JP2015155515A - Propylene-based resin composition, and molded article of the same - Google Patents

Abstract

Provided are a propylene-based resin composition excellent in transparency, rigidity, hue after radiation sterilization, low elution property, and impact resistance, and a molded product molded from the composition. A melt flow rate (hereinafter sometimes abbreviated as MFR) conforming to JIS K7210 (230 ° C., 2.16 kg load) is 3 to 150 g / 10 min, and an ethylene content is 0.5 to 5 60% to 99% by weight of propylene-ethylene random copolymer (I), 1 to 15 g / 10 minutes, 8 to 15% by weight of ethylene, and 6 to 20% by weight of butene. A nucleating agent is contained in an amount of 0.005 to 0.4 parts by weight with respect to 100 parts by weight of a propylene-based resin composed of 1 to 40% by weight of a certain ethylene-propylene-butene copolymer (II). Propylene-based resin composition. [Selection figure] None

Description

  The present invention relates to a propylene-based resin composition excellent in transparency, rigidity, hue after radiation sterilization, low elution property, and impact resistance, and a molded product thereof. More specifically, the present invention relates to a molded product for medical use. Furthermore, the present invention relates to a propylene-based resin composition whose members are radiation-sterilized and a molded product thereof.

  Propylene polymers are excellent in molding processability, mechanical properties, and gas barrier properties. Therefore, they are molded by various methods, and like other resins such as polyvinyl chloride and polystyrene, they are used in food containers, caps, and medical treatments. It is widely used in various applications such as appliances, medical containers, daily necessities, automobile parts, electrical parts, sheets, films, and fibers. Depending on the application, more excellent transparency and impact resistance are strongly demanded for the propylene polymer or the composition thereof. For example, a syringe outer cylinder, which is a medical use member, needs transparency, but may be broken during use or transportation, and not only the transparency but also high impact resistance is required.

Propylene polymers are propylene homopolymers in terms of rigidity, heat resistance and gas barrier properties, and propylene-ethylene random copolymers in terms of transparency and impact resistance. In this respect, a propylene-ethylene block copolymer is suitable, and is selectively used as appropriate depending on the situation.
However, the propylene homopolymer is not as transparent as the propylene-ethylene block copolymer, and it is difficult to exhibit sufficient performance in terms of impact resistance. A conventional propylene-ethylene random copolymer is excellent in transparency but may not have sufficient impact resistance. Although the propylene-ethylene block copolymer has excellent impact resistance, it has a drawback that it is extremely difficult to impart transparency.
Therefore, there is a limit to aiming at product optimization with the performance of only the propylene-based polymer, and the performance has been complemented by blending various combinations of nucleating agents (for example, see Patent Document 1).

  In order to develop transparency, a propylene-ethylene random copolymer added with a nucleating agent is used. Generally, although a nucleating agent can improve transparency and rigidity, Impact resistance cannot be improved. Therefore, a rubber component is added in order to improve impact resistance.

JP 2006-307038 A

  However, depending on the rubber component, there is a drawback that the transparency is deteriorated by addition or the color is changed during sterilization. Especially in medical applications for radiation sterilization, discoloration and material deterioration after sterilization are remarkable, and appropriate compositions are being studied. Specific examples include medical treatments such as syringe outer tubes (syringes) and dialyzers that are radiation sterilized. Currently, propylene-based resin compositions suitable for applications are strongly demanded for products for applications.

  An object (issue) of the present invention is to provide a propylene-based resin composition excellent in transparency, rigidity, hue after radiation sterilization, low elution property, and impact resistance, and a molded product molded from the resin composition. It is in.

  As a result of intensive research to solve the above problems, the present inventor used a nucleating agent for a specific propylene-based polymer, whereby transparency, rigidity, hue after radiation sterilization, low elution, The inventors have found that the resin composition can be excellent in impact resistance and have completed the present invention. The nucleating agent used in the present invention not only increases transparency to a specific polymer called a propylene-based polymer, but also exhibits low elution properties suitable for medical use. Furthermore, it can be said that it contributes to the improvement of physical properties such as impact strength and flexural modulus of the molded product obtained by using the resin composition of the present invention, so that a comprehensive balance was obtained for the entire processed product. Has an effect.

  That is, according to the first invention of the present invention, the melt flow rate (hereinafter sometimes abbreviated as MFR) conforming to JIS K7210 (230 ° C., 2.16 kg load) is 3 to 150 g / 10 min. 60-99% by weight of propylene-ethylene random copolymer (I) having an ethylene content of 0.5-5% by weight, MFR of 1-15 g / 10 minutes, ethylene content of 8-15% by weight, butene The nucleating agent is added in an amount of 0.005 to 0.4 with respect to 100 parts by weight of the propylene-based resin comprising 1 to 40% by weight of the ethylene-propylene-butene copolymer (II) having a content of 6 to 20% by weight. Propylene-based resin composition characterized by containing a weight part is provided.

  According to the second invention of the present invention, the nucleating agent is 0.005 to 0.3 parts by weight of the nucleating agent (A) represented by the following formula (1), and the nucleating agent represented by the following formula (2). 0.005 to 0.25 parts by weight of agent (B), nucleating agent (C) represented by the following formula (3) 0.005 to 0.15 part by weight, nucleating agent represented by the following formula (4) ( D) 0.1 to 0.3 parts by weight, 0.1 to 0.4 parts by weight of a nucleating agent (E) represented by the following formula (5), and a nucleating agent (F) 0 consisting of a triaminobenzene derivative A propylene-based resin composition according to the first invention is provided, which is at least one nucleating agent selected from the group consisting of 0.005 to 0.04 parts by weight.

［式中、Ｒ^１は、直接結合、硫黄、炭素数１〜９のアルキレン基またはアルキリデン基であり、Ｒ^２およびＲ^３は、同一または異なって、それぞれ水素原子または炭素数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、水素原子または炭素数１〜４のアルキル基を示し、Ｒ^２およびＲ^３は、同一または異なって、それぞれ水素原子または炭素数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＝または（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、いずれもリチウムイオンであるか、または共同してカルシウム、ストロンチウム、亜鉛、マグネシウムおよび一塩基性アルミニウムからなる群から互いに独立して選択される単一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）なら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 both lithium ions, or a single metal selected independently from the group consisting of calcium, strontium, zinc, magnesium and monobasic aluminum. 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 (here Any two vicinal (bonded to adjacent carbon) or geminal (bonded to the same carbon) alkyl groups may form together 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 (fluorine, chlorine, bromine and iodine), as well as or phenyl Are each selected from the group consisting. ]

（式中、ｍおよびｎは、独立して１〜５の整数を表し、Ｒ¹およびＲ²は、各々炭素数１〜１８のアルキル基またはハロゲン基を表す。）

(In the formula, m and n independently represent an integer of 1 to 5, and R ¹ and R ² each represents an alkyl group having 1 to 18 carbon atoms or a halogen group.)

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

[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, R ⁶ is a halogen group or a phenyl group, and R ⁶ is an alkyl group having 1 to 20 carbon atoms. ]

  According to the third invention of the present invention, the nucleating agent (E) is a compound represented by the following formula (6), or the nucleating agent (F) is a compound represented by the following formula (7). The propylene-based resin composition described in the second invention is provided.

Ｒ_１〜Ｒ_３：ｔ−ブチル

R _{1 to} R ₃ : t-butyl

According to a fourth aspect of the present invention, there is provided a propylene-based resin composition, wherein the propylene-based resin composition according to any one of the first to third aspects is for medical use.
According to a fifth aspect of the present invention, in the propylene-based resin composition according to any one of the first to fourth aspects, the content of the phenol-based antioxidant is 0 with respect to 100 parts by weight of the propylene-based resin. Propylene-based resin composition characterized by being less than 0.005 part by weight is provided.
According to a sixth aspect of the present invention, there is provided a molded product obtained by using the propylene-based resin composition according to any one of the first to fifth aspects.
According to the seventh aspect of the present invention, there is provided a molded article for medical use that is radiation-sterilized with a dose of 1 kGy to 60 kGy in the molded article according to the sixth invention.
According to an eighth aspect of the present invention, there is provided a molded product characterized in that the molded product according to the sixth or seventh invention is a syringe member.
According to the ninth invention of the present invention, there is provided a molded product characterized in that the molded product according to the sixth or seventh invention is an artificial dialysis member.

  The propylene resin composition of the present invention has unprecedented performance and requires transparency, rigidity, hue after radiation sterilization, low elution, and impact resistance, as typified by products for medical use. It is a propylene-based resin composition suitable for the intended use. Moreover, since the molded article obtained using this composition has the said performance, it can expand | deploy to various uses.

The propylene-based resin composition of the present invention has a melt flow rate (MFR) based on JIS K7210 (230 ° C., 2.16 kg load) of 3 to 150 g / 10 minutes and an ethylene content of 0.5 to 5% by weight. A certain propylene-ethylene random copolymer (I) of 60 to 99% by weight, an MFR of 1 to 15 g / 10 minutes, an ethylene content of 8 to 15% by weight and a butene content of 6 to 20% by weight The nucleating agent is contained in an amount of 0.005 to 0.4 parts by weight with respect to 100 parts by weight of the propylene-based resin composed of 1 to 40% by weight of the propylene-butene copolymer (II).
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] Propylene-ethylene random copolymer (I) constituting the propylene-based resin composition
The propylene-ethylene random copolymer (I) constituting the propylene-based resin composition of the present invention has an ethylene content of 0.5 to 5% by weight, preferably 0.5 to 4% by weight, and more preferably. Is 1.5 to 3.5% by weight, more preferably 2 to 3% by weight. MFR based on JIS K7210 (230 degreeC, 2.16kg load) is 3-150g / 10min, Preferably it is 5-100g / 10min, More preferably, it is 10-50g / 10min, More preferably Is 15 to 35 g / 10 min.
The ethylene content of the propylene-ethylene random copolymer (I) is 0.5 to 5% by weight from the viewpoints of transparency, rigidity, impact resistance and flexibility. The MFR of the propylene-ethylene random copolymer (I) is 3 to 150 g / 10 minutes from the viewpoint of securing fluidity while maintaining a balance of physical properties such as impact resistance.

  The proportion of the propylene-ethylene random copolymer (I) relative to the total amount of the propylene-based resin is 60 to 99% by weight, preferably 65 to 95% by weight, more preferably from the viewpoint of transparency, rigidity and impact resistance. 75 to 85% by weight.

  The propylene-ethylene random copolymer (I) of the present invention is produced by a polymerization method described later, but may be used alone or in combination of two or more. Separately produced propylene-ethylene random copolymer (A) and propylene-ethylene random copolymer (B) are mixed with a mixing device such as a ribbon blender, a Henschel mixer (trade name), a Banbury mixer, a drum tumbler, It may be a mixture obtained by a melt kneading method (melt blending method) using a single or twin screw extruder, a kneader or the like.

The ethylene content in the propylene-ethylene random copolymer (I) is a value measured by ¹³ C-NMR method under the following conditions.
Apparatus: JEOL-GSX270 manufactured by JEOL Ltd.
Concentration: 300 mg / 2 mL
Solvent: Orthodichlorobenzene

  Although it does not specifically limit as a manufacturing method of the propylene-ethylene random copolymer (I) used by this invention, The polymerization method using a stereoregular catalyst is preferable. Examples of stereoregular catalysts include Ziegler catalysts and metallocene catalysts.

  Ziegler catalysts include transition metal components such as titanium trichloride, titanium tetrachloride, trichloroethoxytitanium, and the like, and contact materials between the 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. As an example of the titanium trichloride catalyst, there is a Solvey catalyst.

  The metallocene catalyst is composed of a metallocene complex and an organoaluminum oxy compound, a Lewis acid, an anionic compound, or a clay mineral.

As a metallocene compound having high stereoregularity in a metallocene catalyst, a group 4 having a carbon bridge, a silicon bridge, a germane bridge group and a substituted or unsubstituted cyclopentadiene, indene, fluorene, or azulene as a ligand The transition metal compound can be mentioned. The following are non-limiting specific examples.
(I) Examples of carbon bridges include ethylene bis (2,4-dimethylindenyl) zirconium chloride, ethylenebis (2,4,7-trimethylindenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (fluorenyl) zirconium. Examples include chloride, isopropylidene (3-methylindenyl) (fluorenyl) zirconium chloride, isopropylidene (2-methylcyclopentadienyl) (3-methylindenyl) zirconium dichloride, and the like.
(Ii) Examples of the silicon bridge include dimethylsilylene bis (2-methyl-4-phenylindenyl) zirconium dichloride, diphenylsilylene (2-ethyl-4-phenylindenyl) zirconium dichloride, dimethylsilylene bis (2-methylbenzoindene). Nyl) zirconium dichloride, dimethylsilylenebis (2-isopropyl, 4- (3,5-diisopropylphenyl) indenyl) zirconium dichloride, dimethylsilylenebis (2-propyl-4-phenanthrylindenyl) zirconium dichloride, dimethylsilylenebis (2-ethyl-4- (4-tertbutyl-3-chlorophenyl) azurenyl) zirconium dichloride, and the like.
(Iii) As the germane crosslinking, a compound in which the above (ii) silicon-crosslinked silylene is replaced with germanylene is used. A compound in which zirconium is replaced with hafnium is exemplified as a suitable compound as it is. Furthermore, the dichloride of the exemplified compound may be exemplified by other halides, compounds substituted with a methyl group, an isobutyl group, a phenyl group, a hydride group, a dimethylamide, a diethylamide group, and the like as suitable compounds.

In the metallocene catalyst system, organoaluminum oxy compounds, Lewis acids, ionic compounds, and clay minerals can be used as co-catalysts, and the following can be given as non-limiting specific examples.
(I) Examples of the organic aluminum oxy compound include methylalumoxane, isobutylalumoxane, methylisobutylalumoxane, aluminum butylboronate, tetraisobutylmethylaluminum bispentafluorophenoxide, and the like.
(Ii) As a Lewis acid, a compound represented by BR ₃ (wherein R is a phenyl group which may have a substituent such as a fluorine atom, a methyl group or a trifluoromethyl group or a fluorine atom). For example, trifluoroborane, triphenylborane, tris (4-fluorophenyl) borane, tris (3,5-difluorophenyl) borane, tris (4-fluoromethylphenyl) borane, tris (pentafluorophenyl) Examples include borane, tris (p-tolyl) borane, tris (o-tolyl) borane, tris (3,5-dimethylphenyl) borane, and inorganic compounds such as magnesium chloride and aluminum oxide.
(Iii) Examples of the ionic compound include trialkyl-substituted ammonium salts, N, N-dialkylanilinium salts, dialkylammonium salts, and triarylphosphonium salts. Specifically, examples of the trialkyl-substituted ammonium salt include triethylammonium tetra (phenyl) borate, tripropylammonium tetra (phenyl) borate, tri (n-butyl) ammonium tetra (phenyl) borate and the like. Examples of the dialkylammonium salt include di (1-propyl) ammonium tetrakis (pentafluorophenyl) borate and dicyclohexylammonium tetra (phenyl) borate. Further examples of the ionic compound include triphenylcarbenium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, ferrocenium tetra (pentafluorophenyl) borate, and the like.
Examples of (iv) clay minerals include montmorillonite, mica, teniolite, hectorite, modified products thereof treated with acid / base, and complexes with other inorganic oxides.

2. Ethylene-propylene-butene copolymer (II)
The ethylene-propylene-butene copolymer (II) used in the present invention has an ethylene content of 8 to 15% by weight, preferably 9 to 12% by weight, and a butene content of 6 to 20% by weight, preferably 6 to 6%. 12% by weight. When the ethylene content and the butene content of the ethylene-propylene-butene copolymer (II) are within this range, the compatibility with the propylene-ethylene random copolymer (I) is improved and the transparency is improved. In addition, the ethylene-propylene-butene copolymer (II) exhibits rubbery properties having good impact resistance even after radiation sterilization.
The melt flow rate (MFR) based on JIS K7210 (230 ° C., 2.16 kg load) of this ethylene-propylene-butene copolymer (II) is 1 to 15 g / 10 minutes, preferably 3 to 15 g / 10 minutes. More preferably, it is 5-15 g / 10min, More preferably, it is 6-10 g / 10min. When the MFR is within this range, the ethylene-propylene-butene copolymer (II) is finely dispersed in the propylene-ethylene random copolymer (I) and excellent in transparency.
The ethylene content and butene content in this ethylene-propylene-butene copolymer (II) are values measured by a ¹³ C-NMR method.
The ratio of the ethylene-propylene-butene copolymer (II) to the total amount of the propylene-based resin is 1 to 40% by weight, preferably 5 to 35% by weight, from the viewpoint of transparency, rigidity and impact resistance. Is 15 to 25% by weight.

  Such an ethylene-propylene-butene copolymer (II) is a metallocene catalyst containing a metallocene compound in which a substituent having a cyclopentadiene skeleton is coordinated to a transition metal such as zirconium metal and an organoaluminum oxy compound. It can be produced by copolymerizing ethylene, propylene and 1-butene in the presence of a stereoregular polymerization catalyst. In particular, the ethylene-propylene-butene copolymer (II) produced using a metallocene-based catalyst has a narrow molecular weight distribution and composition distribution, so that it has good extraction resistance by the contents liquid and is medically sterilized by radiation. Suitable as a raw material resin for members.

3. Nucleating Agent The propylene resin composition of the present invention is characterized by containing 0.005 to 0.4 parts by weight of a nucleating agent with respect to 100 parts by weight of the propylene resin. The nucleating agent preferably used in the present invention is a nucleating agent (A) to a nucleating agent (F) described below.
The nucleating agent (A) used in the propylene-based resin composition of the present invention is an organophosphate metal salt compound represented by the formula (1).

［式中、Ｒ^１は、直接結合、硫黄、炭素数１〜９のアルキレン基またはアルキリデン基であり、Ｒ^２およびＲ^３は、同一または異なって、それぞれ水素原子または炭素数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. ]

Specific examples of the organophosphate metal salt compound represented by the formula (1) 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 Phenyl) phosphate, sodium-2,2′-methylene-bis- (4-methyl-6-tert-butylphenyl) phosphate, sodium-2,2′-methylene-bis- (4-ethyl-6-t) -Butylphenyl) phosphate, sodium (4,4'-dimethyl-6,6'-di-t-butyl-2,2'-biphenyl) phosphate, sodium-2,2'-ethylidene-bis- (4 -S-butyl-6-tert-butylphenyl) phosphate, sodium-2,2'-methylene-bis- (4,6-di-methylphenyl) phosphate, sodium-2,2'-methylene-bis- Examples thereof include (4,6-di-ethylphenyl) phosphate and a mixture of two or more thereof. Of these, sodium-2,2′-methylene-bis- (4,6-di-t-butylphenyl) phosphate is particularly preferable.
A commercially available product can be used as such a nucleating agent. Specific examples include NA-11 manufactured by ADEKA.
The content of the nucleating agent (A) used in the propylene-based resin composition is 0.005 to 0.3 parts by weight of the nucleating agent (A) with respect to 100 parts by weight of the propylene-based resin. Preferably, it is 0.03-0.2 weight part, More preferably, it is 0.05-0.15 weight part. When the amount is 0.005 part by weight or more, the effect of the nucleating agent is sufficient, and when the amount is 0.3 part by weight or less, it is advantageous from the viewpoint of the cost to the effect (cost / performance).

  The nucleating agent (B) used in the propylene-based resin composition of the present invention is an aromatic phosphate ester represented by the formula (2).

［式中、Ｒ^１は、水素原子または炭素数１〜４のアルキル基を示し、Ｒ^２およびＲ^３は、同一または異なって、それぞれ水素原子または炭素数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＝または（ＨＯ）_２−を示す。］
式（２）で表される芳香族燐酸エステル類の具体例としては、例えば、ヒドロキシアルミニウム−ビス［２，２’−メチレン−ビス（４，６−ジメチルフェニル）フォスフェート］、ヒドロキシアルミニウム−ビス［２，２’−エチリデン−ビス（４，６−ジメチルフェニル）フォスフェート］、ヒドロキシアルミニウム−ビス［２，２’−メチレン−ビス（４，６−ジエチルフェニル）フォスフェート］、ヒドロキシアルミニウム−ビス［２，２’−エチリデン−ビス（４，６−ジエチルフェニル）フォスフェート］、ヒドロキシアルミニウム−ビス［２，２’−メチレン−ビス（４，６−ジ−ｔ−ブチルフェニル）フォスフェート］、およびヒドロキシアルミニウム−ビス［２，２’−エチリデン−ビス（４，６−ジ−ｔ−ブチルフェニル）フォスフェート］、ヒドロキシアルミニウム−ビス［２，２’−メチレン−ビス（４−メチル−６−ｔ−ブチルフェニル）フォスフェート］、ヒドロキシアルミニウム−ビス［２，２’−エチリデン−ビス（４−メチル−６−ｔ−ブチルフェニル）フォスフェート］、ヒドロキシアルミニウム−ビス［２，２’−メチレン−ビス（４−エチル−６−ｔ−ブチルフェニル）フォスフェート］、ヒドロキシアルミニウム−ビス［２，２’−エチリデン−ビス（４−エチル−６−ｔ−ブチルフェニル）フォスフェート］、ヒドロキシアルミニウム−ビス［２，２’−メチレン−ビス（４−ｉ−プロピル−６−ｔ−ブチルフェニル）フォスフェート］、ヒドロキシアルミニウム−ビス［２，２’−エチリデン−ビス（４−ｉ−プロピル−６−ｔ−ブチルフェニル）フォスフェート］などが挙げられ、好ましくは、ヒドロキシアルミニウム−ビス［２，２’−メチレン−ビス（４，６−ジ−ｔ−ブチルフェニル）フォスフェート］、およびヒドロキシアルミニウム−ビス［２，２’−エチリデン−ビス（４，６−ジ−ｔ−ブチルフェニル）フォスフェート］、およびこれらの２種以上の混合物を例示することができる。

[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- . ]
Specific examples of the aromatic phosphates represented by the formula (2) 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-butylphenyl) phospho Fate], hydroxyaluminum-bis [2,2′-methylene-bis (4-methyl-6-tert-butylphenyl) phosphate], hydroxyaluminum-bis [2,2′-ethylidene-bis (4-methyl- 6-t-butylphenyl) phosphate], hydroxyaluminum-bis [2,2′-methylene-bis (4-ethyl-6-t-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], Hydroxyaluminum-bis [2,2′-ethylidene-bis (4-i-propyl-6-tert-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 mixtures of two or more thereof.

It is effective to use the aromatic phosphates represented by the formula (2) together with an organic alkali metal salt.
The organic alkali metal salt can 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-ketoacetic acid ester 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 carboxylic acids such as naphthene Acid, cyclopentanecarboxylic acid, 1- Tylcyclopentanecarboxylic acid, 2-methylcyclopentanecarboxylic acid, cyclopentenecarboxylic acid, cyclohexanecarboxylic acid, 1-methylcyclohexanecarboxylic acid, 4-methylcyclohexanecarboxylic acid, 3,5-dimethylcyclohexanecarboxylic acid, 4-butylcyclohexanecarboxylic acid Acid, cyclooctenecyclohexane carboxylic acid, cyclohexene carboxylic acid, alicyclic mono- or polycarboxylic acid such as 4-cyclohexene-1,2-dicarboxylic acid, benzoic acid, toluic acid, xylic acid, ethylbenzoic acid, 4-t -Aromatic mono- or polycarboxylic acids such as butyl benzoic acid, salicylic acid, phthalic acid, trimellitic acid and pyromellitic acid.
Examples of the β-diketone compound constituting the alkali metal β-diketonate include acetylacetone, pivaloylacetone, palmitoylacetone, benzoylacetone, pivaloylbenzoylacetone, dibenzoylmethane, and the like.
Examples of the β-ketoacetate constituting the alkali metal β-ketoacetate salt include, for example, ethyl acetoacetate, octyl acetoacetate, lauryl acetoacetate, stearyl acetoacetate, ethyl benzoyl acetate, and benzoyl lauryl acetate. It is done.
The alkali metal carboxylate, alkali metal β-diketonate or alkali metal β-ketoacetate salt, which is a component of the organic alkali metal salt, includes the above alkali metal and carboxylic acid, β-diketone compound or β-ketoacetate, respectively. And can be produced by a conventionally known method. Among these alkali metal salt compounds, alkali metal aliphatic monocarboxylates, particularly lithium aliphatic carboxylates are preferable, and aliphatic monocarboxylates having 8 to 20 carbon atoms are particularly preferable.

A commercially available product can be used as such a nucleating agent. Specifically, NA-21 manufactured by ADEKA can be mentioned.
The content of the nucleating agent (B) used in the propylene-based resin composition is 0.005 to 0.25 parts by weight of the nucleating agent (B) with respect to 100 parts by weight of the propylene-based resin. Preferably, it is 0.03-0.2 weight part, More preferably, it is 0.05-0.2 weight part. When the amount is 0.005 parts by weight or more, the effect of the nucleating agent is sufficient, and when the amount is 0.25 parts by weight or less, it is advantageous from the viewpoint of the cost to the effect (cost / performance).

  The nucleating agent (C) used in the propylene-based resin composition of the present invention is a nucleating agent represented by the formula (3).

［式中、Ｍ_１およびＭ_２は、いずれもリチウムイオンであるか、または共同してカルシウム、ストロンチウム、亜鉛、マグネシウムおよび一塩基性アルミニウムからなる群から互いに独立して選択される単一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）なら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。
式（３）で表される造核剤は、凝集などを防止する目的で、他の化合物を混合して用いても差し支えない。
この様な造核剤としては、市販のものを用いることができる。具体的には、ミリケン社製ハイパフォームＨＰＮ６８Ｌを挙げることができる。ハイパフォームＨＰＮ６８Ｌの造核剤成分の構造を下記に示す。

[Wherein M ₁ and M ₂ are both lithium ions, or a single metal selected independently from the group consisting of calcium, strontium, zinc, magnesium and monobasic aluminum. 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 (here Any two vicinal (bonded to adjacent carbon) or geminal (bonded to the same carbon) alkyl groups may form together 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 (fluorine, chlorine, bromine and iodine), as well as or phenyl Are each selected from the group consisting. ]
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 formula (3) may be used by mixing other compounds for the purpose of preventing aggregation.
A commercially available product can be used as such a nucleating agent. Specific examples include Hyperform HPN68L manufactured by Milliken. The structure of the nucleating agent component of Hyperform HPN68L is shown below.

プロピレン系樹脂組成物に使用する造核剤（Ｃ）の含有量は、プロピレン系樹脂１００重量部に対して、造核剤（Ｃ）０．００５〜０．１５重量部である。
本発明の医療用プロピレン系樹脂組成物に選択的に用いられる造核剤（Ｃ）の含有量は、プロピレン系樹脂１００重量部に対し、０．００５〜０．１５重量部の範囲が好ましく、０．０１〜０．１重量部の範囲がより好ましい。０．００５重量部以上であると造核剤の効果が十分であり、また、０．２５重量部以下であると費用対前記効果（コスト・パフォーマンス）の点から有利である。

The content of the nucleating agent (C) used in the propylene-based resin composition is 0.005 to 0.15 parts by weight of the nucleating agent (C) with respect to 100 parts by weight of the propylene-based resin.
The content 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 resin. A range of 0.01 to 0.1 parts by weight is more preferable. When the amount is 0.005 parts by weight or more, the effect of the nucleating agent is sufficient, and when the amount is 0.25 parts by weight or less, it is advantageous from the viewpoint of the cost to the effect (cost / performance).

  The nucleating agent (D) used in the propylene-based resin composition of the present invention is a sorbitol-based nucleating agent represented by the formula (4).

（式中、ｍおよびｎは、独立して１〜５の整数を表し、Ｒ¹およびＲ²は、各々炭素数１〜１８のアルキル基またはハロゲン基を表す。）
式（４）で表される造核剤としては、１・３，２・４−ジベンジリデンソルビトール、１・３，２・４−ビス（ｐ−メチルベンジリデン）ソルビトール、１・３−ｐ−クロルベンジリデン−２・４−ｐ−メチルべンジリデンソルビトール、１・３，２・４−ビス（ｐ−エチルベンジリデン）ソルビトール、１・３，２・４−ビス（３，４−ジメチルベンジリデン）ソルビトールなどのソルビトール系造核剤を挙げることができる。これらは、２種以上の混合物として用いてもよい。
該ソルビトール系造核剤としては、市販のものを用いることができる。具体的には、新日本理化（株）製ゲルオールＭＤやミリケン社製のミラード３９８８を挙げることができる。

(In the formula, m and n independently represent an integer of 1 to 5, and R ¹ and R ² each represents an alkyl group having 1 to 18 carbon atoms or a halogen group.)
Examples of the nucleating agent represented by the formula (4) include 1,3,2,4-dibenzylidene sorbitol, 1,3,2,4-bis (p-methylbenzylidene) sorbitol, and 1,3-p-chloro. Benzylidene-2,4-p-methylbenzylidene sorbitol, 1,3,2,4-bis (p-ethylbenzylidene) sorbitol, 1,3,2,4-bis (3,4-dimethylbenzylidene) sorbitol, etc. Sorbitol-based nucleating agents. These may be used as a mixture of two or more.
A commercially available product can be used as the sorbitol nucleating agent. Specific examples include Gelall MD manufactured by Shin Nippon Rika Co., Ltd. and Millard 3988 manufactured by Milliken.

The content of the nucleating agent (D) used in the propylene-based resin composition is 0.1 to 0.3 parts by weight of the nucleating agent (D) with respect to 100 parts by weight of the propylene-based resin.
The content of the nucleating agent (D) selectively used in the medical propylene resin composition of the present invention is preferably in the range of 0.1 to 0.3 parts by weight with respect to 100 parts by weight of the propylene resin. The range of 0.15-0.25 weight part is more preferable. When the amount is 0.1 parts by weight or more, the effect of the nucleating agent is sufficient, and when the amount is 0.3 parts by weight or less, it is advantageous from the viewpoints of the cost-effectiveness (cost performance) and dissolution property.

  The nucleating agent (E) used in the propylene-based resin composition of the present invention is a nucleating agent represented by the formula (5), and in particular, a nonitol type nucleating agent which is a compound represented by the formula (6). Are preferable. The compound represented by the formula (6) is 3,5: 4,6-bis [4-propylbenzylidenebis (oxy)]-1,2-nonanediol or the conventional name 1,2,3-trideoxy-4, 6: 5,7-bis-[(4-propylphenyl) methylene] -nonitol.

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

[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, R ⁶ is a halogen group or a phenyl group, and R ⁶ is an alkyl group having 1 to 20 carbon atoms. ]

この様な造核剤としては、市販のものを用いることができる。具体的には、ミリケン社製ＮＸ８０００を挙げることができる。
プロピレン系樹脂組成物に使用する造核剤（Ｅ）の含有量は、プロピレン系樹脂１００重量部に対して、造核剤（Ｅ）０．１〜０．４重量部である。
本発明の医療用プロピレン系樹脂組成物に選択的に用いられる造核剤（Ｅ）の含有量は、プロピレン系樹脂１００重量部に対し、０．１〜０．４重量部の範囲が好ましく、０．２〜０．３重量部の範囲がより好ましい。０．１重量部以上であると造核剤の効果が十分であり、また、０．４重量部以下であると費用対前記効果（コスト・パフォーマンス）および溶出性の点から有利である。

A commercially available product can be used as such a nucleating agent. Specific examples include NX8000 manufactured by Milliken.
The content of the nucleating agent (E) used in the propylene-based resin composition is 0.1 to 0.4 parts by weight with respect to 100 parts by weight of the propylene-based resin.
The content of the nucleating agent (E) selectively used in the medical propylene-based resin composition of the present invention is preferably in the range of 0.1 to 0.4 parts by weight with respect to 100 parts by weight of the propylene-based resin. A range of 0.2 to 0.3 parts by weight is more preferable. When the amount is 0.1 parts by weight or more, the effect of the nucleating agent is sufficient, and when the amount is 0.4 parts by weight or less, it is advantageous from the viewpoints of the cost-effectiveness (cost performance) and dissolution property.

  The nucleating agent (F) used in the propylene-based resin composition of the present invention is a nucleating agent composed of a triaminobenzene derivative, and among them, the compound represented by the formula (7) is preferable.

Ｒ_１〜Ｒ_３：ｔ−ブチル
トリアミノベンゼン誘導体からなる造核剤の例としては、ＢＡＳＦ社製 商品名：ＩＲＧＡＣＬＥＡＲ ＸＴ３８６が挙げられる。
プロピレン系樹脂組成物に使用する造核剤（Ｆ）の含有量は、プロピレン系樹脂１００重量部に対して、造核剤（Ｆ）０．００５〜０．０４重量部である。
本発明の医療用プロピレン系樹脂組成物に選択的に用いられる造核剤（Ｆ）の含有量は、プロピレン系樹脂１００重量部に対し、０．００５〜０．０４重量部の範囲が好ましく、０．０１〜０．０２重量部の範囲がより好ましい。０．００５重量部以上であると造核剤の効果が十分であり、また、０．０４重量部以下であると費用対前記効果（コスト・パフォーマンス）の点から有利である。

R ₁ to R _3: Examples of nucleating agents consisting of t- butyl triaminobenzene derivatives, BASF Corporation, trade name: IRGACLEAR XT386 and the like.
The content of the nucleating agent (F) used in the propylene-based resin composition is 0.005 to 0.04 parts by weight of the nucleating agent (F) with respect to 100 parts by weight of the propylene-based resin.
The content of the nucleating agent (F) used selectively in the medical propylene-based resin composition of the present invention is preferably in the range of 0.005 to 0.04 parts by weight with respect to 100 parts by weight of the propylene-based resin. A range of 0.01 to 0.02 parts by weight is more preferable. When the amount is 0.005 part by weight or more, the effect of the nucleating agent is sufficient, and when the amount is 0.04 part by weight or less, it is advantageous from the viewpoint of the cost to the effect (cost / performance).

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 fatty acid metal salts such as calcium stearate, zinc stearate, and magnesium stearate, hydrotalcite (trade name: DHT-4A, manufactured by Kyowa Chemical Industry Co., Ltd., the following formula (8). Magnesium aluminum composite hydroxide salt), Mizukarak (trade name, lithium aluminum composite hydroxide salt represented by the following formula (9) manufactured by Mizusawa Chemical Industry Co., Ltd.), and the like.

Mg _1-x Al _x (OH) ₂ (CO ₃ ) _{x / 2} · mH ₂ O (8)
[Wherein x is 0 <x ≦ 0.5, and m is a number of 3 or less. ]

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

  The blending amount of the neutralizing agent is preferably in the range of 0.005 to 0.2 parts by weight and more preferably in the range of 0.02 to 0.15 parts by weight with respect to 100 parts by weight of the propylene-based resin.

Lubricant In the propylene-based resin composition of the present invention, a lubricant may be blended within a range in which the effect of the present invention is obtained. Examples of the lubricant include known lubricants, but calcium stearate, butyl stearate and silicone oil are 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, more preferably 0.03 to 100 parts by weight of the propylene-based resin from the viewpoints of effects and economy. -0.1 part by weight is particularly preferred.

Phenol-based antioxidants Phenol-based antioxidants are preferably used as little as possible because they can cause yellowing in radiation sterilization applications.
In the yellowing, the content of the phenolic antioxidant is preferably less than 0.005 parts by weight with respect to 100 parts by weight of the propylene resin.
Examples of phenolic antioxidants include 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 And phenolic antioxidants such as

Other additives In the propylene-based resin composition of the present invention, in addition to the above-described components, various antioxidants, ultraviolet absorbers, light stabilizers and the like used as stabilizers for propylene-based polymers are added. 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, Di-stearyl-β, β′-thio-di-propionate, di-myristyl-β, β′-thio-di-propionate, di-lauryl-β, β′-thio- - propionate, and the like thio-based antioxidants such as.

  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.

  Furthermore, an amine-based antioxidant represented by the following formula (10) or the following formula (11) having no discoloration due to radiation treatment and good NOx gas discoloration resistance, 5,7-di-t-butyl-3- ( Examples thereof include lactone antioxidants such as 3,4-di-methyl-phenyl) -3H-benzofuran-2-one and vitamin E antioxidants such as the following formula (12).

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

[2] Propylene-based resin composition production method The propylene-based resin composition of the present invention comprises a propylene-ethylene random copolymer (I), an ethylene-propylene-butene copolymer (II), a nucleating agent, and further necessary. Depending on the situation, other additives, polyethylene, etc. are put into Henschel mixer (trade name), super mixer, ribbon blender, etc., and mixed, then normal single screw extruder, twin screw extruder, Banbury mixer, plastic bender It can be obtained by melt kneading in a temperature range of 190 to 260 ° C. with a roll or the like.

[3] Molded Product The molded product of the present invention can be obtained by molding the above-described propylene-based resin composition with various molding machines such as a known extrusion molding machine, injection molding machine, and blow molding machine.

As the molded product of the present invention, an injection molded product, an extrusion molded product, a hollow molded product, a compression molded product, a calendar molded product, a laminated molded product, a fluidized immersion molded product, a blow molded product, a slush molded product, a rotational molded product, There are thermoformed products, CCM molded products, etc., which are particularly suitable for injection molded products. Specific molded products include food containers (pudding containers, jelly containers, yogurt containers, tea-steamed containers, instant noodle containers, chilled coffee containers, dessert containers, lunch boxes, etc.), caps (plastic bottle caps, 1-piece caps, 2-piece caps) , Instant coffee caps), medical instruments and containers (disposable syringes and parts thereof, catheters, tubes, infusion bags, blood bags, vacuum blood collection tubes, surgical nonwovens, blood filters, blood circuits, etc. Artificial organ parts such as artificial lungs, colostomy, dialyzers, prefilled syringes, kit preparations, drug containers, test tubes, sutures, compresses, parts of dental materials, parts of orthopedic materials, contact lenses Case, contact lens manufacturing type PTP, SP / packaging, P vial, eye drops container, chemical container, liquid long-term storage container, etc., medical container (infusion pack), daily necessities (costume case, bucket, wash basin, writing instrument), automobile parts (instrument panel) , Bumpers, lamps, etc.), electrical components (such as housings of various electrical devices), solar cell encapsulants, films, fibers, sheets, etc., but this composition is particularly suitable for medical products. Yes.
In the case of medical products, there are many cases of sterilization. Examples of sterilization methods include gas sterilization (EOG), high-pressure steam sterilization, and radiation sterilization (γ rays, electron beams). I can do it. In particular, the composition is suitable for medical use that is subjected to radiation sterilization treatment, and has excellent performance after radiation sterilization. The dose of radiation sterilization is preferably 1 kGy to 60 kGy, more preferably 1 kGy to 50 kGy, and even more preferably 10 kGy to 35 kGy in terms of sterilization effect and material deterioration although it depends on the product.

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

1. Measurement method and evaluation method of physical properties (1) Flexural modulus:
It measured at 23 degreeC based on JISK7171.
(2) Charpy impact strength:
Using a test piece with a notch, measurement was performed at 23 ° C. according to JIS K7111 (unit: kJ / m ² ).
(3) Haze value:
It measured based on JISK7136 using the sheet piece of thickness 1mm.
(4) MFR
It measured based on JISK7210 (230 degreeC, 2.16kg load).
(5) Hue The degree of yellowness of the pellet was confirmed visually.
○: Does not feel yellow.
X: I feel yellow.
(6) Radiation sterilization treatment: Specimens or pellets were irradiated with γ rays at a dose of 25 kGy or 50 kGy, and each measurement was carried out 2 weeks after the irradiation.

2. Resin (1) Propylene-ethylene random copolymer (I)
Specific examples (PP-1 and PP-2) are shown below as equivalent to the propylene-ethylene random copolymer (I).
○ PP-1
Production Example (Propylene-Ethylene Random Copolymer Production Method)

A. Production of transition metal compound component (a) Synthesis of metallocene compound:
Synthesis of (r) -dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4H-azulenyl}] zirconium was performed by the method described in JP-A-11-240909. did.

(B) Preparation of chemically treated ion exchange layered silicate:
To a 10-liter glass separable flask equipped with a stirring blade, 3.75 liters of distilled water was added slowly followed by 2.5 kg of concentrated sulfuric acid (96%). At 50 ° C., 1 kg of montmorillonite (Mizusawa Chemical Co., Ltd. Benclay SL) was further dispersed, the temperature was raised to 90 ° C., and the temperature was maintained for 6.5 hours. After cooling to 50 ° C., the slurry was filtered under reduced pressure to recover the cake. 7 liters of distilled water was added to this cake, and after reslurry, it was filtered. This washing operation was performed until the pH of the washing liquid (filtrate) exceeded 3.5.
The collected cake was dried at 110 ° C. overnight under a nitrogen atmosphere. The weight after drying was 705 g.
The composition (molar) ratio of the obtained ion-exchanged layered silicate was Al / Si = 0.129, Mg / Si = 0.018, Fe / Si = 0.133.
The silicate previously chemically treated was further dried by a kiln dryer. The specifications and conditions of the dryer are as follows.
Rotating cylinder: cylindrical, inner diameter 50 mm, humidification zone 550 mm (electric furnace), with lifting blades Rotation speed: 2 rpm, tilt angle: 20/520, silicate feed rate: 2.5 g / min, gas flow rate: nitrogen, 96 liters / hour, countercurrent drying temperature: 200 ° C. (powder temperature)

(C) Preparation of solid catalyst Into a metal reactor equipped with a stirrer having an internal volume of 13 liters, the mixture of 0.20 kg of the dried silicate obtained above and 0.74 liters of heptane was introduced, and tri-normal octylaluminum 1.26 liters of heptane solution (0.04M) was added to maintain the system temperature at 25 ° C. After the reaction for 1 hour, it was thoroughly washed with heptane, and the silicate slurry was adjusted to 2.0 liters.
0.80 liters of heptane was added to 2.18 g (3.30 mmol) of (r) -dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4H-azulenyl}] zirconium. Then, 33.1 ml of a heptane solution of triisobutylaluminum (0.71 M) was added, and the mixture reacted at room temperature for 1 hour was added to the silicate slurry. After stirring for 1 hour, heptane was added to add 5.0. Adjusted to liters.
Subsequently, at a temperature of 40 ° C., propylene was supplied at a rate of 100 g / hour, and prepolymerization was performed for 4 hours. Further polymerization was carried out for 1 hour.
After completion of the prepolymerization, the residual monomer was purged, and the catalyst was thoroughly washed with heptane. Subsequently, 0.17 L of a heptane solution of triisobutylaluminum (0.71 M / L) was added, followed by drying at 45 ° C. under reduced pressure. By this operation, 0.60 kg of a dried prepolymerized catalyst was obtained.

[Catalyst synthesis]
1 kg of commercially available montmorillonite was dispersed in 6.3 liters of demineralized water in which 1.25 kg of magnesium chloride was dissolved, and the mixture was stirred at 80 ° C. for 1 hour. This solid was washed with water, then dispersed in 7 liters of an 8% aqueous hydrochloric acid solution, stirred at 90 ° C. for 2 hours, and washed with demineralized water. The montmorillonite water slurry was adjusted to a solid content concentration of 15% and spray granulated with a spray dryer to obtain spherical particles. Thereafter, the particles were dried under reduced pressure at 200 ° C. for 2 hours.

[Preparation of catalyst components]
The chemically treated montmorillonite (5.04 g) obtained above was introduced into a glass reactor equipped with a stirring blade having an internal volume of 0.3 liter, and toluene and a toluene solution of triethylaluminum (30.2 mmol) were added, followed by stirring at room temperature. did. After 1 hour, it was washed with toluene (residual liquid ratio: less than 1%).
Next, 30 ml of a toluene slurry solution of 0.0752 mmol of (r) -dimethylsilylenebis (2-methyl-4-phenyldihydroazurenyl) zirconium dichloride of the above synthesis and toluene of triisobutylaluminum (0.75 mmol) were added to a 100 ml flask. 0.93 ml of the solution was added at room temperature and stirred.
Subsequently, 400 ml of normal heptane was introduced into a stirring autoclave having an internal volume of 1.0 liter sufficiently substituted with propylene and kept at 40 ° C. Thereto was added 6.3 ml of a toluene solution of triisobutylaluminum (5.08 mmol), and then the previously prepared montmorillonite was further prepared from the above-prepared (r) -dimethylsilylenebis (2-methyl-4-phenyldihydroazurenyl). ) A mixed solution of zirconium dichloride and triisobutylaluminum was introduced. The pressure was increased to 5 kg · f / cm ² (0.49 MPa), and the temperature and pressure were maintained. After 30 minutes, propylene was purged, and the prepolymerized catalyst slurry was collected with a siphon and dried under reduced pressure at room temperature. By this operation, a prepolymerized catalyst containing 1.47 g of polypropylene per 1 g of catalyst was obtained.

B. Production of Propylene-Ethylene Random Copolymer (I) Liquid propylene 38 kg / hr, ethylene 1.4 kg / hr, hydrogen 0.2 g / hr, and triisobutylaluminum (TIBA) in an agitated autoclave with an internal volume of 270 L Was continuously fed at 9 g / hr. An internal temperature was maintained at 60 ° C., and a constant amount of a liquid paraffin slurry (White Rex 335 manufactured by TonenGeneral Sekiyu KK) of the above catalyst was continuously supplied to obtain 11 kg / hr of a propylene-ethylene random copolymer. . MFR = 7.0 (g / 10 min), ethylene content = 3.4 (% by weight).
This propylene-ethylene random copolymer was designated as PP-1.

○ PP-2
Propylene-ethylene random copolymer: PP-2, conditions adjusted by the same method as PP-1, with MFR = 7.0 (g / 10 min) and ethylene content = 2.0 (wt%) Got.

(2) Ethylene-propylene-butene copolymer (II)
MFR (JIS K7210, 230 ° C., 2.16 kg load) = 6 g / 10 minutes, ethylene content 9.5 wt%, butene content 7.5 wt% (Mitsui Chemicals Co., Ltd.) from ¹³ C-NMR analysis , Trade name: Toughmer PN-9060). This was designated as EPB-1.

Nucleating agent corresponding to nucleating agent / nucleating agent (B) nucleating agent manufactured by ADEKA Co., Ltd. Product name: ADK STAB NA-21 (NA-21)

Phosphorus antioxidant product name: Irgaphos 168 (IF168; manufactured by BASF). Tris (2,4-di-tert-butylphenyl) phosphite.
-Hindered amine type | system | group antioxidant Brand name: Tinuvin 622LD (TNV622LD; BASF Corporation make). Dimethyl succinate, 1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate, calcium stearate (CAST; manufactured by NOF Corporation)

[Example 1, Comparative Examples 1-2]
Polymers and additives were prepared at the blending ratios (parts by weight) shown in Table 1, dry blended for 3 minutes with a super mixer, and then melt-kneaded using a 35 mm diameter twin screw extruder. Extrusion pelletization was performed from the die at a die outlet temperature of 220 ° C. The obtained pellets were injection-molded with an injection molding machine at a resin temperature of 220 ° C. 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 clear from Table 1, Example 1 uses the propylene resin composition of the present invention, and is excellent in rigidity, impact strength after radiation sterilization, transparency, and yellowing after γ-ray irradiation. It turns out that it is an excellent one that is almost absent. In medical applications, there are many products that are sterilized by radiation, and there is a problem that the material strength decreases and breaks after radiation sterilization.Products using the propylene-based resin composition of the present invention are particularly suitable for this application. I think.

  Although the present invention can be used in various applications, it can be suitably used for a syringe member used as a medical instrument to be sterilized by radiation, an artificial dialysis member, or the like.

Claims (9)

  The melt flow rate (hereinafter sometimes abbreviated as MFR) conforming to JIS K7210 (230 ° C., 2.16 kg load) is 3 to 150 g / 10 minutes, and the ethylene content is 0.5 to 5% by weight. Propylene-ethylene random copolymer (I) 60-99 wt%, MFR 1-15 g / 10 min, ethylene content 8-15 wt%, butene content 6-20 wt% ethylene-propylene -Propylene resin composition comprising 0.005 to 0.4 parts by weight of a nucleating agent with respect to 100 parts by weight of a propylene resin comprising 1 to 40% by weight of a butene copolymer (II) object. The nucleating agent is 0.005 to 0.3 parts by weight of a nucleating agent (A) represented by the following formula (1), and 0.005 to 0.25 nucleating agent (B) represented by the following formula (2). Parts by weight, nucleating agent (C) represented by the following formula (3) 0.005 to 0.15 parts by weight, nucleating agent (D) represented by the following formula (4) 0.1 to 0.3 parts by weight A group consisting of 0.1 to 0.4 parts by weight of a nucleating agent (E) represented by the following formula (5) and 0.005 to 0.04 parts by weight of a nucleating agent (F) comprising a triaminobenzene derivative The propylene-based resin composition according to claim 1, wherein the propylene-based resin composition is at least one nucleating agent selected from the group consisting of:

[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 both lithium ions, or a single metal selected independently from the group consisting of calcium, strontium, zinc, magnesium and monobasic aluminum. 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 (here Any two vicinal (bonded to adjacent carbon) or geminal (bonded to the same carbon) alkyl groups may form together 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 (fluorine, chlorine, bromine and iodine), as well as or phenyl Are each selected from the group consisting. ]

(In the formula, m and n independently represent an integer of 1 to 5, and R ¹ and R ² each represents an alkyl group having 1 to 18 carbon atoms or a halogen group.)

[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, R ⁶ is a halogen group or a phenyl group, and R ⁶ is an alkyl group having 1 to 20 carbon atoms. ] The propylene-based resin according to claim 2, wherein the nucleating agent (E) is a compound represented by the following formula (6), or the nucleating agent (F) is a compound represented by the following formula (7). Composition.

R _{1 to} R ₃ : t-butyl   The propylene-based resin composition according to any one of claims 1 to 3, wherein the propylene-based resin composition is for medical use.   The propylene-based resin composition according to any one of claims 1 to 4, wherein the content of the phenol-based antioxidant is less than 0.005 parts by weight with respect to 100 parts by weight of the propylene-based resin. A propylene-based resin composition.   A molded article obtained by using the propylene-based resin composition according to any one of claims 1 to 5.   A molded product for medical use which is sterilized by radiation with a dose of 1 kGy to 60 kGy in the molded product according to claim 6.   The molded product according to claim 6 or 7, which is a syringe member.   The molded product according to claim 6 or 7, which is an artificial dialysis member.