JP2012046692A - Propylenic resin composition and molded article thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a medical propylenic resin composition which satisfies test items of aqueous parenteral injection containers made from polypropylene in Japanese Pharmacopoeia and holds superior heat resistance, rigidity, impact resistance, moldability, and transparency also after autoclave sterilization.SOLUTION: The medical propylenic resin composition comprises 75-98 wt.% of a propylenic copolymer (A) comprising: a propylene homopolymer or propylene having a melt flow rate of 0.5-100 g/10 min; and an α-olefin in an amount of <1 wt.%; and 2-25 wt.% of a propylenic copolymer (B) which is an olefin random copolymer and satisfying the following conditions: (B-i) a propylene-αolefin random copolymer obtained using a metallocene-based catalyst; (B-ii) an ethylene content of 3-17 wt.%; and (B-iii) a melt flow rate of 0.5-80 g/10 min; wherein, in a temperature-loss tangent (tanδ) curve obtained by solid viscoelasticity measurement (DMA), the peak of the tanδ curve describing glass transition observed in the range of -60 to 20°C shows a single peak at or below 0°C.

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, 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 chemical solutions 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 additives used interact 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.

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

  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 found that a resin composition containing a specific amount of a specific propylene polymer is a medical propylene resin composition that satisfies the test items of the Japanese Pharmacopoeia. The present invention has been completed by finding that it can be obtained, and that a further excellent medical propylene-based resin composition can be obtained by using a specific amount of a specific nucleating agent.

That is, according to the first invention of the present invention,
Melt flow rate (230 ° C., 2.16 kg load) of 0.5 to 100 g / 10 min, propylene homopolymer or propylene copolymer consisting of propylene and an α-olefin having a content of less than 1% by weight ( A) 75 to 98% by weight,
The following conditions (Bi) to (B-iii):
(Bi) is a propylene-α-olefin random copolymer obtained using a metallocene catalyst,
(B-ii) The ethylene content is in the range of 3 to 17 wt%.
(B-iii) Propylene copolymer (B) satisfying a melt flow rate (MFR: 230 ° C., 2.16 kg) in a range of 0.5 to 80 g / 10 minutes, and comprising 2 to 25% by weight,
In the temperature-loss tangent (tan δ) curve obtained by solid viscoelasticity measurement (DMA), the peak of the tan δ curve representing the glass transition observed in the range of −60 to 20 ° C. shows a single peak at 0 ° C. or lower. The medical propylene-based resin composition is provided.

According to the second invention of the present invention, in the first invention, the propylene-based copolymer (B) is
30 to 70% by weight of a propylene-ethylene random copolymer (B-1) having an ethylene content of 7 to 25% by weight obtained using a metallocene catalyst, and an α-olefin content obtained using a metallocene catalyst Of propylene-α-olefin random copolymer (B-2) having a melting peak temperature (Tm) of 125 to 145 ° C. and 30 to 70% by weight. A composition is provided.

  Further, according to the third invention of the present invention, in the first or second invention, the nucleating agent further comprises a total of 100 of the (co) polymer (A) and the propylene-based copolymer (B). Provided is a propylene-based resin composition for medical use, which is contained in the range of 0.01 to 0.6 parts by weight with respect to parts by weight.

  According to the fourth invention of the present invention, in the third invention, the nucleating agent and the content thereof are nucleating agent (a) represented by the following general formula (1): 0.01 to 0.6 weight Parts, nucleating agent (b) represented by the following general formula (2) 0.005 to 0.3 parts by weight, nucleating agent (c) represented by the following general formula (3) 0.005 to 0.15 weight , 0.005 to 0.15 parts by weight of the nucleating agent (d) represented by the following general formula (4) or 0.005 parts by weight or more of the nucleating agent (e) represented by the following general formula (5) Provided is a propylene-based resin composition for medical use characterized by being less than 3 parts by weight.

［式（１）中、ｎは、０〜２の整数であり、Ｒ^１〜Ｒ^５は、同一または異なって、それぞれ水素原子もしくは炭素数が１〜２０のアルキル基、アルケニル基、アルコキシ基、カルボニル基、ハロゲン基およびフェニル基であり、Ｒ^６は、炭素数が１〜２０のアルキル基である。］

[In formula (1), n is an integer of 0 to ^2, R 1 to R ⁵ are the same or different, each represents an alkyl group having a hydrogen atom or having 1 to 20 carbon atoms, an alkenyl 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. ]

［式（２）中、Ｒ^１は、直接結合、硫黄又は炭素数１〜９のアルキレン基又はアルキリデン基であり、Ｒ^２及びＲ^３は、同一又は異なって、それぞれ水素原子又は炭素数１〜８のアルキル基であり、ＭはＮａであり、ｎはＭの価数である。］

[In the formula (2), 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 1 to 8 is an alkyl group, M is Na, and n is the valence of M. ]

［式（３）中、Ｒ^１は、水素原子又は炭素数１〜４のアルキル基を示し、Ｒ^２及びＲ^３は、同一又は異なって、それぞれ水素原子又は炭素数１〜１２のアルキル基を示し、Ｍは、周期律表第ＩＩＩ族または第ＩＶ族の金属原子を示し、Ｘは、Ｍが周期律表第ＩＩＩ族の金属原子を示す場合には、ＨＯ−を示し、Ｍが周期律表第ＩＶ族の金属原子を示す場合には、Ｏ＝又は（ＨＯ）_２−を示す。］

[In Formula (3), R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and 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. M 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 a periodic table. When a group IV metal atom is shown, O = or (HO) _2- . ]

［式（４）中、Ｍ_１およびＭ_２は、同一または異なって、カルシウム、ストロンチウム、リチウムおよび一塩基性アルミニウムから選択される少なくとも１種の金属カチオンであり、Ｒ_１、Ｒ_２、Ｒ_３、Ｒ_４、Ｒ_５、Ｒ_６、Ｒ_７、Ｒ_８、Ｒ_９およびＲ_１０は、同一または異なって、水素、Ｃ_１−Ｃ_９アルキル（ここで、いずれか２つのビシナル（隣接炭素に結合）またはジェミナル（同一炭素に結合）アルキル基は、一緒になって６個までの炭素原子を有する炭化水素環を形成してもよい）、ヒドロキシ、Ｃ_１−Ｃ_９アルコキシ、Ｃ_１−Ｃ_９アルキレンオキシ、アミンおよびＣ_１−Ｃ_９アルキルアミン、ハロゲン（フッ素、塩素、臭素および沃素）並びにフェニルからなる群からそれぞれ選択される。］

[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 together may 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)
[In Formula (5), R ¹ is 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, Alternatively, it represents an aromatic polycarboxylic acid residue having 6 to 18 carbon atoms. 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. ]

［但し、式（６）中、ｎは、０〜２の整数であり、Ｒ^１、Ｒ^２、Ｒ^４、Ｒ^５は、水素原子であり、Ｒ^３は、水素原子もしくは炭素数が１〜２０のアルキル基、アルケニル基、アルコキシ基、カルボニル基、ハロゲン基およびフェニル基であり、Ｒ^６は、炭素数が１〜２０のアルキル基である。］ According to a fifth invention of the present invention, in the fourth invention, the nucleating agent (a) is a nucleating agent represented by the following general formula (6), wherein the propylene-based medical A resin composition is provided.

[In the formula (6), 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 carbon number 1 to 1] 20 alkyl groups, alkenyl groups, alkoxy groups, carbonyl groups, halogen groups and phenyl groups, and R ⁶ is an alkyl group having 1 to 20 carbon atoms. ]

  Moreover, according to the sixth invention of the present invention, in any one of the first to fifth inventions, the lubricant is further added in a total of 100 of the (co) polymer (A) and the propylene-based copolymer (B). Provided is a propylene-based resin composition for medical use, which is contained in the range of 0.001 to 0.5 parts by weight with respect to parts by weight.

Moreover, according to 7th invention of this invention, the medical molded article using the medical propylene-type resin composition of any one of 1st-6th invention is provided.
Moreover, according to the eighth invention of the present invention, there is provided a medical molded product characterized in that the medical molded product of the seventh invention is a kit preparation.
Furthermore, according to the ninth aspect of the present invention, there is provided a medical molded product according to the eighth aspect, wherein the kit preparation 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.

The present invention relates to a propylene-based polymer comprising a propylene homopolymer or propylene and an α-olefin having a content of less than 1% by weight with a melt flow rate (230 ° C., 2.16 kg load) of 0.5 to 100 g / 10 min. Copolymer (A) 75 to 98% by weight,
The following conditions (Bi) to (B-iii):
(Bi) is a propylene-α-olefin random copolymer obtained using a metallocene catalyst,
(B-ii) The ethylene content is in the range of 3 to 17 wt%.
(B-iii) Propylene copolymer (B) satisfying a melt flow rate (MFR: 230 ° C., 2.16 kg) in a range of 0.5 to 80 g / 10 minutes, and comprising 2 to 25% by weight,
In the temperature-loss tangent (tan δ) curve obtained by solid viscoelasticity measurement (DMA), the peak of the tan δ curve representing the glass transition observed in the range of −60 to 20 ° C. shows a single peak at 0 ° C. or lower. This is a propylene-based resin composition for medical use, and is useful for molded articles obtained from the composition, particularly kit preparations.

Hereinafter, the constituent components, the method for producing the composition, the molded body, and the like will be described in detail.
The polymer composition constituting the medical propylene-based resin composition of the present invention is 75 to 98% by weight of the propylene-based (co) polymer (A) and 2 to 25% by weight of the propylene-based copolymer (B). Consists of.
The blending amount of the propylene-based (co) polymer (A) is 75 to 98% by weight, specifically 80% by weight, 90% by weight, 95% by weight, etc. without losing the properties of this resin by blending. The following embodiments can be exemplified. On the other hand, the propylene-based copolymer (B) constituting the composition is 2 to 25% by weight, specifically 5% by weight, 10% by weight, 15% by weight, 20% by weight or the like. Embodiments of these can be illustrated, and these two-component resins are blended to prepare 100% by weight.

The polymer composition constituting the medical propylene-based resin composition of the present invention satisfies the following conditions.
In the temperature-loss tangent (tan δ) curve obtained by solid viscoelasticity measurement (DMA), the peak of the tan δ curve representing the glass transition observed in the range of −60 to 20 ° C. shows a single peak at 0 ° C. or lower. .

In the present invention, in order to maintain good compatibility and maintain transparency, the propylene-based (co) polymer (A) and the propylene-based copolymer (B) to be used are not phase-separated. is necessary. 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-separated structure, the glass transition temperature of the amorphous part contained in the propylene-based (co) polymer (A) and the non-crystalline content contained in the propylene-based copolymer (B). Since the glass transition temperatures of the crystal parts are different, there are a plurality of 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.
In the present invention, the peak of the tan δ curve can satisfy a single peak at 0 ° C. or less by adjusting the ethylene content of the propylene-based copolymer (B). The smaller the difference from the ethylene content of the propylene-based (co) polymer (A), the easier it is to obtain a single peak.

[1] Components of the composition Propylene-based (co) polymer (A)
The propylene (co) polymer (A) used in the medical propylene resin composition of the present invention is a propylene homopolymer or a propylene copolymer comprising propylene and an α-olefin having a content of less than 1% by weight. It may be a polymer or a mixture thereof.
The propylene-based (co) polymer (A) 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 treatment, 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 even better impact resistance before and after irradiation.

The α-olefin content used in the propylene-based (co) polymer (A) 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 propylene-based (co) polymer (A) 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 propylene-based (co) polymer (A) 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. When the melt flow rate (MFR) is less than 0.5 g / 10 min, the moldability is deteriorated, and it may be difficult to obtain a satisfactory product. Moreover, when it exceeds 100 g / 10 minutes, there exists a concern about the fall of mechanical strength.
Melt flow rate (MFR) is easy by adjusting the temperature and pressure, which are the polymerization conditions for the propylene-based (co) polymer (A), and by controlling the amount of hydrogen added during the polymerization of a chain transfer agent such as hydrogen. 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.

  Although it does not specifically limit as a manufacturing method of a propylene type | system | group (co) polymer (A), The polymerization method using a stereoregular catalyst is preferable. Examples of stereoregular catalysts include Ziegler catalysts and metallocene catalysts. Preferably, it is better to use a metallocene catalyst having good compatibility with the propylene-based copolymer (B).

  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. It is a catalyst comprising an activatable cocatalyst and, if necessary, (iii) an organoaluminum compound, and 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-3-163888, JP-A-4-30087, JP-A-4-21694, JP-A-5-43616, JP-A-5-209913, JP-A-6 No. 239914, JP-A-7-504934, JP-A-8-85708, etc. can be preferably used.

  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 6,7-tetrahydroindenyl) zirconium dichloride, dimethylsilylene bis [1- (2-methyl-4-phenylindenyl)] zirconium dichloride, dimethylsilylene bis [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-azuleni ] Zirconium dichloride, dimethylsilylenebis [1- (2-ethyl-4- (4-chlorophenyl) -4H-azulenyl)] 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-fluorobiphenyl) Ryl) -4H-azurenyl)] zirconium dichloride, dimethylgermylenebis [1- (2-ethyl-4- (4-chlorophenyl) -4H-azurenyl)] zirconium dichloride, dimethylgermylenebis [1- (2-ethyl) -4-phenylindenyl)] zirconium di 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. It is also preferable to use a mixture of a zirconium compound and a hafnium compound. 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.
Of these, metallocene compounds obtained by crosslinking an indenyl group or an azulenyl group with silicon or a germyl group are particularly 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 Preferred examples include fluorine-containing organic compounds.

  (Iii) Examples of organoaluminum compounds include trialkylaluminum such as triethylaluminum, triisopropylaluminum, triisobutylaluminum, dialkylaluminum halide, alkylaluminum sesquihalide, alkylaluminum dihalide, alkylaluminum hydride, organoaluminum alkoxide. Preferably mentioned.

Propylene-based (co) polymer (A) can be produced by a slurry method using an inert solvent in the presence of the catalyst, a solution method, a gas phase method substantially using no solvent, or a polymerization monomer. And a bulk polymerization method using as a solvent.
For example, in the case of the slurry polymerization method, 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 (A) 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.

The propylene-based copolymer (B) used in the present invention is a propylene-based copolymer that satisfies the following conditions (Bi) to (B-iii).
(Bi) A propylene-α-olefin random copolymer obtained using a metallocene catalyst.
(B-ii) The ethylene content is in the range of 3 to 17 wt%.
(B-iii) Melt flow rate (MFR: 230 ° C., 2.16 kg) is in the range of 0.5 to 80 g / 10 min.
If the ethylene content of the propylene-based copolymer (B) used in the present invention is less than 3 wt%, the impact resistance becomes insufficient, and if it exceeds 17 wt%, there is a concern that transparency may deteriorate due to phase separation. The

When the melt flow rate (MFR: 230 ° C., 2.16 kg) of the propylene-based copolymer (B) used in the present invention is less than 0.5 g / 10 minutes, molding becomes difficult, and when it exceeds 80 g / 10 minutes. Impact resistance may be insufficient.
The melt flow rate (MFR) is easily adjusted by adjusting the temperature and pressure, which are the polymerization conditions for the propylene-based copolymer (B), and by controlling the amount of hydrogen added during polymerization of a chain transfer agent such as hydrogen. Can be performed.
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.

Examples of the α-olefin used for copolymerization of the propylene-based copolymer (B) include α-olefins having 2 to 20 carbon atoms excluding propylene, such as ethylene, butene-1, hexene-1, and octene-1. Can be illustrated. 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.
Specific examples of the propylene-based copolymer (B) include a propylene-ethylene copolymer, a propylene-butene-1 copolymer, a propylene-hexene-1 copolymer, a propylene-octene-1 copolymer, Arbitrary amounts of comonomers, such as propylene-ethylene-butene-1 copolymer, propylene-ethylene-hexene-1 copolymer, propylene-butene-1-octene-1 copolymer, were arbitrarily combined. A binary or ternary copolymer can be exemplified.

As a manufacturing method of a propylene-type copolymer (B), if the metallocene catalyst is used, there will be no limitation in particular, Usually, all the methods for manufacturing a propylene-type copolymer may be used. The metallocene catalyst is the same as that mentioned above.
In the production method of the propylene-based copolymer (B), a catalyst other than a metallocene catalyst, for example, a propylene-based copolymer obtained by using a Ziegler catalyst is very sticky and has poor moldability, and there is a concern about bleeding as a product. The
As the propylene-based copolymer (B), commercially available products can be used, and examples thereof include trade name Versify manufactured by Dow and trade name Vistamax manufactured by ExxonMobil.

In addition, the propylene-based copolymer (B) used in the present invention is
30 to 70% by weight of a propylene-ethylene random copolymer (B-1) having an ethylene content of 7 to 25% by weight obtained using a metallocene catalyst, and an α-olefin content obtained using a metallocene catalyst The propylene-α-olefin random copolymer (B-2) having a melting peak temperature (Tm) of 125 to 145 ° C. is preferably 30 to 70% by weight.

If the blending amount of the propylene-ethylene random copolymer (B-1), which is a component that preferably constitutes the propylene-based copolymer (B), is less than 30 wt%, the impact resistance may be insufficient. If it exceeds 70 wt%, there is a concern about insufficient rigidity. Preferably it is 30-60 wt%, More preferably, it is 40-60 wt%.
If the ethylene content of the propylene-ethylene random copolymer (B-1) is less than 7 wt%, impact resistance may be insufficient, and if it exceeds 25 wt%, the transparency may deteriorate due to phase separation. There is. Preferably it is 7-20 wt%, More preferably, it is 8-15 wt%.

As a manufacturing method of a propylene-ethylene random copolymer (B-1), if the metallocene catalyst is used, there will be no limitation in particular, Usually, using all the methods for manufacturing a propylene-ethylene random copolymer. Good. The metallocene catalyst is the same as that mentioned above.
When a catalyst other than the metallocene catalyst, for example, a Ziegler catalyst, is used in the method for producing the propylene-ethylene random copolymer (B-1), the low molecular weight component of the obtained propylene-ethylene random copolymer may increase.
As such a propylene-ethylene random copolymer (B-1), a commercially available product can be used, for example, trade name Versify manufactured by Dow and trade name Vistamax manufactured by ExxonMobil. Can do.

If the blending amount of the propylene-α-olefin random copolymer (B-2), which is a component that preferably constitutes the propylene copolymer (B), is less than 30 wt%, further improvement in impact resistance cannot be expected. If it exceeds 70 wt%, there is a concern that the impact resistance may decrease due to the decrease in the component (α). Preferably it is 40-70 wt%, More preferably, it is 40-60 wt%.
If the melting peak temperature (Tm) of the propylene-α-olefin random copolymer (B-2) is less than 125 ° C, there is a concern about insufficient rigidity and deterioration of moldability, and if it exceeds 145 ° C, the impact resistance is further improved. Improvement cannot be expected. Preferably it is 125-140 degreeC, More preferably, it is 130-140 degreeC.
The specific measurement of the melting peak temperature (Tm) was performed by 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 melted at a heating rate of 10 ° C./min is defined as a melting peak temperature Tm (° C.).

If the ethylene content of the propylene-α-olefin random copolymer (B-2) is less than 1 wt%, further improvement in impact resistance cannot be expected, and if it exceeds 5 wt%, there is a concern about insufficient rigidity. Preferably it is 2-4 wt%, More preferably, it is 2-3 wt%.
Examples of the α-olefin used for copolymerization of the propylene-α-olefin random copolymer (B-2) include α-olefins having 2 to 20 carbon atoms excluding propylene, such as ethylene, butene-1, hexene- 1, octene-1, etc. can be illustrated. 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.

  Specific examples of the propylene-α-olefin random copolymer (B-2) include propylene-ethylene copolymer, propylene-butene-1 copolymer, propylene-hexene-1 copolymer, propylene-octene. -1 copolymer, propylene-ethylene-butene-1 copolymer, propylene-ethylene-hexene-1 copolymer, propylene-butene-1-octene-1 copolymer, etc. Binary or ternary copolymers that are arbitrarily combined in some amount can be exemplified.

As a manufacturing method of a propylene-alpha-olefin random copolymer (B-2), if a metallocene catalyst is used, there will be no limitation in particular, Usually, all the things for manufacturing a propylene-alpha-olefin random copolymer are used. A method may be used. The metallocene catalyst is the same as that mentioned above.
In the production method of the propylene-α-olefin random copolymer (B-2), when a catalyst other than the metallocene catalyst, for example, a Ziegler catalyst is used, the low molecular weight component of the obtained propylene-α-olefin random copolymer increases. There is a fear.

  As such a propylene-α-olefin random copolymer (B-2), a commercially available product can be used, and examples thereof include trade name WINTEC manufactured by Nippon Polypro Co., Ltd.

2. Nucleating agent The propylene-based resin composition for medical use of the present invention preferably contains a nucleating agent, and the amount of the nucleating agent is such that the (co) polymer (A) and the propylene-based copolymer ( B) is used in the range of 0.01 to 0.6 parts by weight with respect to 100 parts by weight in total. 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 may there be a possibility of failing the test of the polyethylene or polypropylene water-based injection container, but an improvement in performance corresponding to the amount added cannot be expected, which is economically undesirable.

  As the nucleating agent, it is desirable to use the following nucleating agents (a) to (e). 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 following general formula (1), among which a compound represented by the following general formula (6) is preferable, and a compound represented by the following chemical structural formula (7) is more preferable. .

［式（１）中、ｎは、０〜２の整数であり、Ｒ^１〜Ｒ^５は、同一または異なって、それぞれ水素原子もしくは炭素数が１〜２０のアルキル基、アルケニル基、アルコキシ基、カルボニル基、ハロゲン基およびフェニル基であり、Ｒ^６は、炭素数が１〜２０のアルキル基である。］

[In formula (1), n is an integer of 0 to ^2, R 1 to R ⁵ are the same or different, each represents an alkyl group having a hydrogen atom or having 1 to 20 carbon atoms, an alkenyl 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. ]

［式（６）中、ｎは、０〜２の整数であり、Ｒ^１、Ｒ^２、Ｒ^４、Ｒ^５は水素原子であり、Ｒ^３は、水素原子もしくは炭素数が１〜２０のアルキル基、アルケニル基、アルコキシ基、カルボニル基、ハロゲン基およびフェニル基であり、Ｒ^６は、炭素数が１〜２０のアルキル基である。］

[In formula (6), n is an integer of ^{0~2, R 1, R 2,} R 4, R 5 is a hydrogen atom, ^{R 3} is alkyl hydrogen atom or having 1 to 20 carbon atoms A group, an alkenyl 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. ]

  A commercially available product can be used as such a nucleating agent. Specifically, trade name NX8000 manufactured by Milliken Co., Ltd. can be mentioned.

  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 to obtain.

  The compounding quantity of a nucleating agent (a) is used in 0.01-0.6 weight part with respect to 100 weight part of polymer compositions. 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 nucleating agent of the present invention may be nucleating agents (b) to (e) represented by the general formulas (2) to (5), and each of the nucleating agents (a) to (e) is used alone or By using a plurality of them together, 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).

［式（２）中、Ｒ^１は、直接結合、硫黄又は炭素数１〜９のアルキレン基又はアルキリデン基であり、Ｒ^２及びＲ^３は、水素原子又は炭素数１〜８のアルキル基であり、ＭはＮａであり、ｎはＭの価数である。］

[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. Specific examples include NA-11 manufactured by ADEKA Corporation.

  The blending amount of the nucleating agent (b) selectively used in the medical propylene-based resin composition of the present invention is preferably in the range of 0.005 to 0.3 parts by weight with respect to 100 parts by weight of the polymer composition. 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 following general formula (3).

［式（３）中、Ｒ^１は、水素原子又は炭素数１〜４のアルキル基を示し、Ｒ^２及びＲ^３は、水素原子又は炭素数１〜１２のアルキル基を示し、Ｍは、周期律表第ＩＩＩ族または第ＩＶ族の金属原子を示し、Ｘは、Ｍが周期律表第ＩＩＩ族の金属原子を示す場合には、ＨＯ−を示し、Ｍが周期律表第ＩＶ族の金属原子を示す場合には、Ｏ＝又は（ＨＯ）_２−を示す。］

[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 butylbenzoic acid, salicylic acid, phthalic acid, trimellitic acid, pyromellitic acid and the like can be mentioned.

Examples of the β-diketone compound constituting the alkali metal β-diketonate include acetylacetone, pivaloylacetone, palmitoylacetone, benzoylacetone, pivaloylbenzoylacetone, and dibenzoylmethane.
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, ADEKA Corporation brand name NA-21 can be mentioned.

  The amount of the nucleating agent (c) is preferably in the range of 0.005 to 0.15 parts by weight and more preferably in the range of 0.01 to 0.1 parts by weight with respect to 100 parts by weight of the polymer composition. 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 following general formula (4).

［式（４）中、Ｍ_１およびＭ_２は、同一または異なって、カルシウム、ストロンチウム、リチウムおよび一塩基性アルミニウムから選択される少なくとも１種の金属カチオンであり、Ｒ_１、Ｒ_２、Ｒ_３、Ｒ_４、Ｒ_５、Ｒ_６、Ｒ_７、Ｒ_８、Ｒ_９およびＲ_１０は、同一または異なって、水素、Ｃ_１−Ｃ_９アルキル（ここで、いずれか２つのビシナル（隣接炭素に結合）またはジェミナル（同一炭素に結合）アルキル基は、一緒になって６個までの炭素原子を有する炭化水素環を形成してもよい）、ヒドロキシ、Ｃ_１−Ｃ_９アルコキシ、Ｃ_１−Ｃ_９アルキレンオキシ、アミンおよびＣ_１−Ｃ_９アルキルアミン、ハロゲン（フッ素、塩素、臭素および沃素）並びにフェニルからなる群からそれぞれ選択される。］

[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 together may 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. Specifically, trade name Hyperform HPN68L manufactured by Meriken Co., Ltd. can be mentioned. The structure of the nucleating agent component of Hyperform HPN68L is shown below.

  The blending amount of the nucleating agent (d) is preferably in the range of 0.005 to 0.15 parts by weight and more preferably in the range of 0.01 to 0.1 parts by weight with respect to 100 parts by weight of the polymer composition. 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) selectively used is a nucleating agent represented by the following general formula (5).
R ¹ (CONHR ² ) _a (5)
[In Formula (5), R ¹ is 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, Alternatively, it represents an aromatic polycarboxylic acid residue having 6 to 18 carbon atoms. 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. ]

［式（８）中、Ｒ^１は、炭素数３〜１０の３価の飽和脂肪族炭化水素基、炭素数４〜１０の４価の飽和脂肪族炭化水素基、炭素数５〜１５の３価もしくは４価の飽和脂環族炭化水素基、又は炭素数６〜１５の３価もしくは４価の芳香族炭化水素基を表す。Ｒ^２は、同一又は異なって、それぞれ水素原子又は炭素数１〜１０の直鎖状若しくは分岐鎖状のアルキル基を表す。ａは、３又は４の整数を表す。］ The nucleating agent (e) is preferably a nucleating agent represented by the following general formula (8), and more preferably a nucleating agent represented by the following general formula (9).

[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. ]

［式（９）中、Ｒ^１は、１，２，３−プロパントリカルボン酸又は１，２，３，４−ブタンテトラカルボン酸から全てのカルボンキシル基を除いて得られる残基を表す。３個又４個のＲ^２は、互いに同一又は異なって、それぞれ水素原子又は炭素数１〜１０の直鎖状若しくは分岐鎖状のアルキル基を表す。ａは、３又は４の整数を表す。］

[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. ]

  Specific examples of the nucleating agent represented by the following general formula (5) include 1,2,3-propanetricarboxylic acid tricyclohexylamide, 1,2,3-propanetricarboxylic acid tri (2-methylcyclohexylamide), 1 , 2,3-propanetricarboxylic acid tri (3-methylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (4-methylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (2-ethylcyclohexyl) Amide) 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 Li (3-n-propylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (4-n-propylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (2-iso-propylcyclohexylamide) 1,2,3-propanetricarboxylic 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-butyl) (L-cyclohexylamide), 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-propanetricarboxylic acid tri (4-sec-butyl) Cyclohexylamide), 1,2,3-propanetricarboxylic acid tri (2-tert-butylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (3-tert-butylcyclohexylamide), 1,2,3- Propanetricarboxylic acid tri (4-tert-butyl chloride) Hexylamide), 1,2,3-propanetricarboxylic acid tri (4-n-pentylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (4-n-hexylcyclohexylamide), 1,2,3- Propanetricarboxylic acid tri (4-n-heptylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (4-n-octylcyclohexylamide), 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-methylcyclo Kishiruamido)], 1,2,3-propane tricarboxylic acid [di (cyclohexyl amide) (2-methyl-cyclohexyl amide)],

  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-butylcyclohexyl) Amide), 1,2,3-propanetricarboxylic acid tri (3-n-butylcyclohexylamide) 1,2,3-propanetricarboxylic acid tri (4-n-butylcyclohexylamide), 1,2,3-propanetricarboxylic acid Acid tri (2-iso-butylcyclohexylamide), 1,2,3- Propane tricarboxylic acid tri (3-iso-butylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (4-iso-butylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (2-sec-butyl) Cyclohexylamide), 1,2,3-propanetricarboxylic acid tri (3-sec-butylcyclohexylamide) 1,2,3-propanetricarboxylic acid tri (4-sec-butylcyclohexylamide), 1,2,3-propane Tricarboxylic acid tri (2-tert-butylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (3-tert-butylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (4-tert-butylcyclohexyl) Amide),

  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.

Further, when emphasizing the effect of improving the transparency, R ¹ in the general formula (5), (8) or (9) is obtained by removing all carboxyxyl 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.

The above amide compounds can be used alone or in combination of two or more.
The crystal form of the nucleating agent (e) 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, cubic crystal and the like can be used. These crystals are also known or can be produced according to known methods.

  The nucleating agent (e) is preferably substantially 100% pure, but may contain some 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, and particularly preferably 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) is not particularly limited as long as the desired 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) used selectively 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) with respect to the molten propylene polymer. Those having a small particle size are preferred. When the measured value of the particle size obtained by the laser diffraction light scattering method is adopted, the maximum particle size 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) is preferably in the range of 0.005 to 0.3 parts by weight, more preferably in the range of 0.05 to 0.2 parts by weight with respect to 100 parts by weight of the polymer composition. 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, a sorbitol-based nucleating agent, an organic phosphate-based nucleating agent, and an aromatic. 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 (B) a propylene-ethylene copolymer are optionally added. The standard implementation 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 together 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 used in combination of two types.

3) Embodiment in which predetermined amounts 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 used in an optional combination of three types.

4) Embodiment in which a predetermined amount of four kinds 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 used in an optional combination of four types.

5) Embodiment in which a predetermined amount of five types 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, it is also predicted that the difference in the function of the nucleating agent will occur due to the difference in the specifications of the two-component resin mixture comprising the propylene-based (co) polymer (A) and the propylene-based copolymer (B). On the other hand, in order to express the properties of the medical propylene-based resin composition suitable for use including a specific medical device, any of the embodiments having the specifications 1) to 5) described above is suitable. Can decide. 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 mizucarac that does not elute into the liquid that comes into contact is advantageous.

Mg _1-x Al _x (OH) ₂ (CO ₃ ) _{x / 2} · mH ₂ O (10)
[In the formula (10), 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)
[In Formula (11), X is an inorganic or organic anion, n is a valence of an 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 with respect to a total of 100 parts by weight of the (co) polymer (A) and the copolymer (B). The range of -0.2 weight part is preferable, and the range of 0.01-0.05 weight part 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. These lubricants may be used alone or in combination. The lower the viscosity of the silicone (C), the better the releasability effect. However, when the viscosity is too low, elution is likely to occur. Therefore, at 25 ° C., 50 mm ² / s (cst) or more is good, 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 Drug Machine No. 327 (December 20, 1995) Medical Device Lubricant Silicone Oil Standard (1) (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 that is selectively used in the medical propylene-based resin composition of the present invention is preferably 0.001 to 0.5 parts by weight with respect to 100 parts by weight of the polymer composition. 15 parts by weight is more preferable, and 0.03 to 0.1 parts by weight is particularly 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 resin composition of the present invention, in addition to the components described above, various antioxidants, ultraviolet absorbers, light stabilizers and the like used as stabilizers for propylene 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).

（式（１３）中、Ｒ１とＲ２は、炭素数１４〜２２のアルキル基を示す。）

(In formula (13), R1 and R2 represent an alkyl group having 14 to 22 carbon atoms.)

  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, and 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. Furthermore, 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 (co) polymer (A) and a copolymer (B), and a selectively used nucleating agent ( a mixture of at least one of a) to (e) and, if necessary, other additives into a Henschel mixer, a super mixer, a ribbon blender, etc. It can be obtained by melt kneading in a temperature range of 190 to 260 ° C. with a twin screw extruder, Banbury mixer, plastic bender, roll or the like.

[3] Medical molded product The medical molded product of the present invention is obtained by molding the above-mentioned medical propylene-based 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.

Moreover, the medical molded article 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 the double-chamber type has 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 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.
(1) 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 test piece)
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)

(2) Calculation of amount of each component of polymer It calculated using TREF.
(3) 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.

(4) Measured by peak intrinsic viscoelasticity measurement of tan δ curve.
(5) MFR
Measurement was performed at a heating temperature of 230 ° C. and a load of 21.2 N according to JIS K7210.
(6) Haze value The value before sterilization was measured in accordance with JIS K7105 using a sheet piece having a thickness of 1 mm. In addition, autoclave sterilization (high-pressure steam sterilization) is sterilized at 121 ° C for 20 minutes using Alp Co., Ltd. retort high-pressure steam sterilization / cooling device RKZ-30L. Then, the value measured was used as the value after sterilization.

(7) Fifteenth revision Japanese Pharmacopoeia Exam 45 1. Plastic chemical container test method (plastic water-based injection container) In accordance with 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 at 220 ° C. to obtain a sheet piece 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 an appropriate 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.

(8) Flexural modulus Measured at 23 ° C. in accordance with “hard plastic bending test method” of JIS K7203.
(9) Izod (IZOD) impact value It measured at 23 degreeC based on JISK7110: 1999 using the test piece with a notch.

(10) Formability 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 × 2.5 mm). A shape in which 3 × 4 box shapes of 25 mm × 20 mm × 20 mm having a thickness of 1 mm are arranged on a plate), and a molded product obtained by this injection molding is visually observed, and a nucleating agent and other additives In addition, the presence or absence of scratches caused by the deposition and adhesion of reactive substances and the like to 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.
(11) HDT (thermal deformation temperature)
The measurement was performed according to JIS K7207.

The following were used as a propylene polymer, a nucleating agent, and other additives (neutralizing agent, lubricant).
(1) Propylene-based (co) polymer (A)
(I) MA3U
Nippon Polypro Co., Ltd. Homopolypropylene (JIS K7210, 230 ° C., 2.16 kg load) 15 g / 10 min, Ziegler catalyst product, melting point: 167 ° C.
(Ii) WMG03
Nippon Polypro Co., Ltd. random polypropylene (JIS K7210, 230 ° C., 2.16 kg load) 30 g / 10 min, metallocene catalyst product, ethylene content 0.9% by weight, melting point: 141 ° C.
(Iii) WSX02
Nippon Polypro Co., Ltd. random polypropylene (JIS K7210, 230 ° C., 2.16 kg load) 25 g / 10 min, metallocene catalyst product, ethylene content 3.5% by weight, melting point: 125 ° C.

(2) Propylene copolymer (B)
(I) Versify 2400 (trade name by Dow)
(JIS K7210, 230 ° C., 2.16 kg load) 4 g / 10 min, metallocene catalyst product, density 0.859, ethylene content 15% by weight.
(Ii) Product name of Versify 4301 Dow (JIS K7210, 230 ° C., 2.16 kg load) 50 g / 10 min, metallocene catalyst product, density 0.867, ethylene content 12% by weight.
(Iii) VM6202 ExxonMobil brand name (JIS K7210, 230 ° C., 2.16 kg load) 20 g / 10 min, metallocene catalyst product, density 0.861, ethylene content 15% by weight.

(3) Polyethylene Metallocene low density polyethylene Nippon Polyeth Co., Ltd. trade name Kernel KS571)
Density (JIS K7112) 0.907 g / cm ³ , MFR (JIS K7210, 190 ° C., 2.16 kg load) 12.5 g / 10 min.

(4) Nucleating agent (i) Mirad NX8000 (trade name, manufactured by Milliken & Company)
Nucleating agent (a) equivalent product (ii) Organophosphate metal salt compound nucleating agent ADK STAB NA-11 (trade name, manufactured by ADEKA Corporation): Nucleating agent (b) equivalent product (iii) organophosphate metal Salt compound nucleating agent ADK STAB NA-21 (trade name, manufactured by ADEKA): nucleating agent (c) equivalent (iv) Hyperform HPN68L
(Trade name manufactured by Milliken & Company): Nucleator (d) equivalent (v) 1,2,3-propanetricarboxylic acid tris (2-methylcyclohexylamide)
Equivalent to nucleating agent (e) (vi) Sorbitol-based nucleating agent Gerol MD (trade name, manufactured by Shin Nippon Rika Co., Ltd.)
Nucleating agent not corresponding to any of nucleating agents (a) to (e)

(5) Neutralizing agent (i) DHT-4C: Hydrotalcite (trade name, manufactured by Kyowa Chemical Industry Co., Ltd.)
(6) Lubricant (i) Silicone oil:
Dowcorning 360 Medical Fluid-1000 (M360-1000) Product name manufactured by Toray Dow Corning Co., Ltd.

(7) Peroxide (i) PHA25B: Perhexa 25B Nippon Oil & Fats trade name (8) Antioxidant (i) Hindered phenolic antioxidant:
Irganox 1010 (trade name, manufactured by Ciba Specialties)
Tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxylphenyl) propionate] methane (ii) Phosphorous antioxidant: Irgaphos 168 (trade name, manufactured by Ciba Specialties)
Tris (2,4-di-tert-butylphenol) phosphite

(Examples 1-11, Comparative Examples 1-5, Reference Example 1)
After preparing a propylene polymer, a nucleating agent and other additives (antioxidant, neutralizing agent, etc.) at a blending ratio (parts by weight) shown in the following table and dry blending with a super mixer, 35 It melt-kneaded using the twin screw extruder of a millimeter diameter. 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 the table.

  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.

Claims (9)

Melt flow rate (230 ° C., 2.16 kg load) of 0.5 to 100 g / 10 min, propylene homopolymer or propylene copolymer consisting of propylene and an α-olefin having a content of less than 1% by weight ( A) 75 to 98% by weight,
The following conditions (Bi) to (B-iii):
(Bi) is a propylene-α-olefin random copolymer obtained using a metallocene catalyst,
(B-ii) The ethylene content is in the range of 3 to 17 wt%.
(B-iii) Propylene copolymer (B) satisfying a melt flow rate (MFR: 230 ° C., 2.16 kg) in a range of 0.5 to 80 g / 10 minutes, and comprising 2 to 25% by weight,
In the temperature-loss tangent (tan δ) curve obtained by solid viscoelasticity measurement (DMA), the peak of the tan δ curve representing the glass transition observed in the range of −60 to 20 ° C. shows a single peak at 0 ° C. or lower. A medical propylene-based resin composition characterized by the above. Propylene copolymer (B)
30 to 70% by weight of a propylene-ethylene random copolymer (B-1) having an ethylene content of 7 to 25% by weight obtained using a metallocene catalyst, and an α-olefin content obtained using a metallocene catalyst Is 1 to 5% by mass, and the melting peak temperature (Tm) is 125 to 145 ° C. The propylene-α-olefin random copolymer (B-2) is 30 to 70% by weight.
The medical propylene-based resin composition according to claim 1, comprising:   Furthermore, the nucleating agent is contained in a range of 0.01 to 0.6 parts by weight with respect to a total of 100 parts by weight of the (co) polymer (A) and the propylene-based copolymer (B). The medical propylene-based resin composition according to claim 1 or 2. The nucleating agent and the content thereof are 0.01 to 0.6 parts by weight of the nucleating agent (a) represented by the following general formula (1), the nucleating agent (b) 0 represented by the following general formula (2) 0.005 to 0.3 part by weight, nucleating agent (c) represented by the following general formula (3) 0.005 to 0.15 part by weight, nucleating agent (d) 0 represented by the following general formula (4) The nucleating agent (e) represented by .005 to 0.15 parts by weight or the following general formula (5) is 0.005 parts by weight or more and less than 0.3 parts by weight. A propylene-based resin composition for medical use.

[In formula (1), n is an integer of 0 to ^2, R 1 to R ⁵ are the same or different, each represents an alkyl group having a hydrogen atom or having 1 to 20 carbon atoms, an alkenyl 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. ]

[In the formula (2), 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 is a hydrogen atom or 1 to 1 carbon atom. 8 is an alkyl group, M is Na, and n is the valence of M. ]

[In Formula (3), R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and 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. M 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 a periodic table. When a group IV metal atom is shown, O = or (HO) _2- . ]

[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 together may 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)
[In Formula (5), R ¹ is 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, Alternatively, it represents an aromatic polycarboxylic acid residue having 6 to 18 carbon atoms. 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 4, wherein the nucleating agent (a) is a nucleating agent represented by the following general formula (6).

[In the formula (6), 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 carbon number 1 to 1] 20 alkyl groups, alkenyl groups, alkoxy groups, carbonyl groups, halogen groups and phenyl groups, and R ⁶ is an alkyl group having 1 to 20 carbon atoms. ]   Furthermore, the lubricant is contained in a range of 0.001 to 0.5 parts by weight with respect to 100 parts by weight in total of the (co) polymer (A) and the propylene-based copolymer (B). The medical propylene-based resin composition according to any one of claims 1 to 5.   The medical molded article using the medical propylene-type resin composition of any one of Claims 1-6.   The medical molded article according to claim 7, which is a kit preparation.   A kit for medical use according to claim 8, wherein the kit preparation is a prefilled syringe.