JPH1147261A - Medical instrument - Google Patents

Medical instrument

Info

Publication number
JPH1147261A
JPH1147261A JP9208739A JP20873997A JPH1147261A JP H1147261 A JPH1147261 A JP H1147261A JP 9208739 A JP9208739 A JP 9208739A JP 20873997 A JP20873997 A JP 20873997A JP H1147261 A JPH1147261 A JP H1147261A
Authority
JP
Japan
Prior art keywords
vinyl chloride
chloride resin
resin composition
phosphite
antibacterial agent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
JP9208739A
Other languages
Japanese (ja)
Inventor
Kazuhisa Matsuda
和久 松田
Wataru Taguchi
亘 田口
Hajime Tsujikawa
肇 辻川
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nissho Corp
Original Assignee
Nissho Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nissho Corp filed Critical Nissho Corp
Priority to JP9208739A priority Critical patent/JPH1147261A/en
Publication of JPH1147261A publication Critical patent/JPH1147261A/en
Pending legal-status Critical Current

Links

Abstract

PROBLEM TO BE SOLVED: To improve hourly discoloring without impairing antibacterial effect in a medical instrument comprising a vinyl chloride resin composition containing a silver ion carried inorganic antibacterial agent. SOLUTION: This medical instrument comprises a vinyl chloride resin composition which contains an antibacterial agent supporting a silver ion on an inorganic carrier but none of ester phosphate. The vinyl chloride resin has a vinyl chloride structure unit at a rate of 50 wt.% or more of a vinyl chloride resin. The inorganic carrier herein used is at least one selected from a group of zeolite, aluminosilicate, zirconium phosphate, porous glass, porous silica, alumina, aluminum polyphosphate, hydroxy apatite, titania and silica gel.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【0001】[0001]

【発明の属する技術分野】本発明は、銀イオン担持無機
系抗菌剤を含有する塩化ビニル樹脂組成物からなる医療
用具に関し、詳しくは、経時的な変色の改善された前記
医療用具に関する。
The present invention relates to a medical device comprising a vinyl chloride resin composition containing a silver ion-carrying inorganic antibacterial agent, and more particularly, to a medical device improved in discoloration over time.

【0002】[0002]

【従来の技術】従来より無機系抗菌剤を各種の樹脂に混
練もしくはコーティングし、抗菌性の成形物を得ること
が行われている。しかしながら、樹脂として塩化ビニル
樹脂を用い、無機系抗菌剤として抗菌効果の高い銀イオ
ン担持無機系抗菌剤を用いた場合には、成形物が経時的
に茶褐色に変色する傾向が見られ、問題であった。そこ
で、このような変色を改善するために、ゼオライト担体
中に含有させる銀イオン等の抗菌性金属イオンをアンモ
ニア錯体やアミン錯体として導入し、ゼオライト担体表
面に過剰な抗菌性金属イオンが存在しないようにしたも
のや(特公平5−67667号公報)、ゼオライト担体
中に銀イオンと共にアンモニウムイオンを担持させたも
の(特公平4−28646号公報)などが提案されてい
る。しかしながら、これらの無機系抗菌剤を塩化ビニル
樹脂組成物に含有させた場合には、成形品の顕著な経時
的変色の改善が困難であり、成形品の商品価値を著しく
損なうものであった。
2. Description of the Related Art Conventionally, an inorganic antibacterial agent has been kneaded or coated with various resins to obtain an antibacterial molded product. However, when a vinyl chloride resin is used as the resin and a silver ion-carrying inorganic antibacterial agent having a high antibacterial effect is used as the inorganic antibacterial agent, the molded article tends to turn brown over time, which is a problem. there were. Therefore, in order to improve such discoloration, an antibacterial metal ion such as silver ion to be contained in the zeolite carrier is introduced as an ammonia complex or an amine complex so that there is no excess antibacterial metal ion on the zeolite carrier surface. And Japanese Patent Publication No. 5-28667, and a zeolite carrier in which ammonium ions are supported together with silver ions in a zeolite carrier (Japanese Patent Publication No. 4-28646). However, when these inorganic antibacterial agents are contained in the vinyl chloride resin composition, it is difficult to improve the remarkable discoloration of the molded article with time, which significantly impairs the commercial value of the molded article.

【0003】[0003]

【発明が解決しようとする課題】本発明は、如上の事情
に鑑みてなされたもので、銀イオン担持無機系抗菌剤を
含有する塩化ビニル樹脂組成物からなる医療用具におい
て、抗菌効果を損なうことなく経時的変色を改善するこ
とを目的とする。
SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and is intended to impair the antibacterial effect of a medical device comprising a vinyl chloride resin composition containing a silver ion-carrying inorganic antibacterial agent. Without discoloration over time.

【0004】[0004]

【課題を解決するための手段】銀イオン担持無機系抗菌
剤を含有する塩化ビニル樹脂組成物の変色は、光、温
度、水分などにより加速される。本発明者等は、鋭意検
討の結果、塩化ビニル樹脂に一般的に配合される添加
剤、特に亜リン酸エステル系添加剤を添加しない場合、
経時的な変色が顕著に改善されることを見出し、本発明
に到達した。すなわち、本発明は、無機担体に銀イオン
を担持させてなる抗菌剤を含有し、かつ亜リン酸エステ
ルを含有しない、塩化ビニル樹脂組成物からなる医療用
具である。ここで、塩化ビニル樹脂は、50重量%以上
の塩化ビニル構造単位を有するものが好ましく、無機担
体は、ゼオライト、アルミノケイ酸、リン酸ジルコニウ
ム、多孔質ガラス、多孔質シリカ、アルミナ、ポリリン
酸アルミニウム、ヒドロキシアパタイト、チタニア、シ
リカゲルの群から選ばれる少なくとも1つが好ましい。
以下、本発明を詳しく説明する。
The discoloration of a vinyl chloride resin composition containing a silver ion-carrying inorganic antibacterial agent is accelerated by light, temperature, moisture and the like. The present inventors, as a result of intensive studies, additives not generally added to the vinyl chloride resin, especially when not adding a phosphite-based additive,
The present inventors have found that discoloration over time is remarkably improved, and have reached the present invention. That is, the present invention is a medical device comprising a vinyl chloride resin composition containing an antibacterial agent having silver ions carried on an inorganic carrier and containing no phosphite. Here, the vinyl chloride resin preferably has a vinyl chloride structural unit of 50% by weight or more, and the inorganic carrier includes zeolite, aluminosilicate, zirconium phosphate, porous glass, porous silica, alumina, aluminum polyphosphate, At least one selected from the group consisting of hydroxyapatite, titania and silica gel is preferred.
Hereinafter, the present invention will be described in detail.

【0005】塩化ビニル樹脂に配合される添加剤として
は、可塑剤、エポキシ化合物、金属石鹸、亜リン酸エス
テル化合物、フェノール系酸化防止剤、着色剤、充填剤
等が挙げられる。可塑剤としては、フタル酸エステル
類、ジアルキルチオジプロピオン酸エステル類、リン酸
エステル類が挙げられ、これらの中、ジアルキルチオジ
プロピオン酸エステル類、リン酸エステル類が軽度の変
色原因物質である。また、フェノール系酸化防止剤も軽
度の変色原因物質であり、特に強い変色原因物質は亜リ
ン酸エステル化合物である。このような変色原因となる
亜リン酸エステル化合物としては、トリオクチルホスフ
ァイト、トリイソオクチルホスファイト、トリノニルホ
スファイト、トリラウリルホスファイト、トリオクタデ
シルホスファイト、ジオクチルアシットホスファイト、
トリラウリルトリチオホスファイト、ジステアリルペン
タエリスリトールジホスファイト等のアルキルホスファ
イト類、トリフェニルホスファイト、トリクレジルホス
ファイト、トリノニルフェニルホスファイト、ジフェニ
ルデシルホスファイト、4.4, −ブチリデン−ビス
(3−メチル−6−t−ブチルフェニル)ジトリデシル
ホスファイト等のアリールホスファイト類およびアルキ
ルアリールホスファイト類の1種または2種以上の混合
物を挙げることができる。
[0005] Examples of additives to be added to the vinyl chloride resin include a plasticizer, an epoxy compound, a metal soap, a phosphite compound, a phenolic antioxidant, a coloring agent, a filler and the like. Examples of the plasticizer include phthalates, dialkylthiodipropionates, and phosphates, and among these, dialkylthiodipropionates and phosphates are substances causing slight discoloration. . Phenolic antioxidants are also mild discoloration causing substances, and particularly strong discoloration causing substances are phosphite compounds. Examples of the phosphite compound causing such discoloration include trioctyl phosphite, triisooctyl phosphite, trinonyl phosphite, trilauryl phosphite, trioctadecyl phosphite, dioctyl acid phosphite,
Alkyl phosphites such as trilauryl trithio phosphite, distearyl pentaerythritol diphosphite, triphenyl phosphite, tricresyl phosphite, trinonyl phenyl phosphite, diphenyl decyl phosphite, 4.4 , -butylidene-bis One or a mixture of two or more of aryl phosphites such as (3-methyl-6-t-butylphenyl) ditridecyl phosphite and alkylaryl phosphites can be mentioned.

【0006】本発明における塩化ビニル樹脂としては、
ポリ塩化ビニルあるいはエチレン−塩化ビニル共重合
体、プロピレン−塩化ビニル共重合体、塩化ビニル−酢
酸ビニル共重合体、ステアリン酸ビニル−塩化ビニル共
重合体、ラウリルビニルエーテル−塩化ビニル共重合体
等の共重合体、およびエチレンビニルアルコール共重合
体とポリ塩化ビニルのグラフト重合体、ポリ塩化ビニル
と塩素化ポリエチレン、メチルメタクリレート−ブタジ
エン−スチレン共重合体等とのポリマーブレンド等であ
って、塩化ビニル構造単位を50重量%以上有するもの
を挙げることができる。
In the present invention, the vinyl chloride resin includes
Polyvinyl chloride or copolymers of ethylene-vinyl chloride copolymer, propylene-vinyl chloride copolymer, vinyl chloride-vinyl acetate copolymer, vinyl stearate-vinyl chloride copolymer, lauryl vinyl ether-vinyl chloride copolymer, etc. A polymer blend of a polymer, an ethylene-vinyl alcohol copolymer and a polyvinyl chloride, a polyvinyl chloride and a chlorinated polyethylene, a methyl methacrylate-butadiene-styrene copolymer, etc. Having 50% by weight or more.

【0007】本発明における銀イオンの無機担体として
は、ゼオライト、アルミノケイ酸、リン酸ジルコニウ
ム、多孔質ガラス、多孔質シリカ、アルミナ、ポリリン
酸アルミニウム、ヒドロキシアパタイト、チタニア、シ
リカゲル等を挙げることができる。これらの担体は、2
種以上の複合体にすることもでき、その粒径は5ミクロ
ン以下、好ましくは1ミクロン以下である。
The inorganic carrier for silver ions in the present invention includes zeolite, aluminosilicate, zirconium phosphate, porous glass, porous silica, alumina, aluminum polyphosphate, hydroxyapatite, titania, silica gel and the like. These carriers are 2
Composites of more than one species can also be formed, the particle size of which is less than 5 microns, preferably less than 1 micron.

【0008】[0008]

【発明の実施の形態】本発明の医療用具は、塩化ビニル
樹脂に銀イオン担持無機系抗菌剤、可塑剤、エポキシ化
合物、金属石鹸および必要により着色剤を配合した、亜
リン酸エステルを含まない組成物を成形してなるもので
あり、各種カテーテルやチューブ、輸液バッグ、血液バ
ッグ等の形成に採用される。以下に実施例を示すが、本
発明はこれによって限定されるものではない。
BEST MODE FOR CARRYING OUT THE INVENTION The medical device of the present invention does not contain a phosphite in which a vinyl chloride resin is mixed with an inorganic antibacterial agent carrying silver ions, a plasticizer, an epoxy compound, a metal soap and, if necessary, a coloring agent. It is formed by molding a composition and is used for forming various catheters, tubes, infusion bags, blood bags and the like. Examples will be shown below, but the present invention is not limited thereto.

【0009】〔実施例1〕ポリ塩化ビニルにフタル酸ジ
オクチル(DOP)、エポキシ化大豆油(EOP)、Ca
-Zn ステアレート、銀イオン担持無機抗菌剤(ゼオミッ
ク:(株)シナネン製)を配合した表1に示すような塩
化ビニル樹脂組成物を混練してペレットを得、このペレ
ットをポリテトラフルオロエチレン製のシートの間で1
50℃、100kg/cm2 でポットプレスして厚さ
1.5mmのシートに成形した。このシートを60℃、
相対湿度75%の雰囲気で10日間および40日間放置
後、白色濾紙を裏面に当て、日本電色社製E5100型
色差計で色を測定したところ、表2に示すような結果が
得られた。結果はCIF1976によるL* * *
色系(b* は省略)で表している。
[Example 1] Dioctyl phthalate (DOP), epoxidized soybean oil (EOP), Ca
-Zn stearate, a vinyl chloride resin composition as shown in Table 1 blended with silver ion-carrying inorganic antibacterial agent (Zeomic: manufactured by Sinanen Co., Ltd.) was kneaded to obtain pellets, and the pellets were formed of polytetrafluoroethylene. One among the sheets of
It was formed into a 1.5 mm thick sheet by pot pressing at 50 ° C. and 100 kg / cm 2 . 60 ° C
After standing for 10 days and 40 days in an atmosphere at a relative humidity of 75%, the white filter paper was applied to the back surface, and the color was measured using a color difference meter E5100 manufactured by Nippon Denshoku Co., Ltd. The results shown in Table 2 were obtained. The results are expressed in the L * a * b * color system (b * is omitted) according to CIF1976.

【0010】〔実施例2〕実施例1においてゼオミック
の配合量を少なくした表1に示すような塩化ビニル樹脂
組成物を混練してペレットを得、このペレットから実施
例1と同様のシートを成形し、実施例1と同様の色測定
を行ったところ、表2に示すような結果が得られた。
Example 2 A vinyl chloride resin composition as shown in Table 1 in which the amount of Zeomic was reduced in Example 1 was kneaded to obtain pellets, and a sheet similar to that of Example 1 was formed from the pellets. Then, when the same color measurement as in Example 1 was performed, the results shown in Table 2 were obtained.

【0011】〔比較例1〕ポリ塩化ビニルにDOP、E
OP、Ca-Zn ステアレート、ゼオミック、TNPPを配
合した表1に示すような塩化ビニル樹脂組成物を混練し
てペレットを得、このペレットから実施例1と同様のシ
ートを成形し、実施例1と同様の色測定を行ったとこ
ろ、表2に示すような結果が得られた。
Comparative Example 1 DOP and E were added to polyvinyl chloride.
A vinyl chloride resin composition as shown in Table 1 containing OP, Ca-Zn stearate, zeomic and TNPP was kneaded to obtain pellets, and a sheet similar to that of Example 1 was formed from the pellets. When the same color measurement was performed, the results shown in Table 2 were obtained.

【0012】〔比較例2〕ポリ塩化ビニルにDOP、E
OP、Ca-Zn ステアレートを配合した表1に示すような
塩化ビニル樹脂組成物を混練してペレットを得、このペ
レットから実施例1と同様のシートを成形し、実施例1
と同様の色測定を行ったところ、表2に示すような結果
が得られた。
Comparative Example 2 DOP and E were added to polyvinyl chloride.
A vinyl chloride resin composition as shown in Table 1 containing OP and Ca-Zn stearate was kneaded to obtain pellets, and a sheet similar to that of Example 1 was formed from the pellets.
When the same color measurement was performed, the results shown in Table 2 were obtained.

【0013】〔比較例3〕ポリ塩化ビニルにDOP、E
OP、Ca-Zn ステアレート、TNPPを配合した表1に
示すような塩化ビニル樹脂組成物を混練してペレットを
得、このペレットから実施例1と同様のシートを成形
し、実施例1と同様の色測定を行ったところ、表2に示
すような結果が得られた。
Comparative Example 3 DOP and E were added to polyvinyl chloride.
A vinyl chloride resin composition containing OP, Ca-Zn stearate, and TNPP as shown in Table 1 was kneaded to obtain pellets, and a sheet similar to that of Example 1 was formed from the pellets. When the color measurement was performed, the results shown in Table 2 were obtained.

【0014】[0014]

【表1】 [Table 1]

【0015】[0015]

【表2】 [Table 2]

【0016】〔抗菌効果の評価試験〕実施例1〜2、比
較例1〜3で得られたペレットを、一軸押出機を用いて
外径1.55mm、内径1.05mmのカテーテル用チ
ューブを成形し、それらのチューブについて抗菌効果の
評価試験を行ったところ、表3のような結果が得られ
た。抗菌効果の評価試験は、大腸菌(E.Coli:I
FO−3301)を対称菌株として次に示すシェークフ
ラスコ改法により行った。対称菌株をニュートリエント
ブロス培地溶液中で37℃、18時間震盪培養(振幅4
cm、震盪数120回/分)し、次いでこの培養菌液を
ニュートリエントブロス培地に1/100容量加え、同
様に6時間震盪培養し、得られた対数増殖期の菌液をニ
ュートリエントブロス培地を1/500容量含む生理食
塩水(稀釈液)により104 個/mlオーダーに稀釈し
て試験菌液を作成した。次に、この試験菌液10mlを
100ml三角フラスコに採り、この三角フラスコに各
チューブを長さ2cmに切断して表面積が50cm2
なる量を投入する。次に、三角フラスコを25℃の恒温
水槽中で3時間および24時間震盪(振幅4cm、震盪
数120回/分)した後、これを混釈平板培養法により
培養し、生菌数を測定した。測定結果を表3に示す。表
2、3から銀イオン担持無機抗菌剤を含有し、かつ亜リ
ン酸エステルを含有しない塩化ビニル樹脂組成物からな
る実施例1、2の成形品は、経時的な変色が著しく改善
されるとともに、抗菌効果も維持されていることが分か
る。
[Evaluation Test of Antibacterial Effect] The pellets obtained in Examples 1 and 2 and Comparative Examples 1 to 3 were molded into a catheter tube having an outer diameter of 1.55 mm and an inner diameter of 1.05 mm using a single screw extruder. Then, when an evaluation test of the antibacterial effect was performed on those tubes, the results shown in Table 3 were obtained. The evaluation test of the antibacterial effect was performed by using E. coli (I.
FO-3301) as a symmetric strain by the following shake flask modification. The symmetric strain is shake-cultured in a nutrient broth medium solution at 37 ° C. for 18 hours (amplitude: 4).
cm, shaking rate: 120 times / min), then add 1/100 volume of this culture to a nutrient broth medium, shake culture in the same manner for 6 hours, and transfer the resulting logarithmic growth phase bacterial solution to a nutrient broth medium. Was diluted to the order of 10 4 cells / ml with a physiological saline solution (diluent) containing 1/500 volume to prepare a test bacterial solution. Next, 10 ml of the test bacterial solution is taken in a 100 ml Erlenmeyer flask, and each tube is cut into a length of 2 cm and an amount having a surface area of 50 cm 2 is put into the Erlenmeyer flask. Next, the Erlenmeyer flask was shaken (amplitude: 4 cm, shaking rate: 120 times / minute) in a constant temperature water bath at 25 ° C. for 3 hours and 24 hours, and then this was cultured by the pour plate culture method, and the number of viable bacteria was measured. . Table 3 shows the measurement results. From Tables 2 and 3, the molded articles of Examples 1 and 2 comprising the vinyl chloride resin composition containing the silver ion-carrying inorganic antibacterial agent and not containing the phosphite ester have significantly improved discoloration over time, and It can be seen that the antibacterial effect is also maintained.

【0017】[0017]

【表3】 [Table 3]

【0018】[0018]

【発明の効果】以上説明してきたことから明らかなよう
に、本発明の医療用具は、抗菌効果が損なわれることな
く、経時的な変色が著しく改善されている。
As is apparent from the above description, the medical device of the present invention has significantly improved discoloration with time without impairing the antibacterial effect.

Claims (3)

【特許請求の範囲】[Claims] 【請求項1】 無機担体に銀イオンを担持させてなる抗
菌剤を含有し、かつ亜リン酸エステルを含有しない、塩
化ビニル樹脂組成物からなる医療用具。
1. A medical device comprising a vinyl chloride resin composition containing an antibacterial agent comprising silver ions carried on an inorganic carrier and containing no phosphite.
【請求項2】 塩化ビニル樹脂が50重量%以上の塩化
ビニル構造単位を有する請求項1に記載の医療用具。
2. The medical device according to claim 1, wherein the vinyl chloride resin has a vinyl chloride structural unit of 50% by weight or more.
【請求項3】 無機担体が、ゼオライト、アルミノケイ
酸、リン酸ジルコニウム、多孔質ガラス、多孔質シリ
カ、アルミナ、ポリリン酸アルミニウム、ヒドロキシア
パタイト、チタニア、シリカゲルの群から選ばれる少な
くとも1つである請求項1に記載の医療用具。
3. The inorganic carrier is at least one selected from the group consisting of zeolite, aluminosilicate, zirconium phosphate, porous glass, porous silica, alumina, aluminum polyphosphate, hydroxyapatite, titania, and silica gel. 2. The medical device according to 1.
JP9208739A 1997-08-04 1997-08-04 Medical instrument Pending JPH1147261A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP9208739A JPH1147261A (en) 1997-08-04 1997-08-04 Medical instrument

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP9208739A JPH1147261A (en) 1997-08-04 1997-08-04 Medical instrument

Publications (1)

Publication Number Publication Date
JPH1147261A true JPH1147261A (en) 1999-02-23

Family

ID=16561289

Family Applications (1)

Application Number Title Priority Date Filing Date
JP9208739A Pending JPH1147261A (en) 1997-08-04 1997-08-04 Medical instrument

Country Status (1)

Country Link
JP (1) JPH1147261A (en)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006120135A1 (en) * 2005-05-10 2006-11-16 Ciba Specialty Chemicals Holding Inc. Antimicrobial porous silicon oxide particles
JP2008023071A (en) * 2006-07-21 2008-02-07 Kaneka Corp Medical drain tube and production method thereof
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WO2006120135A1 (en) * 2005-05-10 2006-11-16 Ciba Specialty Chemicals Holding Inc. Antimicrobial porous silicon oxide particles
JP2009513203A (en) * 2005-10-28 2009-04-02 ベーリンガー インゲルハイム インターナショナル ゲゼルシャフト ミット ベシュレンクテル ハフツング Inhaler with mouthpiece having microbiological protection function
JP2008023071A (en) * 2006-07-21 2008-02-07 Kaneka Corp Medical drain tube and production method thereof
US9371454B2 (en) 2010-10-15 2016-06-21 Bunge Amorphic Solutions Llc Coating compositions with anticorrosion properties
US9005355B2 (en) 2010-10-15 2015-04-14 Bunge Amorphic Solutions Llc Coating compositions with anticorrosion properties
US9840625B2 (en) 2010-10-15 2017-12-12 Bunge Amorphic Solutions Llc Coating compositions with anticorrosion properties
JP2015520732A (en) * 2012-04-16 2015-07-23 ブンゲ アモルプヒク ソルトイオンス エルエルシー Antibacterial chemical composition
US9611147B2 (en) 2012-04-16 2017-04-04 Bunge Amorphic Solutions Llc Aluminum phosphates, compositions comprising aluminum phosphate, and methods for making the same
US9801385B2 (en) 2012-04-16 2017-10-31 Bunge Amorphic Solutions Llc Antimicrobial chemical compositions
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