JP2010121126A - Propylenic resin composition for medical treatments and its molded article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a propylenic resin composition for medical treatments, satisfying the test requirements of 1, polyethylene or polypropylene aqueous parenteral injection containers in the plastic medicine container test method, and holding excellent heat resistance, rigidity, injection moldability, and transparency, and to provide its molded article. <P>SOLUTION: This propylenic resin composition for the medical treatments comprises 60-99 pts.wt. of a propylenic (co)polymer comprising propylene homopolymer or a propylenic copolymer comprising propylene and an α-olefin in an amount of <1 wt.% and having a melt flow rate of 0.5-100 g/10 min, propylene-ethylene block copolymer obtained by sequentially polymerizing 30-95 wt.% of propylene homopolymer or propylene-ethylene random copolymer component (A) having an ethylene content of ≤7 wt.% in the first process and 70-5 wt.% of a special propylene-ethylene random copolymer component (B) containing ethylene in a larger amount by 3-20 wt.% than that of the component (A) in the second process in the presence of a metallocene catalyst, and 0.01-0.6 pt.wt. of a nucleating agent. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a medical propylene-based resin composition and a molded product thereof, and in particular, among medical-use drugs and chemical storage containers, in particular, the 15th revision Japanese Pharmacopoeia General Test 45. Test method for plastic drug containers 1. The present invention relates to a medical propylene-based resin composition suitable for a medical molded article satisfying all the test items of a polyethylene or polypropylene aqueous injection container and the molded article thereof.

Propylene-based polymers are used in various medical devices by taking advantage of their excellent safety and hygiene, molding processability, mechanical properties, and gas barrier properties. In particular, in recent years, as a storage container for drugs and chemicals that require a high level of safety and hygiene, it has been increasingly used as an alternative container material for ampoules and vials, and materials for such applications are being actively developed. (For example, refer to Patent Document 1).
In such storage containers, the heat resistance, devitrification resistance, additive extraction resistance, and gas barrier properties of water vapor and oxygen during steam sterilization are maintained, and the additive used interacts with preservatives and chemicals. It is necessary to have no effect. Specifically, the 15th revision Japanese Pharmacopoeia General Test 45. Test method for plastic drug containers 1. It is essential to satisfy all the test items of polyethylene or polypropylene aqueous injection containers.

  The propylene-based polymer is preferably a propylene homopolymer in terms of rigidity, heat resistance and gas barrier properties, and a random copolymer with ethylene in terms of transparency and impact resistance. Although used appropriately and selectively, when used in a storage container, it is difficult to exert sufficient performance in terms of transparency and rigidity with only a propylene-based polymer. Various attempts have been made to optimize the essential performance.

However, for example, when a sorbitol-based transparent nucleating agent was used, it did not satisfy the additive extraction resistance and the pharmacopoeia test, and was unsuitable for these applications. In addition, when aluminum-based or organophosphate synthetic nucleating agent is added, the expression of transparency is not sufficient, or when the amount added is increased, satisfactory results are obtained for the ignition residue in the pharmacopoeia test. There wasn't.
Examples of medical uses that require passing a pharmacopoeia test include kit preparations such as prefilled syringes that are pre-filled with a chemical solution.
It was around the mid 1980s (for example, refer to Patent Document 2) that the production of a kit preparation filled with this chemical solution in advance with polypropylene began to be studied (for example, see Patent Document 2). Studies have been conducted on a preparation (for example, see Patent Document 3) in which a drug solution is filled in a transparent syringe barrel or a transparent container made of a nucleating agent.
However, the present situation is that a molded product having high transparency after sterilization, excellent heat resistance and rigidity, passing a pharmacopoeia test, and being satisfactory as a storage container for drugs and chemicals has not been obtained.

  In view of the above problems, the object of the present invention is the fifteenth revised Japanese Pharmacopoeia general test. Test method for plastic drug containers 1. To provide a medical propylene-based resin composition that satisfies the test items of a polyethylene or polypropylene water-based injection container and that has excellent heat resistance, rigidity, injection moldability, and transparency, and a molded product thereof. is there.

  As a result of intensive studies to solve the above problems, the present inventors have satisfied the test items of the Japanese Pharmacopoeia by using a specific amount of a specific nucleating agent for a propylene polymer having a specific melt flow rate. The present invention was completed by finding that a medical propylene-based resin composition can be obtained.

That is, according to the first invention of the present invention, (a) a melt flow rate based on JIS K7210 (230 ° C., 2.16 kg load) is 0.5 to 100 g / 10 min, and a propylene homopolymer, Alternatively, with respect to 60 to 99 parts by weight of a propylene-based polymer which is a copolymer of propylene and an α-olefin and the α-olefin content is less than 1% by weight, the following conditions (A- 1) to 40 parts by weight of a propylene-ethylene block copolymer satisfying i) to (Av), and (iii) 0.01 parts by weight or more and 0.6 parts by weight or less of a nucleating agent. The medical propylene-based resin composition is provided.

(Ai) 30 to 95 wt% of propylene-ethylene random copolymer component (A) having a metallocene catalyst in the first step or propylene-ethylene random copolymer component (A) of 7 wt% or less in the first step, and component (A) in the second step A propylene-ethylene block copolymer obtained by sequential polymerization of 70 to 5 wt% of the propylene-ethylene random copolymer component (B) containing 3 to 20 wt% of ethylene more than (A-ii) ) Melt flow rate (MFR: 230 ° C. 2.16 kg) is in the range of 0.5-100 g / 10 min (A-iii) Melting peak temperature (Tm) measured by DSC method is in the range of 110-150 ° C. (A-iv) The molecular weight distribution (Mw / Mn) measured by the GPC method is in the range of 1.5 to 4 (Av) Solid viscoelasticity measurement More resulting temperature - in the loss tangent curve, tan [delta curve has a single peak at 0 ℃ below.

According to the second invention of the present invention, (c) the nucleating agent (A) represented by the following general formula (1) is 0.01 to 0.6 parts by weight, and the following general formula: The nucleating agent (B) represented by (2) is 0.005 to 0.3 parts by weight, the nucleating agent (C) represented by the following general formula (3) is 0.005 to 0.15 parts by weight, When the nucleating agent (D) represented by the general formula (4) is 0.005 to 0.15 parts by weight and the nucleating agent (E) represented by the following general formula (5) is 0.005 parts by weight or more, it is 0.00. The medical propylene-based resin composition according to claim 1, wherein at least one nucleating agent in a range of less than 3 parts by weight is blended.

[Wherein n is an integer of 0 to 2 and R ^{1 to} R ⁵ are the same or different and each is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an alkenyl group, an alkoxy group, a carbonyl group, a halogen atom. Group and a phenyl group, and R ⁶ is an alkyl group having 1 to 20 carbon atoms. ]

[Wherein, R ¹ is a direct bond, sulfur, an alkylene group having 1 to 9 carbon atoms or an alkylidene group, and R ² and R ³ are the same or different and each represents a hydrogen atom or an alkyl having 1 to 8 carbon atoms. A group, M is Na, and n is the valence of M. ]

[Wherein, R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ² and R ³ are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms; Represents a group III or group IV metal atom of the periodic table, X represents HO— when M represents a group III metal atom of the periodic table, and M represents group IV of the periodic table. When a group metal atom is shown, O = or (HO) _2- . ]

[Wherein, M ₁ and M ₂ are the same or different and are at least one metal cation selected from calcium, strontium, lithium and monobasic aluminum, and R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ are the same or different and are hydrogen, C ₁ -C ₉ alkyl (wherein any two vicinals (bonded to adjacent carbons) or geminal) Alkyl groups (bonded to the same carbon) may combine to form a hydrocarbon ring having up to 6 carbon atoms), hydroxy, C ₁ -C ₉ alkoxy, C ₁ -C ₉ alkyleneoxy, amine and C ₁ -C ₉ alkylamine, halogen is independently selected from the group consisting of (fluorine, chlorine, bromine and iodine) and phenyl. ]

R ¹ (CONHR ² ) _a (5)
[Wherein R ¹ represents a saturated or unsaturated aliphatic polycarboxylic acid residue having 2 to 30 carbon atoms, a saturated or unsaturated alicyclic polycarboxylic acid residue having 4 to 28 carbon atoms, or the number of carbon atoms. Represents 6-18 aromatic polycarboxylic acid residues. R ² represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, or a cycloalkyl group or cycloalkenyl group having 3 to 46 carbon atoms. a represents an integer of 2 to 6. ]

  According to the third invention of the present invention, the medical propylene according to the first or second invention, wherein the nucleating agent (A) is a nucleating agent represented by the following general formula (6): A resin composition is provided.

[Here, n is an integer of ^{0~2, R 1, R 2,} R 4, R 5 is a hydrogen atom, ^{R 3} is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, alkenyl A group, an alkoxy group, a carbonyl group, a halogen group and a phenyl group, and R ⁶ is an alkyl group having 1 to 20 carbon atoms. ]

  According to a fourth invention of the present invention, in any one of the first to third inventions, the lubricant is blended in the range of 0.001 to 0.5 parts by weight. A propylene-based resin composition is provided.

According to the fifth aspect of the present invention, there is provided a medical molded article using the propylene-based resin composition according to any one of the first to fourth aspects.
According to a sixth aspect of the present invention, there is provided a kit preparation characterized in that the medical molded article of the fifth aspect is a kit preparation.
According to a seventh aspect of the present invention, there is provided a prefilled syringe characterized in that the kit preparation of the sixth aspect is a prefilled syringe.

  The medical propylene-based resin composition of the present invention is a 15th revision Japanese Pharmacopoeia general test. Test method for plastic drug containers 1. It satisfies the test items of a polyethylene or polypropylene aqueous injection container and retains excellent heat resistance, rigidity, moldability and transparency.

It is a figure which shows the elution amount by TREF of a propylene-ethylene block copolymer, and elution amount integration.

  In the present invention, (a) the melt flow rate based on JIS K7210 (230 ° C., 2.16 kg load) is 0.5 to 100 g / 10 min, and a propylene homopolymer or a copolymer of propylene and α-olefin is used. With respect to 60 to 99 parts by weight of a propylene-based polymer which is a polymer and has a content of α-olefin of less than 1% by weight, the following conditions (Ai) to (Av) are satisfied. 1 to 40 parts by weight of a propylene-ethylene block copolymer to be filled, and (iii) a propylene-based medical composition characterized in that the nucleating agent is blended in a range of 0.01 parts by weight to 0.6 parts by weight. It is a resin composition and is useful for a molded product obtained from the resin composition, particularly for a kit preparation. Hereinafter, the constituent components, the method for producing the composition, the molded body, etc. will be described in detail.

(Ai) 30 to 95 wt% of propylene-ethylene random copolymer component (A) having propylene alone or ethylene content of 7 wt% or less in the first step using the metallocene catalyst, and component (A) in the second step It is a propylene-ethylene block copolymer obtained by successively polymerizing 70 to 5 wt% of the propylene-ethylene random copolymer component (B) containing 3 to 20 wt% more ethylene than (A-ii) ) Melt flow rate (MFR: 230 ° C. 2.16 kg) is in the range of 0.5 to 100 g / 10 min (A-iii) Melting peak temperature (Tm) measured by DSC method is in the range of 110 to 150 ° C. (A-iv) The molecular weight distribution (Mw / Mn) measured by the GPC method is in the range of 1.5 to 4 (Av) Solid viscoelasticity measurement In the temperature-loss tangent curve obtained by measurement, the tan δ curve has a single peak at 0 ° C. or lower.
The blending amount of the propylene homopolymer or the propylene / α-olefin copolymer (propylene (co) polymer) constituting the medical propylene resin composition loses the properties of the resin due to blending. Examples of the present embodiment are not less than 50 parts by weight, usually 60 to 99 parts by weight, specifically 65 parts by weight, 70 parts by weight, 80 parts by weight, 90 parts by weight, 95 parts by weight, and the like. On the other hand, the propylene-ethylene block copolymer constituting the composition is 50 parts by weight or less, usually 1 to 40 parts by weight, specifically 5 parts by weight, 10 parts by weight, 20 parts by weight. Embodiments such as 30 parts by weight, 30 parts by weight and 35 parts by weight can be exemplified, and these two-component resins are blended to prepare 100 parts by weight of the composition.

Blend amount of propylene-ethylene block copolymer (block copolymer) satisfying specific conditions (Ai) to (Av) is 0.08 parts by weight, 0.05 parts by weight, 0.01 parts by weight If the amount is less than 0.005 parts by weight, effects such as impact resistance and heat resistance are monotonously reduced, and the effects of the present invention cannot be expected. On the other hand, when the blend amount is monotonously increased to 45 parts by weight, 50 parts by weight, and 60 parts by weight, the propylene copolymer tends to lose rigidity, heat resistance, and gas barrier properties. It tends to occur, and there is a risk that the excellent properties of the original propylene copolymer may be lost.
Thus, a propylene homopolymer, or a propylene-based copolymer composed of propylene and an α-olefin having a content of less than 1% by weight, and having a melt flow rate of 0.5 to 100 g / 10 min. It is based on the knowledge of the present inventors that the characteristics of a certain propylene-based (co) polymer (propylene (co) polymer) are modified by blending a specific amount of a specific block copolymer. . The propylene resin composition containing 60 to 99 parts by weight of the propylene polymer and 1 to 40 parts by weight of the specific block copolymer is combined with the polymer, and the blend amount ranges are strength, hardness, heat resistance. It is a blend amount with comprehensive and appropriate properties for medical materials such as cold resistance, impact resistance, radiation resistance, chemical resistance, stability over time, etc. It is a certain material.

Furthermore, such a propylene-based resin composition can be used for various purposes, but in particular, it is exposed to a severe high temperature environment such as sterilization, such as medical use, under pressure heating, microwave heating. It has also been found that the material has physical characteristics that can be applied to severe heat treatment such as, but it is also necessary that the material after the heat treatment does not change. However, in the case of medical molded products, it is possible to improve the safe handling without any misunderstandings that the contents look good, which greatly increases the value as a medical material. Is a rational measure, but it is also necessary to consider the effects of nucleating agents on medical materials and, for example, changes in transparency after heat treatment. On the other hand, as a medical material, it is very important that a material having, for example, a pack, a container, a bottle, non-toxicity, safety and hygiene is required.
As a result of examining various nucleating agents including various general-purpose nucleating agents in consideration of the above points, there are some that satisfy the condition in that they are nucleating agents that simply solve the transparency. right.

However, it is called a propylene-based resin composition containing 60 to 99 parts by weight of a propylene-based (co) polymer and 1 to 40 parts by weight of a block copolymer satisfying specific (Ai) to (Av) conditions. It is a composite material of at least two types of polymer mixtures that are two types of polymers and have different melting points and properties as microstructures, and even for specific propylene-based resin compositions that may have a phase separation structure in some cases, Molding of malodor, workability, welding, etc., as well as the characteristics of solubilization and safety due to elution and contact, which expresses the maximum stable nucleating agent function and meets the challenges of medical materials If it becomes a nucleating agent that sometimes does not hinder, the selection must be careful and the type may be limited.
Furthermore, in the case of medical molded products such as bags, containers, and disposable products, various types of molded products, such as pre-formed films, sheets, etc., are processed into predetermined medical devices by vacuum forming and pressing. It may be subjected to secondary processing such as molding and heat sealing. Even under such processing conditions, there is no influence of bad odor generation, volatilization of the nucleating agent, etc., and there is a stable nucleating agent in which the transparency and physical properties of the molded product before and after processing do not deteriorate or disappear. Desired.

  Furthermore, when actually using medical molded products in the medical field, they may be exposed to harsh environments such as pressurized heating, microwave heating, and boiling for sterilization and sterilization. So-called time-dependent changes, such as little change in properties and properties of the molded product before processing and after pressure heating, especially as little as possible in transparency before and after molding of the molded product It is required to say that there is no. In particular, if the transparency of the molded product is reduced or bleedout of the nucleating agent is promoted, there will be problems in identifying the contents, safety and hygiene. Such characteristics are required. As described above, the present invention investigates problems such as selection of an appropriate nucleating agent and an appropriate amount of additives for increasing the transparency of a composite material called a propylene-based resin composition, In the case of molding of syringes and the like, a product with uniform transparency can be obtained without seeing the weld line, considering the so-called quality, by heat treatment of moldability, workability, secondary workability that there is no odor Decreased transparency, relatively no change in material, use of medical molded products and environmental changes, heat treatment such as sterilization of medical molded products including so-called contents, as in summer and winter Due to the handling of seasonal changes, geographical or regional changes such as north and south, etc., multifaceted measures that are stable over time with no change in properties such as material and transparency are required.

As a result of diligent investigation of additives that can meet these technical problems, the present inventors have examined appropriate ones from among various types of nucleating agents. As a result, they are represented by the general formulas (1) to (5). It has been found that these are the most suitable and meet the requirements of the medical materials. In addition, when a plurality of nucleating agents represented by the general formulas (1) to (5) are combined with a composite material called a specific polymer mixture, the present invention functions properly for each polymer and is stable. It has also been found that the nucleating agent function is expressed uniformly and highly functionally. The addition amount of the nucleating agent represented by the general formulas (1) to (5) is determined within a specific range because the function of the nucleating agent is improved in transparency, rigidity, and flexural modulus in the composite material. Hygiene and safety with maximum stability over time, with no elution and bleeding out of nucleating agents from molded products, taking into account the circumstances of medical materials It was discovered that the addition amount was sufficiently considered.

[1] Components of the composition Propylene-based (co) polymer (a) Propylene-based (co) polymer The (a) propylene-based (co) polymer used in the medical propylene-based resin composition of the present invention is a propylene homopolymer or propylene. It may be a propylene copolymer composed of an α-olefin having a content of less than 1% by weight, or a mixture thereof.
(A) The propylene-based (co) polymer is preferably a homopolymer from the viewpoint of heat resistance during autoclave sterilization, and is preferably a random copolymer composed of propylene and an α-olefin from the viewpoint of transparency. 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. These propylene polymers may be used as a mixture of two or more. In addition, when the α-olefin content is 1% by weight or more, it becomes difficult to use from the viewpoint of heat resistance.
Specific examples of the propylene-based copolymer include propylene-ethylene copolymer, propylene-butene-1 copolymer, propylene-hexene-1 copolymer, propylene-octene-1 copolymer, propylene-ethylene. A binary combination of any amount of comonomers, such as a -butene-1 copolymer, a propylene-ethylene-hexene-1 copolymer, a propylene-butene-1-octene-1 copolymer, or the like A terpolymer can be exemplified.

In medical applications, sterilization is generally performed. Specifically, high-pressure steam sterilization, radiation sterilization, ethylene oxide gas (EOG) sterilization, ultraviolet sterilization, and the like are performed. At that time, in the case of high-pressure steam sterilization treatment at 121 ° C. for 20 minutes, a propylene homopolymer, a block copolymer, or a random copolymer having an ethylene content of less than 1% is preferable. When a random copolymer having a high ethylene content is used, there is a problem that it is deformed by high-pressure steam sterilization. In the case of high-pressure steam sterilization, transparency is likely to deteriorate compared to before sterilization, and those that are difficult to deteriorate are good.
In the case of performing radiation sterilization treatment, a random copolymer having a high ethylene content is preferable, and when a propylene homopolymer is used, the physical property deterioration after the radiation sterilization treatment is extremely undesirable. In addition, a composition obtained by adding a peroxide as a molecular weight modifier to a random copolymer having a high ethylene content has better impact resistance before and after radiation irradiation.

(A) The α-olefin content used in the propylene-based (co) polymer is less than 1% by weight, preferably less than 0.5% by weight. If the α-olefin content is 1% by weight or more, the rigidity is lowered and there is a risk of deformation during autoclave sterilization.
Here, propylene and α-olefin are values measured by ¹³ C-NMR method under the following conditions.
Apparatus: JEOL-GSX270 manufactured by JEOL Ltd.
Concentration: 300 mg / 2 mL
Solvent: Orthodichlorobenzene

When the (a) propylene-based (co) polymer used in the present invention is a propylene homopolymer, the isotactic pentad fraction is preferably 0.90 or more, more preferably 0.94 to 0.00. 98. If the isotactic pentad fraction is less than 0.90, the rigidity and barrier properties may not be satisfactory.
Here, the isotactic pentad fraction is a value measured by a proton decoupling method using ¹³ C-NMR.

  The (a) propylene-based (co) polymer used in the present invention has a melt flow rate (MFR) in the range of 0.5 to 100 g / 10 min in accordance with JIS K7120 (230 ° C., 2.16 kg load). 1 to 50 g / 10 min is preferable, and 2 to 30 g / 10 min is more preferable. If the melt flow rate (MFR) is less than 0.5 g / 10 minutes, there is a risk that molding processability is lowered and a satisfactory product cannot be obtained. Moreover, when it exceeds 100 g / 10 minutes, there exists a concern about the fall of mechanical strength.

  (A) Although it does not specifically limit as a manufacturing method of a propylene type (co) polymer, The polymerization method using a stereoregular catalyst is preferable. Examples of stereoregular catalysts include Ziegler catalysts and metallocene catalysts. Preferably, (i) a metallocene catalyst having good compatibility with the propylene-ethylene block copolymer is used.

  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.

Propylene-based (co) polymer production methods include slurry methods using inert solvents, solution methods, gas phase methods that do not substantially use solvents, or polymerization monomers as solvents in the presence of the catalyst. 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-based (co) 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.

(A) Propylene-ethylene block copolymer (i) The propylene-ethylene block copolymer used in the present invention is a propylene-ethylene random copolymer component having propylene alone or an ethylene content of 7 wt% or less in the first step. After the polymerization of 30 to 95 wt% of (A), the second step sequentially polymerizes 70 to 5 wt% of the propylene-ethylene random copolymer component (B) containing 3 to 20 wt% more ethylene than the first step. Can be obtained.
The propylene-ethylene block copolymer referred to here is a propylene-ethylene random copolymer component (A) (hereinafter referred to as component (A)) and a propylene-ethylene random copolymer component (B) ( Hereinafter, it is a block copolymer in a general name obtained by sequentially polymerizing component (B)), and component (A) and component (B) are not necessarily combined in a block form. It is not necessary.

(1-1) Ethylene content in component (A): [E] A
The component (A) produced in the first step suppresses stickiness of the product (pellet) and expresses heat resistance, so that the propylene homopolymer having a relatively high melting point and crystallinity, or ethylene content is high. The propylene-ethylene random copolymer must be 7 wt% or less. If the ethylene content exceeds 7 wt%, the melting point becomes too low and the heat resistance of the product may be deteriorated. The ethylene content is preferably 5 wt% or less, more preferably 3 wt% or less. In addition, if the pellets are sticky, the pellets may stick together during storage of the pellet bag, which is not preferable.

(1-2) Ethylene content in component (B): [E] B
The component (B) produced in the second step has a role as a rubber elastic component in the propylene-ethylene block copolymer and is a component necessary for imparting impact resistance.
The range of the ethylene content of the component (B) is defined by the difference [E] B- [E] A ([E] gap) from the ethylene content of the component (A) in order to fully exhibit the above effect. . [E] B- [E] A needs to be in the range of 3 to 20 wt%, preferably 6 to 18 wt%, and more preferably 8 to 16 wt%.
[E] When the gap is 3 wt% or less, the impact resistance is not sufficient, which is not preferable. On the other hand, when the content exceeds 20 wt%, the compatibility with the component (A) produced in the first step is deteriorated, so that the transparency is undesirably deteriorated.

(1-3) Ratio of component (A): W (A) and ratio of component (B): W (B)
The content ratio of W (A), which is the proportion of the component (A) constituting the propylene-ethylene block copolymer, and W (B), which is the proportion of the component (B), is 30 to 95 wt% for W (A). And W (B) needs to be in the range of 70 to 5 wt%.
If the ratio of W (A) is less than 30 wt%, the product may become sticky and the heat resistance may be reduced. On the other hand, if the ratio of W (A) exceeds 95 wt%, the rubber elasticity is insufficient and the impact resistance may be insufficient. Preferably, the ratio of W (A) is 40 to 90 wt%, more preferably 50 to 80 wt%.

(1-4) Specification by peak of tan δ curve In the present invention, in order to maintain good compatibility and maintain transparency, the component (A) and the component (A) constituting the propylene-ethylene block copolymer to be used ( B) must not be phase separated. The phase separation conditions are affected not only by the ethylene content but also by the molecular weight and composition. Therefore, in addition to the above-mentioned regulations regarding the ethylene content, a temperature-loss tangent (tan δ) curve obtained by solid viscoelasticity measurement (DMA) Therefore, it is necessary to define the peak of the tan δ curve.
When the propylene-ethylene block copolymer has a phase separation structure, the glass transition temperature of the amorphous part contained in the component (A) is different from the glass transition temperature of the amorphous part contained in the component (B). , There will be multiple peaks. Conversely, when they are compatible, both components are mixed in the order of molecules and have a single peak at a temperature intermediate between the glass transition temperatures of both components. That is, whether or not the phase separation structure is taken can be determined in the temperature-tan δ curve in the solid viscoelasticity measurement, and in order to maintain transparency, the tan δ curve has a single peak at 0 ° C. or lower. is required.
Specifically, solid viscoelasticity measurement is performed by applying a sinusoidal strain of a specific frequency to a strip-shaped sample piece and detecting the generated stress. Here, the frequency is 1 Hz and the measurement temperature is raised stepwise from −60 ° C. until the sample is melted and cannot be measured. Further, it is recommended that the magnitude of distortion is about 0.1 to 0.5%. From the obtained stress, the storage elastic modulus G ′ and the loss elastic modulus G ″ are obtained by a known method, and the loss tangent (= loss elastic modulus / storage elastic modulus) defined by this ratio is plotted against the temperature. It shows a sharp peak in the temperature range below 0 ° C. Generally, the peak of the tan δ curve below 0 ° C. is for observing the glass transition of the amorphous part, and here the peak temperature is defined as the glass transition temperature Tg (° C.). Define.

(1-5) [E] A and [E] B and each component content W (A) and W (B) specific component (A), each ethylene content and amount of (B) is the material balance at the time of manufacture Although it is possible to specify by (material balance), in order to specify these more accurately, it is desirable to use the following analysis.

(1-5-1) Identification of each component amount W (A) and W (B) by temperature rising elution fractionation (TREF) The method for evaluating the crystallinity distribution of a propylene-ethylene random copolymer by TREF This method is well known to those skilled in the art. For example, detailed measurement methods are shown in the following documents.
G. Glockner, J. et al. Appl. Polym. Sci. : Appl. Polym. Symp. 45, 1-24 (1990)
L. Wild, Adv. Polym. Sci. 98, 1-47 (1990)
J. et al. B. P. Soares, A .; E. Hamielec, Polymer; 36, 8, 1639-1654 (1995)
The propylene-ethylene block copolymer in the present invention is greatly different in the crystallinity of each of the components (A) and (B), and each crystallinity distribution is narrowed by being produced using a metallocene catalyst. Therefore, there are very few intermediate components between the two, and both can be discriminated with high accuracy by TREF.
A specific method will be described with reference to the figure showing the elution amount and the elution amount integration by TREF in FIG. In the TREF elution curve (plot of elution amount versus temperature), components (A) and (B) show their elution peaks at T (A) and T (B), respectively, due to the difference in crystallinity, and the difference is sufficiently large. Separation is possible at an intermediate temperature T (C) (= {T (A) + T (B)} / 2).

In addition, the lower limit of the TREF measurement temperature is −15 ° C. in the apparatus used for this measurement, but in the case where the crystallinity of the component (B) is very low or an amorphous component, There may be no peak in the range. (In this case, the concentration of the component (B) dissolved in the solvent is detected at the measurement temperature lower limit (ie, −15 ° C.).)
At this time, T (B) is considered to exist below the lower limit of the measurement temperature, but the value cannot be measured. In such a case, T (B) is the lower limit of the measurement temperature. Defined as ° C.
Here, if the integrated amount of the component eluted before T (C) is defined as W (B) wt%, and the integrated amount of the component eluted at T (C) or higher is defined as W (A) wt%, W (B) Almost corresponds to the amount of the component (B) having low crystallinity or amorphousness, and the integrated amount W (A) of the component eluted at T (C) or higher is the component (A) having relatively high crystallinity. Almost corresponds to the amount of. The elution amount curve obtained by TREF and the above-described methods for calculating the various temperatures and amounts obtained therefrom are performed as illustrated in FIG.

(1-5-2) TREF measuring method In the present invention, the TREF is specifically measured as follows.
A sample is dissolved in o-dichlorobenzene (containing 0.5 mg / mL BHT) at 140 ° C. to obtain a solution. This is introduced into a 140 ° C. TREF column, cooled to 100 ° C. at a rate of 8 ° C./min, subsequently cooled to −15 ° C. at a rate of 4 ° C./min, and held for 60 minutes. Thereafter, o-dichlorobenzene (containing 0.5 mg / mL BHT) as a solvent is flowed through the column at a flow rate of 1 mL / min, and components dissolved in o-dichlorobenzene at −15 ° C. are eluted in the TREF column for 10 minutes. Next, the column is linearly heated to 140 ° C. at a heating rate of 100 ° C./hour to obtain an elution curve.

(1-5-3) Identification of ethylene content [E] A and [E] B in each component (a) Separation of component (A) and component (B) T (C) determined by the previous TREF measurement Based on the temperature-separated column separation method using a preparative separation apparatus, the soluble component (B) in T (C) and the insoluble component (A) in T (C) are separated, and each component is analyzed by NMR. Determine the ethylene content.
The temperature rising column fractionation method refers to a measurement method as disclosed in, for example, Macromolecules, 21 314-319 (1988). Specifically, the following method was used in the present invention.

(B) Fractionation conditions A cylindrical column having a diameter of 50 mm and a height of 500 mm is filled with a glass bead carrier (80 to 100 mesh) and maintained at 140 ° C. Next, 200 mL of the o-dichlorobenzene solution (10 mg / mL) of the sample dissolved at 140 ° C. is introduced into the column. Thereafter, the temperature of the column is cooled to 0 ° C. at a rate of temperature decrease of 10 ° C./hour. After holding at 0 ° C. for 1 hour, the column temperature is heated to T (C) at a heating rate of 10 ° C./hour and held for 1 hour. Note that the temperature control accuracy of the column through a series of operations is ± 1 ° C.
Next, while maintaining the column temperature at T (C), 800 mL of o (dichlorobenzene) of T (C) is allowed to flow at a flow rate of 20 mL / min, whereby components soluble in T (C) existing in the column are obtained. Elute and collect.
Next, the column temperature is increased to 140 ° C. at a temperature rising rate of 10 ° C./min, and after leaving still at 140 ° C. for 1 hour, by flowing 800 mL of a 140 ° C. solvent (o-dichlorobenzene) at a flow rate of 20 mL / min, Elute insoluble components with T (C) and collect.
The solution containing the polymer obtained by fractionation is concentrated to 20 mL using an evaporator and then precipitated in 5 times the amount of methanol. The precipitated polymer is recovered by filtration and then dried overnight in a vacuum dryer.

(C) Measurement of ethylene content by ¹³ C-NMR The ethylene content of each of the components (A) and (B) obtained by the above fractionation was measured by a proton complete decoupling method according to the following conditions: ¹³ C-NMR spectrum It is obtained by analyzing.
Model: GSX-400 manufactured by JEOL Ltd. or equivalent equipment (carbon nuclear resonance frequency of 100 MHz or more)
Solvent: o-dichlorobenzene / heavy benzene = 4/1 (volume ratio)
Concentration: 100 mg / mL
Temperature: 130 ° C
Pulse angle: 90 °
Pulse interval: 15 seconds Integration count: 5,000 times or more The attribution of the spectrum may be performed with reference to, for example, Macromolecules, 17 1950 (1984). The attribution of spectra measured under the above conditions is as shown in the table below. In the table, symbols such as S _αα are in accordance with the notation of Carman et al. (Macromolecules, 10 536 (1977)), P represents a methyl carbon, S represents a methylene carbon, and T represents a methine carbon.

Hereinafter, when “P” is a propylene unit in a copolymer chain and “E” is an ethylene unit, six kinds of triads of PPP, PPE, EPE, PEP, PEE, and EEE may exist in the chain. As described in Macromolecules, 15 1150 (1982), etc., the concentration of these triads and the peak intensity of the spectrum are linked by the following relational expressions (1) to (6).
[PPP] = k × I (T _ββ ) (1)
[PPE] = k × I (T _βδ ) (2)
[EPE] = k × I (T _δδ ) (3)
[PEP] = k × I (S _ββ ) (4)
[PEE] = k × I (S _βδ ) (5)
[EEE] = k × [I (S _δδ ) / 2 + I (S _γδ ) / 4} (6)
Here, [] indicates the fraction of triads, for example, [PPP] is the fraction of PPP triads in all triads. Therefore,
[PPP] + [PPE] + [EPE] + [PEP] + [PEE] + [EEE] = 1
(7)
It is. Further, k is a constant, I indicates the spectral intensity, and for example, I (T _ββ ) means the intensity of the peak at 28.7 ppm attributed to T _ββ .

By using the relational expressions (1) to (7) above, the fraction of each triad is obtained, and the ethylene content is obtained from the following expression.
Ethylene content (mol%) = ([PEP] + [PEE] + [EEE]) × 100
Note that the propylene random copolymer of the present invention contains a small amount of propylene heterogeneous bonds (2,1-bonds and / or 1,3-bonds), thereby producing the following minute peaks.

In order to obtain an accurate ethylene content, it is necessary to include these peaks derived from heterogeneous bonds in the calculation, but it is difficult to completely separate and identify the peaks derived from heterogeneous bonds, and the amount of heterogeneous bonds is small. Therefore, the ethylene content of the present invention is determined using the relational expressions (1) to (7) as in the analysis of the copolymer produced with the Ziegler catalyst that does not substantially contain heterogeneous bonds. .
Conversion from mol% to wt% of ethylene content is carried out using the following formula: ethylene content (wt%) = (28 × X / 100) / {28 × X / 100 + 42 × (1−X / 100) } × 100
Here, X is the ethylene content in terms of mol%. The ethylene content [E] W of the entire propylene-ethylene block copolymer is the ethylene content of each of the components (A) and (B) measured from the above. It is calculated by the following formula from the weight ratios W (A) and W (B) wt% of each component calculated from [E] A, [E] B and TREF.
[E] W = {[E] A × W (A) + [E] B × W (B) / 100 (wt%)

(1-6) Melt flow rate (MFR)
The melt flow rate (MFR) of the (a) propylene-ethylene block copolymer used in the present invention is 0.5 to 100 g / 10 min, preferably 1 to 50 g / 10 min, more preferably 2 to 35 g / 10 min. It is. If the MFR is less than 0.5 g / 10 min, molding becomes difficult, and if it exceeds 100 g / 10 min, impact resistance cannot be expected.
Melt flow rate (MFR) is easily controlled by adjusting the temperature and pressure, which are the polymerization conditions for (i) propylene-ethylene block copolymerization, or by controlling the amount of hydrogen added to the chain transfer agent such as hydrogen during polymerization. Adjustments can be made.
Here, MFR is a value measured at a heating temperature of 230 ° C. and a load of 21.2 N in accordance with JIS K7210.

(1-7) Melting peak temperature (Tm)
The melting peak temperature (Tm) measured by the differential scanning calorimeter (DSC) of (i) propylene-ethylene block copolymer used in the present invention needs to be in the range of 110 to 150 ° C., and 120 to 140 It is preferable that the temperature is C. Those having a Tm of less than 110 ° C. are not preferred because the cooling and solidification rate of the molten propylene resin is slow and may deteriorate the moldability, and those exceeding 150 ° C. are not preferred because the impact resistance may be deteriorated. . In order to adjust Tm, it can adjust easily by controlling the quantity of the alpha olefin supplied to a polymerization reaction system.
Here, the specific measurement of Tm is performed using a differential scanning calorimeter (DSC), taking a sample amount of 5 mg, holding at 200 ° C. for 5 minutes, and then crystallizing to 40 ° C. at a rate of temperature decrease of 10 ° C./min. Further, the peak position of the curve drawn when the film is melted at a temperature rising rate of 10 ° C./min is defined as a melting peak temperature Tm (° C.).

(1-8) Molecular weight distribution (Mw / Mn)
The molecular weight distribution (Mw / Mn) measured by the gel permeation (GPC) method of (i) propylene-ethylene block copolymer used in the present invention must be in the range of 1.5-4. It is preferably 8 or more and less than 3. When Mw / Mn is less than 1.5, it is difficult to obtain with the current polymerization technique, and when it exceeds 4, the product (pellet) may be sticky, which is not preferable. When narrowing the molecular weight distribution of the propylene-ethylene block copolymer, use a metallocene catalyst described later, or polymerize the propylene-ethylene block copolymer and then melt knead using an organic peroxide. Can be adjusted. When making it wide, it can adjust by superposing | polymerizing using the catalyst system which used together 2 or more types of metallocene catalyst components, or the catalyst system which used 2 or more types of metallocene complexes together.
Here, the molecular weight distribution is obtained by the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn), and is obtained by measurement by a gel permeation chromatography (GPC) method.
Conversion from the retention volume to the molecular weight is performed using a standard curve prepared in advance by standard polystyrene.

The standard polystyrenes used are all the following brands manufactured by Tosoh Corporation. F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, A1000
A calibration curve is prepared by injecting 0.2 ml of a solution dissolved in o-dichlorobenzene (containing 0.5 mg / ml BHT) so that each is 0.5 mg / ml.
The calibration curve uses a cubic equation obtained by approximation by the least square method. The following numerical value is used for [η] = K × Mα in the viscosity formula used for conversion to molecular weight.
PS: K = 1.38 × 10 −4 α = 0.7
PP: K = 1.03 × 10−4 α = 0.78
The measurement conditions for GPC are as follows.
Equipment: GPC (ALC / GPC 150C) manufactured by WATERS
Detector: MIRAN 1A IR detector manufactured by FOXBORO (measurement wavelength: 3.42 μm)
Column: AD806M / S (3 pieces) manufactured by Showa Denko KK
Mobile phase solvent: o-dichlorobenzene Measurement temperature: 140 ° C.
Flow rate: 1.0 ml / min
Injection volume: 0.2ml
Sample preparation: Prepare a 1 mg / ml solution using o-dichlorobenzene (containing 0.5 mg / ml BHT) and dissolve it at 140 ° C. for about 1 hour.

(2) Propylene-ethylene block copolymer production method (2-1) Metallocene catalyst The method for producing a propylene-ethylene block copolymer used in the present invention requires the use of a metallocene catalyst. To do.
It is well known to those skilled in the art that stickiness and bleedout deteriorate when the molecular weight and crystallinity distribution are wide in the propylene-ethylene random copolymer, but also in the propylene-ethylene block copolymer used in the present invention, In order to suppress stickiness and bleed-out, it is necessary to polymerize using a metallocene catalyst that has a narrow molecular weight and crystallinity distribution.

The type of the metallocene-based catalyst is not particularly limited as long as it can produce a copolymer having the performance of the present invention. However, in order to satisfy the requirements of the present invention, for example, the following components ( It is preferable to use a metallocene catalyst comprising a), (b), and component (c) used as necessary.
Component (a): At least one metallocene transition metal compound selected from transition metal compounds represented by the following general formula Component (b): At least one selected from the following (b-1) to (b-4) (B-1) a particulate carrier on which an organoaluminoxy compound is supported,
(B-2) Particulate carrier carrying an ionic compound or Lewis acid capable of reacting with component (a) to convert component (a) into a cation (b-3) Solid acid fine particles (b- 4) Ion exchange layered silicate,
Component (c): Organoaluminum compound.

(2-2) Component (a)
As the component (a), at least one metallocene transition metal compound selected from transition metal compounds represented by the following general formula can be used.
^{_{Q (C 5 H 4 -aR 1}} ) (C 5 H 4 -bR 2) MeXY
[Wherein Q represents a divalent linking group that bridges two conjugated five-membered ring ligands, Me represents a metal atom selected from titanium, zirconium, and hafnium, and X and Y represent a hydrogen atom, a halogen atom, An atom, a hydrocarbon group, an alkoxy group, an amino group, a nitrogen-containing hydrocarbon group, a phosphorus-containing hydrocarbon group or a silicon-containing hydrocarbon group is shown, and X and Y may be independently, that is, the same or different. R ¹ and R ² are hydrogen, hydrocarbon group, halogenated hydrocarbon group, silicon-containing hydrocarbon group, nitrogen-containing hydrocarbon group, oxygen-containing hydrocarbon group, boron-containing hydrocarbon group, or phosphorus-containing hydrocarbon group. Show. a and b are the number of substituents. ]

Specifically, Q represents a divalent linking group that bridges two conjugated five-membered ring ligands, and has, for example, a divalent hydrocarbon group, a silylene group, an oligosilylene group, or a hydrocarbon group as a substituent. Examples include a silylene group, an oligosilylene group, or a germylene group having a hydrocarbon group as a substituent. Among these, preferred is a silylene group having a divalent hydrocarbon group and a hydrocarbon group as a substituent.
X and Y each represents a hydrogen atom, a halogen atom, a hydrocarbon group, an alkoxy group, an amino group, a nitrogen-containing hydrocarbon group, a phosphorus-containing hydrocarbon group, or a silicon-containing hydrocarbon group. And chlorine, methyl, isobutyl, phenyl, dimethylamide, diethylamide group and the like. X and Y may be independent, that is, may be the same or different.
R ¹ and R ² are hydrogen, hydrocarbon group, halogenated hydrocarbon group, silicon-containing hydrocarbon group, nitrogen-containing hydrocarbon group, oxygen-containing hydrocarbon group, boron-containing hydrocarbon group, or phosphorus-containing hydrocarbon group. Represents. Specific examples of the hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a phenyl group, a naphthyl group, a butenyl group, and a butadienyl group. In addition, as halogenated hydrocarbon group, silicon-containing hydrocarbon group, nitrogen-containing hydrocarbon group, oxygen-containing hydrocarbon group, boron-containing hydrocarbon group, or phosphorus-containing hydrocarbon group, methoxy group, ethoxy group, phenoxy group Typical examples include trimethylsilyl group, diethylamino group, diphenylamino group, pyrazolyl group, indolyl group, dimethylphosphino group, diphenylphosphino group, diphenylboron group, and dimethoxyboron group. In these, it is preferable that it is a C1-C20 hydrocarbon group, and it is especially preferable that they are a methyl group, an ethyl group, a propyl group, and a butyl group. By the way, adjacent R ¹ and R ² may combine to form a ring, on which a hydrocarbon group, halogenated hydrocarbon group, silicon-containing hydrocarbon group, nitrogen-containing hydrocarbon group, oxygen-containing You may have a substituent which consists of a hydrocarbon group, a boron containing hydrocarbon group, or a phosphorus containing hydrocarbon group.
Me is a metal atom selected from titanium, zirconium and hafnium, preferably zirconium and hafnium.

Among the components (a) described above, (i) a propylene-ethylene random block copolymer used in the present invention is preferably a silylene group, a germylene group or an alkylene group having a hydrocarbon substituent. It is a transition metal compound comprising a ligand having a bridged substituted cyclopentadienyl group, substituted indenyl group, substituted fluorenyl group, substituted azulenyl group, particularly preferably a silylene group having a hydrocarbon substituent or a germylene group It is a transition metal compound comprising a ligand having a 2,4-position-substituted indenyl group and a 2,4-position-substituted azulenyl group which are cross-linked by
Non-limiting specific examples include dimethylsilylene bis (2-methyl-4-phenylindenyl) zirconium dichloride, diphenylsilylene bis (2-methyl-4-phenylindenyl) zirconium dichloride, dimethylsilylene bis (2-methyl). Benzoindenyl) zirconium dichloride, dimethylsilylenebis {2-isopropyl-4- (3,5-diisopropylphenyl) indenyl} zirconium dichloride, dimethylsilylenebis (2-propyl-4-phenanthrylindenyl) zirconium dichloride, dimethyl Silylenebis (2-methyl-4-phenylazurenyl) zirconium dichloride, dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) azurenyl} zirconium dichloride, dimethylsilylenebi (2-Ethyl-4-phenylazurenyl) zirconium dichloride, dimethylsilylenebis (2-isopropyl-4-phenylazurenyl) zirconium dichloride, dimethylsilylenebis {2-ethyl-4- (2-fluorobiphenyl) azurenyl} zirconium Examples thereof include dichloride and dimethylsilylenebis {2-ethyl-4- (4-t-butyl-3-chlorophenyl) azurenyl} zirconium dichloride. A compound in which the silylene group of these specific examples is replaced with a germylene group and zirconium is replaced with hafnium is also exemplified as a suitable compound. In addition, since the catalyst component is not an important element of the present invention, it avoids complicated listing and is limited to a representative example, but it is obvious that the effective range of the present invention is not limited by this. It is.

(2-3) Component (b)
As the component (b), at least one solid component selected from the components (b-1) to (b-4) described above is used. Each of these components is known and can be used by appropriately selecting from known techniques. Specific examples and manufacturing methods thereof are described in detail in JP-A No. 2002-284808, JP-A No. 2002-53609, JP-A No. 2002-69116, JP-A No. 2003-105015, and the like.
Here, as the particulate carrier used for the component (b-1) and the component (b-2), inorganic oxides such as silica, alumina, magnesia, silica alumina, silica magnesia, magnesium chloride, magnesium oxychloride, chloride Examples thereof include inorganic halides such as aluminum and lanthanum chloride, and porous organic carriers such as polypropylene, polyethylene, polystyrene, styrene divinyl benzene copolymer, and acrylic acid copolymer.
Further, as a non-limiting specific example of the component (B), a particulate carrier on which methylalumoxane, isobutylalumoxane, methylisobutylalumoxane, aluminum butylboronate tetraisobutyl, etc. are supported as the component (b-1). As component (b-2), triphenylborane, tris (3,5-difluorophenyl) borane, tris (pentafluorophenyl) borane, triphenylcarbonium tetrakis (pentafluorophenyl) borate, N, N-dimethyl Particulate carrier carrying anilinium tetrakis (pentafluorophenyl) borate, etc. as component (b-3), alumina, silica alumina, magnesium chloride, etc. as component (b-4), montmorillonite, zakonite, beidellite , Nontronic , Saponite, hectorite, stevensite, bentonite, smectite group such as taeniolite, vermiculite, and the like mica group. These may form a mixed layer.
Particularly preferred among the above components (b) is the ion-exchange layered silicate of component (b-4), and more preferred are chemical treatments such as acid treatment, alkali treatment, salt treatment, and organic matter treatment. It is an ion exchange layered silicate applied.

(2-4) Component (c)
Examples of organoaluminum compounds used as component (c) as needed are:
General formula AlR _a P _3-a
(Wherein R is a hydrocarbon group having 1 to 20 carbon atoms, P is hydrogen, halogen, alkoxy group, a is a number of 0 <a ≦ 3), trimethylaluminum, triethylaluminum, tripropylaluminum, tri Trialkylaluminum such as isobutylaluminum or halogen or alkoxy-containing alkylaluminum such as diethylaluminum monochloride, diethylaluminum monomethoxide. In addition, aluminoxanes such as methylaluminoxane can also be used. Of these, trialkylaluminum is particularly preferred.

(2-5) Formation of catalyst Component (a) is contacted with component (b) and, if necessary, component (c) to form a catalyst. The contact method is not particularly limited, but the contact can be made in the following order. Moreover, this contact may be performed not only at the time of catalyst preparation but also at the time of prepolymerization with olefin or at the time of polymerization of olefin.
1) Contact component (a) and component (b) 2) Add component (c) after contacting component (a) and component (b) 3) Contact component (a) and component (c) 4) Add component (b) after contact 4) Add component (a) after contacting component (b) and component (c), or contact three components simultaneously.

The amount of components (a), (b) and (c) used in the present invention is arbitrary. For example, the amount of component (a) used relative to component (b) is preferably in the range of 0.1 μmol to 1,000 μmol, particularly preferably 0.5 μmol to 500 μmol, relative to 1 g of component (b). The amount of component (c) used relative to component (b) is preferably such that the amount of transition metal is 0.001 to 100 μmol, particularly preferably 0.005 to 50 μmol, relative to 1 g of component (b). Therefore, the amount of the component (c) to the component (a) is preferably in the range of 10 ⁻⁵ to 50, particularly preferably 10 ^{−4 to} 5 in terms of the molar ratio of the transition metal.

The catalyst used in the (i) propylene-ethylene block copolymer of the present invention is preferably subjected to a prepolymerization treatment in which a small amount of polymer is brought into contact with an olefin in advance. The olefin to be used is not particularly limited, but ethylene, propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, 3-methyl-1-butene, vinylcycloalkane, styrene and the like can be used. In particular, it is preferable to use propylene. The olefin can be supplied by any method such as a supply method for maintaining the olefin at a constant speed or in a constant pressure state, a combination thereof, or a stepwise change. The prepolymerization temperature and time are not particularly limited, but are preferably in the range of −20 ° C. to 100 ° C. and 5 minutes to 24 hours, respectively. The amount of prepolymerization is preferably 0.01 to 100, more preferably 0.1 to 50 with respect to the component (b). After completion of the prepolymerization, the catalyst can be used as it is, depending on the usage form of the catalyst. However, if necessary, drying can be performed.
Furthermore, a polymer such as polyethylene, polypropylene, or polystyrene, or an inorganic oxide solid such as silica or titania can be allowed to coexist during or after the contact of the above components.

(2-6) Polymerization Method (2-6-1) Sequential Polymerization (i) When the propylene-ethylene block copolymer used in the present invention is produced, component (A) and component (B) are polymerized sequentially. It is necessary to.
(I) When the propylene-ethylene copolymer is a random copolymer obtained by simply copolymerizing ethylene with propylene, if the ethylene content is low, flexibility / impact resistance and transparency are not sufficient. Increasing the ethylene content to improve impact resistance and transparency degrades the heat resistance and it is difficult to satisfy all of these.
Therefore, in the present invention, (i) the propylene-ethylene block copolymer is a block copolymer obtained by sequentially polymerizing components having different ethylene contents in the first step and the second step. It is necessary to balance all properties and heat resistance.
In the present invention, since a copolymer having a low molecular weight and easily sticking alone may be used as the component (B), in order to prevent problems such as adhesion to the reactor, the component (A) is polymerized. It is necessary to use a method for polymerizing component (B).
When performing sequential polymerization, either a batch method or a continuous method can be used, but it is generally desirable to use a continuous method from the viewpoint of productivity.

In the case of a batch method, it is possible to polymerize component (A) and component (B) separately using a single reactor by changing the polymerization conditions with time. As long as the effect of the present invention is not impaired, a plurality of reactors may be connected in parallel.
In the case of a continuous process, it is necessary to use a production facility in which two or more reactors are connected in series because it is necessary to polymerize component (A) and component (B) separately, as long as the effect of the present invention is not impaired. A plurality of reactors may be connected in series and / or in parallel for each of component (A) and component (B).

(2-6-2) Polymerization process As the polymerization process, any polymerization method such as a slurry method, a bulk method, or a gas phase method can be used. Although supercritical conditions can be used as intermediate conditions between the bulk method and the gas phase method, they are substantially the same as the gas phase method, and are therefore included in the gas phase method without particular distinction.
Since component (B) is easily soluble in organic solvents such as hydrocarbons and liquefied propylene, it is desirable to use a gas phase method for the production of component (B).
There is no particular problem in using any process for the production of component (A). However, when producing component (A) having relatively low crystallinity, a vapor phase method is used to avoid problems such as adhesion. It is desirable to use
Therefore, it is most desirable to first polymerize component (A) by the bulk method or gas phase method using the continuous method, and then polymerize component (B) by the gas phase method.

(2-6-3) Other polymerization conditions The polymerization temperature can be used without any particular problem as long as it is within a commonly used temperature range. Specifically, a range of 0 ° C. to 200 ° C., more preferably 40 ° C. to 100 ° C. can be used.
The polymerization pressure varies depending on the process to be selected, but it can be used without any problem as long as it is in a pressure range usually used. Specifically, a range of greater than 0 to 200 MPa, more preferably 0.1 MPa to 50 MPa can be used. At this time, an inert gas such as nitrogen may coexist.
When the component (A) is sequentially polymerized in the first step and the component (B) is sequentially polymerized in the second step, it is desirable to add a polymerization inhibitor to the system in the second step. In the case of producing a propylene-ethylene block copolymer, if a polymerization inhibitor is added to a reactor that performs ethylene-propylene random copolymerization in the second step, the particle properties (fluidity, etc.) of the resulting powder, gel, etc. Can improve the product quality. Various technical studies have been made on this method, and examples thereof include Japanese Patent Publication No. 63-54296, Japanese Patent Application Laid-Open No. 7-25960, Japanese Patent Application Laid-Open No. 2003-2939, and the like. It is desirable to apply the method to the present invention.

(3) (A) Method for controlling constituent elements of propylene-ethylene block copolymer Each element of the propylene-ethylene block copolymer used in the present invention is controlled as follows and is necessary for the copolymer of the present invention. It can be manufactured to meet the required configuration requirements.

(3-1) Component (A)
For component (A), it is necessary to control the ethylene content [E] A and T (A).
In the present invention, in order to control [E] A within a predetermined range, the amount ratio of propylene and ethylene supplied to the polymerization tank in the first step may be appropriately adjusted. The relationship between the supply ratio and the ethylene content in the resulting propylene-ethylene random copolymer varies depending on the type of metallocene catalyst used, but the component (A) having the ethylene content [E] A required by adjusting the supply ratio is selected. Can be manufactured.
For example, when [E] A is controlled to be less than 7 wt%, the supply weight ratio of ethylene to propylene may be in the range of 0.3 or less, preferably in the range of 0.2 or less.
At this time, the component (A) has a narrow crystallinity distribution, and T (A) decreases as [E] A increases.
Therefore, in order for T (A) to satisfy the scope of the present invention, [E] A and their relationship are grasped and adjusted so as to take a target range.

(3-2) Component (B)
For component (B), it is necessary to control the ethylene content [E] B, T (B) and [η] cxs.
In the present invention, in order to control [E] B within a predetermined range, similarly to [E] A, the ratio of ethylene supply to propylene in the second step may be controlled. For example, when [E] B is controlled to 3 to 27 wt%, the supply weight ratio of ethylene to propylene may be in the range of 0.005 to 6, preferably in the range of 0.01 to 3.
At this time, although the crystallinity distribution of the component (B) is slightly increased as the ethylene content is increased, the T (B) is decreased as [E] B is increased as in the case of the component (A).
Therefore, in order for T (B) to satisfy the scope of the present invention, the relationship between [E] B and T (B) is grasped, and [E] B is controlled to be within a predetermined range. That's fine.

(3-3) W (A) and W (B)
The amount W (A) of the component (A) and the amount W (B) of the component (B) change the ratio of the production amount of the first step for producing the component (A) and the production amount of the component (B). Can be controlled. For example, in order to increase W (A) and decrease W (B), the production amount of the second step may be reduced while maintaining the production amount of the first step, which shortens the residence time of the second step. It can be easily controlled by lowering the polymerization temperature or increasing the amount of the polymerization inhibitor. The reverse is also true.
When actually setting the conditions, it is necessary to consider the activity decay. That is, in the range of the ethylene contents [E] A and [E] B carried out in the present invention, generally, when the ratio of ethylene supply to propylene is increased in order to increase the ethylene content, the polymerization activity is increased. The activity decay tends to increase. Therefore, in order to maintain the activity of the second step, it is necessary to suppress the polymerization activity of the first step. Specifically, in the first step, the ethylene content [E] A is lowered and the production amount W (A ), And if necessary, lower the polymerization temperature and / or shorten the polymerization time (residence time), or increase the ethylene content [E] B in the second step and increase the production W (B). If necessary, the conditions may be set by a method that raises the polymerization temperature and / or lengthens the polymerization time (residence time).

(3-4) Glass transition temperature Tg
The (i) propylene-ethylene block copolymer used in the present invention has a glass transition temperature Tg of 0 ° C. or less, which is a temperature at which a tan δ curve obtained in a temperature-loss tangent curve obtained by solid viscoelasticity measurement shows a peak. Need to have a single peak. In order for Tg to have a single peak, the difference [E] gap (= [E] between the ethylene content [E] A in component (A) and the ethylene content [E] B in component (B) ] B- [E] A) may be 20 wt% or less, preferably 16 wt% or less, and [E] gap may be reduced to a range where Tg becomes a single peak in actual measurement.
According to the ethylene content [E] A in the component (A), the supply amount of ethylene to propylene during the polymerization of the component (B) so that the ethylene content [E] B in the component (B) falls within an appropriate range. By setting the ratio, a propylene-ethylene block copolymer having a predetermined [E] gap can be obtained.
Further, the Tg of the propylene-ethylene block copolymer which does not have a phase separation structure as used in the present invention is the ethylene content [E] A in the component (A) and the ethylene in the component (B). It is affected by the content [E] B and the quantity ratio of both components. In the present invention, the amount of the component (B) is 5 to 70 wt%, but in this range, Tg is more strongly affected by the ethylene content [E] B in the component (B).
That is, Tg reflects the glass transition of the amorphous part. In (i) the propylene-ethylene block copolymer used in the present invention, the component (A) has crystallinity and a relatively amorphous part. This is because the component (B) is low crystalline or amorphous, and most of it is an amorphous part. Therefore, the value of Tg is almost controlled by [E] B, and the control method of [E] B is as described above.

2. Nucleating agent The compounding amount of the nucleating agent used in the medical propylene-based resin composition of the present invention is 0.01 to 0.6 wt. Used in the range of parts. If it is less than 0.01 part by weight, the transparency may not be expressed. If it exceeds 0.6 part by weight, the 15th revised Japanese Pharmacopoeia General Test 45. Test method for plastic drug containers 1. Not only is there a possibility that the test of the polyethylene or polypropylene aqueous injection container may be rejected, but an improvement in performance corresponding to the added amount cannot be expected, which is economically undesirable.
As such a nucleating agent, the nucleating agents (A) to (E) shown below are desirable. In cases other than these nucleating agents (A) to (E), the 15th revised Japanese Pharmacopoeia General Test 45. Test method for plastic drug containers 1. There is a high possibility of failing the test of an aqueous injection container made of polyethylene or polypropylene.
The nucleating agent (A) is a compound represented by the general formula (1), among which the compound represented by the general formula (6) is preferable, and the compound represented by the chemical structural formula (7) is more preferable.

[Wherein n is an integer of 0 to 2 and R ^{1 to} R ⁵ are the same or different and each is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an alkenyl group, an alkoxy group, a carbonyl group, a halogen atom. Group and a phenyl group, and R ⁶ is an alkyl group having 1 to 20 carbon atoms. ]

[N is an integer of 0 to 2, R ¹ , R ² , R ⁴ and R ⁵ are hydrogen atoms, and R ³ is a hydrogen atom or an alkyl group or alkenyl group having 1 to 20 carbon atoms. , An alkoxy group, a carbonyl 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 NX8000 manufactured by Milliken Corporation.

  The nucleating agent (A) used in the present invention has excellent transparency in the resulting molded product and has extremely low dissolution properties, and has passed the 15th revised Japanese Pharmacopoeia test with strict acceptance criteria. It is one of the few nucleating agents that can be obtained.

  The blending amount of the nucleating agent (A) used in the medical propylene-based resin composition of the present invention is 0.01 to 0.6 weight with respect to 100 parts by weight of the propylene-based polymer (A) + (I). Used in the range of parts. If the amount is less than 0.01 parts by weight, it is difficult to obtain a sufficient effect. If the amount exceeds 0.6 parts by weight, further improvement in performance cannot be expected and it is uneconomical. Fails in items such as “bubble generation” and “ultraviolet absorption spectrum” of the test. 0.1-0.4 weight part is preferable and 0.2-0.35 weight part is further more preferable.

  Further, the (c) nucleating agent of the present invention may be the nucleating agents (B) to (E) represented by the general formulas (2) to (5), and the nucleating agents (A) to (E) respectively. When used alone or in combination, transparency, rigidity, moldability (increase in crystallization temperature), and the like can be further improved.

  In the medical propylene-based resin composition of the present invention, the nucleating agent (B) used selectively is an organophosphate metal salt compound represented by the general formula (2).

[In formula (2), ^{R 1} represents a direct bond, a sulfur or an alkylene group or alkylidene group having 1 to 9 carbon atoms, ^{R 2} and ^{R 3} is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms , M is Na, and n is the valence of M. ]

Specific examples of the organophosphate metal salt compound represented by the general formula (2) include sodium-2,2′-methylene-bis- (4,6-di-t-butylphenyl) phosphate, sodium-2. , 2'-ethylidene-bis- (4,6-di-t-butylphenyl) phosphate, sodium-2,2'-ethylidene-bis- (4-i-propyl-6-t-butylphenyl) phosphate Sodium-2,2′-butylidene-bis- (4,6-dimethylphenyl) phosphate, sodium-2,2′-butylidene-bis- (4,6-di-t-butylphenyl) phosphate, sodium -2,2'-t-octylmethylene-bis- (4,6-methylphenyl) phosphate, sodium-2,2'-t-octylmethylene-bis- (4,6-di-t-butyl) Tilphenyl) phosphate, sodium-2,2′-methylene-bis- (4-methyl-6-tert-butylphenyl) phosphate, sodium-2,2′-methylene-bis- (4-ethyl-6-t) -Butylphenyl) phosphate, sodium (4,4'-dimethyl-6,6'-di-t-butyl-2,2'-biphenyl) phosphate, sodium-2,2'-ethylidene-bis- (4 -S-butyl-6-tert-butylphenyl) phosphate, sodium-2,2'-methylene-bis- (4,6-di-methylphenyl) phosphate, sodium-2,2'-methylene-bis- Examples thereof include (4,6-di-ethylphenyl) phosphate and a mixture of two or more thereof. Of these, sodium-2,2′-methylene-bis- (4,6-di-t-butylphenyl) phosphate is particularly preferable.
A commercially available product can be used as such a nucleating agent. Specifically, NA-11 manufactured by ADEKA Corporation can be mentioned.
The grade of NA11 is divided according to the particle size as follows, and the average particle size is preferably 15 μm or less, but 1 μm or less is preferable because of excellent transparency. Moreover, since the one where a particle size distribution is wider is effective in prevention of re-aggregation, it is preferable that the maximum particle size is 10 times or more with respect to the average particle size (center value).

Adegas tub Average particle size (center value) Maximum particle size NA11 5-10 μm 45 μm
NA11UF 10-15μm 150μm
NA11SF <1μm 1.8μm

  The blending amount of the nucleating agent (B) selectively used in the medical propylene resin composition of the present invention is 0.005 to 0 with respect to 100 parts by weight of the propylene polymer (A) + (I). The range of 0.3 parts by weight is preferable, and the range of 0.01 to 0.2 parts by weight is more preferable. If it is less than 0.005 parts by weight, the effect cannot be obtained, and if it exceeds 0.3 parts by weight, not only a further effect cannot be obtained but also economically not preferable.

  In the medical propylene-based resin composition of the present invention, the nucleating agent (C) used selectively is an aromatic phosphate ester represented by the general formula (3).

[In Formula (3), R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ² and R ³ represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and M represents a period. Represents a Group III or Group IV metal atom, X represents HO— when M represents a Group III metal atom, and M represents a Group IV metal of the Periodic Table When showing an atom, it shows O = or (HO) _2- . ]

  Specific examples of the aromatic phosphates represented by the general formula (3) include, for example, hydroxyaluminum-bis [2,2′-methylene-bis (4,6-dimethylphenyl) phosphate], hydroxyaluminum- Bis [2,2′-ethylidene-bis (4,6-dimethylphenyl) phosphate], hydroxyaluminum-bis [2,2′-methylene-bis (4,6-diethylphenyl) phosphate], hydroxyaluminum— Bis [2,2′-ethylidene-bis (4,6-diethylphenyl) phosphate], hydroxyaluminum-bis [2,2′-methylene-bis (4,6-di-t-butylphenyl) phosphate] And hydroxyaluminum-bis [2,2′-ethylidene-bis (4,6-di-tert-butylphenol) Nyl) phosphate], hydroxyaluminum-bis [2,2′-methylene-bis (4-methyl-6-tert-butylphenyl) phosphate], hydroxyaluminum-bis [2,2′-ethylidene-bis (4 -Methyl-6-tert-butylphenyl) phosphate], hydroxyaluminum-bis [2,2′-methylene-bis (4-ethyl-6-tert-butylphenyl) phosphate], hydroxyaluminum-bis [2, 2′-ethylidene-bis (4-ethyl-6-tert-butylphenyl) phosphate], hydroxyaluminum bis [2,2′-methylene-bis (4-i-propyl-6-tert-butylphenyl) phosphate Fate], hydroxyaluminum-bis [2,2′-ethylidene-bis (4-i-propyl-6- -Butylphenyl) phosphate], etc., preferably hydroxyaluminum-bis [2,2′-methylene-bis (4,6-di-t-butylphenyl) phosphate], and hydroxyaluminum-bis [ 2,2′-ethylidene-bis (4,6-di-t-butylphenyl) phosphate], and a mixture of two or more thereof.

It is effective to use the aromatic phosphates represented by the general formula (3) in combination with an organic alkali metal salt.
The organic alkali metal salt may be at least one organic alkali metal salt selected from the group consisting of alkali metal carboxylates, alkali metal β-diketonates and alkali metal β-ketoacetate salts.
Examples of the alkali metal constituting the organic alkali metal salt include lithium, sodium, and potassium.
Examples of the carboxylic acid constituting the alkali metal carboxylate include acetic acid, propionic acid, acrylic acid, octylic acid, isooctylic acid, nonanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, Ricinoleic acid, 12-hydroxystearic acid, behenic acid, montanic acid, melicic acid, β-dodecylmercaptoacetic acid, β-dodecylmercaptopropionic acid, β-N-laurylaminopropionic acid, β-N-methyl-lauroylaminopropionic acid Aliphatic monocarboxylic acids such as malonic acid, succinic acid, adipic acid, maleic acid, azelaic acid, sebacic acid, dodecanedioic acid, citric acid, butanetricarboxylic acid, butanetetracarboxylic acid, and other polyvalent aliphatic carboxylic acids such as naphthene Acid, cyclopentanecarboxylic acid, 1-methyl Cyclopentanecarboxylic acid, 2-methylcyclopentanecarboxylic acid, cyclopentenecarboxylic acid, cyclohexanecarboxylic acid, 1-methylcyclohexanecarboxylic acid, 4-methylcyclohexanecarboxylic acid, 3,5-dimethylcyclohexanecarboxylic acid, 4-butylcyclohexanecarboxylic acid , Cyclooctenecyclohexanecarboxylic acid, cyclohexenecarboxylic acid, cycloaliphatic mono- or polycarboxylic acid such as 4-cyclohexene-1,2-dicarboxylic acid, benzoic acid, toluic acid, xylyl acid, ethylbenzoic acid, 4-t- Aromatic mono- or polycarboxylic acids such as butyl benzoic acid, salicylic acid, phthalic acid, trimellitic acid and pyromellitic acid.

  Examples of the β-diketone compound constituting the alkali metal β-diketonate include acetylacetone, pivaloylacetone, palmitoylacetone, benzoylacetone, pivaloylbenzoylacetone, dibenzoylmethane, and the like.

  Examples of the β-ketoacetate constituting the alkali metal β-ketoacetate include ethyl acetoacetate, octyl acetoacetate, lauryl acetoacetate, stearyl acetoacetate, ethyl benzoyl acetate, benzoyl acetate lauryl and the like. It is done.

  The alkali metal carboxylate, alkali metal β-diketonate, or alkali metal β-ketoacetate salt, which is a component of the organic alkali metal salt, includes the above alkali metal and carboxylic acid, β-diketone compound, or β-ketoacetate, respectively. And can be produced by a conventionally known method. Among these alkali metal salt compounds, alkali metal aliphatic monocarboxylates, particularly lithium aliphatic carboxylates are preferable, and aliphatic monocarboxylates having 8 to 20 carbon atoms are particularly preferable.

  A commercially available product can be used as such a nucleating agent. Specifically, NA-21 manufactured by ADEKA Corporation can be mentioned.

  The blending amount of the nucleating agent (C) selectively used in the medical propylene-based resin composition of the present invention is 0.005 to 0 with respect to 100 parts by weight of the propylene-based polymer of (A) + (I). A range of .15 parts by weight is preferable, and a range of 0.01 to 0.1 parts by weight is more preferable. If it is less than 0.005 parts by weight, the effect cannot be obtained, and if it exceeds 0.15 parts by weight, not only a further effect cannot be obtained but also economically not preferable.

  In the medical propylene-based resin composition of the present invention, the nucleating agent (D) that is selectively used is a nucleating agent represented by the general formula (4).

[In Formula (4), M ₁ and M ₂ are the same or different and are at least one metal cation selected from calcium, strontium, lithium and monobasic aluminum, and R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ are the same or different and each represents hydrogen, C ₁ -C ₉ alkyl (wherein any two vicinal (bonded to adjacent carbons) ) Or geminal (bonded to the same carbon) alkyl group may combine to form a hydrocarbon ring having up to 6 carbon atoms), hydroxy, C ₁ -C ₉ alkoxy, C ₁ -C ₉ alkyleneoxy, amine and C ₁ -C ₉ alkylamine, halogen is independently selected from the group consisting of (fluorine, chlorine, bromine and iodine) and phenyl. ]

  Here, the term “monobasic aluminum” is well known and is intended to include an aluminum hydroxide group as a single cation having two carboxylic acid groups attached thereto. Further, in each of these possible salts, the configuration of the asymmetric carbon atom may be either cis or trans, with cis being preferred.

The nucleating agent represented by the general formula (4) may be used in combination with other compounds for the purpose of preventing aggregation and the like.
A commercially available product can be used as such a nucleating agent. Specific examples include Hyperform HPN68L manufactured by Meriken Co., Ltd. The structure of the nucleating agent component of Hyperform HPN68L is shown below.

  The blending amount of the nucleating agent (D) selectively used in the medical propylene-based resin composition of the present invention is 0.005 to 0 with respect to 100 parts by weight of the propylene-based polymer (A) + (I). A range of .15 parts by weight is preferable, and a range of 0.01 to 0.1 parts by weight is more preferable. If it is less than 0.005 parts by weight, the effect cannot be obtained, and if it exceeds 0.15 parts by weight, the pharmacopoeia test may be rejected.

In the medical propylene-based resin composition of the present invention, the nucleating agent (E) used selectively is a nucleating agent represented by the general formula (5). A nucleating agent represented by the general formula (8) is preferable, and a nucleating agent represented by the general formula (9) is more preferable.
R ¹ (CONHR ² ) _a (5)
[Wherein R ¹ represents a saturated or unsaturated aliphatic polycarboxylic acid residue having 2 to 30 carbon atoms, a saturated or unsaturated alicyclic polycarboxylic acid residue having 4 to 28 carbon atoms, or the number of carbon atoms. Represents 6-18 aromatic polycarboxylic acid residues. R ² represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, or a cycloalkyl group or cycloalkenyl group having 3 to 46 carbon atoms. a represents an integer of 2 to 6. ]

[In the formula (8), R ¹ represents a trivalent saturated aliphatic hydrocarbon group having 3 to 10 carbon atoms, a tetravalent saturated aliphatic hydrocarbon group having 4 to 10 carbon atoms, or 3 having 5 to 15 carbon atoms. Represents a trivalent or tetravalent saturated alicyclic hydrocarbon group, or a trivalent or tetravalent aromatic hydrocarbon group having 6 to 15 carbon atoms. R ² are the same or different and each represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms. a represents an integer of 3 or 4. ]

[In Formula (9), R ¹ represents a residue obtained by removing all carboxyxyl groups from 1,2,3-propanetricarboxylic acid or 1,2,3,4-butanetetracarboxylic acid. Three or four R ^{2 s} are the same or different from each other and each represent a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms. a represents an integer of 3 or 4. ]

Specifically, 1,2,3-propanetricarboxylic acid tricyclohexylamide, 1,2,3-propanetricarboxylic acid tri (2-methylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (3-methyl) Cyclohexylamide), 1,2,3-propanetricarboxylic acid tri (4-methylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (2-ethylcyclohexylamide) 1,2,3-propanetricarboxylic acid tri ( 3-ethylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (4-ethylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (2-n-propylcyclohexylamide), 1,2,3 -Propanetricarboxylic acid tri (3-n-propylcyclohexyla ), 1,2,3-propanetricarboxylic acid tri (4-n-propylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (2-iso-propylcyclohexylamide), 1,2,3-propane Tricarboxylic acid tri (3-iso-propylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (4-iso-propylcyclohexylamide),
1,2,3-propanetricarboxylic acid tri (2-n-butylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (3-n-butylcyclohexylamide) 1,2,3-propanetricarboxylic acid tri ( 4-n-butylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (2-iso-butylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (3-iso-butylcyclohexylamide), 1 , 2,3-propanetricarboxylic acid tri (4-iso-butylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (2-sec-butylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri ( 3-sec-butylcyclohexylamide) 1,2,3-propanetrica Boronic acid tri (4-sec-butylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (2-tert-butylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (3-tert-butylcyclohexyl) Amide), 1,2,3-propanetricarboxylic acid tri (4-tert-butylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (4-n-pentylcyclohexylamide), 1,2,3-propane Tricarboxylic acid tri (4-n-hexylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (4-n-heptylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (4-n-octylcyclohexyl) Amide), 1,2,3-propanetricarboxylic acid tri 4- (2-ethylhexyl) cyclohexylamide], 1,2,3-propanetricarboxylic acid tri (4-n-nonylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (4-n-decylcyclohexylamide) 1,2,3-propanetricarboxylic acid [(cyclohexylamide) di (2-methylcyclohexylamide)], 1,2,3-propanetricarboxylic acid [di (cyclohexylamide) (2-methylcyclohexylamide)],

  1,2,3,4-butanetetracarboxylic acid tetracyclohexylamide, 1,2,3,4-butanetetracarboxylic acid tetra (2-methylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid tetra (3-methylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid tetra (4-methylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid tetra (2-ethylcyclohexylamide) 1 , 2,3,4-Butanetetracarboxylic acid tetra (3-ethylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid tetra (4-ethylcyclohexylamide), 1,2,3,4-butane Tetracarboxylic acid tetra (2-n-propylcyclohexylamide), 1,2,3,4-butanetetracarboxylic Tetra (3-n-propylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid tetra (4-n-propylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid tetra (2- iso-propylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid tetra (3-iso-propylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid tetra (4-iso-propylcyclohexyl) Amide), 1,2,3,4-butanetetracarboxylic acid tetra (2-n-butylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid tetra (3-n-butylcyclohexylamide) 1, 2,3,4-butanetetracarboxylic acid tetra (4-n-butylcyclohexylamide), 1,2,3 4-Butanetetracarboxylic acid tetra (2-iso-butylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid tetra (3-iso-butylcyclohexylamide) 1,2,3,4-butanetetracarboxylic Acid tetra (4-iso-butylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid tetra (2-sec-butylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid tetra (3 -Sec-butylcyclohexylamide) 1,2,3,4-butanetetracarboxylic acid tetra (4-sec-butylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid tetra (2-tert-butylcyclohexyl) Amide), 1,2,3,4-butanetetracarboxylic acid tetra (3-tert-butyl) Lucyclohexylamide) 1,2,3,4-butanetetracarboxylic acid tetra (4-tert-butylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid tetra (4-n-pentylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid tetra (4-n-hexylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid tetra (4-n-heptylcyclohexylamide), 1,2, 3,4-butanetetracarboxylic acid tetra (4-n-octylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid tetra [4- (2-ethylhexyl) cyclohexylamide], 1,2,3 4-Butanetetracarboxylic acid tetra (4-n-nonylcyclohexylamide), 1,2,3,4-butanetetra Carboxylic acid tetra (4-n-decyl cyclohexyl amide), 1,2,3,4-butane tetracarboxylic acid [di (cyclohexyl amide) di (2-methylcyclohexyl amide)] and the like.

Among the amide compounds, R ² in the general formula (8) or (9) is a hydrogen atom or a linear or branched chain having 1 to 4 carbon atoms, particularly from the viewpoint of nucleating action (nucleating agent effect). Amide compounds that are alkyl groups are preferred.
Specifically, 1,2,3-propanetricarboxylic acid tricyclohexylamide, 1,2,3-propanetricarboxylic acid tri (2-methylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (3-methyl) Cyclohexylamide), 1,2,3-propanetricarboxylic acid tri (4-methylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (2-ethylcyclohexylamide) 1,2,3-propanetricarboxylic acid tri ( 3-ethylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (4-ethylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (2-n-propylcyclohexylamide), 1,2,3 -Propanetricarboxylic acid tri (3-n-propylcyclohexyla ), 1,2,3-propanetricarboxylic acid tri (4-n-propylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (2-iso-propylcyclohexylamide), 1,2,3-propane Tricarboxylic acid tri (3-iso-propylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (4-iso-propylcyclohexylamide),
1,2,3-propanetricarboxylic acid tri (2-n-butylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (3-n-butylcyclohexylamide) 1,2,3-propanetricarboxylic acid tri ( 4-n-butylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (2-iso-butylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (3-iso-butylcyclohexylamide), 1 , 2,3-propanetricarboxylic acid tri (4-iso-butylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (2-sec-butylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri ( 3-sec-butylcyclohexylamide) 1,2,3-propanetrica Boronic acid tri (4-sec-butylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (2-tert-butylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (3-tert-butylcyclohexyl) Amide), 1,2,3-propanetricarboxylic acid tri (4-tert-butylcyclohexylamide),

  1,2,3,4-butanetetracarboxylic acid tetra (cyclohexylamide), 1,2,3,4-butanetetracarboxylic acid tetra (2-methylcyclohexylamide), 1,2,3,4-butanetetracarboxylic Acid tetra (3-methylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid tetra (4-methylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid tetra (2-ethylcyclohexylamide) ) 1,2,3,4-butanetetracarboxylic acid tetra (3-ethylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid tetra (4-ethylcyclohexylamide), 1,2,3,4 -Butanetetracarboxylic acid tetra (2-n-propylcyclohexylamide), 1,2,3,4-butanetetracar Acid tetra (3-n-propylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid tetra (4-n-propylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid tetra ( 2-iso-propylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid tetra (3-iso-propylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid tetra (4-iso-) Propylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid tetra (2-n-butylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid tetra (3-n-butylcyclohexylamide) 1,2,3,4-butanetetracarboxylic acid tetra (4-n-butylcyclohexylamide), 1,2 3,4-butanetetracarboxylic acid tetra (2-iso-butylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid tetra (3-iso-butylcyclohexylamide) 1,2,3,4-butane Tetracarboxylic acid tetra (4-iso-butylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid tetra (2-sec-butylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid tetra (3-sec-butylcyclohexylamide) 1,2,3,4-butanetetracarboxylic acid tetra (4-sec-butylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid tetra (2-tert- Butylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid tetra (3-tert- Butylcyclohexylamide) 1,2,3,4-butanetetracarboxylic acid tetra (4-tert-butylcyclohexylamide) and the like.

Among these preferable amide compounds, amide compounds in which R ² in the general formula (8) or (9) is a hydrogen atom or a methyl group are particularly preferable from the viewpoint of balance of transparency and rigidity and easy availability of raw materials. preferable. Specifically, 1,2,3-propanetricarboxylic acid tricyclohexylamide, 1,2,3-propanetricarboxylic acid tri (2-methylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (3-methyl) Cyclohexylamide), 1,2,3-propanetricarboxylic acid tri (4-methylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid tetracyclohexylamide, 1,2,3,4-butanetetracarboxylic acid Tetra (2-methylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid tetra (3-methylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid tetra (4-methylcyclohexylamide) Etc. are exemplified.

When emphasizing the effect of improving transparency, R ¹ in the general formula (5), (8) or (9) can be obtained by removing all carboxylic xyl groups from 1,2,3-propanetricarboxylic acid. Particularly preferred is an amide compound which is a residue obtained. Specifically, 1,2,3-propanetricarboxylic acid tricyclohexylamide, 1,2,3-propanetricarboxylic acid tri (2-methylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (3-methyl) Cyclohexylamide), 1,2,3-propanetricarboxylic acid tri (4-methylcyclohexylamide) and the like.

  Said amide type compound can be used individually or in combination of 2 or more types as appropriate.

  The crystal form of the nucleating agent (E) selectively used in the present invention is not particularly limited as long as the effects of the present invention can be obtained, and any crystal form such as hexagonal crystal, monoclinic crystal and cubic crystal can be used. . These crystals are also known or can be produced according to known methods.

  The nucleating agent (E) selectively used in the present invention preferably has a purity of substantially 100%, but may contain a slight amount of impurities. Even when impurities are contained, the purity of the nucleating agent (E) is preferably 90% by weight or more, more preferably 95% by weight or more, particularly 97% by weight or more. Examples of the impurities include monoamide dicarboxylic acid derived from a reaction intermediate or unreacted substance or an ester compound thereof, diamide monocarboxylic acid or an ester compound thereof, an imide compound derived from a side reaction product, and the like.

  The method for producing the nucleating agent (E) selectively used in the present invention is not particularly limited as long as the target nucleating agent (E) can be obtained. For example, a conventionally known method from a specific aliphatic polycarboxylic acid component and a specific alicyclic monoamine component (for example, JP-A-2006-298882, JP-A-2007-291029, PCT / JP2006 / 307246, JP-A-HEI 7-242610, etc.).

  Examples of the aliphatic polycarboxylic acid component include 1,2,3-propanetricarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, acid chlorides and anhydrides of the polycarboxylic acid, and the polycarboxylic acid. Examples thereof include derivatives such as esters with lower alcohols having 1 to 4 carbon atoms. These aliphatic polycarboxylic acid components can be used for amidation alone or in combination of two kinds.

The alicyclic monoamine component is at least one selected from the group consisting of cyclohexylamine and a cyclohexylamine substituted with a linear or branched alkyl group having 1 to 10 carbon atoms (preferably 1 to 4 carbon atoms). It can be used for amidation alone or in combination of two or more.
Specifically, cyclohexylamine, 2-methylcyclohexylamine, 3-methylcyclohexylamine, 4-methylcyclohexylamine methylcyclohexylamine, 2-ethylcyclohexylamine, 2-n-propylcyclohexylamine, 2-iso-propylcyclohexyl Examples include amines, 2-n-butylcyclohexylamine, 2-iso-butylcyclohexylamine, 2-sec-butylcyclohexylamine, 2-tert-butylcyclohexylamine and the like.

  The cyclohexylamine substituted with the above alkyl group may be any of a cis isomer, a trans isomer and a mixture of these stereoisomers. The preferred cis: trans ratio is preferably in the range of 50:50 to 0: 100, particularly preferably in the range of 35:65 to 0: 100.

  The particle size of the nucleating agent (E) selectively used in the present invention is not particularly limited as long as the effects of the present invention are obtained, but can be made from the viewpoint of the dissolution rate (or dissolution time) in the molten propylene polymer. Those having a small particle size are preferred. When the measured value of the particle diameter obtained by the laser diffraction light scattering method is adopted, the maximum particle diameter of the nucleating agent (E) is 200 μm or less, preferably 100 μm or less, more preferably 50 μm, particularly 10 μm. The following are recommended:

  As a method for adjusting the maximum particle size within the above range, a method using a known pulverizer in this field is generally used, and a known classifier can be used if necessary. Specifically, a fluidized bed type counter jet mill 100AFG (trade name, manufactured by Hosokawa Micron Corporation), a supersonic jet mill PJM-200 (trade name, manufactured by Nippon Pneumatic Co., Ltd.), a pin mill, etc. And dry classifiers (such as cyclones and micron separators).

  The blending amount of the nucleating agent (E) selectively used in the medical propylene resin composition of the present invention is 0.005 to 0 with respect to 100 parts by weight of the propylene polymer (A) + (I). The range of 3 parts by weight is preferable, and the range of 0.05 to 0.2 parts by weight is more preferable. If less than 0.005 parts by weight, the effect is not obtained, and if it exceeds 0.3 parts by weight, the 15th revised Japanese Pharmacopoeia General Test 45. Test method for plastic drug containers 1. It may fail a test (a pharmacopoeia test) of a polyethylene or polypropylene aqueous injection container.

In addition to the nucleating agents (A) to (E), the medical propylene-based resin composition of the present invention includes, as other nucleating agents, sorbitol nucleating agents, organophosphate nucleating agents, and aromatics. Known nucleating agents such as phosphate esters and talc can be added within a range that does not significantly impair the effects of the present invention.
Nucleating agents (A) to (E) used in combination with a two-component resin mixture (resin mixture) composed of (a) a propylene-based (co) polymer and (ii) a propylene-ethylene block copolymer are optionally added. An embodiment that is typically implemented is as follows.
1) Embodiment in which a predetermined amount of nucleating agent (A) to (E) is used alone (1) Resin mixture + nucleating agent (A)
(2) Resin mixture + nucleating agent (B)
(3) Resin mixture + nucleating agent (C)
(4) Resin mixture + nucleating agent (D)
(5) Resin mixture + nucleating agent (E)
2) Embodiment in which two kinds of nucleating agents are used in combination in a predetermined amount (1) Resin mixture + nucleating agent (A) + nucleating agent (B) or nucleating agent (C)
(2) Resin mixture + nucleating agent (A) + nucleating agent (D) or nucleating agent (E)
(3) Resin mixture + nucleating agent (B) + nucleating agent (C) or nucleating agent (D)
(4) Resin mixture + nucleating agent (C) + nucleating agent (D) or nucleating agent (E)
(5) Resin mixture + nucleating agent (D) + nucleating agent (E)
The nucleating agents (A) to (E) are optionally combined in two types.
3) Embodiment in which a predetermined amount of three kinds of nucleating agents are used in combination (1) Resin mixture + nucleating agent (A) + nucleating agent (B) + nucleating agent (C)
(2) Resin mixture + nucleating agent (A) + nucleating agent (D) + nucleating agent (E)
(3) Resin mixture + nucleating agent (B) + nucleating agent (C) + nucleating agent (D)
(4) Resin mixture + nucleating agent (C) + nucleating agent (D) + nucleating agent (E)
(5) Resin mixture + nucleating agent (D) + nucleating agent (E) + nucleating agent (B)
The nucleating agents (A) to (E) as described above are arbitrarily combined in three types.
4) Embodiment in which a predetermined amount of four types of nucleating agents are used in combination (1) Resin mixture + nucleating agent (A) + nucleating agent (B) + nucleating agent (C) + nucleating agent (D)
(2) Resin mixture + nucleating agent (B) + nucleating agent (C) + nucleating agent (D) + nucleating agent (E)
(3) Resin mixture + nucleating agent (C) + nucleating agent (D) + nucleating agent (E) + nucleating agent (A)
(4) Resin mixture + nucleating agent (D) + nucleating agent (E) + nucleating agent (A) + nucleating agent (B)
The nucleating agents (A) to (E) as described above are optionally combined in four types.
5) Embodiment in which a predetermined amount of five kinds of nucleating agents are used in combination (1) Two-component resin mixture + nucleating agent (A) + nucleating agent (B) or nucleating agent (C)
+ Nucleating agent (D) + Nucleating agent (E)

Thus, the difference in specifications of the two-component resin mixture consisting of (a) propylene-based (co) polymer and (ii) propylene-ethylene block copolymer may cause slight differences in the function of the nucleating agent. On the other hand, any of the embodiments consisting of the specifications of 1) to 5) is suitable in order to develop properties suitable for the use of the medical propylene-based resin composition including a specific medical device. You can decide what to do. In any case, in the two-component resin mixture comprising (a) a propylene-based (co) polymer and (b) a propylene-ethylene block copolymer, the specific nucleating agent (A) to (E) of the present invention is used. It is based on the knowledge of the present inventors that the specific specifications shown in 1) to 5) can express a predetermined nucleating agent function suitable for medical use.

3. Neutralizer In the medical propylene-based resin composition of the present invention, it is desirable to add a neutralizer. 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 (10) of Kyowa Chemical Industry Co., Ltd.) Aluminum complex hydroxide salt), Mizukarak (lithium aluminum composite hydroxide salt represented by the following general formula (11)), 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 (10)
[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 (11)
[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 selectively used in the medical propylene-based resin composition of the present invention is 0.005 to 0.2 weight with respect to 100 parts by weight of the propylene-based polymer (A) + (I). The range of parts is preferable, and the range of 0.01 to 0.05 parts by weight is more preferable.

4). Lubricant In the medical propylene-based resin composition of 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, and silicone oil is particularly 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. The lower the viscosity of the silicone (C), the better the releasability effect. However, since the elution is facilitated when the viscosity is too low, 50 mm ² / s (cst) or more is good at 25 ° C., and 100 mm ² / More than s (cst) is better, and more than 1000 mm ² / s (cst) is more preferable. Furthermore, those that comply with the drug machine No. 327 (December 20, 1995) medical device lubricant silicone oil standards (1) and (2) are more preferable.
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 selectively used in the medical propylene-based resin composition of the present invention is 0.001 to 0.5 parts by weight with respect to 100 parts by weight of the propylene-based polymer (A) + (I). Preferably, 0.01-0.15 weight part is more preferable, and 0.03-0.1 weight part is especially preferable. If the amount is less than 0.001 part by weight, the effect cannot be expected. If the amount exceeds 0.5 part by weight, not only a further effect cannot be expected, but also economically undesirable.

5). Other Additives In the medical propylene-based resin composition of the present invention, in addition to the components described above, various antioxidants, ultraviolet absorbers, light stabilizers and the like that are used as stabilizers for propylene-based polymers, etc. Additives can be blended.

  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-ββ'-thio-di-propionate, di-myristyl-ββ'-thio-di-propionate, di-lauryl-ββ'-thio-di-propionate An antioxidant etc. are mentioned.

  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.

  Further, amine-based antioxidants represented by the following general formula (12) and the following general formula (13), which have no discoloration and good NOx gas discoloration resistance due to 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 (14).

In addition, an antistatic agent, a slip agent, a dispersant such as a fatty acid metal salt, a dye, a pigment, polyethylene, an olefin-based elastomer, and the like can be blended within a range that does not impair the object of the present invention.
Other polymers, polyethylene, ethylene-propylene copolymer, ethylene-propylene-diene copolymer, ethylene, as long as the properties such as properties, functions, and transparency of the medical propylene resin composition of the present invention are not impaired. 1 to 30 parts by weight of one-, two- and three-component copolymers such as -butene-1 copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylate copolymer, acrylate polymer Can be added. Similarly, an elastomer such as natural rubber, butyl rubber, diene rubber, EPR and EPDM can be blended in an amount of 1 to 30 parts by weight. Further, general-purpose inorganic fillers such as talc, calcium carbonate, silica, alumina, gypsum, and mica can be used in combination.

[2] Method for Producing Medical Propylene Resin Composition The medical propylene resin composition of the present invention comprises (a) + (b) propylene polymer, selectively used nucleating agent (A) to After mixing at least one mixture of (E) and other additives as required into a Henschel mixer, super mixer, ribbon blender, etc., ordinary single screw extruder, twin screw extrusion It can be obtained by melt-kneading in a temperature range of 190 to 260 ° C. using a machine, a Banbury mixer, a plastic bender, a roll or the like.

[3] Medical molded product The medical molded product of the present invention is obtained by molding the above-described medical propylene resin composition by various molding methods such as injection molding, extrusion molding, and blow molding, which are known methods. However, an injection molding method with high dimensional accuracy and easy to make a complicated shape is desirable.
The molded article for medical use of the present invention is useful as a kit preparation, suitable for a syringe barrel and a storage container filled with a drug solution, and particularly suitable for a prefilled syringe. A prefilled syringe is a syringe-shaped preparation that is pre-filled with a chemical solution or a drug, and includes a single chamber type that is filled with one kind of liquid and a double chamber type that is filled with two kinds of drugs. Most prefilled syringes are single-chamber types, but there are two types of double-chamber types: a liquid / powder type formulation consisting of powder and its solution, and a liquid / liquid type formulation consisting of two types of liquids. An example of the single chamber type internal solution is a heparin solution.
The medical molded article may be subjected to a known sterilization treatment such as autoclave sterilization, radiation sterilization, EOG sterilization, ultraviolet sterilization, microwave, boiling water, and steam. The present invention is particularly effective for autoclave sterilization.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited at all by these description. In each Example and Comparative Example, the physical properties used were measured by the following methods, and the following were used as propylene-based polymers, nucleating agents, and other additives (neutralizing agents, lubricants).

1. Measurement method (1) TREF
The TREF measurement method is as described above.
[apparatus]
(TREF part)
TREF column: 4.3 mmφ × 150 mm stainless steel column Column packing material: 100 μm Surface inactive glass beads Heating method: Aluminum heat block Cooling method: Peltier element (Peltier element is cooled by water)
Temperature distribution: ± 0.5 ° C
Temperature controller: Chino Corporation 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 volume: Loop size 0.1ml
Inlet heating method: Aluminum heat block measurement temperature: 140 ° C
(Detection unit)
Detector: Fixed wavelength type infrared detector MIOX 1A made by FOXBORO
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 long circle Synthetic sapphire window measurement temperature: 140 ° C
(Pump part)
Liquid feed pump: SSC-3461 pump manufactured by Senshu Kagaku Co. [Measurement conditions]
Solvent: o-dichlorobenzene (containing 0.5 mg / mL BHT)
Sample concentration: 5 mg / mL
Sample injection volume: 0.1 mL
Solvent flow rate: 1 mL / min

(2) Measurement of solid viscoelasticity A sample cut into a strip of 10 mm width × 18 mm length × 2 mm thickness from a 2 mm thick sheet injection molded under the following conditions was used. The apparatus used was ARES manufactured by Rheometric Scientific. The frequency is 1 Hz. The measurement temperature was raised stepwise from −60 ° C., and the measurement was performed until the sample melted and became impossible to measure. The strain was performed in the range of 0.1 to 0.5%.
(Creation of specimen)
Standard number: JIS-7152 (ISO294-1)
Molding machine: TU-15 injection molding machine manufactured by Toyo Machine Metal Co., Ltd. Setting temperature: 80, 80, 160, 200, 200, 200 ° C. from below the hopper
Mold temperature: 40 ℃
Injection speed: 200 mm / s (speed in the mold cavity)
Injection pressure: 800 kgf / cm ²
Holding pressure: 800 kgf / cm ²
Holding time: 40 seconds
Mold shape: Flat plate (2mm thickness, 30mm width, 90mm length)

(3) Calculation of each component amount It calculated by the method mentioned above using TREF.

(4) Calculation of ethylene content
The ethylene content in the random copolymer was measured by infrared spectroscopy using a characteristic absorber of 733 cm ⁻¹ with an ethylene / propylene random copolymer whose composition was verified by ¹³ C-NMR as a reference substance. The pellets were formed into a film having a thickness of about 500 microns by press molding.

(5) Measured by peak intrinsic viscoelasticity measurement of tan δ curve.

(6) MFR: Measured according to JIS K7210 at a heating temperature of 230 ° C. and a load of 21.2 N.

(7) Melting peak temperature: Using a Seiko DSC, take 5.0 mg of sample, hold at 200 ° C. for 5 minutes, crystallize to 40 ° C. at a rate of temperature decrease of 10 ° C./min, and further 10 ° C./min. The melting peak temperature was measured when melting at a heating rate.

(8) Molecular weight distribution: measured by the method described above.

(9) Haze value: Using a sheet piece having a thickness of 1 mm, the value before sterilization was measured according to JIS K7105. In addition, autoclave sterilization (high pressure steam sterilization) is performed using a retort high pressure steam sterilization / cooling device RKZ-30L manufactured by Alp Co., Ltd. for 20 minutes at 121 ° C., and compliant with JIS K7105 after one week of sterilization. Then, the value measured was used as the value after sterilization.

(10) Fifteenth revision Japanese Pharmacopoeia test: 45. 1. Plastic chemical container test method (plastic water-based injection container) According to the test method in the section of polyethylene or polypropylene aqueous injection container, transparency, heavy metal, lead, cadmium, ignition residue, foaming, PH, potassium permanganate reducing substance, ultraviolet absorption spectrum, evaporation residue It was measured. However, the sample was prepared by weighing pellets with a thickness of 0.5 mm corresponding to a surface area of 1200 cm ² and pressing them at 220 ° C. to obtain sheet pieces having a length of about 5 cm and a width of about 0.5 cm. After being cut into pieces, washed with water, and dried at room temperature. Put this in a hard glass container with an internal volume of about 300 ml, add exactly 200 ml of water, seal it with a suitable stopper, heat it at 121 ° C for 1 hour using a high-pressure steam sterilizer, and leave it to room temperature. Then, this solution was used as a test solution, and separately with water, a blank test solution was prepared in the same manner.

(11) Flexural modulus: measured at 23 ° C. in accordance with JIS K7203 “Bending test method of hard plastic”.

(12) Izod (IZOD) impact value: measured at 23 ° C. in accordance with JIS K7110: 1999 using a notched test piece.

(13) Moldability: Each pellet was injection molded by an injection molding machine at a resin temperature of 240 ° C., an injection pressure of 900 kg / cm ² and a mold temperature of 40 ° C., and a molded product for moldability evaluation (12 cm × 12 cm × 2. On a 5mm plate, a 3mm x 4mm box of 25mm x 20mm x 20mm is formed, and the molded product obtained by this injection molding is visually observed to add a nucleating agent and other additives The presence or absence of scratches caused by depositing and adhering agents, reactive substances, etc. on the mold during molding was confirmed and evaluated in the following two stages.
Scratch present: Even if a large number of moldings are made, almost no fine scratches are generated.
No scratch: When a large number of moldings are made, fine scratches are generated on the molded product.

2. Materials used (1) (A) Propylene polymer

(I) Propylene homopolymer (HPP1): Novatec MA3Q (manufactured by Nippon Polypro Co., Ltd.), catalyst: Ziegler catalyst, MFR: 10 g / 10 min, isotactic pentad fraction 0.96 (by ¹³ C-NMR Measurement).
(Ii) Propylene homopolymer (HPP2): Novatec MA5Q (manufactured by Nippon Polypro Co., Ltd.), catalyst: Ziegler catalyst, MFR: 5 g / 10 min, isotactic pentad fraction 0.96 (by ¹³ C-NMR Measurement).
(Iii) Ethylene / propylene random copolymer (RPP1): Novatec MG3FQ (manufactured by Nippon Polypro Co., Ltd.), catalyst: Ziegler catalyst. Ethylene concentration 2.5% by weight, MFR: 8g / 10min

(2) (I) Propylene-ethylene block copolymer Propylene-ethylene block copolymers (PP-1) to (PP-3) used in the present invention are produced by the following production examples 1 to 3 according to the following production examples 1 to 3. According to Example 4, a propylene-ethylene block copolymer (PP-4) different from that used in the present invention was obtained.

[Production Example PP-1]
Preparation of prepolymerization catalyst (chemical treatment of ion-exchange layered silicate)
To a 10-liter glass separable flask with a stirring blade, 3.75 liters of distilled water was added slowly followed by 2.5 kg of concentrated sulfuric acid (96%). At 50 ° C., 1 kg of montmorillonite (Menzawa Chemical Co., Ltd. Benclay SL; average particle size = 25 μm, particle size distribution = 10-60 μm) was dispersed, heated to 90 ° C., and maintained at that temperature for 6.5 hours. After cooling to 50 ° C., the slurry was filtered under reduced pressure to recover the cake. 7 liters of distilled water was added to this cake to reslurry it, and then filtered. This washing operation was performed until the pH of the washing solution (filtrate) exceeded 3.5. The collected cake was dried at 110 ° C. overnight under a nitrogen atmosphere. The weight after drying was 707 g.
(Drying of ion-exchanged layered silicate) The silicate previously chemically treated was dried by a kiln dryer. Specifications and drying conditions are as follows. Rotating cylinder: Cylindrical inner diameter 50 mm Heating zone 550 mm (Electric furnace) Speed with rotating blade: 2 rpm Tilt angle: 20/520 Silicate feed rate: 2.5 g / min Gas flow rate: Nitrogen 96 liters / hour Countercurrent drying Temperature: 200 ° C (powder temperature)

(Preparation of catalyst) An autoclave having an internal volume of 16 liters having a stirring and temperature control device was sufficiently replaced with nitrogen. 200 g of the silicate was introduced, 1,160 ml of mixed heptane and 840 ml of a heptane solution of triethylaluminum (0.60 M) were added and stirred at room temperature. After 1 hour, the mixture was washed with mixed heptane to prepare 2,000 ml of silicate slurry. Next, 9.6 ml of a heptane solution of triisobutylaluminum (0.71 ML) was added to the silicate slurry prepared above and reacted at 25 ° C. for 1 hour. In parallel, 270 ml of (r) -dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4H-azulenyl}] zirconium and 2,180 mg (0.3 mM) of mixed heptane Then, 33.1 ml of a heptane solution of triisobutylaluminum (0.71 M) was added, and the mixture reacted at room temperature for 1 hour was added to the silicate slurry. After stirring for 1 hour, 5,000 ml was added with mixed heptane. Prepared.

(Preliminary polymerization / washing) Subsequently, the temperature in the tank was raised by 40 ° C., and when the temperature was stabilized, propylene was supplied at a rate of 100 g / hour to maintain the temperature. After 4 hours, the supply of propylene was stopped and maintained for another 2 hours. After completion of the prepolymerization, the residual monomer was purged, stirring was stopped and the mixture was allowed to stand for about 10 minutes, and then the supernatant was decanted to 2,400 ml. Subsequently, 9.5 ml of a heptane solution of triisobutylaluminum (0.71 ML) and 5600 ml of mixed heptane were further added, stirred at 40 ° C. for 30 minutes, allowed to stand for 10 minutes, and then 5600 ml of the supernatant was removed. This operation was further repeated 3 times. When the component analysis of the final supernatant was conducted, the concentration of the organoaluminum component was 1.23 mmol / liter, the Zr concentration was 8.6 × 10 ⁻⁶ g / L, and the abundance in the supernatant with respect to the amount charged. Was 0.016%. Subsequently, 170 ml of a heptane solution of triisobutylaluminum (0.71 ML) was added, followed by drying at 45 ° C. under reduced pressure. A prepolymerized catalyst containing 2.0 g of polypropylene per 1 g of catalyst was obtained. Using this prepolymerized catalyst, a propylene-ethylene block copolymer was produced according to the following procedure.

First Step In the first step, propylene-ethylene random copolymerization was performed using a liquid phase polymerization layer with an agitator having an internal volume of 0.4 m ³ . Liquefied propylene, liquefied ethylene, and triisobutylaluminum were continuously fed at 90 kg / hour, 4.2 kg / hour, and 21.2 g / hour, respectively. The hydrogen supply amount was adjusted so that the MFR in the first step became a target value. Further, the above prepolymerized catalyst was supplied as a catalyst (excluding the weight of the prepolymerized polymer) so as to be 7.9 g / hour. The polymerization tank was cooled so that the polymerization temperature was 45 ° C.
When the propylene-ethylene random copolymer obtained in the first step was analyzed, BD (bulk density) was 0.46 g / cc, MFR was 2.0 g / 10 min, and ethylene content was 3.7 wt%. .

Second step
In the second step, propylene-ethylene random copolymerization was carried out using a stirred gas phase polymerization tank having an internal volume of 0.5 m ³ . The slurry containing polymer particles was continuously extracted from the liquid phase polymerization tank in the first step, and after liquefied propylene was flushed, the pressure was increased with nitrogen and continuously supplied to the gas phase polymerization tank. The polymerization tank was controlled so that the temperature was 80 ° C. and the total partial pressure of propylene, ethylene, and hydrogen was 1.5 MPa. At that time, the concentrations of propylene, ethylene, and hydrogen in the total partial pressure of propylene, ethylene, and hydrogen were controlled to be 66.99 vol%, 32.99 vol%, and 150 volppm, respectively. Furthermore, ethanol was supplied to the gas phase polymerization tank as an activity inhibitor. The supply amount of ethanol was set to 0.3 mol / mol with respect to aluminum in TIBA supplied along with the polymer particles supplied to the gas phase polymerization tank.
When the propylene-ethylene block copolymer thus obtained was analyzed, the activity was 7.6 kg / g-catalyst, the BD was 0.41 g / cc, the MFR was 2.0 g / 10 min, and the ethylene content was 8.7 wt. % PP-1 was obtained.
The PP-1 has an ethylene content of component (A) of 3.7 wt%, a composition ratio of 50 wt%, an ethylene content of component (B) of 13.7 wt%, a composition ratio of 50 wt%, and a tan δ curve of −16.4 ° C. Have a single peak. The production conditions are shown in Table 3.

[Production Example PP-2]
Except for the conditions described in Table 3, BD (bulk density) is 0.46 g / cc, MFR is 7.0 g / 10 min, and ethylene content is 1st step in accordance with Production Example PP-1. Propylene-ethylene random copolymer of 1.5 wt% was obtained, and PP-2 with a BD of 0.41 g / cc, MFR of 2.0 g / 10 min, and an ethylene content of 6.5 wt% was obtained in the second step. .
The PP-2 has an ethylene content of component (A) of 1.5 wt%, a composition ratio of 50 wt%, an ethylene content of component (B) of 11.5 wt%, a composition ratio of 50 wt%, and a tan δ curve of −12.3 ° C. Have a single peak.

[Production Example PP-3]
Except for the conditions described in Table 3, BD (bulk density) is 0.46 g / cc, MFR is 2.0 g / 10 min in the first step, and ethylene content is based on Production Example PP-1. A propylene-ethylene random copolymer of 2.2 wt% was obtained. In the second step, PP-3 having a BD of 0.41 g / cc, an MFR of 2.0 g / 10 min, and an ethylene content of 7.9 wt% was obtained. .
The PP-3 has an ethylene content of component (A) of 2.2 wt%, a composition ratio of 50 wt%, an ethylene content of component (B) of 12.2 wt%, a composition ratio of 50 wt%, and a tan δ curve of −13.8 ° C. Have a single peak.

[Production Example PP-4]
Except for the conditions described in Table 3, BD (bulk density) is 0.46 g / cc, MFR is 2.0 g / 10 min, and ethylene content is 1st step in accordance with Production Example PP-1. Obtained 3.7 wt% of propylene-ethylene random copolymer, and in the second step, PP-4 with 0.41 g / cc of BD, 2.0 g / 10 min of MFR, and 11.7 wt% of ethylene content was obtained. .
The PP-4 has an ethylene content of component (A) of 3.7 wt%, a composition ratio of 50 wt%, an ethylene content of component (B) of 19.7 wt%, a composition ratio of 50 wt%, and a tan δ curve of −12.4 ° C. And two peaks at −33 ° C.

(3) Polyethylene Metallocene low density polyethylene (b): Density (JIS K7112) 0.898 g / cm ³ , MFR (JIS K7210, 230 ° C., 2.16 kg load) 4.0 g / 10 min, (Mw / Mn) 2.2. (Kernel KF262 manufactured by Nippon Polytech Co., Ltd.)

(4) Nucleating agent (i) Mirad NX8000 (NX8000; manufactured by Milliken & Company): Nucleating agent (A) equivalent: Chemical structural formula (7) below

(Ii) Organophosphate metal salt compound nucleating agent ADK STAB NA-11 (NA-11; manufactured by ADEKA Corporation): equivalent to nucleating agent (B) (iii) Organophosphate metal salt compound nucleating agent ADK STAB NA21 (NA-21; manufactured by ADEKA Corporation): equivalent to nucleating agent (C) (iv) Hyperform HPN68L (HPN68L; manufactured by Milliken & Company): equivalent to nucleating agent (D) ( v) 1,2,3-propanetricarboxylic acid tris (2-methylcyclohexylamide): equivalent to the nucleating agent (E) (vi) sorbitol nucleating agent Gerol MD (manufactured by Shin Nippon Rika Co., Ltd.): nucleating Nucleating agents not corresponding to any of the agents (A) to (E)

(5) Neutralizing agent (i) DHT-4C: Hydrotalcite (manufactured by Kyowa Chemical Industry Co., Ltd.)
(Ii) CAST: Calcium stearate (6) Lubricant (i) Silicone oil: Dowcorning 360 Medical Fluid-1000 (M360-1000) Toray Dow Corning Co., Ltd. (7) Peroxide (i) PHA25B: Perhexa 25B Nippon Oil & Fats (8) Antioxidant (i) Hindered phenol antioxidant: Irganox 1010 (IR1010; manufactured by Ciba), tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-] Hydroxylphenyl) propionate] Methane (ii) Phosphorous antioxidant: Irgaphos 168 (IF168; manufactured by Ciba), Tris (2,4-di-tert-butylphenol) phosphite (iii) Hindered amine UV stabilizer: TINUVIN 622LD ( TNV622 Manufactured by Ciba Inc.), dimethyl succinate 2- (4-hydroxy-2,2,6,6-tetramethylpiperidine) ethanol condensate

(Examples 1 to 10, Comparative Examples 1 to 4, Reference Example 1)
A propylene polymer, a nucleating agent and other additives (antioxidants, neutralizing agents, etc.) were prepared in the blending ratios (parts by weight) shown in Table 4, and after dry blending with a super mixer, the diameter of 35 mm Were melt-kneaded using a twin-screw extruder. Extruded pellets from the die at a die outlet temperature of 230 ° C. The obtained pellets were injection molded by an injection molding machine at a resin temperature of 230 ° C., an injection pressure of 600 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 results are shown in Table 4.

  As can be seen from Table 4, Examples 1 to 3 were prepared by blending 10 parts by weight of the propylene homopolymer with (10) propylene-ethylene block copolymer of the present invention. It can be seen that it is used, has impact resistance, and maintains transparency to some extent even after autoclaving. It can also be seen that the moldability is improved by adding silicone oil. In Examples 4 to 8, each of the nucleating agents was used, and it was found that the nucleating agent has impact resistance and retains a certain degree of transparency even after autoclaving. In Example 9, (b) 30 parts by weight of propylene-ethylene block copolymer was blended, impact resistance was good, and transparency after sterilization was also good. In Example 10, (a) It is a blend of 5 parts by weight of a propylene-ethylene block copolymer, which shows that it has high rigidity, improved impact resistance, and good transparency after sterilization. Moreover, in all of Examples 1-13, it turns out that the 15th revision Japanese Pharmacopoeia test is passed (conformity).

  In Comparative Examples 1 and 2, (i) a propylene-ethylene block copolymer was not blended, and it was found that the impact resistance was low and the molded product was easily cracked. Comparative Example 3 uses polyethylene as an impact modifier instead of (i) the propylene-ethylene block copolymer of the present invention, and maintains an excellent balance of physical properties before autoclaving. However, it can be seen that the transparency has deteriorated significantly after autoclaving. Comparative Example 4 and Comparative Example 5 are (i) a propylene-ethylene copolymer outside the scope of the present invention was used as an impact modifier instead of the propylene-ethylene block copolymer. Thus, almost no improvement in impact resistance is observed, and it can be seen that Comparative Example 5 has no transparency.

Reference Example 1 is obtained by adding Gelol MD, which is a nucleating agent having an effect on transparency different from the nucleating agents (A) to (E). When this nucleating agent is used, the 15th revised Japan No longer pass the pharmacopoeia test. Thus, depending on the nucleating agent used, there are some that cannot be used for prefilled syringes.
A general disposable syringe that is not pre-filled with a chemical solution can be used even if it does not pass the 15th revised Japanese Pharmacopoeia test (especially the dissolution test conducted by heating at 121 ° C. for 1 hour). This propylene-based resin composition can be used for a disposable syringe. However, if Gelol MD, which is a sorbitol-based nucleating agent as used here, is used as a nucleating agent for imparting excellent transparency, it failed the 15th revised Japanese Pharmacopoeia test, Since it cannot be used for a prefilled syringe filled with a chemical solution, it is not desirable as a nucleating agent used in the present invention.

(Example 14)
The pellets obtained in Example 2 were injection molded by an injection molding machine at a resin temperature of 240 ° C. and a mold temperature of 35 ° C., and had an outer diameter of 3 cm, a cylinder length of 6.5 cm, and a side wall thickness of 1 mm. A syringe (prefilled syringe) was molded. When the haze with a thickness of 1 mm was measured at 121 ° C. for 20 minutes at the syringe outer cylinder, the value was 32%, and the 15th revised Japanese Pharmacopoeia General Test with this molded product 45. Test method for plastic drug containers 1. When the test of the polyethylene or polypropylene aqueous injection container was conducted, it was confirmed that all the test items were satisfied. It turns out that the member for prefilled syringes obtained by this invention is excellent in transparency, and passes the 15th revision Japanese Pharmacopoeia general test.

  The medical propylene-based resin composition of the present invention is a 15th revision Japanese Pharmacopoeia general test. Test method for plastic drug containers 1. A book that satisfies the test items of polyethylene or polypropylene water-based injection containers and retains excellent heat resistance, rigidity, impact resistance, moldability, and transparency even after autoclaving. The kit preparation of the invention is found to be very useful for obtaining an excellent molded article having good transparency and passing the 15th revised Japanese Pharmacopoeia general test, and as a syringe, a medical instrument and a medical container, It is suitable for a kit preparation such as a storage container filled with a drug solution or a prefilled syringe.

JP-A-1-178541 JP-A-62-194866 JP-A-5-222078

Claims (7)

It is a propylene homopolymer or a propylene-based copolymer composed of propylene and an α-olefin having a content of less than 1% by weight, and has a melt flow rate of 0.00 according to JIS K7210 (230 ° C., 2.16 kg load). 60 to 99 parts by weight of a propylene-based (co) polymer that is 5 to 100 g / 10 minutes, 1 to 40 parts by weight of a propylene-ethylene block copolymer that satisfies the following conditions (Ai) to (Av), and A medical propylene-based resin composition comprising 0.01 to 0.6 parts by weight of a nucleating agent.

(Ai) 30 to 95 wt% of propylene-ethylene random copolymer component (A) having a metallocene catalyst in the first step or propylene-ethylene random copolymer component (A) of 7 wt% or less in the first step, and component (A) in the second step A propylene-ethylene block copolymer obtained by sequential polymerization of 70 to 5 wt% of the propylene-ethylene random copolymer component (B) containing 3 to 20 wt% of ethylene more than (A-ii) ) Melt flow rate (MFR: 230 ° C. 2.16 kg) is in the range of 0.5-100 g / 10 min (A-iii) Melting peak temperature (Tm) measured by DSC method is in the range of 110-150 ° C. (A-iv) The molecular weight distribution (Mw / Mn) measured by the GPC method is in the range of 1.5 to 4 (Av) Solid viscoelasticity measurement More resulting temperature - in the loss tangent curve, tan [delta curve has a single peak at 0 ℃ below.
The nucleating agent is 0.01 to 0.6 parts by weight of a nucleating agent (A) represented by the following general formula (1), and 0.005 to 0 nucleating agent (B) represented by the following general formula (2). .3 parts by weight, nucleating agent (C) represented by the following general formula (3) 0.005 to 0.15 parts by weight, nucleating agent (D) represented by the following general formula (4) 0.005 to 0 .15 parts by weight and a nucleating agent (E) represented by the following general formula (5) in the range of 0.005 parts by weight or more and less than 0.3 parts by weight. It is (E), The medical propylene-type resin composition of Claim 1 characterized by the above-mentioned.

[Wherein n is an integer of 0 to 2 and R ^{1 to} R ⁵ are the same or different and each is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an alkenyl group, an alkoxy group, a carbonyl group, a halogen atom. Group and a phenyl group, and R ⁶ is an alkyl group having 1 to 20 carbon atoms. ]


[Wherein, R ¹ is a direct bond, sulfur, an alkylene group having 1 to 9 carbon atoms or an alkylidene group, and R ² and R ³ are the same or different and each represents a hydrogen atom or an alkyl having 1 to 8 carbon atoms. A group, M is Na, and n is the valence of M. ]

[Wherein, R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ² and R ³ are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms; Represents a group III or group IV metal atom of the periodic table, X represents HO— when M represents a group III metal atom of the periodic table, and M represents group IV of the periodic table. When a group metal atom is shown, O = or (HO) _2- . ]
[Wherein, M ₁ and M ₂ are the same or different and are at least one metal cation selected from calcium, strontium, lithium and monobasic aluminum, and R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ are the same or different and are hydrogen, C ₁ -C ₉ alkyl (wherein any two vicinals (bonded to adjacent carbons) or geminal) Alkyl groups (bonded to the same carbon) may combine to form a hydrocarbon ring having up to 6 carbon atoms), hydroxy, C ₁ -C ₉ alkoxy, C ₁ -C ₉ alkyleneoxy, amine and C ₁ -C ₉ alkylamine, halogen is independently selected from the group consisting of (fluorine, chlorine, bromine and iodine) and phenyl. ]
R ¹ (CONHR ² ) _a (5)
[Wherein R ¹ represents a saturated or unsaturated aliphatic polycarboxylic acid residue having 2 to 30 carbon atoms, a saturated or unsaturated alicyclic polycarboxylic acid residue having 4 to 28 carbon atoms, or the number of carbon atoms. Represents 6-18 aromatic polycarboxylic acid residues. R ² represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, or a cycloalkyl group or cycloalkenyl group having 3 to 46 carbon atoms. a represents an integer of 2 to 6. ] The medical propylenic resin composition according to claim 1 or 2, wherein the nucleating agent (A) is a nucleating agent represented by the following general formula (6).

[Here, n is an integer of ^{0~2, R 1, R 2,} R 4, R 5 is a hydrogen atom, ^{R 3} is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, alkenyl A group, an alkoxy group, a carbonyl group, a halogen group and a phenyl group, and R ⁶ is an alkyl group having 1 to 20 carbon atoms. ]
  The medical propylene-based resin composition according to any one of claims 1 to 3, wherein the lubricant is blended in a range of 0.001 to 0.5 parts by weight.   The medical molded article using the propylene-type resin composition of any one of Claims 1-4.   A kit preparation, wherein the medical molded article according to claim 5 is a kit preparation. A prefilled syringe, wherein the kit preparation according to claim 6 is a prefilled syringe.