JP2006061505A - Medical container molding material and medical container - Google Patents

Medical container molding material and medical container Download PDF

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JP2006061505A
JP2006061505A JP2004249100A JP2004249100A JP2006061505A JP 2006061505 A JP2006061505 A JP 2006061505A JP 2004249100 A JP2004249100 A JP 2004249100A JP 2004249100 A JP2004249100 A JP 2004249100A JP 2006061505 A JP2006061505 A JP 2006061505A
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medical container
molding material
container
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propylene
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Akira Yotsutsuji
晃 四つ辻
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COKI ENGINEERING Inc
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COKI ENGINEERING Inc
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
    • A61B50/00—Containers, covers, furniture or holders specially adapted for surgical or diagnostic appliances or instruments, e.g. sterile covers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61J—CONTAINERS SPECIALLY ADAPTED FOR MEDICAL OR PHARMACEUTICAL PURPOSES; DEVICES OR METHODS SPECIALLY ADAPTED FOR BRINGING PHARMACEUTICAL PRODUCTS INTO PARTICULAR PHYSICAL OR ADMINISTERING FORMS; DEVICES FOR ADMINISTERING FOOD OR MEDICINES ORALLY; BABY COMFORTERS; DEVICES FOR RECEIVING SPITTLE
    • A61J1/00—Containers specially adapted for medical or pharmaceutical purposes
    • A61J1/05—Containers specially adapted for medical or pharmaceutical purposes for collecting, storing or administering blood, plasma or medical fluids ; Infusion or perfusion containers
    • A61J1/10—Bag-type containers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
    • A61M5/00—Devices for bringing media into the body in a subcutaneous, intra-vascular or intramuscular way; Accessories therefor, e.g. filling or cleaning devices, arm-rests
    • A61M5/178—Syringes
    • A61M5/31—Details
    • A61M5/3129—Syringe barrels

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Abstract

<P>PROBLEM TO BE SOLVED: To provide a molding material which enables the molding of a medical container capable of satisfying all characteristics required for a medical container molding, and the medical container as the molding. <P>SOLUTION: In the medical container molding material, a 0.001-5.0 pts.wt. phosphate compound, which is expressed by formula (1), is added as a clarifying nucleating agent to a 100 pts.wt. propylene-based polymer. In formula (1), R<SP>1</SP>, R<SP>2</SP>, R<SP>3</SP>and R<SP>4</SP>represent each hydrogen atom, or a straight chain, a branched chain or an annular alkyl group; R represents a direct coupling or an alkylidene group; and M represents a trivalent metal atom. The medical container is provided as the molding of the medical container molding material. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

本発明は、医療用容器成形材料及び医療用容器に関する。   The present invention relates to a medical container molding material and a medical container.

注射筒等の医療用容器である成形体には、薬剤液の濁り、投与量の確認等のために透明性に優れること、薬剤液を充填して長期間保存した場合に成形体から薬剤液への溶出物が少ないこと、蒸気滅菌に耐える耐熱性を有すること、及び成形品の滅菌工程であるガンマ線照射に耐性を示すことという特性が要求される。   The molded body, which is a medical container such as a syringe barrel, has excellent transparency for confirming the turbidity of the drug solution, dosage, etc., and when the drug solution is filled and stored for a long time, There are required properties such as a small amount of leached product, heat resistance to withstand steam sterilization, and resistance to gamma irradiation, which is a sterilization process of molded products.

従来、注射筒等の医療用容器として、プロピレン系重合体に、透明化核剤としてソルビトール系化合物を添加した成形品が、知られている。しかし、この成形品には、薬剤液への溶出物が多く、又薬剤を変質させる場合があるため長期保存に耐えないという問題があった。   Conventionally, as a medical container such as a syringe, a molded product in which a sorbitol-based compound is added as a transparent nucleating agent to a propylene-based polymer is known. However, this molded product has a problem that it cannot withstand long-term storage because it contains a large amount of eluate in the drug solution and may alter the drug.

上記問題を解決するため、プロピレン系重合体に、リン酸エステル系の透明化核剤を添加した成形体が公知である（特許文献１参照）。この特許で核剤として使用されている代表的な化合物は、下記式で表されるメチレンビス（２，４−ジ−ｔ−ブチルフェノール）フォスフェートＮａ塩である。   In order to solve the above problems, a molded body obtained by adding a phosphate ester-based transparent nucleating agent to a propylene-based polymer is known (see Patent Document 1). A typical compound used as a nucleating agent in this patent is methylene bis (2,4-di-t-butylphenol) phosphate Na salt represented by the following formula.

Figure 2006061505
Figure 2006061505

また、該核剤として、上記化合物のＮａに代えて、Ｌｉ、Ｋ等の一価金属が置換した化合物、Ｍｇ、Ｃａ、Ｓｒ、Ｂａ等の二価金属が置換し且つ二量体とした化合物、Ａｌ等の三価金属が置換し且つ三量体とした化合物を例示している。   In addition, as the nucleating agent, a compound in which a monovalent metal such as Li or K is substituted in place of Na in the above compound, a compound in which a divalent metal such as Mg, Ca, Sr or Ba is substituted and a dimer is formed Examples of the compound substituted with a trivalent metal such as Al and trimer are illustrated.

しかし、上記核剤はプロピレン系重合体に対して分散性が悪い場合があり、又上記核剤をプロピレン系重合体に添加した成形材料から得られる成形体は、透明性が十分とはいえず日本薬局方の規格値をクリアできない場合がある、ガンマ線照射耐性が低い等の問題点をかかえている。
特許第３１９５４３４号公報 However, the nucleating agent may have poor dispersibility with respect to the propylene-based polymer, and a molded body obtained from a molding material obtained by adding the nucleating agent to the propylene-based polymer may not be sufficiently transparent. It has problems such as inability to clear Japanese Pharmacopoeia standard values and low gamma irradiation resistance.
Japanese Patent No. 3195434

本発明の目的は、透明性に優れること、溶出物が少ないこと、蒸気滅菌に耐える耐熱性を有すること及びガンマ線照射耐性が高いことという医療用容器成形体に要求される特性を全て満足し得る医療用容器を成形できる成形材料及び該成形体である医療用容器を提供することにある。   The object of the present invention can satisfy all of the properties required for a medical container molded article, which is excellent in transparency, has few eluates, has heat resistance to withstand steam sterilization, and has high gamma irradiation resistance. It is providing the molding material which can shape | mold a medical container, and the medical container which is this molded object.

本発明者は、上記特許文献１に記載されたリン酸エステル系の透明化核剤をプロピレン系重合体に添加した成形材料から得られる成形体の問題点を解消すべく鋭意研究した。   The present inventor has intensively studied to solve the problems of a molded product obtained from a molding material obtained by adding a phosphate ester-based transparent nucleating agent described in Patent Document 1 to a propylene-based polymer.

その結果、特定構造のリン酸エステル化合物である透明化核剤はプロピレン系重合体に対して分散性が良いこと、成形体の透明化能及び成形体からの溶出防止能が優れること、得られる成形体の耐熱性及びガンマ線照射耐性に優れること等を見出した。本発明は、かかる新たな知見に基づいて、完成されたものである。   As a result, the clarification nucleating agent which is a phosphate ester compound having a specific structure has good dispersibility with respect to the propylene polymer, and is excellent in the transparency of the molded product and the ability to prevent elution from the molded product. It has been found that the molded article has excellent heat resistance and gamma irradiation resistance. The present invention has been completed based on such new findings.

本発明は、以下の医療用容器用成形材料及び医療用容器を提供するものである。   The present invention provides the following molding materials for medical containers and medical containers.

１．プロピレン系重合体１００重量部に、透明化核剤として一般式（１）   1. In 100 parts by weight of a propylene polymer, the general formula (1)

Figure 2006061505
Figure 2006061505

（式中、Ｒ1、Ｒ2、Ｒ3及びＲ4は、同一又は異なって、水素原子又は直鎖、分岐鎖もしくは環状のアルキル基を示す。Ｒは、直接結合又はアルキリデン基を示す。Ｍは、三価の金属原子を示す。）で表されるリン酸エステル化合物を０．００１〜５．０重量部配合してなる医療用容器用成形材料。 (In the formula, R 1 , R 2 , R 3 and R 4 are the same or different and each represents a hydrogen atom or a linear, branched or cyclic alkyl group. R represents a direct bond or an alkylidene group. M Represents a trivalent metal atom.) A molding material for medical containers comprising 0.001 to 5.0 parts by weight of a phosphate ester compound represented by the formula:

２．一般式（１）におけるＭが、Ａｌである上記項１に記載の成形材料。   2. Item 2. The molding material according to Item 1, wherein M in the general formula (1) is Al.

３．上記項１に記載の成形材料を成形して得られる医療用容器。   3. A medical container obtained by molding the molding material according to item 1.

４．医療用容器が、注射筒である上記項３に記載の容器。   4). Item 4. The container according to Item 3, wherein the medical container is a syringe.

５．医療用容器が、点滴用容器である上記項３に記載の容器。   5. Item 4. The container according to Item 3, wherein the medical container is an infusion container.

６．医療用容器が、輸液用容器である上記項３に記載の容器。   6). Item 4. The container according to Item 3, wherein the medical container is an infusion container.

本発明の成形材料によれば、透明性に優れ、薬剤液を充填して長期間保存しても溶出物が少なく、蒸気滅菌に耐える耐熱性を有し、且つガンマ線照射耐性が高いという医療用容
器成形体に要求される特性を全て満足し得る医療用容器成形品が得られるという顕著な効果が奏される。 According to the molding material of the present invention, it is excellent in transparency, has a small amount of eluate even after being stored for a long time after filling with a drug solution, has heat resistance to withstand steam sterilization, and has high gamma irradiation resistance. The remarkable effect that the medical container molded product which can satisfy all the characteristics requested | required of a container molded object is obtained is show | played.

従って、本発明成形材料から得られる成形体は、使い捨て用注射筒、薬剤充填用注射筒、点滴用容器、輸液用容器等の医療用容器として好適に使用できる。   Therefore, the molded body obtained from the molding material of the present invention can be suitably used as a medical container such as a disposable syringe, a drug filling syringe, an infusion container, an infusion container, and the like.

本発明の医療用容器成形材料は、基材であるプロピレン系重合体、及び透明化核剤である一般式（１）のリン酸エステル化合物を含有することを特徴とする。   The medical container molding material of the present invention is characterized by containing a propylene polymer as a base material and a phosphate ester compound of the general formula (1) as a clarification nucleating agent.

プロピレン系重合体としては、プロピレン単独重合体に限定されず、プロピレンを主体とする重合体であれば、他のモノマーとの結晶性の共重合体や、結晶性ポリプロピレンと他のポリマーとのブレンド物をも包含する。プロピレンを主体とした結晶性の共重合体としては、プロピレン・エチレンランダム共重合体、プロピレン・ブテン−１共重合体等が好ましい。また、結晶性ポリプロピレンにブレンドする他のポリマーとしては、エチレン・ブテン共重合体等が挙げられる。   The propylene polymer is not limited to a propylene homopolymer, and a propylene-based polymer may be a crystalline copolymer with another monomer or a blend of crystalline polypropylene and another polymer. It also includes things. As the crystalline copolymer mainly composed of propylene, propylene / ethylene random copolymer, propylene / butene-1 copolymer and the like are preferable. Other polymers blended with crystalline polypropylene include ethylene / butene copolymers.

これらのプロピレン系重合体のうち、特にプロピレンホモポリマー、又はプロピレンにエチレンを０．５〜７重量％（より好ましくは０．５〜５重量％）共重合させたエチレン・プロピレンランダム共重合体が透明性、耐ガンマ線耐性等の点で好ましい。   Among these propylene polymers, in particular, propylene homopolymers, or ethylene / propylene random copolymers obtained by copolymerizing propylene with 0.5 to 7% by weight (more preferably 0.5 to 5% by weight) of ethylene. It is preferable in terms of transparency and resistance to gamma rays.

本発明成形材料においては、プロピレン系重合体に配合される透明化核剤として、前記一般式（１）で表されるリン酸エステル化合物を用いることが必要である。このリン酸エステル化合物は、三価の金属原子に一個の水酸基及び特定の２個のリン酸エステルが結合した構造を有しており、プロピレン系重合体に対する分散性が良い。   In the molding material of the present invention, it is necessary to use the phosphate ester compound represented by the general formula (1) as a clearing nucleating agent blended in the propylene-based polymer. This phosphate ester compound has a structure in which one hydroxyl group and two specific phosphate esters are bonded to a trivalent metal atom, and has good dispersibility in a propylene-based polymer.

一般式（１）において、Ｒで示されるアルキリデン基としては、例えば、メチリデン基、エチリデン基、イソプロピリデン基、ブチリデン基等の炭素数１〜６の低級アルキリデン基が好ましい。Ｒ1、Ｒ2、Ｒ3及びＲ4で示されるアルキル基としては、例えば、メチル基、エチル基、イソプロピル基、ｎ−プロピル基、ｎ−ブチル基、イソブチル基、ｓ−ブチル基、ｔ−ブチル基等の直鎖、分岐鎖又は環状の炭素数１〜６の低級アルキル基が好ましい。また、Ｍで示される三価の金属原子としては、アルミニウム（Ａｌ）、鉄（Ｆｅ）、ボロン（Ｂ）等が好ましい。三価の金属原子としては、アルミニウム及び鉄がより好ましく、アルミニウムが最も好ましい。 In the general formula (1), the alkylidene group represented by R is preferably a lower alkylidene group having 1 to 6 carbon atoms such as a methylidene group, an ethylidene group, an isopropylidene group, or a butylidene group. Examples of the alkyl group represented by R 1 , R 2 , R 3 and R 4 include a methyl group, ethyl group, isopropyl group, n-propyl group, n-butyl group, isobutyl group, s-butyl group, t- A linear, branched or cyclic lower alkyl group having 1 to 6 carbon atoms such as a butyl group is preferred. The trivalent metal atom represented by M is preferably aluminum (Al), iron (Fe), boron (B), or the like. As the trivalent metal atom, aluminum and iron are more preferable, and aluminum is most preferable.

一般式（１）で表されるリン酸エステル化合物の内、好ましい化合物である下記一般式（２）で表される金属原子がＡｌである化合物及び下記一般式（３）で表される金属原子がＦｅである化合物を、示す。   Among the phosphoric acid ester compounds represented by the general formula (1), preferred compounds are those in which the metal atom represented by the following general formula (2) is Al and the metal atoms represented by the following general formula (3) A compound in which is Fe.

Figure 2006061505
Figure 2006061505

Figure 2006061505
Figure 2006061505

各式中、Ｒ1、Ｒ2、Ｒ3、Ｒ4及びＲは前記に同じ。 In each formula, R 1 , R 2 , R 3 , R 4 and R are the same as above.

一般式（１）で表されるリン酸エステル化合物のプロピレン系重合体に対する配合量は、該重合体１００重量部に対して、該リン酸エステル化合物を０．００１〜５．０重量部である。配合量が、０．００１重量部未満では、得られる成形体の透明性が不十分な場合があり、又薬剤液を充填した場合の溶出防止が不十分な場合がある。一方、５．０重量部を超えて配合しても、それ以上の効果は得られ難い。該リン酸エステル化合物添加量は、好ましくは０．０１〜３．０重量部程度、より好ましくは０．０５〜０．５重量部程度である。   The compounding quantity with respect to the propylene-type polymer of the phosphate compound represented by General formula (1) is 0.001-5.0 weight part of this phosphate compound with respect to 100 weight part of this polymer. . If the blending amount is less than 0.001 part by weight, the resulting molded article may have insufficient transparency, and may be insufficient in preventing elution when filled with a drug solution. On the other hand, even if it exceeds 5.0 parts by weight, it is difficult to obtain further effects. The addition amount of the phosphate ester compound is preferably about 0.01 to 3.0 parts by weight, more preferably about 0.05 to 0.5 parts by weight.

本発明の成形材料には、必要に応じて、酸化防止剤、中和剤、帯電防止剤、有機過酸化物等を添加することができる。   If necessary, an antioxidant, a neutralizing agent, an antistatic agent, an organic peroxide, and the like can be added to the molding material of the present invention.

上記酸化防止剤としては、フェノール系酸化防止剤、ホスファイト系酸化防止剤等が挙げられる。   Examples of the antioxidant include phenolic antioxidants and phosphite antioxidants.

フェノール系酸化防止剤の代表例として、テトラキス〔メチレン−３（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート〕メタン、１，３，５−トリス（３，５−ジ−ｔ−ブチル−４−ヒドロキシベンジル）−イソシアヌレート、１，３，５−トリス（３，５−ジ−ｔ−ブチル−４−ヒドロキシベンジル）−２，４，６−トリメチルベンゼン等を挙げることができる。テトラキス〔メチレン−３（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート〕メタンの市販品として、「イルガノックス１０１０」（商標、チバ・スペシャリティ・ケミカルズ（株）製）を使用することができる。   Representative examples of phenolic antioxidants include tetrakis [methylene-3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, 1,3,5-tris (3,5-di-t -Butyl-4-hydroxybenzyl) -isocyanurate, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene . Tetrakis [methylene-3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, "Irganox 1010" (trademark, manufactured by Ciba Specialty Chemicals Co., Ltd.) is used. be able to.

ホスファイト系化合物の特に好ましい例として、トリス（２，４−ジ−ｔ−ブチルフェニル）フォスファイトを挙げることができる。この化合物の市販品として、「イルガフォス１６８」（商標、チバ・スペシャリティ・ケミカルズ（株）製）を使用することができる。   A particularly preferred example of the phosphite compound is tris (2,4-di-t-butylphenyl) phosphite. As a commercial product of this compound, “Irgaphos 168” (trademark, manufactured by Ciba Specialty Chemicals Co., Ltd.) can be used.

本発明の成形材料は、通常、プロピレン系重合体に本発明特定の核剤及び必要に応じて酸化防止剤等の任意成分を添加して、ドライブレンドし、これを押出機により溶融混合し、ペレット化される。このペレット化した成形材料は、成型機の加熱シリンダ中で再び加熱溶融し、１８０〜２８０℃程度の温度範囲、好ましくは２００〜２３０℃程度の温度範囲で、射出成形、ブロー成形等の方法により、目的の形状に成形することができる。   The molding material of the present invention is usually a propylene-based polymer added with the nucleating agent specific to the present invention and, if necessary, optional components such as an antioxidant, dry blended, melt-mixed by an extruder, Pelletized. This pelletized molding material is heated and melted again in a heating cylinder of a molding machine, and is subjected to a temperature range of about 180 to 280 ° C., preferably about 200 to 230 ° C. by a method such as injection molding or blow molding. , It can be molded into the desired shape.

かくして、本発明成形材料から、使い捨て用注射筒、薬剤充填用注射筒、点滴用容器、輸液用容器等の医療用容器を容易に製造できる。   Thus, medical containers such as disposable syringes, drug filling syringes, infusion containers, and infusion containers can be easily produced from the molding material of the present invention.

以下、実施例及び比較例を挙げて、本発明をより一層具体的に説明する。   Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples.

実施例１
ポリプロピレンホモポリマー（熱変形温度：１１７℃、比重：０．９０、メルトインデックス：８．０ｇ／１０ｍｉｎ）１００ｇに、核剤として下記式（４）で表されるアルミニウム，ヒドロキシビス［２，４，８，１０−テトラキス（１，１−ジメチルエチル）−６−（ヒドロキシ−．カッパ．Ｏ）−１２Ｈ−ジベンゾ［ｄ，ｇ］［１，３，２］ジオキサフォスフォシン ６−オキシダト］０．０１ｇ及び酸化防止剤０．５ｇ（「イルガノックス１０１０」及び「イルガフォス１６８」を各々０．２５ｇ）を添加し、タンブラーでドライブレンドし、押し出し機を用いて、２００〜２２０℃の温度で押し出して、ペレット状の成形材料とした。 Example 1
100 g of polypropylene homopolymer (thermal deformation temperature: 117 ° C., specific gravity: 0.90, melt index: 8.0 g / 10 min), aluminum, hydroxybis [2,4,4 represented by the following formula (4) as a nucleating agent 8,10-tetrakis (1,1-dimethylethyl) -6- (hydroxy-.kappa.O) -12H-dibenzo [d, g] [1,3,2] dioxaphosphine 6-oxidate] 0 Add 0.01 g and 0.5 g of antioxidant (0.25 g each of “Irganox 1010” and “Irgaphos 168”), dry blend with a tumbler, and extrude at a temperature of 200-220 ° C. using an extruder. Thus, a pellet-shaped molding material was obtained.

Figure 2006061505
Figure 2006061505

上記ペレット化した成形材料を用いて、材料可塑化温度２２０℃、射出成型圧力８００ｋｇｆ/ｃｍ2、金型温度２０℃、射出率５０ｍｌ／ｓｅｃ、冷却時間２０秒及び射出時間５秒の成形条件で、注射筒（形状：外径；１４．１ｍｍ、内径；１２．５ｍｍ、長さ；６７ｍｍ、内容量：５ｍｌ）を射出成形した。 Using the pelletized molding material, the molding conditions were a material plasticization temperature of 220 ° C., an injection molding pressure of 800 kgf / cm 2 , a mold temperature of 20 ° C., an injection rate of 50 ml / sec, a cooling time of 20 seconds, and an injection time of 5 seconds. A syringe barrel (shape: outer diameter: 14.1 mm, inner diameter: 12.5 mm, length: 67 mm, inner volume: 5 ml) was injection molded.

実施例２
ポリプロピレンホモポリマー（熱変形温度：１１７℃、比重：０．９０、メルトインデックス：８．０ｇ／１０ｍｉｎ）１００ｇに、前記の式（４）で表される核剤０．２ｇ、及び酸化防止剤０．５ｇ（「イルガノックス１０１０」及び「イルガフォス１６８」を各々０．２５ｇ）を添加し、実施例１と同様にして、ペレット状の成形材料とした。 Example 2
100 g of polypropylene homopolymer (thermal deformation temperature: 117 ° C., specific gravity: 0.90, melt index: 8.0 g / 10 min), 0.2 g of the nucleating agent represented by the above formula (4), and antioxidant 0 .5 g ("Irganox 1010" and "Irgaphos 168" 0.25 g each) was added, and a pellet-shaped molding material was obtained in the same manner as in Example 1.

上記ペレット化した成形材料を用いて、実施例１と同様の成形条件で、実施例１と同じ形状及び内容量の注射筒を射出成形した。   Using the pelletized molding material, a syringe barrel having the same shape and content as in Example 1 was injection molded under the same molding conditions as in Example 1.

実施例３
ポリプロピレンホモポリマー（熱変形温度：１１７℃、比重：０．９０、メルトインデックス：８．０ｇ／１０ｍｉｎ）１００ｇに、前記の式（４）で表される核剤０．３ｇ、及び酸化防止剤０．５ｇ（「イルガノックス１０１０」及び「イルガフォス１６８」を各々０．２５ｇ）を添加し、実施例１と同様にして、ペレット状の成形材料とした。 Example 3
100 g of polypropylene homopolymer (thermal deformation temperature: 117 ° C., specific gravity: 0.90, melt index: 8.0 g / 10 min), 0.3 g of the nucleating agent represented by the above formula (4), and antioxidant 0 .5 g ("Irganox 1010" and "Irgaphos 168" 0.25 g each) was added, and a pellet-shaped molding material was obtained in the same manner as in Example 1.

上記ペレット化した成形材料を用いて、実施例１と同様の成形条件で、実施例１と同じ形状及び内容量の注射筒を射出成形した。   Using the pelletized molding material, a syringe barrel having the same shape and content as in Example 1 was injection molded under the same molding conditions as in Example 1.

実施例４
プロピレン・エチレンランダムコポリマー（エチレン共重合量：３重量％、熱変形温度：１１０℃、比重：０．９１、メルトインデックス：２５．０ｇ／１０ｍｉｎ）１００ｇに、前記の式（４）で表される核剤０．０２ｇ、及び酸化防止剤０．５ｇ（「イルガノックス１０１０」及び「イルガフォス１６８」を各々０．２５ｇ）を添加し、実施例１と同様にして、ペレット状の成形材料とした。 Example 4
100 g of propylene / ethylene random copolymer (ethylene copolymerization amount: 3 wt%, heat distortion temperature: 110 ° C., specific gravity: 0.91, melt index: 25.0 g / 10 min) is expressed by the above formula (4). 0.02 g of a nucleating agent and 0.5 g of an antioxidant (0.25 g each of “Irganox 1010” and “Irgaphos 168”) were added to obtain a pellet-shaped molding material in the same manner as in Example 1.

上記ペレット化した成形材料を用いて、実施例１と同様の成形条件で、実施例１と同じ形状及び内容量の注射筒を射出成形した。   Using the pelletized molding material, a syringe barrel having the same shape and content as in Example 1 was injection molded under the same molding conditions as in Example 1.

比較例１
ポリプロピレンホモポリマー（熱変形温度：１１７℃、比重：０．９０、メルトインデックス：８．０ｇ／１０ｍｉｎ）１００ｇに、核剤として１，３：２，４−ジ−ｐ−メチルジベンジリデンソルビトール０．２５ｇ、及び酸化防止剤０．５ｇ（「イルガノックス１０１０」及び「イルガフォス１６８」を各々０．２５ｇ）を添加し、実施例１と同様にして、ペレット状の成形材料とした。 Comparative Example 1
100 g of polypropylene homopolymer (thermal deformation temperature: 117 ° C., specific gravity: 0.90, melt index: 8.0 g / 10 min), 1,3: 2,4-di-p-methyldibenzylidene sorbitol as a nucleating agent 25 g and 0.5 g of antioxidant ("Irganox 1010" and "Irgafos 168" each 0.25 g) were added, and a pellet-shaped molding material was obtained in the same manner as in Example 1.

上記ペレット化した成形材料を用いて、実施例１と同様の成形条件で、実施例１と同じ形状及び内容量の注射筒を射出成形した。   Using the pelletized molding material, a syringe barrel having the same shape and content as in Example 1 was injection molded under the same molding conditions as in Example 1.

比較例２
ポリプロピレンホモポリマー（熱変形温度：１１７℃、比重：０．９０、メルトインデックス：８．０ｇ／１０ｍｉｎ）１００ｇに、核剤としてメチレンビス（２，４−ジ−ｔ−ブチルフェノール）フォスフェートＮａ塩０．２５ｇ、及び酸化防止剤０．５ｇ（「イルガノックス１０１０」及び「イルガフォス１６８」を各々０．２５ｇ）を添加し、実施例１と同様にして、ペレット状の成形材料とした。 Comparative Example 2
100 g of polypropylene homopolymer (thermal deformation temperature: 117 ° C., specific gravity: 0.90, melt index: 8.0 g / 10 min), methylene bis (2,4-di-t-butylphenol) phosphate Na salt as a nucleating agent 25 g and 0.5 g of antioxidant ("Irganox 1010" and "Irgafos 168" each 0.25 g) were added, and a pellet-shaped molding material was obtained in the same manner as in Example 1.

上記ペレット化した成形材料を用いて、実施例１と同様の成形条件で、実施例１と同じ形状及び内容量の注射筒を射出成形した。   Using the pelletized molding material, a syringe barrel having the same shape and content as in Example 1 was injection molded under the same molding conditions as in Example 1.

医療用容器は、内容物である水、薬剤溶液等に対して、核剤及び酸化防止剤等の樹脂添加剤成分の溶出があってはならない。例えば、内容物が注射液である場合は、直接生体内へ入る為に、生体内における添加剤成分による血液毒性、急性毒性等の各種毒性が重大な問題となるからである。また、内容物の確認のため、透明性も必要である。   The medical container must be free of elution of resin additive components such as nucleating agents and antioxidants with respect to the contents of water, drug solution, and the like. For example, when the content is an injection solution, since it enters directly into the living body, various toxicities such as blood toxicity and acute toxicity due to additive components in the living body become a serious problem. In addition, transparency is necessary to confirm the contents.

従って、実施例１〜４及び比較例１〜２で得られた各注射筒について、日本薬局方に規定されたプラスチック製医薬品容器試験法の基準に沿って、(1)透明性試験及び(2)溶出物試験を行った。各試験方法を以下に示す。   Therefore, for each of the syringes obtained in Examples 1 to 4 and Comparative Examples 1 and 2, in accordance with the criteria of the plastic drug container test method prescribed in the Japanese Pharmacopoeia, (1) Transparency test and (2 ) The eluate test was conducted. Each test method is shown below.

(1)透明性試験
注射筒の胴部を、約０．９×４ｃｍの大きさに切断し、純水が充満された石英ガラスセルに浸漬し、厚さ方向に光線が透過するように試験片をセットし、純水だけを満たしたセルを対照として、４５０ｎｍの可視光線の透過率（％）を測定した。透過率の測定は、分光光度計（商品名「Ｖ−５６０型」、日本分光（株）製）を用いて行った。透過率は、５５％以上が合格である。 (1) Transparency test The barrel of the syringe barrel is cut to a size of about 0.9 x 4 cm, immersed in a quartz glass cell filled with pure water, and tested so that light can be transmitted in the thickness direction. The transmittance | permeability (%) of 450 nm visible light was measured for the cell which set the piece and filled only with the pure water as a control. The transmittance was measured using a spectrophotometer (trade name “V-560 type”, manufactured by JASCO Corporation). A transmittance of 55% or more is acceptable.

(2)溶出物試験
注射筒のできるだけ湾曲が少なく、厚さの均一な部分をとって切断し、厚みが０．５ｍｍ以下のときは、表裏の表面積の合計が約１，２００ｃｍ2になるように、又厚みが０．
５ｍｍを超えるときは、約６００ｃｍ2になるように切断片を集め、更にこれらを長さ約
５ｃｍ、幅約０．５ｃｍの大きさに切断し、水で洗った後、室温で乾燥する。これを内容約３００ｍＬの硬質ガラス製容器に入れ、水２００ｍＬを正確に加え、適当に密封した後、高圧蒸気滅菌器を用いて１２１℃で１時間加熱し、室温になるまで放置し、この液を試験液とした。この試験液について、過マンガン酸カリウム還元性物質試験、紫外線吸収スペクトル吸収物質検出試験及びｐＨ試験を、下記方法により行った。 (2) Elution test When the syringe barrel is cut as little as possible and has a uniform thickness, and the thickness is 0.5 mm or less, the total surface area of the front and back should be about 1,200 cm 2 In addition, the thickness is 0.
When it exceeds 5 mm, the cut pieces are collected so as to be about 600 cm 2 , further cut into a size of about 5 cm in length and about 0.5 cm in width, washed with water, and dried at room temperature. Put this in a hard glass container with a content of about 300 mL, add 200 mL of water accurately, seal it appropriately, heat it at 121 ° C. for 1 hour using a high-pressure steam sterilizer, and let it stand until it reaches room temperature. Was used as a test solution. About this test liquid, the potassium permanganate reducing substance test, the ultraviolet absorption spectrum absorption substance detection test, and the pH test were done by the following method.

過マンガン酸カリウム還元性物質試験
試験液２０ｍＬを共栓三角フラスコにとり、０．００２ｍｏｌ／Ｌ過マンガン酸カリウム液２０ｍＬ及び希塩酸１ｍＬを加え、３分間煮沸し、冷後、これにヨウ化カリウム液０．１０ｇを加えて密栓し、振り混ぜて１０分間放置した後、０．０１ｍｏｌ／Ｌチオ硫酸ナトリウム液で滴定した（指示薬：デンプン試液５滴）。別に、対象として空試験液２０．０ｍＬを用い、同様に操作した。試験液及び空試験液の０．００２ｍｏｌ／Ｌ過マンガン酸カリウム液消費量の差を算出する。消費量の差１．０ｍＬ以下が合格であり、１．０ｍＬを超えた場合は不合格である。 Potassium permanganate reducing substance test Take 20 mL of test solution in a stoppered Erlenmeyer flask, add 20 mL of 0.002 mol / L potassium permanganate solution and 1 mL of dilute hydrochloric acid, boil for 3 minutes, cool, and then add potassium iodide solution 0 10 g was added, sealed, shaken and allowed to stand for 10 minutes, and then titrated with 0.01 mol / L sodium thiosulfate solution (indicator: 5 drops of starch test solution). Separately, 20.0 mL of a blank test solution was used as a target, and the same operation was performed. The difference between the 0.002 mol / L potassium permanganate solution consumption of the test solution and the blank test solution is calculated. A difference in consumption of 1.0 mL or less is acceptable, and when it exceeds 1.0 mL, it is unacceptable.

紫外線吸収スペクトル吸収物質検出試験
試験液につき、空試験液を対象とし、紫外線吸光度測定法により試験を行ったとき、波長２２０〜２４０ｎｍの区間における最大吸光度が０．０８以下であること、波長２４１〜３５０ｎｍの区間における最大吸光度が０．０５以下であることが合格の基準である。吸光度の測定は、分光光度計（商品名「Ｖ−５６０型」、日本分光（株）製）を用いて行った。 UV Absorption Spectrum Absorbing Substance Detection Test For the test solution, when the blank test solution is the target and the test is performed by the ultraviolet absorbance measurement method, the maximum absorbance in the section of wavelength 220 to 240 nm is 0.08 or less, the wavelength 241 to 241 The acceptance criterion is that the maximum absorbance in the 350 nm section is 0.05 or less. The absorbance was measured using a spectrophotometer (trade name “V-560 type”, manufactured by JASCO Corporation).

ｐＨ試験
試験液及び空試験液２０ｍＬずつをとり、これに塩化カリウム１．０ｇを水に溶かして１，０００ｍＬとした液１．０ｍＬずつを加え、両液のｐＨを測定して、その差を算出した。差が１．５以下が合格である。 pH test Take 20 mL each of the test solution and the blank test solution, add 1.0 mL of a solution made by dissolving 1.0 g of potassium chloride in water to 1000 mL, measure the pH of both solutions, and determine the difference between them. Calculated. A difference of 1.5 or less is acceptable.

透明性試験及び溶出物試験の結果を、表１に示す。   Table 1 shows the results of the transparency test and the eluate test.

Figure 2006061505
Figure 2006061505

また、実施例１〜４及び比較例１〜２で得られた各注射筒について、下記方法により、(3)ガンマ線照射試験を行った。   Moreover, about each syringe obtained in Examples 1-4 and Comparative Examples 1-2, the (3) gamma-ray irradiation test was done with the following method.

(3)ガンマ線照射試験
注射筒に２５ＫＧｙのガンマ線を照射し、この試料について、前記紫外線吸収スペクトル吸収物質検出試験を行った。 (3) Gamma ray irradiation test The syringe was irradiated with 25 KGy of gamma rays, and the ultraviolet absorption spectrum absorbing substance detection test was performed on this sample.

ガンマ線照射試験の結果を、表２に示す。   Table 2 shows the results of the gamma irradiation test.

Figure 2006061505
Figure 2006061505

表１及び２の結果より、次の点が明らかである。   From the results of Tables 1 and 2, the following points are clear.

従来の成形材料を用いて得られた比較例１の注射筒は溶出試験が不合格でガンマ線照射耐性が低く、比較例２の注射筒は透明性が不合格でガンマ線照射耐性が低い。   The syringe of Comparative Example 1 obtained using a conventional molding material has a poor elution test and low resistance to gamma irradiation, and the syringe of Comparative Example 2 has poor transparency and low resistance to gamma irradiation.

これに対して、実施例１〜４の本発明の成形材料を用いて得られた注射筒は、透明性、溶出試験における過マンガン酸カリウム液消費量、紫外線吸収スペクトルによる超微量溶出物及び材料の変質耐性を示すｐＨ試験、並びにガンマ線照射耐性等の医療用容器として要求される諸特性を全て満足していることが明らかである。   On the other hand, the syringes obtained using the molding materials of the present invention in Examples 1 to 4 are transparent, the amount of potassium permanganate liquid consumption in the dissolution test, and the ultra-small amount of eluate and material based on the ultraviolet absorption spectrum. It is clear that all the properties required for medical containers such as a pH test showing the alteration resistance of gamma rays and resistance to gamma irradiation are satisfied.

Claims (6)

プロピレン系重合体１００重量部に、透明化核剤として一般式（１）
Figure 2006061505
 （式中、Ｒ1、Ｒ2、Ｒ3及びＲ4は、同一又は異なって、水素原子又は直鎖、分岐鎖もしくは環状のアルキル基を示す。Ｒは、直接結合又はアルキリデン基を示す。Ｍは、三価の金属原子を示す。）で表されるリン酸エステル化合物を０．００１〜５．０重量部配合してなる医療用容器成形材料。 In 100 parts by weight of a propylene polymer, the general formula (1)
Figure 2006061505
 (In the formula, R 1 , R 2 , R 3 and R 4 are the same or different and each represents a hydrogen atom or a linear, branched or cyclic alkyl group. R represents a direct bond or an alkylidene group. M Represents a trivalent metal atom.) A medical container molding material comprising 0.001 to 5.0 parts by weight of a phosphate compound represented by the formula: 一般式（１）におけるＭが、Ａｌである請求項１に記載の成形材料。 The molding material according to claim 1, wherein M in the general formula (1) is Al. 請求項１に記載の成形材料を成形して得られる医療用容器。 A medical container obtained by molding the molding material according to claim 1. 医療用容器が、注射筒である請求項３に記載の容器。 The container according to claim 3, wherein the medical container is a syringe. 医療用容器が、点滴用容器である請求項３に記載の容器。 The container according to claim 3, wherein the medical container is a drip container. 医療用容器が、輸液用容器である請求項３に記載の容器。 The container according to claim 3, wherein the medical container is an infusion container.
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