JP2008150571A - Injection molded article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an injection molded article which satisfies all the testing requirements of a polyethylene-made or polypropylene-made aqueous injection container in plastic-made medicine container test method 1 in general test 45 listed in the 14<SP>th</SP>reversion Pharmacopoeia of Japan, and holds excellent heat resistance, rigidity, injection moldability, and transparency. <P>SOLUTION: This injection molded article is characterized by injection-molding a resin composition comprising 100 pts.wt. of a propylenic polymer having a melt flow rate of 0.5 to 100 g/10 min in accordance with JIS K7210 (230°C, 2.16 kg load), 0.005 to 0.3 pt.wt. of a nucleating agent (A) represented by general formula (1): R<SP>1</SP>(CONHR<SP>2</SP>)<SB>a</SB>, and furthermore another specific nucleating agent. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an injection molded product, and more particularly to an injection molded product having excellent heat resistance, rigidity, moldability, and transparency.

Propylene polymers are used in various food containers, caps, medical equipment, physics and chemistry laboratory equipment, automobile parts, and electrical parts, taking advantage of their excellent safety and hygiene, molding processability, mechanical properties, and gas barrier properties. Has been. In particular, in recent years, the use of ampoules and vials as alternative container materials has been increasingly seen as storage containers for drugs and chemicals 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 storage containers maintain heat resistance, devitrification resistance, additive extraction resistance, gas barrier properties of water vapor and oxygen during steam sterilization, and additives used interact with preservatives and chemicals. In particular, the 14th revised Japanese Pharmacopoeia General Examination 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 preferably a propylene homopolymer in terms of rigidity, heat resistance and gas barrier properties, and a random copolymer with ethylene in terms of transparency and impact resistance, and is appropriately selected according to the situation. However, when used in storage containers, it is difficult to exhibit sufficient performance in terms of transparency and rigidity with only propylene-based polymers, so various nucleating agents and neutralizing agents are used. In combination, attempts have been made to optimize key performance.

However, for example, when a sorbitol-based transparent nucleating agent is used, it does not satisfy additive extraction resistance and pharmacopoeia testing and is not suitable for these applications. In the case of adding, transparency was not sufficiently exhibited, 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 prefilled syringe filled with this chemical solution in advance with polypropylene began to be studied (for example, see Patent Document 2). Studies have been conducted on a preparation (for example, see Patent Document 3) in which a drug solution is filled in a transparent syringe barrel or a transparent container made of a nucleating agent.
However, the present situation is that a molded product having high transparency, passing a pharmacopoeia test, and having satisfactory heat resistance and rigidity as a storage container for drugs and chemicals has not been obtained.
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. An object of the present invention is to provide an injection molded product that satisfies the test items of a polyethylene or polypropylene aqueous injection container and that retains excellent heat resistance, rigidity, injection moldability, and transparency.

  As a result of intensive studies to solve the above problems, the present inventors have obtained an injection molded product that satisfies the test items of the Japanese Pharmacopoeia by using a specific nucleating agent combination for the propylene polymer. The present invention has been completed.

That is, according to 1st invention of this invention, with respect to 100 weight part of propylene-type polymers whose melt flow rate based on JISK7210 (230 degreeC, 2.16kg load) is 0.5-100g / 10min. The nucleating agent (A) represented by the general formula (1) is blended in an amount of 0.005 parts by weight or more and less than 0.3 parts by weight. 005 to 0.3 parts by weight, 0.005 to 0.15 parts by weight of nucleating agent (C) represented by general formula (3), or 0 to nucleating agent (D) represented by general formula (4) There is provided an injection-molded article obtained by using a resin composition containing 0.005 to 0.15 parts by weight of at least one nucleating agent and injection-molding the resin composition.
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. ]

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

[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。］

[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- . ]

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

[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. ]

  According to the second invention of the present invention, in the first invention, the nucleating agent (A) is at least one amide compound represented by the following general formula (5), injection molding Goods are 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。］

[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 third aspect of the present invention, in the first aspect, the nucleating agent (A) is at least one amide-based compound represented by the following general formula (6). Goods are 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 the fourth invention of the present invention, in any one of the first to third inventions, the resin composition comprises 0.001 to 0.5 parts by weight of a lubricant with respect to 100 parts by weight of the propylene polymer. An injection-molded article characterized by being blended is provided.

  According to a fifth invention of the present invention, in any one of the first to fourth inventions, the propylene polymer is a propylene homopolymer having an isotactic pentad fraction of 0.90 or more, or An injection-molded article is provided which is a propylene-based copolymer of propylene and another α-olefin.

  According to a sixth aspect of the present invention, there is provided an injection molded product according to any one of the first to fifth aspects, wherein the injection molded product is a medical propylene molded product.

  The injection-molded product of the present invention is a 14th revision Japanese Pharmacopoeia general test with strict acceptance criteria. Test method for plastic drug containers 1. It is a molded article that satisfies the test items of a polyethylene or polypropylene aqueous injection container and is excellent in heat resistance, rigidity, injection moldability, and transparency.

  The present invention is represented by the general formula (1) with respect to 100 parts by weight of a propylene polymer having a melt flow rate of 0.5 to 100 g / 10 min in accordance with JIS K7210 (230 ° C., 2.16 kg load). The nucleating agent (A) is blended in an amount of 0.005 parts by weight or more and less than 0.3 parts by weight, and the nucleating agent (B) represented by the general formula (2) is further added in an amount of 0.005 to 0.3 parts by weight. 0.005 to 0.15 parts by weight of the nucleating agent (C) represented by the formula (3), or 0.005 to 0.15 of the nucleating agent (D) represented by the general formula (4). This is an injection molded product obtained by injection molding a resin composition containing at least one nucleating agent composed of parts by weight. Hereinafter, the constituent components, the method for producing the composition, the molded body, and the like will be described in detail.

[1] Component of resin composition Propylene Polymer The propylene polymer used in the propylene resin composition of the present invention may be a propylene homopolymer, a propylene copolymer, or a mixture thereof.
The propylene-based copolymer is a copolymer of propylene and α-olefin, which may be a random copolymer or a block copolymer, but is a random copolymer from the viewpoint of transparency. Is desirable. Examples of the α-olefin used for copolymerization include α-olefins having 2 to 20 carbon atoms excluding propylene, and examples thereof include ethylene, butene-1, hexene-1, and octene-1. One or more α-olefins copolymerized with propylene may be used. Of these, ethylene and butene-1 are preferred. More preferably, ethylene is suitable. These propylene polymers may be used as a mixture of two or more.

In medical applications, sterilization is generally performed, and specific examples include high-pressure steam sterilization, radiation sterilization, sterilization with ethylene oxide gas, and ultraviolet sterilization. For example, when high-pressure steam sterilization is performed at 121 ° C. for 20 minutes, a propylene homopolymer, a block copolymer, or a random copolymer having an ethylene content of less than 1% is preferable. When a random copolymer having a high ethylene content is used, there is a problem that it is deformed during high-pressure steam sterilization.
Moreover, when performing a radiation sterilization process, a random copolymer with much ethylene content is preferable, and when a propylene homopolymer or a block copolymer is used, the physical property fall after a radiation sterilization process is remarkably unpreferable. In addition, a composition obtained by adding a peroxide as a molecular weight modifier to a random copolymer having a high ethylene content has even better impact resistance before and after irradiation.

The content of α-olefin used for copolymerization is preferably 15% by weight or less. If the content of α-olefin exceeds 15% by weight, the rigidity becomes low and it may not be suitable as a container or the like.
Here, propylene and α-olefin are values measured by ¹³ C-NMR method under the following conditions.
Apparatus: JEOL-GSX270 manufactured by JEOL Ltd.
Concentration: 300 mg / 2 mL
Solvent: Orthodichlorobenzene

The propylene homopolymer used in the present invention preferably has an isotactic pentad fraction of 0.90 or more, more preferably 0.94 to 0.98. If the isotactic pentad fraction is less than 0.90, the rigidity and barrier properties may not be satisfactory.
Here, the isotactic pentad fraction is a value measured by a proton decoupling method using ¹³ C-NMR.

  The propylene polymer used in the present invention has a melt flow rate in accordance with JIS K7120 (230 ° C., 2.16 kg load) in the range of 0.5 to 100 g / 10 min, and 1 to 50 g / 10 min. Is preferable, and 2 to 30 g / 10 min is more preferable. When the melt flow rate is less than 0.5 g / 10 min, there is a risk that molding processability is lowered and it is difficult to obtain a satisfactory product. Moreover, when it exceeds 100 g / 10 minutes, there exists a concern about the fall of mechanical strength.

  Although it does not specifically limit as a manufacturing method of a propylene polymer, The polymerization method using a stereoregular catalyst is preferable. Examples of stereoregular catalysts include Ziegler catalysts and metallocene catalysts.

  As Ziegler catalysts, transition metal components such as titanium trichloride, titanium tetrachloride, trichloroethoxytitanium, etc., contact materials of the above-mentioned titanium halide compounds and magnesium compounds represented by magnesium halide, and alkylaluminum Compounds or their two-component catalysts with organic metal components such as halides, hydrides, alkoxides, and further, electron-donating compounds containing nitrogen, carbon, phosphorus, sulfur, oxygen, silicon, etc. are added to these components 3 Component-based catalysts can be mentioned.

  The metallocene catalyst includes (i) a transition metal compound belonging to Group 4 of the periodic table (so-called metallocene compound) containing a ligand having a cyclopentadienyl skeleton, and (ii) a stable ionic state by reacting with the metallocene compound. A catalyst comprising an activatable cocatalyst and, if necessary, (iii) an organoaluminum compound, any known catalyst can be used. The metallocene compound is preferably a bridged metallocene compound capable of stereoregular polymerization of propylene, and more preferably a bridged metallocene compound capable of isoregular polymerization of propylene.

  (I) Examples of the metallocene compound include, for example, JP-A-2-131488, JP-A-2-76887, JP-A-3-163088, JP-A-4-300787, JP-A-4-21694, JP-A-5-43616, JP-A-5-209913, JP-A-6 No. 239914, JP-A-7-504934, and JP-A-8-85708.

More specifically, methylene bis (2-methylindenyl) zirconium dichloride, ethylenebis (2-methylindenyl) zirconium dichloride, ethylene 1,2- (4-phenylindenyl) (2-methyl-4-phenyl) -4H-azulenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride, isopropylidene (4-methylcyclopentadienyl) (3-t-butylindenyl) zirconium dichloride, dimethylsilylene (2- Methyl-4-t-butyl-cyclopentadienyl) (3′-t-butyl-5′-methyl-cyclopentadienyl) zirconium dichloride, dimethylsilylenebis (indenyl) zirconium dichloride, dimethylsilylenebis (4,5 , , 7-tetrahydroindenyl) zirconium dichloride, dimethylsilylenebis [1- (2-methyl-4-phenylindenyl)] zirconium dichloride, dimethylsilylenebis [1- (2-ethyl-4-phenylindenyl)] zirconium Dichloride, dimethylsilylenebis [4- (1-phenyl-3-methylindenyl)] zirconium dichloride, dimethylsilylene (fluorenyl) t-butylamidozirconium dichloride, methylphenylsilylenebis [1- (2-methyl-4, ( 1-naphthyl) -indenyl)] zirconium dichloride, dimethylsilylenebis [1- (2-methyl-4,5-benzoindenyl)] zirconium dichloride, dimethylsilylenebis [1- (2-methyl-4-phenyl-4H) -Azulenyl) ] Zirconium dichloride, dimethylsilylenebis [1- (2-ethyl-4- (4-chlorophenyl) -4H-azurenyl)] zirconium dichloride, dimethylsilylenebis [1- (2-ethyl-4-naphthyl-4H-azurenyl)] Zirconium dichloride, diphenylsilylene bis [1- (2-methyl-4- (4-chlorophenyl) -4H-azulenyl)] zirconium dichloride, dimethylsilylene bis [1- (2-ethyl-4- (3-fluorobiphenylyl) ) -4H-azurenyl)] zirconium dichloride, dimethylgermylenebis [1- (2-ethyl-4- (4-chlorophenyl) -4H-azurenyl)] zirconium dichloride, dimethylgermylenebis [1- (2-ethyl-) 4-phenylindenyl)] zirconium Zirconium compounds such as chloride can be exemplified. In the above, compounds in which zirconium is replaced with titanium or hafnium can be used in the same manner. In some cases, a mixture of a zirconium compound and a hafnium compound can be used. Further, the chloride can be replaced with other halogen compounds, hydrocarbon groups such as methyl, isobutyl and benzyl, amide groups such as dimethylamide and diethylamide, alkoxide groups such as methoxy group and phenoxy group, hydride groups and the like.
Among these, a metallocene compound in which an indenyl group or an azulenyl group is crosslinked with silicon or a germyl group is preferable.

The metallocene compound may be used by being supported on an inorganic or organic compound carrier. The carrier is preferably an inorganic or organic porous compound. Specifically, ion-exchange layered silicate, zeolite, SiO ₂ , Al ₂ O ₃ , silica alumina, MgO, ZrO ₂ , TiO ₂ , B Examples include inorganic compounds such as ₂ O ₃ , CaO, ZnO, BaO, and ThO ₂ , organic compounds composed of porous polyolefin, styrene / divinylbenzene copolymer, olefin / acrylic acid copolymer, and the like, or a mixture thereof. It is done.

  (Ii) As a co-catalyst that can be activated to a stable ionic state by reacting with a metallocene compound, an organoaluminum oxy compound (for example, an aluminoxane compound), an ion-exchange layered silicate, a Lewis acid, a boron-containing compound, an ionic compound And fluorine-containing organic compounds.

  (Iii) Examples of the organoaluminum compound include trialkylaluminum such as triethylaluminum, triisopropylaluminum, triisobutylaluminum, dialkylaluminum halide, alkylaluminum sesquihalide, alkylaluminum dihalide, alkylaluminum hydride, organoaluminum alkoxide. Can be mentioned.

Propylene-based polymers can be produced by a slurry method using an inert solvent, a solution method, a gas phase method substantially using no solvent, or a bulk polymerization using a polymerization monomer as a solvent in the presence of the above catalyst. Legal etc. are mentioned.
For example, in the case of the slurry polymerization method, it can be carried out in an inert hydrocarbon or liquid monomer such as n-butane, isobutane, n-pentane, isopentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene and the like. . The polymerization temperature is usually −80 to 150 ° C., preferably 40 to 120 ° C. The polymerization pressure is preferably 1 to 60 atmospheres, and the molecular weight of the resulting propylene polymer can be adjusted with hydrogen or other known molecular weight regulators. The polymerization is carried out by a continuous or batch reaction, and the conditions may be those usually used. Furthermore, the polymerization reaction may be performed in one stage or in multiple stages.

2. Nucleating agent The nucleating agent used in the injection-molded article of the present invention includes the nucleating agent (A) represented by the general formula (1) and the nucleating agent (B) represented by the general formulas (2) to (4). ~ (D) is blended with at least one nucleating agent.

  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-propa 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 Tricarboxylic 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 (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.

When emphasizing the effect of improving transparency, R ¹ in the general formula (1), (5) or (6) can be obtained by removing all carboxyxyl groups from 1,2,3-propanetricarboxylic acid. Particularly preferred is an amide compound which is a residue obtained. Specifically, 1,2,3-propanetricarboxylic acid tricyclohexylamide, 1,2,3-propanetricarboxylic acid tri (2-methylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (3-methyl) Cyclohexylamide), 1,2,3-propanetricarboxylic acid tri (4-methylcyclohexylamide) and the like.

  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.

  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 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 (A) used in the present invention is not particularly limited as long as the effect of the present invention is obtained, but from the viewpoint of the dissolution rate (or dissolution time) for the molten propylene polymer, the particle size is as much as possible. Are preferred. 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 type counter jet mill 100AFG (trade name, manufactured by Hosokawa Micron Corporation), a supersonic jet mill PJM-200 (trade name, manufactured by Nippon Pneumatic Co., Ltd.), a pin mill, etc. And dry classifiers (such as cyclones and micron separators).

  The 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 blending amount of the nucleating agent (A) used in the injection molded product of the present invention is 0.005 parts by weight or more and less than 0.3 parts by weight with respect to 100 parts by weight of the propylene polymer. When the amount is less than 0.005 part by weight, it is difficult to obtain a sufficient effect. When 0.3 part by weight or more is used, further performance improvement cannot be expected, and it is not economical. It is rejected in the item of potassium reducing substance. 0.01-0.25 weight part is preferable and 0.02-0.2 weight part is further more preferable.

  In the injection-molded article of the present invention, at least one of the nucleating agents (B) to (D) represented by the general formulas (2) to (4) is blended. Transparency, rigidity, moldability, etc. can be further improved by using nucleating agents (B) to (D) alone or in combination.

  In the injection-molded article of the present invention, the nucleating agent (B) used selectively 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 blending amount of the nucleating agent (B) selectively used in the injection-molded article 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, 0.01 The range of -0.2 weight part 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 injection-molded article of the present invention, the nucleating agent (C) used selectively is an aromatic phosphate ester 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、水素原子又は炭素数１〜１２のアルキル基を示し、Ｍは、周期律表第ＩＩＩ族または第ＩＶ族の金属原子を示し、Ｘは、Ｍが周期律表第ＩＩＩ族の金属原子を示す場合には、ＨＯ−を示し、Ｍが周期律表第ＩＶ族の金属原子を示す場合には、Ｏ＝又は（ＨＯ）_２−を示す。］

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

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

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

  Examples of the β-diketone compound constituting the alkali metal β-diketonate include acetylacetone, pivaloylacetone, palmitoylacetone, benzoylacetone, pivaloylbenzoylacetone, 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 injection-molded article 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, 0.01 The range of -0.1 weight part 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 injection-molded article of the present invention, the nucleating agent (D) that is selectively used 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、リチウムおよび一塩基性アルミニウムから選択される少なくとも１種の金属カチオンであり、Ｒ_１、Ｒ_２、Ｒ_３、Ｒ_４、Ｒ_５、Ｒ_６、Ｒ_７、Ｒ_８、Ｒ_９およびＲ_１０は、同一または異なって、水素、Ｃ_１−Ｃ_９アルキル（ここで、いずれか２つのビシナル（隣接炭素に結合）またはジェミナル（同一炭素に結合）アルキル基は、一緒になって６個までの炭素原子を有する炭化水素環を形成してもよい）、ヒドロキシ、Ｃ_１−Ｃ_９アルコキシ、Ｃ_１−Ｃ_９アルキレンオキシ、アミンおよびＣ_１−Ｃ_９アルキルアミン、ハロゲン（フッ素、塩素、臭素および沃素）並びにフェニルからなる群からそれぞれ選択される。］
ここで、「一塩基性アルミニウム」なる用語は周知であり、２つのカルボン酸基が結合した単一カチオンとしてアルミニウムヒドロキシド基を含むことを意図している。さらに、これら可能な塩のそれぞれにおいて、非対称炭素原子の立体配置は、シスまたはトランスのいずれでもよいが、シスが好ましい。

[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 injection-molded article 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, 0.01 The range of -0.1 weight part 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 addition to the nucleating agents (A) to (D), the injection molded product of the present invention includes, as other nucleating agents, a sorbitol nucleating agent, an organic phosphate nucleating agent, and aromatic phosphate esters, A known nucleating agent such as talc can be added within a range that does not significantly impair the effects of the present invention.

3. Neutralizing agent In the injection-molded article of the present invention, it is desirable to add a neutralizing agent. 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 (7) of Kyowa Chemical Industry Co., Ltd.) Aluminum complex hydroxide salt), Mizukarak (lithium aluminum composite hydroxide salt represented by the following general formula (8)), 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 (7)
[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 (8)
[Wherein, X is an inorganic or organic anion, n is the valence of the anion (X), and m is 3 or less. ]

  The blending amount of the neutralizing agent selectively used in the injection molded product of the present invention is preferably in the range of 0.005 to 0.2 parts by weight with respect to 100 parts by weight of the propylene polymer. A range of 05 parts by weight is more preferred.

4). Lubricant In the injection molded product 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 selectively used in the injection molded product of the present invention is preferably 0.001 to 0.5 parts by weight, and 0.01 to 0.15 parts by weight with respect to 100 parts by weight of the propylene polymer. More preferred is 0.03 to 0.1 parts by weight. If the amount is less than 0.001 part by weight, the effect cannot be expected. If the amount exceeds 0.5 part by weight, not only a further effect cannot be expected, but also economically undesirable.

5. Other Additives In the injection molded product of the present invention, in addition to the components described above, additives such as various antioxidants, ultraviolet absorbers, light stabilizers and the like used as stabilizers for propylene polymers are added. 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 (9) and the following general formula (10), which have no 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 (11).

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

[2] Propylene resin composition production method The propylene resin composition used in the present invention comprises a propylene polymer and a nucleating agent (at least one of a nucleating agent (A) and a nucleating agent (B) to (D)). 1 type of mixture) and, if necessary, other additives added to a Henschel mixer, a super mixer, a ribbon blender or the like and mixed, and then a normal single screw extruder, twin screw extruder, Banbury mixer, It can be obtained by melt-kneading in a temperature range of 190 to 260 ° C. with a plastic bender, roll or the like.

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

Examples of the injection-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, SP / packaging, P vials, eye drop containers, chemical liquid containers, liquid long-term storage containers, caps and the like can be mentioned.
The injection-molded product may be subjected to known sterilization processes such as autoclave sterilization, radiation sterilization, and EOG sterilization.

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

1. Test Method (1) Ethylene Concentration: The ethylene content in the random copolymer was measured by infrared spectroscopy using a characteristic absorber of 733 cm ⁻¹ using an ethylene / propylene random copolymer whose composition was verified by ¹³ C-NMR as a reference substance. . The pellets were formed into a film having a thickness of about 500 microns by press molding.
(2) MFR: Measured according to JIS K7120, 230 ° C. 2.16 kg load.
(3) Haze value: Measured according to JIS K7105 using a sheet piece having a thickness of 2 mm.
(4) 14th revision Japanese Pharmacopoeia general trial: 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.
(5) Flexural modulus: Measured at 23 ° C. in accordance with JIS K7203 “Bending test method of hard plastic”.
(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: The molded product obtained by injection molding is visually observed, and the nucleating agent and other additives are deposited and adhered to the mold during molding, and the presence or absence of scratches on the molded product, and the target Based on whether or not the dimensional accuracy can be maintained, it was evaluated in the following three stages.
A: A molded product having almost no fine scratches and good dimensional accuracy can be obtained.
○: Although there are some fine scratches, a molded product with good dimensional accuracy can be obtained.
×: Molded product with many scratches or poor dimensional accuracy.
(8) Deflection temperature under load (thermal deformation temperature): Measured according to JIS K7207. The higher the temperature, the better the molded product obtained.

2. Materials used (1) Propylene polymer (i) Propylene homopolymer (HPP): MFR 10 g / 10 min (ii) Ethylene / propylene random copolymer (RPP): Ethylene concentration 2.5% by weight, MFR 10 g / 10 min (Iii) Propylene homopolymer (HPP2): MFR 0.3 g / 10 min (iv) Propylene homopolymer (HPP3): MFR 22 g / 10 min (2) Nucleating agent (i) 1,2,3-propanetricarboxylic acid Tris (2-methylcyclohexylamide): Corresponding to nucleating agent (A) (ii) NA-11: Organophosphate metal salt compound nucleating agent (Asahi Denka Kogyo Co., Ltd.): Nucleating agent (B) (Iii) Gelol MD: Sorbitol-based nucleating agent (manufactured by Shin Nippon Rika Co., Ltd.): Nucleating agent not corresponding to any of nucleating agents (A) to (D) (iv) NA-21: Fragrance Group phosphoric acid nucleating agent (Asahi Denka Kogyo Co., Ltd.): equivalent to nucleating agent (C) (v) Hyperform HPN68L: Milliken Co., Ltd .: equivalent to nucleating agent (D) (3) Neutralizer (i) DHT-4A: Hydrotalcite (manufactured by Kyowa Chemical Industry Co., Ltd.)
(Ii) Calcium stearate (4) Lubricant (i) Silicone oil: Dowcorning 360 Medical Fluid (silicon) -100 manufactured by Toray Dow Corning Co., Ltd. (ii) Silicone oil: Dowcorning 360 Medical Fluid (silicone)-1000 Toray Dow Corning Co., Ltd. Made (iii) Butyl stearate (5) Peroxide (i) Perhexa 25B Made by NOF

(Example 1)
For 100 parts by weight of homopolypropylene (HPP), 0.10 parts by weight of 1,2,3-propanetricarboxylic acid tris (2-methylcyclohexylamide) as the nucleating agent (A), the nucleating agent (B) 0.10 parts by weight of NA-11, 0.03 parts by weight of DHT-4A as a neutralizing agent, and 0.1 parts by weight of Adegas Tab 2112 (manufactured by Asahi Denka Kogyo Co., Ltd.) as a phosphite antioxidant In addition, 0.05 part by weight of TINUVIN622LD (Ciba Specialty Chemicals Co., Ltd.) as a hindered amine UV stabilizer was blended, 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 250 ° 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 (12 cm × 12 cm × 2.5 mm plate) A shape in which 3 × 4 box shapes of 25 mm × 20 mm × 20 mm having a thickness of 1 mm are arranged on top is prepared. Using the obtained molded product, its moldability was measured. The results are shown in Table 1.

(Examples 2 to 12, Comparative Examples 1 to 16)
A test piece was obtained according to Example 1 except that the propylene-based polymer, nucleating agent, neutralizing agent and lubricant were changed to those shown in Table 1 and the amounts thereof, and the physical properties thereof were measured. The results are shown in Tables 1 and 2.

As is clear from Tables 1 and 2, Examples 1 to 12 are nucleating agents (A) within the scope of the present invention, and nucleating agents (B) to (D) within the scope of the present invention alone or in combination. It can be seen that transparency, rigidity, and crystallization temperature can be improved by using together, and pass the 14th revised Japanese Pharmacopoeia test. Moreover, it turns out that Examples 9-11 can pass a 14th revision Japanese Pharmacopoeia test by using a specific lubricant together, and can further improve injection moldability.
On the other hand, in Comparative Examples 1 and 2, 1,2,3-propanetricarboxylic acid tris (2-methylcyclohexylamide) corresponding to the nucleating agent (A) within the scope of the present invention was added to HPP or RPP by 0. It is understood that 20 parts by weight is blended and none of the nucleating agents (B) to (D) is blended, the transparency, heat resistance and rigidity are inferior, and the crystallization temperature is low. In Comparative Examples 3 and 4, since no nucleating agent is used, transparency is remarkably poor and heat resistance and rigidity are low. In Comparative Examples 5 to 7, NA-11 corresponding to the nucleating agent (B) is used as the nucleating agent, but the nucleating agent alone has poor transparency and is usually blended in the nucleating agent. Transparency is improved by increasing the amount, but the nucleating agent has no effect of improving transparency. In Comparative Examples 8 and 9, NA-21 corresponding to the nucleating agent (C) is used as the nucleating agent, but the nucleating agent alone cannot be said to have sufficient transparency and has good transparency. If the blending amount is increased in order to obtain properties, the 14th revised Japanese Pharmacopoeia test will be rejected. In Comparative Examples 10 and 11, HPN68L corresponding to the nucleating agent (D) is used as the nucleating agent, but the transparency is poor and the transparency is not improved even if the blending amount is increased. Deteriorated and failed the 14th Japanese Pharmacopoeia Exam. In Comparative Example 12, 1,0,3-propanetricarboxylic acid tris (2-methylcyclohexylamide) corresponding to the nucleating agent (A) was compounded in an amount of 0.30 parts by weight. The 14th revised Japanese Pharmacopoeia test will not pass. In Comparative Example 13, as the nucleating agent, any of 1,2,3-propanetricarboxylic acid tris (2-methylcyclohexylamide) corresponding to the nucleating agent (A) and the nucleating agents (A) to (D). However, this combination of nucleating agents does not improve the transparency, heat resistance and crystallization temperature, and is not acceptable for the 14th revised Japanese Pharmacopoeia test. Pass. In Comparative Examples 14 and 15, 0.20 wt% of NA-21 corresponding to the nucleating agent (C) and HPN68L corresponding to the nucleating agent (D) as the nucleating agent with respect to the ethylene / propylene random copolymer. In this formulation, the 14th revised Japanese Pharmacopoeia test fails. Comparative Example 16 uses a propylene-based polymer having an MFR outside the scope of the present invention, and when this polymer is used, the nucleating agent (A) and the nucleating agent (B) specified in the present invention are used. Even if it is used, an injection molded product cannot be obtained by injection molding.

(Example 13, Comparative Examples 17-20)
A test piece and a molded product were obtained according to Example 1 except that the propylene-based polymer and the nucleating agent were changed to those shown in Table 3 and the amounts thereof, and the physical properties thereof were measured. The results are shown in Table 3.

As can be seen from Table 3, in Example 13, the nucleating agent (A) within the scope of the present invention and the nucleating agent (B) within the scope of the present invention were used in combination to achieve transparency and moldability. It can be improved and it turns out that it passes the 14th revision Japanese Pharmacopoeia examination.
On the other hand, in Comparative Example 17, 0.15 parts by weight of 1,2,3-propanetricarboxylic acid tris (2-methylcyclohexylamide) corresponding to the nucleating agent (A) within the scope of the present invention was added to HPP3. However, it is understood that none of the nucleating agents (B) to (D) is blended and is inferior in transparency. Comparative Example 18 uses Gelall MD, which is a nucleating agent that does not correspond to any of the nucleating agents (A) to (D), as the nucleating agent, and this nucleating agent is excellent in transparency. However, he failed the 14th revised Japanese Pharmacopoeia test. Comparative Example 19 is a blend of 0.60 parts by weight of 1,2,3-propanetricarboxylic acid tris (2-methylcyclohexylamide) corresponding to the nucleating agent (A). Transparency deteriorates and the 14th revised Japanese Pharmacopoeia test does not pass. Since Comparative Example 20 does not use any nucleating agent, the transparency is extremely poor.

  The injection-molded article of the present invention is very useful for obtaining a molded article excellent in transparency, rigidity, heat resistance, and injection moldability, such as food containers, caps, medical instruments, physics and chemistry laboratory instruments, automobile parts, Suitable for electrical parts and the like. Among them, the 14th revised Japanese Pharmacopoeia general examination with strict acceptance criteria 45. 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 most suitable for a syringe, a medical instrument and a medical container, a syringe and a container filled with a drug solution, and the like.

Claims (6)

A nucleating agent represented by the general formula (1) with respect to 100 parts by weight of a propylene polymer having a melt flow rate based on JIS K7210 (230 ° C., 2.16 kg load) of 0.5 to 100 g / 10 min ( A) is blended in an amount of 0.005 parts by weight or more and less than 0.3 parts by weight. Further, the nucleating agent (B) represented by the general formula (2) is added in an amount of 0.005 to 0.3 parts by weight, and the general formula (3) At least one kind comprising 0.005 to 0.15 parts by weight of the nucleating agent (C) represented by the formula (1) or 0.005 to 0.15 parts by weight of the nucleating agent (D) represented by the general formula (4) An injection molded product obtained by injection molding the resin composition using a resin composition containing the nucleating agent.
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. ]

[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. ] The injection-molded article according to claim 1, wherein the nucleating agent (A) is at least one amide 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 injection-molded article according to claim 1, wherein the nucleating agent (A) is at least one amide compound represented by the following general 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. ]   4. The resin composition according to claim 1, wherein 0.001 to 0.5 parts by weight of a lubricant is blended with 100 parts by weight of the propylene-based polymer. Injection molded product.   The propylene polymer is a propylene homopolymer having an isotactic pentad fraction of 0.90 or more, or a propylene copolymer of propylene and another α-olefin. The injection molded product according to any one of -4.   The injection-molded product according to any one of claims 1 to 5, wherein the injection-molded product is a medical propylene molded product.