JP2008255326A - Propylenic resin composition and its molded article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a propylenic resin composition which satisfies the standards of general tests in the Pharmacopoeia of Japan and is excellent in heat resistance, rigidity, impact resistance, injection moldability, transparency, and gas barrier property, and to provide a molded article thereof. <P>SOLUTION: This propylenic resin composition comprises (a) 60 to 99 pts.wt. of propylene homopolymer having a melt flow rate of 2 to 80 g/10 min at 230°C under a load of 2.16 kg, (b) 1 to 40 pts.wt. of polyethylene having a melt flow rate of 1 to 60 g/10 min at 190°C under a load of 2.16 kg and a density of 0.860 to 0.940 g/cm<SP>3</SP>, and (c) a nucleating agent (A) represented by general formula (1): R<SP>1</SP>(CONHR<SP>2</SP>)<SB>a</SB>in an amount of 0.005 to 0.3 pts.wt. per 100 pts.wt. of the polymer mixture of the components (a) and (b). <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a propylene-based resin composition and a molded product thereof. More specifically, the present invention is excellent in the balance between rigidity, impact resistance, heat resistance, and transparency, and among drugs for medical use and chemical solution storage containers, in particular, No. 14 Revised Japanese Pharmacopoeia General Examination 45. Test method for plastic drug containers 1. The present invention relates to a propylene-based resin composition that satisfies all the test items of a polyethylene or polypropylene aqueous injection container and a molded product 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, the use of ampules and vials as alternative container materials has been increasingly seen as storage containers for drugs and chemical solutions that require a high level of safety and health, and materials for such applications have been developed. (For example, refer to Patent Document 1).
These resins for storage containers are required to have rigidity, impact resistance, transparency, heat resistance during steam sterilization, resistance to devitrification, and additive extraction resistance as storage containers. 45. It is necessary that the additive to be used does not interact with the preserving drug or drug solution. Specifically, the 14th 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 polymer is a propylene homopolymer in terms of rigidity, heat resistance and gas barrier properties, an ethylene-propylene random copolymer in terms of transparency and impact resistance, and ethylene- in terms of heat resistance and impact resistance. Propylene block copolymer is suitable and is used appropriately and selectively according to the situation, but when used in a storage container, propylene homopolymer should exhibit sufficient performance in terms of impact resistance. In the case of ethylene-propylene random copolymer, heat resistance during steam sterilization is not sufficient, and there is a problem that it deforms. In the case of ethylene-propylene block copolymer, it is sufficient in terms of transparency. It was difficult to demonstrate the performance.
Therefore, the optimization of the main performance as a storage container has to be relied on an additive formulation in which various nucleating agents and neutralizing agents are combined.

However, for example, when a sorbitol-based transparent nucleating agent is used, it does not satisfy additive extraction resistance and pharmacopoeia testing, and is unsuitable for these uses. In the case where the agent was added, the transparency was not sufficiently developed, and when the addition amount was increased, satisfactory results were not obtained in the ignition residue of the pharmacopoeia test.
Examples of medical applications that need to pass a pharmacopoeia test include prefilled syringes and kit preparations that are pre-filled with a chemical solution.
It was around the middle of the 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 transparent syringe or a transparent container composed of a nucleating agent is filled with a drug solution.
In addition, products such as prefilled syringes have hitherto been cited as a problem that impacts are applied and the products are damaged when transported or used, and materials with higher impact resistance have been demanded.
However, there are currently no molded products that have high transparency and impact resistance, pass pharmacopoeia tests, and have satisfactory heat resistance, rigidity, moldability, etc. as storage containers for drugs and chemicals. Met.
JP-A-1-178541 JP-A-62-194866 JP-A-5-222078

  The object of the present invention is, in view of the above problems, the 14th revised Japanese Pharmacopoeia General Test 45. Test method for plastic drug containers 1. A propylene-based resin composition that satisfies the test item standards of a polyethylene or polypropylene aqueous injection container and has excellent heat resistance, rigidity, impact resistance, injection moldability, transparency, and gas barrier properties, and its It is to provide a molded article.

  As a result of intensive research to solve the above problems, the present inventors have used a specific amount of a specific nucleating agent for a polymer mixture containing a specific amount of a specific propylene homopolymer and a specific polyethylene. Found that the propylene-based resin composition is excellent in heat resistance, rigidity, impact resistance, injection moldability, transparency and gas barrier properties, and can satisfy the standards of Japanese Pharmacopoeia test items. The present invention has been completed.

That is, according to the first invention of the present invention, (a) 60 to 99 parts by weight of a propylene homopolymer having a melt flow rate of 2 to 80 g / 10 min at 230 ° C. and a load of 2.16 kg, and (b) With respect to 100 parts by weight of a polymer mixture comprising 1 to 40 parts by weight of polyethylene having a melt flow rate of 1 to 60 g / 10 min at 190 ° C. and a load of 2.16 kg and a density of 0.860 to 0.940 g / cm ³ And (c) a propylene-based resin composition characterized in that 0.005 to 0.3 parts by weight of a nucleating agent (A) represented by the following general formula (1) is blended.
R ¹ (CONHR ² ) _a (1)
[Wherein, R ¹ represents a saturated or unsaturated aliphatic polycarboxylic acid residue having 2 to 30 carbon atoms, a saturated or unsaturated alicyclic polycarboxylic acid residue having 4 to 28 carbon atoms, or the number of carbon atoms. Represents 6-18 aromatic polycarboxylic acid residues. R ² represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, or a cycloalkyl group or cycloalkenyl group having 3 to 46 carbon atoms. a represents an integer of 2 to 6. ]

  Further, according to the second invention of the present invention, in the first invention, 0.005 to 0.3 parts by weight of the structure represented by the following general formula (2) is further added to 100 parts by weight of the polymer mixture. Nucleating agent (B), 0.005 to 0.15 parts by weight of the nucleating agent (C) represented by the following general formula (3), or 0.005 to 0.15 parts by weight of the following formula (4) There is provided a propylene-based resin composition comprising at least one nucleating agent selected from the nucleating agent (D).

［式中、Ｒ^１は、直接結合、硫黄又は炭素数１〜９のアルキレン基若しく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。］

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

［式中、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族又は第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。］

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

［式中、Ｍ_１およびＭ_２は、同一又は異なって、カルシウム、ストロンチウム、リチウム又は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、同一又は異なって、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、アミン及び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。］

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

  According to a third invention of the present invention, in the first or second invention, the nucleating agent (A) is at least one amide compound represented by the following general formula (5). A propylene-based resin composition is provided.

［式中、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価若しくは４価の飽和脂環族炭化水素基、又は炭素数６〜１５の３価若しくは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。］

[Wherein, 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, a trivalent or 4 carbon atoms having 5 to 15 carbon atoms. Represents a saturated 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. ]

  According to a fourth invention of the present invention, in the first or second invention, the nucleating agent (A) is at least one amide compound represented by the following formula (6). A resin composition is provided.

［式中、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。］

[Wherein, 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. ]

According to a fifth invention of the present invention, in any one of the first to fourth inventions, the propylene-based resin composition is characterized in that the polyethylene has a density of 0.860 to 0.915 g / cm ^3. Provided.
According to the sixth invention of the present invention, in any one of the first to fifth inventions, the polyethylene is polymerized using a metallocene catalyst to obtain a weight average molecular weight (Mw) and a number average molecular weight (Mn). A propylene-based resin composition having a ratio (Mw / Mn) of less than 3.5 is provided.
Furthermore, according to the seventh invention of the present invention, in any one of the first to sixth inventions, 0.001 to 0.5 parts by weight of a lubricant is further blended with 100 parts by weight of the polymer mixture. A propylene-based resin composition is provided.

According to the eighth aspect of the present invention, there is provided a molded article obtained by injection molding the propylene-based resin composition according to any one of the first to seventh aspects.
According to a ninth aspect of the present invention, there is provided a molded product according to the eighth aspect, which is a syringe, a medical instrument or a medical container.
Furthermore, according to the tenth aspect of the present invention, in the ninth aspect, there is provided a molded product characterized by being a kit preparation.
Still further, according to the eleventh aspect of the present invention, there is provided the molded product according to the tenth aspect, wherein the kit preparation is a prefilled syringe.

  The propylene-based resin composition of the present invention is obtained by blending a specific propylene homopolymer with a specific propylene homopolymer, resulting in a change in material morphology and a polymer mixture having good impact resistance. A composition containing a specific amount of a nucleating agent to improve the rigidity and transparency in a well-balanced manner, and to maintain excellent heat resistance and gas barrier properties. In addition, the 14th revised Japanese Pharmacopoeia General Test 45 . Test method for plastic drug containers 1. Satisfies the test item standard for polyethylene or polypropylene aqueous injection containers.

The propylene-based resin composition of the present invention comprises (a) 60 to 99 parts by weight of a propylene homopolymer having a melt flow rate of 2 to 80 g / 10 min at 230 ° C. and a load of 2.16 kg, and (b) 190 ° C. With respect to 100 parts by weight of a polymer mixture composed of 1 to 40 parts by weight of polyethylene having a melt flow rate of 1 to 60 g / 10 min at a load of 2.16 kg and a density of 0.860 to 0.940 g / cm ³ ( c) The nucleating agent (A) represented by the general formula (1) is blended in an amount of 0.005 to 0.3 parts by weight.
Hereinafter, the component which comprises a propylene-type resin composition, the manufacturing method of a resin composition, and a molded article are demonstrated in detail.

[I] Components of propylene-based resin composition Propylene homopolymer (a)
The propylene homopolymer (a) used in the propylene-based resin composition of the present invention has a melt flow rate (MFR) at 230 ° C. and a load of 2.16 kg of 2 to 80 g / 10 minutes, preferably 7 to 13 g / 10 minutes. It is. When the MFR is within this range, a resin composition suitable for a high production rate derived from the rigidity and impact resistance of the resin composition and the molding temperature is provided. When the MFR is less than 2 g / 10 minutes, molding becomes difficult. On the other hand, when it exceeds 80 g / 10 minutes, good impact resistance cannot be obtained.
Here, MFR at 230 ° C. is a value measured under a load of 230 ° C. and 2.16 kg in accordance with JIS K7210.

Further, the stereoregularity is preferably 96% or more, and more preferably 96.5% or more. If the stereoregularity is less than 96%, the rigidity and the heat distortion temperature tend to decrease, and the molded product may be easily deformed during molding.
Here, the stereoregularity is a value measured by a ¹³ C-NMR method.

  The catalyst used for obtaining the propylene homopolymer (a) used in the present invention is not particularly limited, and a known catalyst can be used. For example, a so-called Ziegler-Natta catalyst in which a titanium compound and an organoaluminum compound are combined, or a metallocene catalyst (for example, described in JP-A-5-295022) can be used. In the present invention, since a propylene homopolymer having a good balance between rigidity and impact resistance is particularly preferable, a Ziegler-Natta catalyst generally having high stereoregularity is more preferable. Moreover, the propylene homopolymer (a) manufactured using a metallocene catalyst has good compatibility and is more preferable when the polyethylene (b) is a low density polyethylene manufactured using a metallocene catalyst.

2. Polyethylene (b)
The polyethylene (b) used in the propylene-based resin composition of the present invention is a polyethylene having a density of 0.860 to 0.940 g / cm ³ and may be an ethylene homopolymer, but 30 wt.% Of polyethylene (b) %, Preferably 15 to 25 wt%, a polymer obtained by copolymerization with another α-olefin is used, the impact resistance is improved. Examples of other α-olefins include propane, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-heptene, 1-octene, 1-octene, Decene etc. can be mentioned.
Also, the value of (weight average molecular weight) / (number average molecular weight), which is an index of the width of the molecular weight distribution, should be less than 7.0, preferably less than 3.5, and more preferably less than 3.0. The physical property balance between rigidity and impact resistance is good.

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

The melt flow rate (MFR) of polyethylene (b) at 190 ° C. is 1 to 60 g / 10 minutes, preferably 3 to 40 g / 10 minutes. Within this range, the propylene homopolymer (a) and polyethylene (b) constituting the resin composition are well mixed, and a well-balanced resin composition excellent in transparency can be obtained. When the MFR of the polyethylene (b) is less than 1 g / 10 minutes or exceeds 60 g / 10 minutes, the dispersion into the propylene homopolymer (a) is deteriorated and a stable composition cannot be obtained.
Here, MFR at 190 ° C. is a value measured under a load of 190 ° C. and 2.16 kg in accordance with JIS K7210.

In addition, when the polyethylene (b) is mixed with the propylene homopolymer (a), when the MFR difference between the polyethylene (b) and the propylene homopolymer (a) becomes small, the polyethylene (b) becomes a propylene homopolymer ( Since there is a tendency to exist as a finely dispersed matrix in a), it is preferable to use a polyethylene (b) that has a small MFR difference from the propylene homopolymer (a) as the polyethylene (b). .
Specifically, the MFR of the MFR / propylene homopolymer (a) of polyethylene (b) is preferably 0.05 to 1.1, more preferably 0.1 to 0.9, and 0.15 to 0.00. 7 is particularly preferred.

Moreover, the density of polyethylene (b) is 0.860-0.940 g / cm < ³ >. When the density is less than 0.860 g / cm ³ , the rigidity becomes insufficient, and when it exceeds 0.940 g / cm ³ , the transparency is remarkably deteriorated. When polyethylene is blended with a propylene homopolymer, the transparency tends to be deteriorated. However, when a material with a low density is used, the tendency to deteriorate the transparency can be alleviated and the impact resistance can be improved. Therefore, the density of polyethylene (b) is preferably 0.925 g / cm ³ or less, and more preferably 0.915 g / cm ³ or less.
Here, the density is a value measured according to JIS K7112.

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

Moreover, the polyethylene (b) used for the propylene-type resin composition of this invention can be used 1 type, or in combination of 2 or more types in the range which does not impair the effect of this invention.
The polyethylene (b) used in the propylene-based resin composition of the present invention includes, as commercially available products, Novatec LL series, Harmolex series, Kernel series, Mitsui Chemicals Tuffmer P series manufactured by Nippon Polyethylene Co., Ltd. Examples include Tuffmer A series, Evolue series manufactured by Prime Polymer Co., Ltd., Sumikasen E, EP series, and Excellen GMH series manufactured by Sumitomo Chemical Co., Ltd.
Moreover, as polyethylene (b) polymerized using a metallocene catalyst, Harmolex series, Kernel series, Evolue series made by Prime Polymer, Exelen FX series made by Sumitomo Chemical Co., Ltd., etc. are available. Can be illustrated.

3. Propylene Homopolymer (a) and Polyethylene (b) Blending Ratio In the propylene-based resin composition of the present invention, the propylene homopolymer (a) and polyethylene (b) are blended in proportion to the propylene homopolymer (a). 60 to 99 parts by weight, polyethylene (b) is 40 to 1 part by weight, preferably propylene homopolymer (a) is 80 to 95 parts by weight, and polyethylene (b) is 20 to 5 parts by weight. Within this range, the resin composition has excellent impact resistance.
In addition to the propylene homopolymer (a) and polyethylene (b), the polymer mixture used in the present invention includes a random or block copolymer of propylene and α-olefin as long as the effects of the present invention are not impaired. Polymers can be used. Here, examples of the α-olefin as the copolymer component include ethylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene and the like.

4). Nucleating agent The nucleating agent used in the present invention is the nucleating agent (A) represented by the general formula (1). Moreover, as a nucleating agent preferably used for this invention, the nucleating agent (B)-(D) shown by General formula (2)-(4) can be mentioned.
The nucleating agent (A) is an amide compound represented by the general formula (1). Among them, an amide compound represented by the general formula (5) is preferable, and an amide compound represented by the general formula (6) is preferable. More preferred.

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

［式（５）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。］

[In the formula (5), 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（６）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 (6), R ¹ represents a residue obtained by removing all carboxyxyl groups from 1,2,3-propanetricarboxylic acid or 1,2,3,4-butanetetracarboxylic acid. Three or four R ^{2 s} are the same or different from each other and each represent a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms. a represents an integer of 3 or 4. ]

  Specifically, 1,2,3-propanetricarboxylic acid tricyclohexylamide, 1,2,3-propanetricarboxylic acid tri (2-methylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (3-methyl) Cyclohexylamide), 1,2,3-propanetricarboxylic acid tri (4-methylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (2-ethylcyclohexylamide) 1,2,3-propanetricarboxylic acid tri ( 3-ethylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (4-ethylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (2-n-propylcyclohexylamide), 1,2,3 -Propanetricarboxylic acid tri (3-n-propylcyclohexyla ), 1,2,3-propanetricarboxylic acid tri (4-n-propylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (2-iso-propylcyclohexylamide), 1,2,3-propane Tricarboxylic acid tri (3-iso-propylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (4-iso-propylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (2-n-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- Lopantricarboxylic 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-propane Tricarboxylic acid tri (4-n-pentylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (4-n-hexylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (4-n-heptylcyclohexyl) Amide), 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-methylcyclohexylamide)], 1,2,3-propane Polycarboxylic 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 (5) or (6) 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- Lopantricarboxylic 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 (5) or (6) 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 (1), (5) or (6) is obtained by removing all carboxylic xyl groups from 1,2,3-propanetricarboxylic acid. Particularly preferred is an amide compound which is a residue obtained. Specifically, 1,2,3-propanetricarboxylic acid tricyclohexylamide, 1,2,3-propanetricarboxylic acid tri (2-methylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (3-methyl) Cyclohexylamide), 1,2,3-propanetricarboxylic acid tri (4-methylcyclohexylamide) and the like.
Said amide type compound can be used individually or in combination of 2 or more types as appropriate.

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

The nucleating agent (A) used in the present invention preferably has a purity of substantially 100%, but may contain some impurities. Even when impurities are contained, the purity of the nucleating agent (A) is preferably 90% by weight or more, more preferably 95% by weight or more, and particularly 97% by weight or more. Examples of the impurities include monoamide dicarboxylic acid derived from a reaction intermediate or unreacted substance or an ester compound thereof, diamide monocarboxylic acid or an ester compound thereof, an imide compound derived from a side reaction product, and the like.
However, for the purpose of controlling the crystallization speed, the weight ratio of the nucleating agent (A): the fatty acid metal salt of the formula (7) is changed to at least one fatty acid metal salt represented by the following formula (7). You may use it in the range which does not inhibit the effect of this invention by the mixture ratio of 100: 0-30: 70.

(R ¹ COO) _n M (7)
[Wherein R ¹ represents a residue obtained by removing a carboxyl group from a saturated or unsaturated aliphatic monocarboxylic acid having 8 to 32 carbon atoms which may have one or more hydroxyl groups in the molecule. To express. n represents an integer of 1 or 2, and when n = 2, two R ^{1 s} may be the same or different. M represents a monovalent or divalent metal. ]

  The method for producing the nucleating agent (A) used in the present invention is not particularly limited as long as the desired nucleating agent (A) can be obtained. For example, it can be produced from a specific aliphatic polycarboxylic acid component and a specific alicyclic monoamine component according to a conventionally known method (for example, JP-A-7-242610).

  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 admixture 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 (A) used in the present invention is not particularly limited as long as the effects of the present invention can be obtained. From the viewpoint of the dissolution rate (or dissolution time) in the molten propylene polymer, the particle size is as much as possible. A thing with a small diameter is preferable. When the measurement value of the particle diameter obtained by the laser diffraction light scattering method is adopted, the maximum particle diameter of the nucleating agent (A) 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 counter jet mill 100AFG (trade name, manufactured by Hosokawa Micron Corporation) as a pulverizer, 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 nucleating agent (A) used in the present invention has the characteristics that it gives excellent transparency to the obtained molded product and has very little elution from the obtained molded product. It is one of the few nucleating agents that can pass pharmacopoeia tests.

  The compounding quantity of the nucleating agent (A) used for this invention is used in 0.005 to 0.3 weight part with respect to 100 weight part of polymer mixtures. If the amount is less than 0.005 parts by weight, it is difficult to obtain a sufficient effect. On the other hand, if the amount exceeds 0.3 parts by weight, further improvement in performance cannot be expected, which is not economical and the 14th revised Japanese Pharmacopoeia. Fails the test item for potassium permanganate reducing substances. 0.01-0.25 weight part is preferable and 0.02-0.2 weight part is further more preferable.

  The propylene-based resin composition of the present invention is blended with the nucleating agent (A), and at least one of the nucleating agents (B) to (D) represented by the general formulas (2) to (4). Types may be blended. Transparency, rigidity, moldability, etc. can be further improved by using nucleating agents (B) to (D) singly or in combination.

  The nucleating agent (B) is an organophosphate metal salt compound represented by the following 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 Asahi Denka Kogyo Co., Ltd.

  The amount of the nucleating agent (B) is preferably in the range of 0.005 to 0.3 parts by weight and more preferably in the range of 0.01 to 0.2 parts by weight with respect to 100 parts by weight of the polymer mixture. 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.

  The nucleating agent (C) is an aromatic phosphate represented by the 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、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- . ]

  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, dibenzoylmethane, and the like.

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

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

  A commercially available product can be used as such a nucleating agent. Specific examples include NA-21 manufactured by Asahi Denka Kogyo Co., Ltd.

  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 mixture. If it is less than 0.005 parts by weight, no effect can be obtained. On the other hand, if it exceeds 0.15 parts by weight, not only a further effect can be obtained but also economically undesirable.

  The nucleating agent (D) is a nucleating agent represented by the 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、リチウム又は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, or 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. Specific examples include Hyperform HPN68L manufactured by Meriken Co., Ltd. The structure of the nucleating agent component of Hyperform HPN68L is shown below.

  The 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 mixture. If the amount is less than 0.005 parts by weight, the effect cannot be obtained. On the other hand, if the amount exceeds 0.15 parts by weight, the pharmacopoeia test may be rejected.

  In addition to the nucleating agents (A) to (D), the propylene-based resin composition of the present invention includes, as other nucleating agents, sorbitol-based nucleating agents, organic phosphate-based nucleating agents, and aromatic phosphate esters. Known nucleating agents such as talc can be added as long as the effects of the present invention are not significantly impaired.

5. Neutralizer In the 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 (8) of Kyowa Chemical Industry Co., Ltd.) Aluminum complex hydroxide salt), Mizukarak (lithium aluminum composite hydroxide salt represented by the following general formula (9)), 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 (8)
[Wherein x is 0 <x ≦ 0.5, and m is a number of 3 or less. ]

[Al ₂ Li (OH) ₆ ] _n X · mH ₂ O (9)
[Wherein, X is an inorganic or organic anion, n is the valence of the anion (X), and m is 3 or less. ]

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

6). Lubricant In the 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.
When silicone such as dimethylpolysiloxane is added, not only can scratches that occur during molding be prevented, but also burns that can occur in cylinders and hot runners can be prevented.

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

7). Other additives In the propylene-based resin composition of the present invention, in addition to the above-mentioned components, addition of various antioxidants, ultraviolet absorbers, light stabilizers and the like used as stabilizers for propylene-based polymers An agent 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 (10) and the following general formula (11), which are free from discoloration by radiation treatment and have good resistance to NOx gas discoloration, 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 (12).

  In addition, an antistatic agent, a slip agent, a dispersant such as a fatty acid metal salt, high-density polyethylene, an olefin-based elastomer, and the like can be blended within a range that does not impair the object of the present invention.

[2] Method for Producing Propylene Resin Composition The propylene resin composition of the present invention comprises a propylene homopolymer (a), polyethylene (b), a nucleating agent (nucleating agent (A) and as necessary. A mixture of at least one nucleating agent (B) to (D)) 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 screw extruder, twin screw extruder, Banbury mixer, plastic bender, roll or the like.

[3] Molded Product The molded product of the present invention is obtained by injection molding the above propylene resin composition with a known injection molding machine.

Examples of the molded article of the present invention include food containers, caps, medical instruments, physics and chemistry laboratory instruments, automobile parts, and electrical parts. Among them, the 14th revised Japanese Pharmacopoeia general test with strict acceptance criteria. Test method for plastic drug containers 1. Since all the test items of the polyethylene or polypropylene aqueous injection container can be satisfied, it is suitable for a syringe, a medical instrument and a medical container, a syringe and a container filled with a drug solution, and the like.
Specifically, disposable syringes and parts thereof, catheters and tubes, infusion bags, blood bags, vacuum blood collection tubes, surgical nonwoven fabrics, blood filters, blood circuits, and other disposable devices, and artificial organs such as artificial lungs and anus Parts, dialyzer, prefilled syringe, kit formulation, drug container, test tube, suture, compress base material, dental material part, orthopedic material part, contact lens case, PTP (PRESS THROUGH PACKAGE), SP (STRIP PACKAGE) / packaging, P vial (plastic vial), eye drop container, drug solution container, liquid long-term storage container, cap and the like can be mentioned.
The molded product of the present invention may be subjected to a known sterilization treatment such as autoclave sterilization, radiation sterilization, EOG sterilization.

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

1. Measurement method and evaluation method of physical properties (1) Flexural modulus:
The measurement was performed at 23 ° C. in accordance with JIS K7203 “Bending test method of hard plastic”.
(2) Izod impact strength (IZOD impact):
Using a test piece with a notch, measurement was performed at 23 ° C. according to JIS K7203 (unit: KJ / m ² ).
(3) Haze value:
It measured based on JISK7105 using the sheet piece of thickness 1mm.
(4) Deflection temperature under load (thermal deformation temperature: HDT):
Measurement was performed at a load of 0.45 MPa in accordance with JIS K7207. The higher this temperature, the better the molded product obtained.
(5) Formability:
A molded product for evaluation of formability (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 12 cm × 12 cm × 2.5 mm plate) was prepared. The moldability was evaluated from the obtained molded product and the mold release resistance at the time of mold release.
Here, if the mold release resistance (hardness of mold release) when releasing the molded product obtained by injection molding from the mold is large, the ejector pin must be moved by excessive stress. Therefore, the probability of occurrence of cracking and whitening is increased, it is difficult to obtain a high-quality molded product, and the defect rate is increased. Also, if the ejector pin is moved at high speed under such circumstances, the probability of further cracking and whitening increases, so the speed at which the molded product is released from the mold must be reduced, and the molding cycle Will be reduced.
For the reasons described above, if the mold release resistance of the molded product is large (the mold release property is poor), the moldability deteriorates. Therefore, the mold release resistance of the molded product was measured and the moldability was evaluated. The smaller the mold release resistance, the easier it is to release the molded product from the mold (good moldability). Conversely, the higher the mold release resistance, the harder the mold is released from the mold (poor moldability). It shows that.

(6) 14th revision Japanese Pharmacopoeia General Examination (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.

2. Resin, additive (A-1) Propylene homopolymer (a): MFR (JIS K7210, 230 ° C., 2.16 kg load) 14 g / 10 min, stereoregularity 97% (Novatech SA2E, manufactured by Nippon Polypro Co., Ltd.) )
(A-2) Propylene homopolymer (a): MFR (JIS K7210, 230 ° C., 2.16 kg load) 11 g / 10 min, stereoregularity 95% (Novatech MA3 manufactured by Nippon Polypro Co., Ltd.)
(A-3) ethylene-propylene random copolymer: ethylene content 2.5 wt%, MFR (JIS K7210, 230 ° C., 2.16 kg load) 9 g / 10 min (MG3F manufactured by Nippon Polypro Co., Ltd.)

(B-1) Metallocene polyethylene (b): Density (JIS K7112) 0.898 g / cm ³ , MFR (JIS K7210, 190 ° C., 2.16 kg load) 2.2 g / 10 min, (Mw / Mn) 2 .2. (Nippon Polyethylene Corporation Kernel KF262)
(B-2) Ziegler-Natta polyethylene (b): Density (JIS K7112) 0.920 g / cm ³ , MFR (JIS K7210, 190 ° C., 2.16 kg load) 2.1 g / 10 min, (Mw / Mn) 3.8. (Novatec UF240 manufactured by Nippon Polyethylene Co., Ltd.)
(B-3) Ziegler-Natta polyethylene: density (JIS K7112) 0.951 g / cm ³ , MFR (JIS K7210, 190 ° C., 2.16 kg load) 5.5 g / 10 min, (Mw / Mn) 4.6 . (Novatec HJ360, manufactured by Nippon Polyethylene Corporation)

(C-1) 1,2,3-propanetricarboxylic acid tris (2-methylcyclohexylamide): equivalent to nucleating agent (A) (C-2) NA-11: organophosphate metal salt compound nucleating agent (Asahi Denka Kogyo Co., Ltd.): Equivalent to nucleating agent (B) (C-3) Gelol MD: Sorbitol nucleating agent (manufactured by Shin Nippon Rika Co., Ltd.): Nucleating agents (A) to (D Nucleating agents not equivalent to any of

(D-1) Phosphorous antioxidant: Tris (2,4-di-tert-butylphenol) phosphite (D-2) Hindered amine antioxidant: dimethyl succinate 1- (2-hydroxyethyl) -4 -Hydroxy-2,2,6,6-tetramethylpiperidine polycondensate (E) DHT-4A: Hydrotalcite (manufactured by Kyowa Chemical Industry Co., Ltd.)
(F) Silicone oil: Dowcorning 360 Medical Fluid (silicone) -1000 manufactured by Toray Dow Corning Co., Ltd.

[Examples 1-7, Comparative Examples 1-6]
Resins and additives were prepared in the blending ratios (parts by weight) shown in Table 1, dry blended with a super mixer, and then melt-kneaded using a 35 mm diameter twin screw extruder. Extrusion pelletized from the die at a die outlet temperature of 240 ° C. The obtained pellets were injection-molded with 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. to prepare test pieces. The physical properties were measured using the obtained test pieces.
Further, the obtained pellets were injection-molded with 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 (for release resistance measurement) (12 cm 3 × 4 box shapes of 25 mm × 20 mm × 20 mm having a thickness of 1 mm are arranged on a × 12 cm × 2.5 mm plate, and have a shape in which resistance at the time of release is increased. The moldability was evaluated by measuring the mold release resistance at the time of mold release of the obtained molded product.
The evaluation results are shown in Table 1.

As is clear from Table 1, Example 1 uses the propylene resin composition of the present invention and is excellent in rigidity, impact resistance, transparency, heat resistance and moldability, and is used in the Japanese Pharmacopoeia test. Can be obtained, and an excellent molded product can be obtained.
In Example 2, the blending amount of the nucleating agent (A) is increased. By increasing the blending amount, the transparency is further improved and the pharmacopoeia test is also adapted.
Furthermore, Example 3 is a combination of the nucleating agent (A) and the nucleating agent (B), and is superior in rigidity, transparency, and heat resistance to the case where only the nucleating agent (A) is used. Also suitable for the Japanese Pharmacopoeia test.
In addition, Example 4 uses polyethylene (b) having a low MFR, which is slightly inferior in rigidity, but is excellent in impact resistance, transparency, heat resistance and moldability, and conforms to the Japanese Pharmacopoeia test. An excellent molded product can be obtained.
Furthermore, in Example 5, silicone is blended. With such a blending amount, the releasability can be remarkably improved while conforming to the Japanese Pharmacopoeia test.
Moreover, Example 6 is what raises the compounding ratio of the polyethylene (b) used by this invention, and it turns out that impact resistance is remarkably improved by this.
Furthermore, Example 7 uses propylene homopolymer (a) with a little low stereoregularity, and it turns out that rigidity and heat resistance are in a tendency to fall a little with the fall of stereoregularity.

On the other hand, since Comparative Example 1 does not use the polyethylene (b) used in the present invention, the impact resistance is considerably inferior to that of the propylene resin composition of the present invention. It is likely to cause damage.
Comparative Example 2 is a blend of a nucleating agent (A) to an ethylene-propylene random copolymer, which is a conventional resin that has been used for molded products that require transparency and impact resistance, Compared to the propylene-based resin composition of the present invention, although it is excellent in transparency, it tends to be low in rigidity and impact resistance, inferior in heat resistance, and molded under conditions of high-pressure steam sterilization and high load There is a high possibility of causing deformation of the product.
Further, Comparative Examples 3 to 4 are propylene resin compositions in which the nucleating agent (A) used in the present invention is not blended. In Comparative Example 3, the nucleating agent (B) is used in place of the nucleating agent (A), and it can be seen that when compared with Example 2, the transparency is clearly inferior. Moreover, Comparative Example 4 uses Gelol MD, which is a nucleating agent having excellent transparency, instead of the nucleating agent (A), and is excellent in transparency, but cannot be adapted to the Japanese Pharmacopoeia test.
Moreover, it turns out that the comparative example 5 uses polyethylene from which the density range of the polyethylene (b) used by this invention remove | deviates, and is inferior to transparency remarkably.
Further, Comparative Example 6 uses an ethylene-propylene random copolymer instead of the propylene homopolymer (a) used in the present invention. However, compared with Example 3, the rigidity tends to be low. It can be seen that the heat resistance is remarkably inferior.

  The propylene-based resin composition of the present invention has good rigidity, impact resistance, and transparency, passes the 14th revised Japanese Pharmacopoeia general test, and is found to be very useful for obtaining an excellent molded product. Especially for products that have been subjected to high-pressure steam sterilization, it is possible to obtain molded products that are transparent and have excellent heat distortion resistance and impact resistance, and are very suitable for syringes, medical instruments, and medical containers. Among them, it is suitable for syringes and containers filled with a drug solution, specifically, prefilled syringes and kit preparations.

Claims (11)

(A) 60 to 99 parts by weight of a propylene homopolymer having a melt flow rate of 2 to 80 g / 10 min at 230 ° C. and a load of 2.16 kg; and (b) 1 melt flow rate of 190 ° C. and a load of 2.16 kg. (C) represented by the following general formula (1) with respect to 100 parts by weight of a polymer mixture consisting of 1 to 40 parts by weight of polyethylene having a density of 0.860 to 0.940 g / cm ^3. The propylene-based resin composition, wherein 0.005 to 0.3 parts by weight of the nucleating agent (A) to be produced is blended.
R ¹ (CONHR ² ) _a (1)
[Wherein, R ¹ represents a saturated or unsaturated aliphatic polycarboxylic acid residue having 2 to 30 carbon atoms, a saturated or unsaturated alicyclic polycarboxylic acid residue having 4 to 28 carbon atoms, or the number of carbon atoms. Represents 6-18 aromatic polycarboxylic acid residues. R ² represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, or a cycloalkyl group or cycloalkenyl group having 3 to 46 carbon atoms. a represents an integer of 2 to 6. ] Further, 0.005 to 0.3 parts by weight of the nucleating agent (B) represented by the following general formula (2) and 0.005 to 0.15 parts by weight of the following general formula with respect to 100 parts by weight of the polymer mixture. At least one nucleating agent selected from the nucleating agent (C) represented by (3) or 0.005 to 0.15 parts by weight of the nucleating agent (D) represented by the following formula (4) is blended. The propylene-based resin composition according to claim 1, wherein

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

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

[Wherein, M ₁ and M ₂ are the same or different and are at least one metal cation selected from calcium, strontium, lithium or monobasic aluminum, and R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ are the same or different and are hydrogen, C ₁ -C ₉ alkyl (wherein any two vicinals (bonded to adjacent carbon) or geminal) (same carbon bond) alkyl group may form a hydrocarbon ring having up to 6 carbon atoms together), hydroxy, C ₁ -C ₉ alkoxy, C ₁ -C ₉ alkyleneoxy, amines and C ₁ -C ₉ alkylamine, halogen is independently selected from the group consisting of (fluorine, chlorine, bromine and iodine) and phenyl. ] The propylene-based resin composition according to claim 1 or 2, wherein the nucleating agent (A) is at least one amide-based compound represented by the following general formula (5).

[Wherein, 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, a trivalent or 4 carbon atoms having 5 to 15 carbon atoms. Represents a saturated 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. ] The propylene resin composition according to claim 1 or 2, wherein the nucleating agent (A) is at least one amide compound represented by the following formula (6).

[Wherein, 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. ] The propylene-based resin composition according to any one of claims 1 to 4, wherein the polyethylene has a density of 0.860 to 0.915 g / cm ³ .   The polyethylene is polymerized using a metallocene catalyst, and the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is less than 3.5. The propylene-based resin composition according to any one of the above.   The propylene-based resin composition according to any one of claims 1 to 6, further comprising 0.001 to 0.5 parts by weight of a lubricant based on 100 parts by weight of the polymer mixture.   The molded article formed by injection-molding the propylene-type resin composition of any one of Claims 1-7.   The molded article according to claim 8, wherein the molded article is a syringe, a medical instrument, or a medical container.   The molded article according to claim 9, which is a kit preparation.   The molded product according to claim 10, wherein the kit preparation is a prefilled syringe.