption band of 733 cm ^-1 using the ethylene-propylene random copolymer whose composition was verified by C-NMR as a reference material (calibration curve preparation). Based on the prepared calibration curve, the ethylene content of the pellet sample of the propylene resin composition was measured by infrared spectroscopy using a film having a thickness of about 500 μm by press molding.
Here, the contents of propylene and ethylene as reference substances for preparing a calibration curve are values measured by the ¹³ C-NMR method under the following conditions. ¹³ The spectrum of C-NMR was analyzed according to the analysis method described in JP-A-2006-307120, and the contents of propylene and ethylene were calculated.
Equipment: JEOL-GSX270 manufactured by JEOL Ltd.
Concentration: 300 mg / 2 mL
Solvent: Orthodichlorobenzene (2) Extreme viscosity Using a Ubbelohde viscometer as a solvent, decalin was used, and pellet samples of the propylene-based resin composition were measured at a temperature of 135 ° C.

(3) Eluted component (TREF)
A pellet sample of the propylene resin composition is dissolved in o-dichlorobenzene (containing 0.5 mg / ml BHT) at 140 ° C. to prepare a solution. After introducing this into a TREF column at 140 ° C., it is cooled to 100 ° C. at a temperature lowering rate of 8 ° C./min, followed by cooling to −15 ° C. at a temperature lowering rate of 4 ° C./min, and held for 60 minutes. Then, the solvent o-dichlorobenzene (including 0.5 mg / ml BHT) was flowed through the column at a flow rate of 1 ml / min, and the components dissolved in o-dichlorobenzene at -15 ° C. in the TREF column were added. Elute for 10 minutes, then linearly heat the column to 140 ° C. at a heating rate of 100 ° C./hour to obtain an elution curve.
〔Device〕
(TREF section)
TREF column: 4.3 mmφ x 150 mm Stainless steel column Column filler: 100 μm Surface-inactivated glass beads Heating method: Aluminum heat block Cooling method: Pelche element (Cooling of Pelche element is water cooling)
Temperature distribution: ± 0.5 ° C
Temperature controller: Chino Digital Program Controller KP1000 (valve oven)
Heating method: Air bath oven Measurement temperature: 140 ° C
Temperature distribution: ± 1 ° C
Valve: 6-way valve 4-way valve (sample injection part)
Injection method: Loop injection method Injection amount: Loop size 0.1 ml
Injection inlet heating method: Aluminum heat block measurement temperature: 140 ° C
(Detection unit)
Detector: Fixed wavelength infrared detector FOXBORO MIRAN 1A
Detection wavelength: 3.42 μm
High temperature flow cell: Micro flow cell for LC-IR Optical path length 1.5 mm Window shape 2φ x 4 mm Oval synthetic sapphire Window plate Measurement temperature: 140 ° C
(Pump section)
Liquid feed pump: SSC-3461 pump manufactured by Senshu Kagaku Co., Ltd. [Measurement conditions]
Solvent: o-dichlorobenzene (containing 0.5 mg / ml BHT)
Sample concentration: 5 mg / ml
Sample injection amount: 0.1 ml
Solvent flow rate: 1 ml / min

(4) Measurement of Volatile Component Content The volatile component content (oligomer amount having 30 or less carbon atoms) generated from the propylene resin composition was measured by Dynamic Headspace (DHS) -GC / MS. The volatile component content is the ratio of the volatile component content to the propylene-based resin composition (unit: ppm by weight). The measurement method is shown below.

(4.1) Outline of measurement and evaluation After heating a pellet sample of a propylene resin composition to 100 ° C and collecting the volatile components generated there at -150 ° C, a gas chromatograph (GC) / mass spectrometer (GC) / mass spectrometer ( MS) was used to separate, detect and identify each volatile component. For the calibration curve, an aliphatic linear hydrocarbon having 10 to 32 carbon atoms and 2 carbon atoms was used as a standard mixed solution having a concentration of 1000 μg / ml in an n-heptane solvent, and the measurement was performed under the same conditions as the sample to obtain a gas chromatogram /. It was measured and prepared by mass spectrometry. The quantification was calculated using the standard value of n-icosane.

(4.2) Equipment and measurement method
(I) Heat expulsion (dynamic headspace) device:
Approximately 50 mg of a pellet sample of a propylene-based resin composition is precisely weighed and filled in a heat-discharging tube (TDS tube manufactured by GRESTEL), and approximately 10 mg of quartz wool (GL Sciences, Cat. No. 3001-) is placed on both ends thereof. 12404) was packed. After charging the above TDS tube into a heating and extracting device (TDS-A manufactured by GERSTEL) at 40 ° C, the inside of the tube is replaced with helium, the temperature is raised to 100 ° C at a rate of 60 ° C / min, and 30 at 100 ° C. Heated for minutes. During this heating period, the GC inlet (CIS4 manufactured by GL STEL) filled with quartz wool (manufactured by GL Sciences) was cooled to −150 ° C. to collect volatile components generated from the sample. The collected components were vaporized by rapidly heating the collected portion to 320 ° C. and introduced into a GC column for GC / MS analysis.
(Ii) Gas chromatograph (GC):
Agilent HP6890
Column: DB-5ms
Column temperature rise conditions: 40 ° C x 5 min to 10 ° C / min to 300 ° C x 15 min
(Iii) Mass spectrometer (MS):
Agilent Mass Sensitive Detector 5973N
The electron impact (EI) method was used for ionization of the measured components.

(5) Crystallization temperature Measured with a differential scanning calorimeter according to JIS K7121.
Crystallization temperature when 5.0 mg of pellet sample of propylene resin composition was taken using DSC manufactured by Seiko, held at 200 ° C. for 5 minutes, and then crystallized to 40 ° C. at a temperature lowering rate of 10 ° C./min. (Peak value) was Tc (unit: ° C.).

(6) Tensile yield stress Measured according to JIS K7161.

(7) Flexural strength Measured according to JIS K7171.

(8) Deflection temperature under load Measured according to JIS K7191.

(9) Charpy impact intensity (before and 2 weeks after irradiation with gamma ray 25 kGy)
The Charpy impact strength at 23 ° C. was measured according to JIS K7111.

(10) Haze (before and 2 weeks after irradiation with gamma ray 25 kGy)
The haze with a wall thickness of 1 mm was measured according to JIS K7136.

(11) Appearance In an injection-molded product having a diameter of 10 cm × 10 cm × 1 mm, a white foreign substance having a diameter of 0.1 mm or more was visually confirmed.

(12) Compatibility with related members of dialysis type artificial kidney device (after irradiation with gamma ray 25 kGy)
Of the dialysis-type artificial kidney device approval criteria indicated by the notification of the Chief of the Examination Division, Pharmaceutical Affairs Bureau, Ministry of Health and Welfare, to the head of each prefecture's hygiene department (bureau) as Pharmaceutical Trial No. 401 on June 20, 1983, dialysate supply Measurements were carried out according to the quality of the part and dialysate circuit and the test method 1 (2). The criteria for the dissolution test results are as follows.
(I) Appearance: colorless lamp, no foreign matter (ii) Awadachi: disappears within 3 minutes (iii) pH: difference from blank is 1.5 or less (iv) Zinc: standard solution or less (v) Potassium permanganate reduction Sex substance: Difference in potassium permanganate consumption from standard solution 1.0 ml or less (vi) Evaporation residue: 1.0 mg or less (vii) Ultraviolet absorption spectrum: 0.1 or less

<2. Resins, additives>
2-1. Production of Ziegler-based propylene-based polymer (1) Production example 1 RPP1
<Manufacturing of solid titanium catalyst component>
3.7 L of decane and 3.5 L of 2-ethylhexyl alcohol were heated and reacted at 130 ° C. for 2 hours to make a uniform solution with 700 g of anhydrous magnesium chloride, and then 165 g of phthalic anhydride was added to this solution at 130 ° C. Further, stirring and mixing is performed for 1 hour to dissolve phthalic anhydride in the uniform solution. After cooling the uniform solution thus obtained to room temperature, the entire amount is added dropwise to 30 g of titanium tetrachloride kept at −20 ° C. over 1 hour. After the charging is completed, the temperature of this mixed solution is raised to 110 ° C. over 4 hours, 0.4 L of diisobutylphthalate is added when the temperature reaches 110 ° C., and the mixture is kept at the same temperature for 2 hours under stirring. .. After the reaction for 2 hours is completed, the solid part is collected by hot filtration and thoroughly washed with 110 ° C. decane and hexane until no free titanium compound is detected in the washing liquid. The titanium catalyst component synthesized by the above production method was dried with a dryer. The composition (main component) of the titanium catalyst component thus obtained was 2.3% by weight of titanium, 58.0% by weight of chlorine, 18.0% by weight of magnesium and 14.0% by weight of diisobutylphthalate.

<Prepolymerized titanium catalyst component>
200 ml of purified hexane was placed in a 400 ml glass reactor substituted with nitrogen, 20 mmol of triethylaluminum, 4 mmol of dicyclopentyldimethoxysilane, and 2 mmol of the titanium catalyst component were added in terms of titanium atom, and then 5.9 Nl / hour. Propylene was supplied at a rate for 1 hour to polymerize 2.8 g of propylene per 1 g of Ti catalyst component.
After the completion of this prepolymerization, the liquid phase portion was removed by filtration, and the separated solid portion (prepolymerization catalyst) was dispersed again in the decan.

<Manufacturing of propylene-ethylene copolymer>
After sufficiently replacing the inside of the stirring autoclave having an internal volume of 200 liters with propylene, 45 kg of liquefied propylene was introduced. To this, 0.3 kg of ethylene, 470 ml of a triethylaluminum / n-heptane solution (concentration of triethylaluminum was 50 g / l) and 1.9 g of cyclohexylmethyldimethoxysilane were added, and the internal temperature was maintained at 30 ° C. Next, 300 L of hydrogen (as a standard volume) and 3.8 g of the prepolymerization catalyst were press-fitted with argon to start the polymerization, and at the same time, the temperature was raised to 70 ° C. over 40 minutes. After 1.0 hour had passed while the polymerization temperature was maintained at 70 ° C., 100 ml of ethanol was added to stop the reaction, and the residual gas was purged. The yield of the obtained polymer per 1 g of the solid catalyst was 27 kg, the MFR was 20.0 g / 10 minutes, and the ethylene content was 1.9% by weight. This was designated as RPP1.

(2) Production Example 2 RPP2
In Production Example 1 <Production of Propylene-Ethylene Copolymer>, which is an example of production of RPP1, the same production was performed except that ethylene was 0.24 kg and hydrogen was 200 L. The yield was 23 kg and the MFR was 15.0 g / 10. The ethylene content was 1.5% by weight. This was designated as RPP2.

(3) Production Example 3 RPP3
In Production Example 1 <Production of Propylene-Ethylene Copolymer>, which is an example of production of RPP1, the same production was performed except that ethylene was 0.44 kg and hydrogen was 500 L. The yield was 27 kg and the MFR was 35.0 g / 10. The ethylene content was 2.4% by weight. This was designated as RPP3.

The ethylene content of the propylene-ethylene copolymer of the present invention can be adjusted by the amount of ethylene charged, and if the amount of ethylene charged is increased, the ethylene content of the propylene-ethylene copolymer can also be increased. By reducing the amount of ethylene in the propylene-ethylene copolymer, the ethylene content of the propylene-ethylene copolymer can also be reduced. By reducing the amount of ethylene, the tensile yield stress, bending strength, and deflection temperature under load can be adjusted high, while by increasing the amount of ethylene, the Charpy impact strength can be adjusted high. Further, in the combination of the catalytic performance and the nucleating agent (A), the haze can be adjusted by adjusting the amount of ethylene, and the volatile component and the elution component of the temperature-raising elution fraction can be adjusted by the amount of hydrogen. Further, the ultimate viscosity [η] can be adjusted by the amount of hydrogen, and the ultimate viscosity [η] can be lowered by increasing the amount of hydrogen.

(4) Production Example 4 RPP4
<Manufacturing of solid catalyst components>
The catalyst (solid catalyst component) described in Example 1 (1) of Japanese Patent No. 4644352 was produced.
<Manufacturing of propylene-ethylene random copolymer>
A propylene-ethylene random copolymer was produced using a continuous polymerization tank consisting of a liquid phase polymerization tank with an internal volume of 0.9 m ³ and a stirring type gas phase polymerization tank of 1.9 m ³ .
Liquefied propylene was continuously fed to the liquid phase polymerization tank at 115 kg / Hr, and hydrogen and ethylene were continuously fed so as to be 13.0 mol% and 2.2 mol%, respectively, with respect to propylene. Further, triethylaluminum was continuously fed at 30.6 g / Hr, and tert-butyl-ethyldimethoxysilane was continuously fed at 1.3 g / Hr. Further, the catalyst (solid catalyst component) described in Example 1 (1) of Japanese Patent No. 4644352 is continuously fed at 0.30 g / Hr, the pressure in the polymerization tank is 3.02 MPaG, and the internal temperature. The propylene-ethylene random copolymer (I) was produced by adjusting the temperature to 61 ° C. and the residence time to 1.5 Hr.
The propylene-ethylene random copolymer (I) obtained in the liquid phase polymerization tank had an MFR of 35.3 g / 10 minutes, an ethylene content of 3.0% by weight, and a catalytic efficiency of 125,000 g / g. ..
The powder obtained by the liquid phase polymerization is then transferred to the gas phase polymerization tank, and the liquefied propylene accompanying during that time is vaporized by flushing and undergoes a step of separating the gas and the powder.
Then, the obtained copolymer (I) is transferred to a gas phase polymerization tank, where a propylene-ethylene random copolymer (II) is produced. As a production condition, hydrogen (/ propylene + ethylene) and ethylene (/ propylene + ethylene) are continuously fed so as to be 5.3 mol% and 3.8 mol%, respectively, and the pressure in the polymerization tank is 1.75 MPaG. The propylene-ethylene random copolymer (III), which is a multi-stage polymer composed of the copolymer (I) and the copolymer (II), is prepared by adjusting the internal temperature to 75 ° C. and the residence time to 0.9 Hr. Obtained. Further, ethanol was continuously supplied to the gas phase polymerization tank at an ethanol / Al = 0.3 mol ratio as a polymerization activity inhibitor for adjusting the polymerization amount of the propylene-ethylene random copolymer (II).
The propylene-ethylene random copolymer (III) had an MFR of 30 g / 10 minutes and an ethylene content of 3.8% by weight. The ratio of the propylene-ethylene random copolymer (II) was 22% by weight, and the propylene-ethylene random copolymer (II) had an MFR of 16.9 g / 10 minutes and an ethylene content of 6.6% by weight. Was calculated as%. This propylene-ethylene random copolymer (III) was designated as RPP4.

(5) Production Example 5 HPP
<Manufacturing of solid catalyst components>
20 L of dehydrated and deoxidized n-heptane was introduced into a tank with a stirrer having an internal volume of 50 liters (L) sufficiently substituted with nitrogen, and then 10 mol of magnesium chloride (MgCl ₂ ) and tetrabutoxytitanium [Ti (O-). 20 mol of n-C _{4H 9} ) ₄ ] was introduced and reacted at 95 ° C. for 2 hours. After completion of the reaction, the temperature was lowered to 40 ° C., 12 L of methylhydropolysiloxane [kinematic viscosity: 20 centistokes (cSt) = 2 × ^10-5 m ² / s] was introduced, and the reaction was carried out for 3 hours. The solid component produced was washed with n-heptane.
Subsequently, using the tank with a stirrer, 5 L of n-heptane purified in the same manner as above was introduced into the tank, and 3 mol of the solid component synthesized above was introduced in terms of Mg atoms. Next, 5 mol of tetrachlorosilane (SiCl ₄ ) was mixed with 2.5 L of n-heptane, introduced into a flask at 30 ° C. for 30 minutes, and reacted at 70 ° C. for 3 hours. After completion of the reaction, the cells were washed with n-heptane.
Next, 2.5 L of n-heptane was introduced into the tank with a stirrer, 0.3 mol of phthalic acid chloride was mixed, introduced at 70 ° C. for 30 minutes, and reacted at 90 ° C. for 1 hour. After completion of the reaction, the cells were washed with n-heptane. Subsequently, 2 L of tetrachlorotitanium (TiCl ₄ ) was introduced and reacted at 110 ° C. for 3 hours. After completion of the reaction, the solid component (a1) for producing the solid catalyst component (a) was obtained by washing with n-heptane. The titanium content of this solid component was 2.0% by weight.
Then, 8 L of n-heptane and 400 g of the solid component (a1) synthesized above were introduced into the nitrogen-substituted tank with a stirrer, 0.6 L of _SiCl4 was introduced as the component (a2), and the temperature was 90 ° C. for 2 hours. It was reacted. After completion of the reaction, 0.54 mol of vinyltrimethylsilane [(CH ₂ = CH) Si (CH ₃ ) ₃ ] as the component (a3) and t-butylmethyldimethoxysilane [(t-C ₄ ) as the component (a4). H ₉ ) (CH ₃ ) Si (OCH ₃ ) ₂ ] 0.27 mol and 1.5 mol of triethylaluminum [Al (C ₂ H ₅ ) ₃ ] as component (a5) were sequentially introduced and 2 at 30 ° C. Contacted for hours.
After the contact was completed, the mixture was thoroughly washed with n-heptane to obtain 390 g of a solid catalyst component (a) mainly composed of magnesium chloride. The titanium content of this solid catalyst component (a) was 1.8% by weight.

<Manufacturing of propylene homopolymer>
Polymerization was carried out using a fluidized bed reactor having an internal volume of 230 L as a continuous reactor. The reactor was continuously supplied with a polymerization temperature of 85 ° C., a propylene partial pressure of 1.8 MPa (absolute pressure), and hydrogen as a molecular weight control agent so that the molar ratio of hydrogen / propylene was 0.010. Further, triethylaluminum was supplied at 5.25 g / hr and the catalyst described above was supplied as the solid catalyst component (a) so that the polymer polymerization rate was 20 kg / hr to produce a propylene homopolymer.
The powder polymerized in the reactor was continuously withdrawn into a vessel so that the amount of powder retained in the reactor was 60 kg. A nitrogen gas containing water was supplied to terminate the reaction, and a propylene homopolymer was obtained.
The MFR of this propylene homopolymer was 11 g / 10 min, and the melting point (Tm) was 160 ° C. This was designated as HPP.

2-2. Hydroxylating agent (NA-21) Hydroxyaluminum bis (2,4,8,10-tetra-trans-butyl-6-hydroxy-12-dibenzo [d, g] [1.3], which is a nucleating agent (A) .2] Dioxaphosphosin-6-oxide (compound represented by the above formula (1) (R ¹ is a hydrogen atom, R ² and R ³ are tert-butyl groups, M is aluminum, and X is a hydroxyl group). A complex nucleating agent consisting of a mixture containing)) as the main component. Made by ADEKA Co., Ltd. Product name "Adecastab NA-21"
(GAMD) 1,3,2.4-bis (p-methylbenzylidene) sorbitol. Made by New Japan Rika Co., Ltd. Product name "Gelall MD"

2-3. Other Additives (IF168) Tris (2,4-di-t-butylphenyl) phosphite. Made by BASF Product name: "Irgafos 168"
(TNV622) Dimethyl succinate 1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate. Product name manufactured by BASF; "TINUVIN622LD"
(CAST) Calcium stearate. Made by NOF CORPORATION

<3. Examples 1 to 3, Comparative Examples 1 to 3>
The polymer and additives are prepared at the blending ratios (parts by weight) shown in Table 1, dry-blended with a super mixer, and then the die outlet temperature using a TEM-35B twin-screw extruder manufactured by Toshiba Machine Co., Ltd. It was melt-kneaded at 220 ° C. and pelletized. The obtained pellets were injection molded by an EC100SX injection molding machine manufactured by Toshiba Machine Co., Ltd. at a resin temperature of 200 and a mold temperature of 40 ° C. to prepare test pieces. Each of the obtained physical properties was measured using the obtained pellets or test pieces. The evaluation results are shown in Table 1.

As is clear from Table 1, in Examples 1 to 3, a Ziegler-based propylene-ethylene copolymer having an ethylene content of 1.5 to 2.4% by weight according to the present invention, and a nucleating agent (A) It can be seen that the product contains a specified amount of ethylene, and is excellent in rigidity, moldability, heat resistance, impact resistance, transparency, mold stain resistance, and product appearance.
It can be seen that Comparative Example 1 has poor mold contamination due to a large amount of volatile components, and Comparative Example 3 has foreign substances and is not preferable for the application of the present invention in which cleanliness is required. Further, Comparative Example 2 is not suitable for the application of the present invention, which is excellent in rigidity and heat resistance, but has low impact strength after gamma ray treatment and is not allowed to crack.

The artificial dialysis member of the present invention satisfies the quality of the dialysate supply unit and the dialysate circuit and the test method 1 (2) among the approval criteria for the dialysis-type artificial kidney device, and has rigidity, moldability, and heat resistance. It can be seen that the product is excellent in impact resistance, transparency, mold stain resistance, and product appearance. Further, although the artificial dialysis member of the present invention is sterilized by radiation, the deterioration of physical properties due to irradiation is extremely small. Furthermore, regarding the outer cylinder and header of the dialyzer, the excellent transparency allows the internal state during use to be clearly observed from the outside, and the elution characteristics are also excellent, so it is safe for artificial dialysis. It can be put to practical use with all your heart.

1 Arm of the person undergoing dialysis 2 Tube 3 Blood pump 4 Air trap 5 Dializer 6 Console 7 Blood inlet 8 Blood outlet 9 Dialysis fluid inlet 10 Dialysis fluid outlet 10 Hollow fiber 12 Dializer outer cylinder 13 Dializer header

Claims (4)

The nucleating agent (A) represented by the following formula (1) is added from 0.1 to 100 parts by weight of the Ziegler-based propylene-ethylene copolymer having an ethylene content of 1.5 to 2.4% by weight. A composition having the following characteristics (i) to (ix), which contains 0.3 parts by weight and does not contain silicone, and is used by treating with an electron beam or gamma ray of 10 to 60 kGy for an artificial dialysis member. Silicone resin composition.
(I) The tensile yield stress according to JIS K7161 is 30 to 40 MPa.
(Ii) The crystallization temperature (peak value) obtained by a differential scanning calorimeter based on JIS K7121 is 110 to 130 ° C.
(Iii) Flexural strength according to JIS K7171 is 35 to 50 MPa
(Iv) Deflection temperature under load (0.45 MPa) according to JIS K7191 is 90 to 110 ° C.
(V) Charpy impact strength (23 ° C.) conforming to JIS K7111 is 3.0 to 5.5 kJ / m ²
(Vi) Haze (thickness 1 mm) conforming to JIS K7136 is 8 to 25%.
(Vii) Volatile component content is 60 ppm by weight or less (viii) In the measurement of temperature elution fractionation (TREF) using orthodichlorobenzene as a solvent, 3.5% by weight of the component elutes at a temperature of 40 ° C. or lower. Below (ix), the ultimate viscosity [η] measured in decalin at 135 ° C. is 1.3 to 1.8 dl / g.

... (1)
(In the formula, R ¹ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ² and R ³ are the same or different alkyl groups having a hydrogen atom or 1 to 12 carbon atoms, respectively, and M. Is a metal atom of Group 3 or 4 of the Periodic Table, X is HO- when M is a metal atom of Group 3 of the Periodic Table, and M is a metal of Group 4 of the Periodic Table. In the case of an atom, O = or (HO) _2- ).
The propylene-based product for an artificial dialysis member according to claim 1, wherein the injection-molded product having a diameter of 0.1 mm or more and having 3 or less white foreign substances in a 10 cm × 10 cm × 1 mm injection-molded product using a propylene-based resin composition for an artificial dialysis member is used. Resin composition A molded product for an artificial dialysis member using the propylene-based resin composition for an artificial dialysis member according to claim 1 or 2. A molded product for an artificial dialysis member according to claim 3, wherein the molded product for an artificial dialysis member is an outer cylinder and / or a header of a dialyzer.

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