JP2009120803A - Propylene-based resin composition and its molded article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a propylene-based resin composition that satisfies standards of general tests in Japan Pharmacopoeia and has excellent heat resistance, rigidity, shock resistance, injection molding property, transparency and gas barrier property, and to provide a molded article of the composition. <P>SOLUTION: A medical propylene-based resin composition is disclosed, in which 0.01 to 0.6 part by weight of at least one kind of nucleating agent (A) expressed by general formula (1) is compounded into 100 parts by weight of a polymer mixture comprising (a) 60 to 99 parts by weight of an ethylene-propylene block copolymer and (b) 1 to 40 parts by weight of polyethylene. <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. 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. It is necessary to be maintained and the additive used does not interact with preservatives and chemicals. 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 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 the additive extraction resistance and pharmacopoeia test, and is not suitable for these applications. 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 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 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 been hitherto cited 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

  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. 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 studies to solve the above problems, the present inventors have found that a specific nucleating agent is added to a polymer mixture containing a specific amount of a specific ethylene-propylene block copolymer and a specific polyethylene. The propylene resin composition used in a specific amount can be a resin composition that is excellent in heat resistance, rigidity, impact resistance, injection moldability, transparency, gas barrier properties, and satisfies the standards of Japanese Pharmacopoeia test items. As a result, the present invention has been completed.

That is, according to the first invention of the present invention, (a) an ethylene-propylene block copolymer comprising a polypropylene segment and an ethylene / propylene copolymer segment, which has a melt flow at 230 ° C. and a load of 2.16 kg. Ethylene having a rate of 2 to 80 g / 10 min, a total ethylene content of 0.5 to 12% by weight, and an ethylene / propylene copolymer segment content in the ethylene-propylene block copolymer of 1 to 30% by weight -60 to 99 parts by weight of a propylene block copolymer, (b) polyethylene having a melt flow rate of 2 to 120 g / 10 min at 230 ° C and a load of 2.16 kg, and a density of 0.860 to 0.940 g / cm ^3. (C) represented by the following general formula (1) with respect to 100 parts by weight of a polymer mixture comprising 1 to 40 parts by weight A propylene-based resin composition characterized in that 0.01 to 0.6 parts by weight of the nucleating agent (A) to be produced is blended is provided.



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

Further, according to the second invention of the present invention, in the first invention, the nucleating agent (B) represented by the following general formula (2) is 0.005 to 0 with respect to 100 parts by weight of the propylene polymer. .3 parts by weight, the nucleating agent (C) represented by the following general formula (3) is 0.005 to 0.15 parts by weight, and the nucleating agent (D) represented by the following general formula (4) is 0.005. -0.15 parts by weight and at least one nucleating agent comprising 0.005 parts by weight or more and less than 0.3 parts by weight of the nucleating agent (E) represented by the following general formula (5) is blended. A medical propylene-based resin composition is provided.

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

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

[Wherein, M ₁ and M ₂ are the same or different and are at least one metal cation selected from calcium, strontium, lithium and monobasic aluminum, and R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ are the same or different and are hydrogen, C ₁ -C ₉ alkyl (wherein any two vicinals (bonded to adjacent carbon) or geminal) Alkyl groups (bonded to the same carbon) 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)
[Wherein, R ¹ represents a saturated or unsaturated aliphatic polycarboxylic acid residue having 2 to 30 carbon atoms, a saturated or unsaturated alicyclic polycarboxylic acid residue having 4 to 28 carbon atoms, or the number of carbon atoms. Represents 6-18 aromatic polycarboxylic acid residues. R ² represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, or a cycloalkyl group or cycloalkenyl group having 3 to 46 carbon atoms. a represents an integer of 2 to 6. ]

According to the third invention of the present invention, in the first or second invention, the nucleating agent (A) is a nucleating agent represented by the following general formula (6), and is represented by the general formula (5). A propylenic resin composition for medical use is provided in which the nucleating agent (E) to be produced is represented by the following general formula (7).

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

[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 fourth aspect of the present invention, in any one of the first to third aspects, 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 fifth invention of the present invention, in any one of the first to fourth inventions, the polyethylene is polymerized using a metallocene catalyst, and the weight average molecular weight (Mw) and the 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 sixth invention of the present invention, in any one of the first to fifth 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 seventh 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 sixth aspects.
According to an eighth aspect of the present invention, there is provided an injection molded product according to the seventh aspect, which is a medical molded product.
Furthermore, according to the ninth invention of the present invention, in the eighth invention, there is provided a molded product characterized by being a kit preparation.
Still further, according to a tenth aspect of the present invention, there is provided a molded product according to the ninth aspect, wherein the kit preparation is a prefilled syringe.

  The propylene-based resin composition of the present invention is obtained by blending a specific polyethylene with a specific ethylene-propylene block copolymer, whereby the morphology of the material is changed, and a polymer mixture having good impact resistance is obtained. It is a composition that contains a specific amount of a specific nucleating agent, improves rigidity and transparency in a well-balanced manner, and retains excellent heat resistance and gas barrier properties. 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 is an ethylene-propylene block copolymer comprising (a) a polypropylene segment and an ethylene / propylene copolymer segment, and has a melt flow rate of 2 at 230 ° C. and a load of 2.16 kg. ~ 80g / 10min, Stereoregularity of polypropylene segment is 0.960 or more, and total ethylene content is 0.5 ~ 12wt%, ethylene / propylene copolymer segment content in ethylene-propylene block copolymer 60 to 99 parts by weight of an ethylene-propylene block copolymer in which 1 to 30% by weight, (b) a melt flow rate of 2 to 120 g / 10 min at 230 ° C. and a load of 2.16 kg, and a density of 0.860 to Polymer mixing consisting of 1 to 40 parts by weight of polyethylene of 0.940 g / cm ³ (C) 0.01 to 0.6 parts by weight of the nucleating agent (A) represented by the general formula (1) is blended with 100 parts by weight of the product.
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 Ethylene-propylene block copolymer (a)
The (a) ethylene-propylene block copolymer (hereinafter sometimes referred to as block copolymer (a)) used in the propylene-based resin composition of the present invention may be referred to as a polypropylene segment (hereinafter referred to as homo part). ) And an ethylene / propylene copolymer segment, and a polyethylene segment may coexist if necessary. The polypropylene segment is crystalline and contributes to imparting mechanical strength such as rigidity to the block copolymer (a). The ethylene / propylene copolymer segment has rubber-like properties and forms a rubber portion in the block copolymer (a), thereby contributing to imparting impact resistance.
The polypropylene segment in the block copolymer (a) is preferably 70 to 99% by weight, more preferably 86 to 98% by weight, and the ethylene / propylene copolymer segment is 1 to 30% by weight. Preferably, it is 2 to 14% by weight. Within this range, it is suitable for improving various mechanical properties of the resin composition.

The melt flow rate (MFR) at 230 ° C. and 2.16 kg load of the block copolymer (a) is 2 to 80 g / 10 minutes, preferably 5 to 40 g / 10 minutes, more preferably 10 to 30 g / 10 minutes. is there. 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 obtained. When the MFR is less than 2 g / 10 min, molding becomes difficult, When it exceeds 80 g / 10 min, 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.

The stereoregularity of the homo part is preferably 90% or more, and more preferably 95% or more. If the stereoregularity is less than 90%, 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.

Furthermore, the total ethylene content in the block copolymer (a) is 0.5 to 12% by weight, preferably 2 to 9% by weight. Within this range, the resin composition is suitable for impact resistance. When the total ethylene content is less than 0.5% by weight, the impact resistance is insufficient, while when it exceeds 12% by weight, the rigidity becomes insufficient.
Here, the ethylene content is a value measured by the IR method.

  Such a block copolymer (a) is a so-called propylene homopolymerization in the presence of an olefin stereoregular polymerization catalyst, followed by a copolymerization of propylene and ethylene, and if necessary, a homopolymerization of ethylene. It can manufacture by employ | adopting a multistage polymerization method. Further, it can also be produced by mechanically melting and kneading a propylene homopolymer, a copolymer of propylene and ethylene, and if necessary, an ethylene homopolymer.

  The catalyst used for obtaining the block copolymer (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 or a metallocene catalyst (for example, described in JP-A-5-295022) in which a titanium compound and organoaluminum are combined can be used. In the present invention, since a propylene block copolymer having a good balance between rigidity and impact resistance is particularly preferable, a Ziegler-Natta catalyst having high stereoregularity is generally more preferable. Further, when the polyethylene (b) is a low density polyethylene produced using a metallocene catalyst, the block copolymer (a) produced using a metallocene catalyst is particularly compatible with the block copolymer (a). Is excellent in compatibility.

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.
Specifically, ethylene-propane copolymer, ethylene-1-butene copolymer, ethylene-1-pentene copolymer, ethylene-1-hexene copolymer, ethylene-4-methyl-1-pentene copolymer Examples thereof include a copolymer, an ethylene-3-methyl-1-pentene copolymer, an ethylene-1-heptene copolymer, an ethylene-1-octene copolymer, and an ethylene-1-decene copolymer.
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. The value of (weight average molecular weight) / (number average molecular weight) can be measured by general GPC.

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 was 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 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 230 ° C. is 2 to 120 g / 10 minutes, preferably 6 to 80 g / 10 minutes. Within this range, the block copolymer (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 2 g / 10 minutes or more than 120 g / 10 minutes, the dispersion into the block copolymer (a) is deteriorated and a stable composition cannot be obtained.
Here, MFR at 230 ° C. is a value measured at 230 ° C. under a 2.16 kg load in accordance with JIS K7210.

When polyethylene (b) is mixed with ethylene-propylene block copolymer (a), polyethylene (b) is taken into the ethylene / propylene copolymer segment part of ethylene-propylene block copolymer (a). The MFR of the ethylene / propylene copolymer segment can be changed. At that time, when the MFR difference with the homo part is small, the ethylene / propylene copolymer segment part tends to be dispersed as a matrix stretched with respect to the homo part. As the segment part becomes more stretched, the transparency tends to be better. Therefore, use a polyethylene (b) having a smaller MFR difference between the homo part and the ethylene / propylene copolymer segment part. It is desirable.
Specifically, the MFR / homo part MFR of the ethylene / propylene copolymer segment part after mixing the polyethylene (b) is preferably 0.1 to 2.2, more preferably 0.2 to 1.8. Preferably, 0.3 to 1.4 is particularly preferable.

The calculation of MFR (x) of the ethylene / propylene copolymer segment part after mixing the polyethylene (b) is when the ratio of the ethylene / propylene copolymer segment part after mixing the polyethylene (b) is 1. , The ratio of polyethylene (b) is Q, MFR of polyethylene (b) is y, the ratio of ethylene / propylene copolymer segment part is (1-Q), and the MFR of ethylene / propylene copolymer segment part is z. Then, (1−Q) logz + Qlogie = logx, which can be derived from this equation.
Similarly, the calculation of the MFR (x) of the polypropylene segment part after mixing the other propylene-based polymer is performed when the ratio of the polypropylene segment part after mixing the other propylene-based polymer is 1, When the ratio of the propylene polymer is Q, the MFR of the other propylene polymer is y, the ratio of the polypropylene segment part is (1-Q), and the MFR of the polypropylene segment part is z, (1-Q) logz + Qlogy = logx, which can be derived from this equation.

The density of polyethylene (b) is 0.860 to 0.940 g / cm ³ , preferably 0.860 to 0.925 g / cm ³ , and more preferably 0.860 to 0.915 g / cm 3. ³ . When the density is less than 0.860 g / cm ³ , the rigidity is insufficient, and when it exceeds 0.940 g / cm ³ , the transparency is deteriorated. Moreover, it is more excellent in transparency and impact resistance if polyethylene having a low density is added to the resin composition.
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, it can be produced by copolymerizing ethylene with an α-olefin such as propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, if necessary. In order to reduce (weight average molecular weight) / (number average molecular weight) and to reduce the density, it is desirable to use a metallocene catalyst as the olefin stereoregular polymerization catalyst to produce by a high pressure method or a solution method.

The polyethylene (b) used in the propylene-based resin composition of the present invention can be used singly or in combination of two or more without departing from the effects of the present 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. Blending ratio of ethylene-propylene block copolymer (a) and polyethylene (b) The blending ratio of ethylene-propylene block copolymer (a) and polyethylene (b) in the propylene resin composition of the present invention is ethylene- The propylene block copolymer (a) is 60 to 99 parts by weight, and the polyethylene (b) is 40 to 1 parts by weight. Preferably, the ethylene-propylene block copolymer (a) is 80 to 95 parts by weight, polyethylene ( b) is 20 to 5 parts by weight. Within this range, the resin composition has excellent impact resistance.
In addition to the ethylene-propylene block copolymer (a) and polyethylene (b), the polymer mixture used in the present invention includes a propylene homopolymer, or propylene, as long as the effects of the present invention are not impaired. Random or block copolymers with α-olefins 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 (A) used in the medical propylene-based resin composition of the present invention is a compound represented by the general formula (1), among which the compound represented by the general formula (6) is preferable. A compound represented by the chemical structural formula (8) is more preferable.

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

[N is an integer of 0 to 2, R ¹ , R ² , R ⁴ and R ⁵ are hydrogen atoms, and R ³ is a hydrogen atom or an alkyl group or alkenyl group having 1 to 20 carbon atoms. , An alkoxy group, a carbonyl group, a halogen group and a phenyl group, and R ⁶ is an alkyl group having 1 to 20 carbon atoms. ]

  A commercially available product can be used as such a nucleating agent. Specific examples include NX8000 manufactured by Milliken Corporation.

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

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

In the medical propylene resin composition of the present invention, at least one of the nucleating agents (B) to (E) represented by the general formulas (2) to (5) may be blended. desirable. Transparency, rigidity, moldability, etc. can be further improved by using nucleating agents (B) to (E) alone or in combination.
If a specific combination mode is clearly shown, with respect to 100 parts by weight of the polymer mixture,
(A) The nucleating agent (B) represented by the following general formula (2) is 0.005 to 0.005 to 0.1 parts by weight of the nucleating agent (A) represented by the general formula (1). Two-component nucleating agent used in combination with 0.3 parts by weight,
(B) The nucleating agent (C) represented by the following general formula (3) is 0.005 to 0.01 to 0.6 parts by weight of the nucleating agent (A) represented by the general formula (1). Two-component nucleating agent used in combination with 0.15 parts by weight,
(C) The nucleating agent (D) represented by the following general formula (4) is 0.005 to 0.01 to 0.6 parts by weight of the nucleating agent (A) represented by the general formula (1). The two-component nucleating agent used in combination with 0.15 parts by weight, and (d) the nucleating agent (A) represented by the general formula (1) has the following general formula ( There is a blending form of a two-component nucleating agent formed by using the nucleating agent (E) represented by 5) in a range of 0.005 parts by weight or more and less than 0.3 parts by weight. further,
(E) The nucleating agent (B) represented by the following general formula (2) is 0.005 with respect to 0.01 to 0.6 parts by weight of the nucleating agent (A) represented by the general formula (1). A so-called general formula (1) such as a three-component nucleating agent in which 0.003 to 0.1 parts by weight and a nucleating agent (C) represented by the following general formula (3) are combined with 0.005 to 0.15 parts by weight The nucleating agent represented by the following general formula (2) to the nucleating agent (B) to the general formula (5) with respect to 0.01 to 0.6 parts by weight of the nucleating agent (A) represented by There is a blending form of a three-component nucleating agent in which at least two kinds of nucleating agents comprising a predetermined amount of the agent (E) are arbitrarily selected and combined.

The nucleating agent (A) represented by the general formula (1) alone functions to improve transparency, rigidity and moldability by an excellent nucleating action, but the nucleating agent (A) On the other hand, in the case of a so-called two-component nucleating agent or a three-component nucleating agent using at least one or two types selected from the nucleating agent (B) to the nucleating agent (E). For example, the amount of the nucleating agent (A) alone or slightly higher than that contained in the range of 0.01 to 0.6 parts by weight of the nucleating agent (A) is compared with that of the nucleating agent (A) alone. In order to achieve a synergistic overall excellent nucleating agent effect, the heat resistance and crystallization temperature are improved, and advantageous functions in rigidity, transparency and heat resistance are exhibited.
Although it is difficult to specify this technical reason, in the case of a two-component nucleating agent, the scope of application that functions as a nucleating agent is relatively widened. The other nucleating agent may act supplementarily or additionally to add or synergistically nucleate. In the case of the present invention, an ethylene composed of (a) a polypropylene segment and an ethylene / propylene copolymer segment, which has slightly different monomers, polymer structure, melting point, properties, etc., and may have a microphase separation structure -Even if it is a two-component polymer mixture consisting of two types of resins or two types of resins containing various additives, that is, a polymer mixture consisting of a propylene block copolymer and (b) polyethylene. The combined nucleating agent is considered to be a nucleating agent having a function that can be applied to a wide range, that is, can function properly as a nucleating agent for any resin. In addition, a wide range of nucleation, such as injection molding, to mitigate differences in nucleation conditions that affect the properties of the molded product due to subtle differences in resin mixing conditions, molding temperature, and molding conditions Although it can be expected that it has an agent function, it is difficult to predict the technical reasons in a unified manner in the current state of the prior art of the present invention.

However, (a) an ethylene-propylene block copolymer comprising a polypropylene segment and an ethylene / propylene copolymer segment, and (b) a polymer mixture comprising a specific composite resin, such as a polymer mixture comprising polyethylene. In particular, the nucleating agent (A) and the nucleating agent (B) to the nucleating agent, as well as the nucleating agent (A) consisting of a specific compound, in particular, in terms of transparency, rigidity, impact resistance and moldability It is based on the knowledge of the present inventors that the composite component nucleating agent in which at least one of (E) is used in combination functions advantageously with respect to the specific polymer mixture.
Furthermore, the addition of the nucleating agent (A) or the composite component nucleating agent to the polymer mixture of the present invention can be sufficiently achieved by using a relatively small amount as described above. It is. The small amount of addition is not only the problem of lowering the price of the propylene-based resin composition material for medical use, but also some nucleating agents that are relatively safe for the human body, When used in medical molded articles such as syringes, medical instruments, and medical containers, there is a concern about the effects of elution, but the present invention can advantageously solve such problems.

  The propylene-based resin composition of the present invention is a medical liquid storage container, a medical instrument, a syringe, and other medical molded products that are peculiar use forms of medical materials. , Boiling sterilization, low-temperature sterilization, drug sterilization, autoclave sterilization, and in some cases, transparency, rigidity, impact resistance inherent to medical products even if left in an inert gas or under reduced pressure Since it has a property that can withstand use without losing characteristics such as the above, it has very advantageous characteristics for medical materials.

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

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

Specific examples of the organophosphate metal salt compound represented by the general formula (2) include sodium-2,2′-methylene-bis- (4,6-di-t-butylphenyl) phosphate, sodium-2. , 2'-ethylidene-bis- (4,6-di-t-butylphenyl) phosphate, sodium-2,2'-ethylidene-bis- (4-i-propyl-6-t-butylphenyl) phosphate Sodium-2,2′-butylidene-bis- (4,6-dimethylphenyl) phosphate, sodium-2,2′-butylidene-bis- (4,6-di-t-butylphenyl) phosphate, sodium -2,2'-t-octylmethylene-bis- (4,6-methylphenyl) phosphate, sodium-2,2'-t-octylmethylene-bis- (4,6-di-t-butyl) Tilphenyl) phosphate, sodium-2,2′-methylene-bis- (4-methyl-6-tert-butylphenyl) phosphate, sodium-2,2′-methylene-bis- (4-ethyl-6-t) -Butylphenyl) phosphate, sodium (4,4'-dimethyl-6,6'-di-t-butyl-2,2'-biphenyl) phosphate, sodium-2,2'-ethylidene-bis- (4 -S-butyl-6-tert-butylphenyl) phosphate, sodium-2,2'-methylene-bis- (4,6-di-methylphenyl) phosphate, sodium-2,2'-methylene-bis- Examples thereof include (4,6-di-ethylphenyl) phosphate and a mixture of two or more thereof. Of these, sodium-2,2′-methylene-bis- (4,6-di-t-butylphenyl) phosphate is particularly preferable.
A commercially available product can be used as such a nucleating agent. Specific examples include NA-11 manufactured by Asahi Denka Kogyo Co., Ltd.

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

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

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

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

It is effective to use the aromatic phosphates represented by the general formula (3) in combination with an organic alkali metal salt.
The organic alkali metal salt may be at least one organic alkali metal salt selected from the group consisting of alkali metal carboxylates, alkali metal β-diketonates and alkali metal β-ketoacetate salts.
Examples of the alkali metal constituting the organic alkali metal salt include lithium, sodium, and potassium.
Examples of the carboxylic acid constituting the alkali metal carboxylate include acetic acid, propionic acid, acrylic acid, octylic acid, isooctylic acid, nonanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, Ricinoleic acid, 12-hydroxystearic acid, behenic acid, montanic acid, melicic acid, β-dodecylmercaptoacetic acid, β-dodecylmercaptopropionic acid, β-N-laurylaminopropionic acid, β-N-methyl-lauroylaminopropionic acid Aliphatic monocarboxylic acids such as malonic acid, succinic acid, adipic acid, maleic acid, azelaic acid, sebacic acid, dodecanedioic acid, citric acid, butanetricarboxylic acid, butanetetracarboxylic acid and other polyvalent aliphatic carboxylic acids such as naphthene Acid, cyclopentanecarboxylic acid, 1-methyl Cyclopentanecarboxylic acid, 2-methylcyclopentanecarboxylic acid, cyclopentenecarboxylic acid, cyclohexanecarboxylic acid, 1-methylcyclohexanecarboxylic acid, 4-methylcyclohexanecarboxylic acid, 3,5-dimethylcyclohexanecarboxylic acid, 4-butylcyclohexanecarboxylic acid , Cyclooctenecyclohexanecarboxylic acid, cyclohexenecarboxylic acid, cycloaliphatic mono- or polycarboxylic acid such as 4-cyclohexene-1,2-dicarboxylic acid, benzoic acid, toluic acid, xylyl acid, ethylbenzoic acid, 4-t- Aromatic mono- or polycarboxylic acids such as 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 blending amount of the nucleating agent (C) selectively used in the medical propylene-based resin composition of the present invention is preferably in the range of 0.005 to 0.15 parts by weight with respect to 100 parts by weight of the propylene-based polymer. The range of 0.01 to 0.1 parts by weight is more preferable. If it is less than 0.005 parts by weight, the effect cannot be obtained, and if it exceeds 0.15 parts by weight, not only a further effect cannot be obtained but also economically not preferable.

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

[In Formula (4), M ₁ and M ₂ are the same or different and are at least one metal cation selected from calcium, strontium, lithium and monobasic aluminum, and R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ are the same or different and each represents hydrogen, C ₁ -C ₉ alkyl (wherein any two vicinal (bonded to adjacent carbons) ) Or geminal (bonded to the same carbon) alkyl group 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 blending amount of the nucleating agent (D) selectively used in the medical propylene resin composition of the present invention is preferably in the range of 0.005 to 0.15 parts by weight with respect to 100 parts by weight of the propylene polymer. The range of 0.01 to 0.1 parts by weight is more preferable. If it is less than 0.005 parts by weight, the effect cannot be obtained, and if it exceeds 0.15 parts by weight, the pharmacopoeia test may be rejected.

In the medical propylene-based resin composition of the present invention, the nucleating agent (E) used selectively is a nucleating agent represented by the general formula (5). A nucleating agent represented by the general formula (9) is preferable, and a nucleating agent represented by the general formula (10) is more preferable.
R ¹ (CONHR ² ) a (5)
[Wherein, R ¹ represents a saturated or unsaturated aliphatic polycarboxylic acid residue having 2 to 30 carbon atoms, a saturated or unsaturated alicyclic polycarboxylic acid residue having 4 to 28 carbon atoms, or the number of carbon atoms. Represents 6-18 aromatic polycarboxylic acid residues. R ² represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, or a cycloalkyl group or cycloalkenyl group having 3 to 46 carbon atoms. a represents an integer of 2 to 6. ]

[In the formula (9), R ¹ is a trivalent saturated aliphatic hydrocarbon group having 3 to 10 carbon atoms, a tetravalent saturated aliphatic hydrocarbon group having 4 to 10 carbon atoms, or 3 having 5 to 15 carbon atoms. Represents a trivalent or tetravalent saturated alicyclic hydrocarbon group, or a trivalent or tetravalent aromatic hydrocarbon group having 6 to 15 carbon atoms. R ² are the same or different and each represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms. a represents an integer of 3 or 4. ]

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

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

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

Among the amide compounds, R ² in the general formula (9) or (10) is a hydrogen atom or a linear or branched chain having 1 to 4 carbon atoms, particularly from the viewpoint of nucleating action (nucleating agent effect). Amide compounds that are alkyl groups are preferred.
Specifically, 1,2,3-propanetricarboxylic acid tricyclohexylamide, 1,2,3-propanetricarboxylic acid tri (2-methylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (3-methyl) Cyclohexylamide), 1,2,3-propanetricarboxylic acid tri (4-methylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (2-ethylcyclohexylamide) 1,2,3-propanetricarboxylic acid tri ( 3-ethylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (4-ethylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (2-n-propylcyclohexylamide), 1,2,3 -Propanetricarboxylic acid tri (3-n-propylcyclohexyla ), 1,2,3-propanetricarboxylic acid tri (4-n-propylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (2-iso-propylcyclohexylamide), 1,2,3-propane Tricarboxylic acid tri (3-iso-propylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (4-iso-propylcyclohexylamide),
1,2,3-propanetricarboxylic acid tri (2-n-butylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (3-n-butylcyclohexylamide) 1,2,3-propanetricarboxylic acid tri ( 4-n-butylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (2-iso-butylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (3-iso-butylcyclohexylamide), 1 , 2,3-propanetricarboxylic acid tri (4-iso-butylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (2-sec-butylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri ( 3-sec-butylcyclohexylamide) 1,2,3-propanetrica Boronic acid tri (4-sec-butylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (2-tert-butylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (3-tert-butylcyclohexyl) Amide), 1,2,3-propanetricarboxylic acid tri (4-tert-butylcyclohexylamide),

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

Among these preferable amide compounds, particularly from the viewpoint of balance of transparency and rigidity and easy availability of raw materials, amide compounds in which R ² in the general formula (9) or (10) is a hydrogen atom or a methyl group are particularly preferable. preferable. Specifically, 1,2,3-propanetricarboxylic acid tricyclohexylamide, 1,2,3-propanetricarboxylic acid tri (2-methylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (3-methyl) Cyclohexylamide), 1,2,3-propanetricarboxylic acid tri (4-methylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid tetracyclohexylamide, 1,2,3,4-butanetetracarboxylic acid Tetra (2-methylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid tetra (3-methylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid tetra (4-methylcyclohexylamide) Etc. are exemplified.

When emphasizing the effect of improving transparency, R ¹ in the general formula (5), (9) or (10) can be obtained by removing all carboxylic xyl groups from 1,2,3-propanetricarboxylic acid. Particularly preferred is an amide compound which is a residue obtained. Specifically, 1,2,3-propanetricarboxylic acid tricyclohexylamide, 1,2,3-propanetricarboxylic acid tri (2-methylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (3-methyl) Cyclohexylamide), 1,2,3-propanetricarboxylic acid tri (4-methylcyclohexylamide) and the like.

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

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

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

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

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

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

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

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

  As a method for adjusting the maximum particle size within the above range, a method using a known pulverizer in this field is generally used, and a known classifier can be used if necessary. Specifically, a fluidized bed 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).

  In addition to the nucleating agents (A) to (E), the medical propylene-based resin composition of the present invention includes, as other nucleating agents, sorbitol nucleating agents, organophosphate nucleating agents, and aromatics. Known nucleating agents such as phosphate esters and talc can be added within a range that does not significantly impair the effects of the present invention.

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, magnesium stearate, hydrotalcite (trade name: magnesium represented by the following general formula (11) of Kyowa Chemical Industry Co., Ltd.) Aluminum complex hydroxide salt), Mizukarak (lithium aluminum composite hydroxide salt represented by the following general formula (12)), 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 (11)
[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 (12)
[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 (11) and the following general formula (12), which have no discoloration by radiation treatment and have good NOx gas discoloration resistance, 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 (13).

  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 an ethylene-propylene block copolymer (a), polyethylene (b), a nucleating agent (necessary with a nucleating agent (A). Nucleating agent (B) to (E) at least one mixture) and, if necessary, other additives are added to a Henschel mixer, super mixer, ribbon blender, etc., and mixed, It can be obtained by melt-kneading in a temperature range of 190 to 260 ° C. with an ordinary single-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.
Among these, it is particularly 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 among kit preparations. 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 molded article of the present invention may be subjected to known sterilization treatments such as autoclave sterilization, radiation sterilization, EOG sterilization, and ultraviolet 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 of physical property values, evaluation method (1) MFR: Measured according to JIS K7120, 230 ° C. 2.16 kg load.
(2) Flexural modulus:
The measurement was performed at 23 ° C. in accordance with JIS K7203 “Bending test method of hard plastic”.
(3) 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 ).
(4) Haze value:
It measured based on JISK7105 using the sheet piece of thickness 1mm.
(5) 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.
(6) Crystallization temperature (peak value): Measured using a differential scanning calorimeter in accordance with “Method for measuring plastic transition temperature” of JIS K7121. The higher this temperature, the shorter the molding time in injection molding, and the higher the productivity.
(7) 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. On a 5 mm plate, a shape of 3 x 4 boxes of 25 mm x 20 mm x 20 mm with a thickness of 1 mm) is created, and the molded product obtained by this injection molding is visually observed to add a nucleating agent and other additives The presence or absence of scratches caused by depositing and adhering agents, reactants, etc. on the mold during molding was confirmed and evaluated in the following two stages.
Scratch present: Even if a large number of moldings are made, almost no fine scratches are generated.
No scratch: When a large number of moldings are made, fine scratches are generated on the molded product.
(8) 15th 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 them at 220 ° C. to obtain sheet pieces having a length of about 5 cm and a width of about 0.5 cm. After being cut into pieces, washed with water, and dried at room temperature. Put this in a hard glass container with an internal volume of about 300 ml, add exactly 200 ml of water, seal it with 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) ethylene-propylene block copolymer (a): ethylene content 4.8 wt%, ethylene / propylene copolymer segment 8 wt%, MFR (JIS K7210, 230 ° C., 2.16 kg load) ) 26 g / 10 min, MFR of ethylene / propylene copolymer segment (JIS K7210, 230 ° C., 2.16 kg load) 0.2 g / 10 min, MFR of polypropylene segment (JIS K7210, 230 ° C., 2.16 kg load) 40 g / 10 min, homo part stereoregularity 0.970 (Novatech BC03CQ manufactured by Nippon Polypro Co., Ltd.)
(A-2) Ethylene-propylene block copolymer (a): ethylene content 2.4 wt%, ethylene / propylene copolymer segment 4 wt%, MFR (JIS K7210, 230 ° C., 2.16 kg load) 10 g / 10 Min, MFR of ethylene / propylene copolymer segment (JIS K7210, 230 ° C., 2.16 kg load) 0.2 g / 10 min, MFR of polypropylene segment (JIS K7210, 230 ° C., 2.16 kg load) 12 g / 10 min Homo part stereoregularity 0.970
(A-2) is the above-mentioned BC03CQ blended with MA5Q at BC03CQ: MA5Q = 1: 1.
MA5Q is a propylene homopolymer: MFR (JIS K7210, 230 ° C., 2.16 kg load) 5 g / 10 minutes, stereoregularity 0.970 (Novatech MA5Q manufactured by Nippon Polypro Co., Ltd.).

(Production method of A-1):
(I) Production of solid catalyst component (a) 20 liters of dehydrated and deoxygenated n-heptane was introduced into a tank equipped with a stirrer with an internal volume of 50 liters purged with nitrogen, then 10 moles of magnesium chloride and 20 moles of tetrabutoxy titanium And then reacting at 95 ° C. for 2 hours, lowering the temperature to 40 ° C., introducing 12 liters of methylhydropolysiloxane (viscosity 20 centistokes), and further reacting for 3 hours. The solid component produced was removed and washed with n-heptane.
Subsequently, 5 liters of dehydrated and deoxygenated n-heptane was introduced into the tank using the tank equipped with a stirrer, and then 3 mol of the solid component synthesized above was introduced in terms of magnesium atom. Subsequently, 5 mol of silicon tetrachloride was mixed with 2.5 liters of n-heptane and introduced at 30 ° C. for 30 minutes. The temperature was raised to 70 ° C. and reacted for 3 hours. Then, the reaction solution was taken out, The resulting solid component was washed with n-heptane.
Subsequently, 2.5 liters of dehydrated and deoxygenated n-heptane was introduced into the tank using the tank with a stirrer, and 0.3 mol of phthalic acid chloride was mixed and introduced at 90 ° C. for 30 minutes. And reacted at 95 ° C. for 1 hour. After completion of the reaction, washing with n-heptane was performed. Next, 2 liters of titanium tetrachloride was added at room temperature, and the temperature was raised to 100 ° C., followed by reaction for 2 hours. After completion of the reaction, washing with n-heptane was performed. Further, 0.6 liters of silicon tetrachloride and 8 liters of n-heptane were introduced, reacted at 90 ° C. for 1 hour, and sufficiently washed with n-heptane to obtain a solid component. This solid component contained 1.30% by weight of titanium.
Next, 8 liters of n-heptane, 400 g of the solid component obtained above, 0.27 mol of t-butyl-methyl-dimethoxysilane and 0.27 mol of vinyltrimethylsilane were introduced into the tank equipped with a stirrer substituted with nitrogen. And contacted at 30 ° C. for 1 hour. Next, the mixture was cooled to 15 ° C., 1.5 mol of triethylaluminum diluted in n-heptane was introduced over 15 minutes under 15 ° C., and after the introduction, the temperature was raised to 30 ° C. and reacted for 2 hours. -Washing with heptane gave 390 g of solid catalyst component (a).
The obtained solid catalyst component (a) contained 1.22% by weight of titanium.
Further, 6 liters of n-heptane and 1 mol of triisobutylaluminum diluted in n-heptane were introduced over 30 minutes at 15 ° C., and then about 0.4 kg of propylene was controlled so as not to exceed 20 ° C. Per hour for 1 hour to conduct prepolymerization. As a result, a polypropylene-containing solid catalyst component (a) in which 0.9 g of propylene was polymerized per 1 g of solid was obtained.

(Ii) Production of propylene-ethylene block copolymer Polymerization was carried out using a continuous reaction apparatus formed by connecting two fluidized bed reactors having an internal volume of 230 liters.
First, in a first reactor, a polymerization temperature of 85 ° C., a propylene partial pressure of 22 kg / cm ² (absolute pressure), and hydrogen as a molecular weight control agent are continuously added so that the molar ratio of hydrogen / propylene is 0.013. At the same time, 5.25 g / hr of triethylaluminum was fed as the solid catalyst component (a) so that the polymer polymerization rate was 20 kg / hr. The powder polymerized in the first reactor (crystalline propylene polymer) was continuously withdrawn so that the amount of powder held in the reactor was 60 kg, and continuously transferred to the second reactor (preliminary polymerization step). ).
Propylene and ethylene were continuously supplied at a polymerization temperature of 80 ° C. and a pressure of 1.5 MPa so that the molar ratio of ethylene / propylene was 1.15, and hydrogen as a molecular weight control agent was further added. While continuously supplying a hydrogen / propylene molar ratio of 0.010, ethyl alcohol was supplied as an active hydrogen compound so that the molar ratio was 3.0 times that of triethylaluminum. The powder polymerized in the second reactor is continuously withdrawn into the vessel so that the amount of powder held in the reactor becomes 40 kg, and the reaction is stopped by supplying moisture-containing nitrogen gas. A polymer was obtained (second-stage polymerization step). The obtained propylene / ethylene block copolymer was defined as (A-1).

(A-4) Ethylene-propylene random copolymer: ethylene content 2.5 wt%, MFR (JIS K7210, 230 ° C., 2.16 kg load) 8 g / 10 min (Nippon Polypro Corp., Novatec MG3F)

(B-1) Metallocene low density polyethylene (b): Density (JIS K7112) 0.907 g / cm ³ , MFR (JIS K7210, 230 ° C., 2.16 kg load) 24 g / 10 min, (Mw / Mn) 2 .4. (Kernel KS571 manufactured by Japan Polytechnic Co., Ltd.)
(B-2) Metallocene low-density polyethylene (b): density (JIS K7112) 0.898 g / cm ³ , MFR (JIS K7210, 230 ° C., 2.16 kg load) 4.0 g / 10 min, (Mw / Mn ) 2.2. (Kernel KF262 manufactured by Nippon Polytech Co., Ltd.)
(B-3) Ziegler-Natta high density polyethylene: density (JIS K7112) 0.964 g / cm ³ , MFR (JIS K7210, 230 ° C., 2.16 kg load) 13.0 g / 10 min, (Mw / Mn) 4 .6. (Novatech HJ560, manufactured by Nippon Polytech Co., Ltd.)
(B-4) Ziegler-Natta low-density polyethylene (b): density (JIS K7112) 0.923 g / cm ³ , MFR (JIS K7210, 230 ° C., 2.16 kg load) 7.2 g / 10 minutes, (Mw / Mn) 6.6 (Nippon Polytech Co., Ltd. Novatec LC520)

(C-1) Mirad NX8000: (NX8000; manufactured by Milliken & Company): Nucleator (A) Equivalent: Chemical structural formula (8) below
(C-2) Organophosphate metal salt compound nucleating agent ADK STAB NA-11 (NA-11; manufactured by ADEKA Corporation): equivalent to nucleating agent (B) (C-3) Organophosphate metal salt compound Nucleating agent ADK STAB NA21 (NA-21; manufactured by ADEKA Corporation): equivalent to nucleating agent (C) (C-4) Hyperform HPN68L (HPN68L; manufactured by Milliken & Company): nucleating agent Corresponding to (D) (C-5) 1,2,3-propanetricarboxylic acid tris (2-methylcyclohexylamide): equivalent to nucleating agent (E) (C-6) sorbitol nucleating agent Gerol MD (new Nippon Rika Co., Ltd.): Nucleating agent not corresponding to any of nucleating agents (A) to (E)

(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 1-8, 10 and Comparative Examples 1-7)
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. 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 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.
Example 9
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. Extruded pellets from the die at a die outlet temperature of 230 ° C. The obtained pellets were injection molded with an injection molding machine at a resin temperature of 200 ° C., an injection pressure of 900 kg / cm ² and a mold temperature of 40 ° C. to prepare test pieces. The physical properties were measured using the obtained test pieces.

The evaluation results are shown in Table 1.

As is apparent from Table 1, Examples 1 to 4 are those using the propylene-based resin composition of the present invention, which is extremely excellent in impact resistance and also in transparency, rigidity, and heat resistance. Excellent, conforms to the Japanese Pharmacopoeia test, and gives excellent molded products.
When the 1 mm injection molded product for haze measurement of Example 4 was autoclaved at 121 ° C. for 30 minutes, the haze was 20 before sterilization, but deteriorated to about 52. However, within this range, it can be used. In addition, each test piece of Example 4 was irradiated with γ-rays of 25KGY and the physical properties were measured one month later. As a result, the haze with a thickness of 1 mm was 20, the flexural modulus was 1130 MPa, and the IZOD impact strength was 41 KJ / m ² . Excellent balance of physical properties is maintained even after radiation sterilization.
In Example 5, silicone is blended. With this blending amount, the releasability can be greatly improved while conforming to the Japanese Pharmacopoeia test.
In addition, Examples 6 to 9 are a combination of the nucleating agent (A) and the nucleating agents (B) to (E), and are more resistant to heat than the case of using only the nucleating agent (A). It improves the crystallization temperature and is compatible with the Japanese Pharmacopoeia test.
Furthermore, although it uses the low density polyethylene (B-4) manufactured using the Ziegler-Natta catalyst and is slightly inferior to Example 5 using the metallocene low density polyethylene, It can be seen that it excels in properties and conforms to the Japanese Pharmacopoeia test, resulting in excellent molded products.

On the other hand, since Comparative Example 1 does not use the polyethylene (b) used in the present invention, it is extremely inferior in transparency, and is not very usable for applications such as prefilled syringe outer cylinders that require transparency. I understand that.
Further, Comparative Example 2 uses polyethylene other than the polyethylene used in the present invention, and is inferior in transparency like Comparative Example 1, and it can be seen that it is not very usable for applications such as prefilled syringe outer cylinders. .
Further, in Comparative Example 3, the nucleating agent (B) is used instead of the nucleating agent (A), and, as compared with Examples 3 and 4, it is inferior in transparency as apparent.
Comparative Example 4 is a blend of polyethylene (b) and nucleating agent (A) used in the present invention in an ethylene-propylene random copolymer that has been conventionally used for molded products that require transparency. Compared with the propylene-based resin composition of the present invention, although it is excellent in transparency, it is inferior in heat resistance and is likely to cause deformation of the container during high-pressure steam sterilization.
In Comparative Example 5, the nucleating agent (A) used in the present invention was added beyond the range of the present invention, and although it was excellent in transparency, it was not compatible with the Japanese Pharmacopoeia test and was used for prefilled syringe outer cylinders, etc. Cannot be used for
In Comparative Example 6, the nucleating agent (A) used in the present invention was supplemented with a highly transparent nucleating agent Gelol MD, and although heat resistance was improved, it could not be adapted to the Japanese Pharmacopoeia test and prefilled It cannot be used for applications such as syringe outer cylinders.
In Comparative Example 7, polyethylene (b) used in the present invention is added beyond the range of the present invention, and although the transparency is excellent, the heat resistance is remarkably inferior and the container may be deformed during high-pressure steam sterilization. Is expensive.

  The propylene-based resin composition of the present invention has good rigidity, impact resistance, and transparency, and passes the 15th revised Japanese Pharmacopoeia general test, and is found to be very useful for obtaining an excellent molded product. In particular, in the case of high-pressure steam sterilization treatment, 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. Above all, it is suitable for syringes and containers filled with a drug solution, specifically, prefilled syringes and kit preparations.

Claims (10)

(A) An ethylene-propylene block copolymer comprising a polypropylene segment and an ethylene / propylene copolymer segment, having a melt flow rate of 2 to 80 g / 10 min at 230 ° C. and a load of 2.16 kg, and containing all ethylene 60-99 parts by weight of an ethylene-propylene block copolymer having an amount of 0.5-12% by weight and an ethylene / propylene copolymer segment content in the ethylene-propylene block copolymer of 1-30% by weight; (B) A polymer mixture consisting of 1 to 40 parts by weight of polyethylene having a melt flow rate of 2 to 120 g / 10 min at 230 ° C. and a load of 2.16 kg and a density of 0.860 to 0.940 g / cm ^3. (C) 0.01 to 0.6 weight of the nucleating agent (A) represented by the following general formula (1) A propylene-based resin composition for medical use, characterized in that it is blended in an amount.

[Wherein n is an integer of 0 to 2 and R ^{1 to} R ⁵ are the same or different and each is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an alkenyl group, an alkoxy group, a carbonyl group, a halogen atom. Group and a phenyl group, and R ⁶ is an alkyl group having 1 to 20 carbon atoms. ] The nucleating agent (B) represented by the following general formula (2) is 0.005 to 0.3 parts by weight based on 100 parts by weight of the polymer mixture, and the nucleating agent represented by the following general formula (3) ( C) is 0.005 to 0.15 parts by weight, nucleating agent (D) represented by the following general formula (4) is 0.005 to 0.15 parts by weight, and nucleating represented by the following general formula (5) 2. The medical propylene-based resin according to claim 1, wherein at least one nucleating agent comprising 0.005 parts by weight or more and less than 0.3 parts by weight of the agent (E) is blended. Composition.
[Wherein, R ¹ is a direct bond, sulfur, an alkylene group having 1 to 9 carbon atoms or an alkylidene group, and R ² and R ³ are the same or different and each represents a hydrogen atom or an alkyl having 1 to 8 carbon atoms. A group, M is Na, and n is the valence of M. ]

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

[However, n is an integer of 0 to 2, R ¹ , R ² , R ⁴ and R ⁵ are hydrogen atoms, R ³ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, alkenyl A group, an alkoxy group, a carbonyl group, a halogen group, and a phenyl group, and R ⁶ is an alkyl group having 1 to 20 carbon atoms. ] The propylene-based resin composition according to any one of claims 1 to ³ , 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 medical use according to any one of claims 1 to 5, wherein the lubricant is blended in an amount of 0.001 to 0.5 parts by weight with respect to 100 parts by weight of the propylene polymer. Propylene-based resin composition.   The molded article formed by injection-molding the propylene-type resin composition of any one of Claims 1-6.   The medical molded article using the propylene-type resin composition of any one of Claims 1-6.   A kit preparation, wherein the medical molded article according to claim 8 is a kit preparation.   The prefilled syringe, wherein the kit preparation according to claim 9 is a prefilled syringe.