JP3422151B2 - Antibacterial material and antibacterial molded product using the same - Google Patents

Antibacterial material and antibacterial molded product using the same

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Publication number
JP3422151B2
JP3422151B2 JP30011995A JP30011995A JP3422151B2 JP 3422151 B2 JP3422151 B2 JP 3422151B2 JP 30011995 A JP30011995 A JP 30011995A JP 30011995 A JP30011995 A JP 30011995A JP 3422151 B2 JP3422151 B2 JP 3422151B2
Authority
JP
Japan
Prior art keywords
antibacterial
antibacterial material
tube
group
molded article
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.)
Expired - Fee Related
Application number
JP30011995A
Other languages
Japanese (ja)
Other versions
JPH09135894A (en
Inventor
一裕 棚橋
和雄 寺本
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.)
Toray Industries Inc
Original Assignee
Toray Industries Inc
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Priority to JP30011995A priority Critical patent/JP3422151B2/en
Publication of JPH09135894A publication Critical patent/JPH09135894A/en
Application granted granted Critical
Publication of JP3422151B2 publication Critical patent/JP3422151B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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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、高分子基材に塗布
可能な、抗菌性材料およびそれを用いた抗菌性成型品に
関する。
TECHNICAL FIELD The present invention relates to an antibacterial material that can be applied to a polymer substrate and an antibacterial molded article using the same.

【0002】[0002]

【従来の技術】医療の分野においては、ポリウレタンな
どの高分子材料から成る医療用具を患者の体内に挿入・
留置している間に起こる感染症が合併症の一つとして問
題視されている。従来、医療用具の留置に伴う感染症を
防止するために、医療用具を使用直前にクロロヘキシジ
ンやポピドンヨードなどの抗菌剤や消毒剤を含む水溶液
に浸漬するなどして消毒するか、あるいは治療中に交換
可能な医療用具に関しては頻繁な交換が行われてきた。
しかしながら、抗菌剤・消毒剤は時間と共にカテーテル
表面から消失するため消毒の効果に持続性がなく、医療
用具を長期間にわたって使用する場合には徐々に効果が
低下していくことは明らかである。また、医療用具の頻
繁な交換も医療従事者にとっては大きな負担となる。そ
こで更なる感染防止の手段の一つとして、医療用具に種
々の抗菌加工が施されてきた。その代表的なものとして
は、クロロヘキシジンをはじめとする抗菌剤や、銀・銅
をはじめとする金属またはその化合物を含有する層で表
面を被覆したカテーテルがある。これらのカテーテルに
おいては、抗菌作用をもつ物質を体内で一定量ずつ徐放
するシステムが採用されており、カテーテルを使用直前
に消毒する場合に比べて良好な効果を示す。
2. Description of the Related Art In the medical field, a medical device made of a polymer material such as polyurethane is inserted into a patient's body.
Infection that occurs during detention is regarded as one of the complications. Conventionally, in order to prevent infectious diseases associated with the placement of medical devices, they are disinfected by immersing them in an aqueous solution containing an antibacterial agent or disinfectant such as chlorohexidine or povidone iodine immediately before use, or replaced during treatment. Frequent replacements have been made for possible medical devices.
However, since the antibacterial agent / disinfectant disappears from the catheter surface over time, the disinfecting effect is not sustainable, and it is clear that the effect gradually decreases when the medical device is used for a long period of time. Frequent replacement of medical equipment also places a heavy burden on medical personnel. Therefore, various antibacterial treatments have been applied to medical devices as one of means for further preventing infection. Typical examples thereof include a catheter whose surface is coated with a layer containing an antibacterial agent such as chlorohexidine and a metal such as silver / copper or a compound thereof. For these catheters, a system is adopted in which a substance having an antibacterial action is gradually released in the body in a fixed amount, and it exhibits a better effect than when the catheter is disinfected immediately before use.

【0003】[0003]

【発明が解決しようとする課題】しかしながら、抗菌物
質が徐放するシステムでは依然として使用期間に限りが
あり効力が次第に低下していくことは避けられない。銀
などの金属あるいはその化合物については徐放後の体内
動態が不明であり、人体への害も考えられる。また、使
用後の医療用具廃棄物に銀が残存している場合には、廃
棄に際して回収などの特別の処置が必要になる。
However, in a system in which an antibacterial substance is gradually released, it is unavoidable that the period of use is still limited and the efficacy gradually decreases. The pharmacokinetics of metals such as silver and its compounds after sustained release are unknown, and they may be harmful to the human body. In addition, if silver remains in the medical device waste after use, special treatment such as recovery is required at the time of disposal.

【0004】そのため、徐放型でなく、それ自身で抗菌
性のあるポリマーとして第四アンモニウム基をもつポリ
マーが種々提案されてきている。しかし、これらポリマ
ーは加工性が悪く、単独では成型品にできないので、機
械的特性の優れたポリマーを成型したものの表面にコー
ティングするか、あるいは、該ポリマーと混合成型する
ことが必要になる。機械的特性のよい基材ポリマーほど
他のポリマーとの相溶性が悪い。相溶性が悪いとコーテ
ィングしたポリマーが剥離したり、裂け目が生じる。現
在、基材ポリマーとの相溶性が十分な抗菌性ポリマーは
知られていない。 そこで、本発明はかかる従来技術の
問題点に鑑み、複雑な形をした医療用具にも適用できる
ような柔軟な膜を形成し、かつ、種々のポリマーとの相
溶性・接着性の良い抗菌性材料を提供することを目的と
する。
For this reason, various polymers having a quaternary ammonium group have been proposed as polymers having antibacterial properties by themselves rather than the sustained release type. However, since these polymers have poor processability and cannot be formed into a molded product by themselves, it is necessary to coat the surface of the molded product with a polymer having excellent mechanical properties or to mix and mold the polymer. The base polymer having better mechanical properties has poorer compatibility with other polymers. If the compatibility is poor, the coated polymer peels off or cracks occur. At present, no antibacterial polymer having sufficient compatibility with the base polymer is known. Therefore, in view of the problems of the prior art, the present invention forms a flexible film that can be applied to a medical device having a complicated shape, and has good antibacterial properties and compatibility with various polymers. Intended to provide material.

【0005】[0005]

【課題を解決するための手段】このような目的を達成す
るため、本発明は、以下の構成を有する。
In order to achieve such an object, the present invention has the following constitution.

【0006】「(1) 水酸基の一部が下記一般式(1)
(但し、式中、Aは、エーテル基又はエステル基を含む
結合基を示し、R1 はメチレン基を、R2 、R3 は炭素
数1〜4のアルキル基を、R4 はアルキル基を示す。X
はハロゲンイオン、硫酸イオンおよびカルボン酸イオン
から選ばれる。)で表される官能基で置換されているフ
ェノキシ樹脂からなることを特徴とする抗菌性材料。
"(1) Some of the hydroxyl groups are represented by the following general formula (1)
(In the formula, A represents a linking group containing an ether group or an ester group, R 1 represents a methylene group, R 2 and R 3 represent an alkyl group having 1 to 4 carbon atoms, and R 4 represents an alkyl group. Show X
Is selected from halogen ions, sulfate ions and carboxylate ions. ) An antibacterial material comprising a phenoxy resin substituted with a functional group represented by

【0007】[0007]

【化2】 (2) 基材に、上記1項記載の抗菌性材料を主成分として
なる組成物を被覆してなることを特徴とする抗菌性成型
品。」
[Chemical 2] (2) An antibacterial molded article, characterized in that the base material is coated with the composition containing the antibacterial material as described in 1 above as a main component. "

【0008】[0008]

【発明の実施の形態】続いて、本発明についてさらに詳
細に説明する。
BEST MODE FOR CARRYING OUT THE INVENTION Next, the present invention will be described in more detail.

【0009】本発明におけるフェノキシ樹脂とは、可溶
性のビスフェノールA−エピクロルヒドリン共重合体で
実質上エポキシド官能性をもたないフェノキシ樹脂を言
う。本発明における式(1)で示される官能基におい
て、R1 はメチレン基であり、好ましくは炭素数1〜
17のメチレン基であり、さらに好ましくは3〜10であ
る。R1 は抗菌官能基の自由度に関与し、短すぎると官
能基が自由に動けずに菌体と接触しにくくなる傾向があ
り、また長すぎても疎水性が強くなるため菌体を含む水
系の媒体中では抗菌官能基が菌体と接触しにくくなる傾
向がある。R2 、R3 はアルキル基であり、炭素数が多
いと疎水性が強くなるため抗菌官能基が菌体と接触しに
くくなる傾向があるので、炭素数は1〜4であることが
好ましく、最も炭素数が少ないメチル基が最良である。
抗菌性に関係するのはR4 のアルキル基である。最も好
ましい抗菌効果を示すメチレン鎖の長さが細菌によって
異なり、例えばグラム陽性菌である黄色ブドウ球菌では
炭素数4〜16が好ましい。また、メチレン鎖長が24個以
上のものは材料が入手しにくい。これらのアルキル基
は、枝別れしていると動きが制限されるので直鎖状であ
ることが望ましい。
The phenoxy resin in the present invention refers to a phenoxy resin which is a soluble bisphenol A-epichlorohydrin copolymer and has substantially no epoxide functionality. In the functional group represented by the formula (1) in the present invention, R 1 is a methylene group, preferably having 1 to 1 carbon atoms.
17 methylene groups, more preferably 3-10. R 1 contributes to the degree of freedom of the antibacterial functional group, and if it is too short, the functional group tends to be unable to move freely and tends to come into contact with bacterial cells, and if it is too long, it becomes strongly hydrophobic and contains bacterial cells. In an aqueous medium, antibacterial functional groups tend to be less likely to come into contact with bacterial cells. R 2 and R 3 are alkyl groups, and when the number of carbon atoms is large, the hydrophobicity tends to be strong and the antibacterial functional group tends to be difficult to contact with the cells, so the number of carbon atoms is preferably 1 to 4, The methyl group having the smallest number of carbon atoms is the best.
It is the alkyl group of R 4 that is associated with antibacterial properties. The length of the methylene chain exhibiting the most preferable antibacterial effect differs depending on the bacterium, and for example, the gram-positive bacterium Staphylococcus aureus preferably has 4 to 16 carbon atoms. Also, if the methylene chain length is 24 or more, it is difficult to obtain the material. It is desirable that these alkyl groups are straight-chain because their movement is restricted when they are branched.

【0010】本発明における式(1)の官能基は、フェ
ノキシ樹脂にエーテル基またはエステル基で結合されて
いることが重要である。これらの結合は動きやすく、ポ
リマーに柔軟性を付与するので好ましい。具体的には、
例えばO−CO、O−CO−NH、O−CS−NHなど
から選ばれる少なくとも1種を含む結合基が好ましく用
いられる。ポリマー中の官能基の量は多すぎると基材ポ
リマーとの相溶性およびコーティング性が悪くなり、少
なすぎると抗菌性能が低下する傾向があるため、通常繰
り返し単位1モルあたり0.1〜0.8モル、とりわ
け、0.4〜0.6が好ましい。
It is important that the functional group of the formula (1) in the present invention is bound to the phenoxy resin by an ether group or an ester group. These bonds are preferable because they are easy to move and impart flexibility to the polymer. In particular,
For example, a bonding group containing at least one selected from O-CO, O-CO-NH, O-CS-NH and the like is preferably used. When the amount of the functional group in the polymer is too large, the compatibility with the base polymer and the coating property are deteriorated, and when the amount is too small, the antibacterial performance tends to be lowered. 8 mol, especially 0.4 to 0.6 is preferable.

【0011】本発明の抗菌性能を有する材料の製造方法
は任意であるが、以下に例をあげて説明する。
The method for producing the material having antibacterial properties according to the present invention is arbitrary, but will be described below with reference to examples.

【0012】ビスフェノールA−エピクロルヒドリン共
重合体であるフェノキシ樹脂に、ハロアシル基を導入す
る。さらにハロアシル化フェノキシ樹脂を前記構造に基
づく3級アミンと反応処理することによって本発明の抗
菌性能を有する材料が製造される。また、フェノキシ樹
脂にハロアルキルアミノカルボキシル基を導入し、さら
にハロアシル化フェノキシ樹脂を前記構造に基づく3級
アミンと反応処理することによっても本発明の抗菌性能
を有する材料を製造することもできる。
A haloacyl group is introduced into a phenoxy resin which is a bisphenol A-epichlorohydrin copolymer. Further, by reacting the haloacylated phenoxy resin with a tertiary amine based on the above structure, the material having antibacterial performance of the present invention is produced. The material having antibacterial properties of the present invention can also be produced by introducing a haloalkylaminocarboxyl group into a phenoxy resin and further subjecting the haloacylated phenoxy resin to a reaction treatment with a tertiary amine based on the above structure.

【0013】本発明の抗菌性材料は、基材表面に塗布す
ることによって、細菌感染の防止が必要な任意の成型
品、特に医療用具などとして好適に使用することができ
る。例えば長期間にわたり体内に留置される血管カテー
テル、ドレナージチューブ、コネクター、アクセスポー
ト、排液バック、血液回路などに適用することができ
る。徐放システムの材料に比べて、抗菌官能基がフェノ
キシ樹脂に共有結合で固定化されているため人体にとっ
て安全で効果が持続する。さらに、基材素材としては、
例えばポリウレタン、天然ゴム、シリコン樹脂、ポリ塩
化ビニル、ポリアミドなどが好適に用いられる。
By applying the antibacterial material of the present invention to the surface of a base material, it can be suitably used as an arbitrary molded article which requires prevention of bacterial infection, particularly as a medical device. For example, it can be applied to a blood vessel catheter, a drainage tube, a connector, an access port, a drain bag, a blood circuit, etc., which is left in the body for a long period of time. Compared with the material of the sustained release system, the antibacterial functional group is covalently immobilized on the phenoxy resin, so it is safe for the human body and the effect lasts. Furthermore, as the base material,
For example, polyurethane, natural rubber, silicone resin, polyvinyl chloride, polyamide, etc. are preferably used.

【0014】以下、実施例により本発明をさらに具体的
に説明するが、本発明は当該実施例に限定されるもので
はない。
Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the examples.

【0015】[0015]

【実施例】【Example】

実施例1 市販のフェノキシレジン(ユニエンカーバイト社製、P
henoxy) 10gをジメチルホルムアミド70mlに溶解
後、11ブロモウンデカノイルクロリド 4mlを加えて80℃
で 3時間反応させた。この溶液をメタノール中に投じポ
リマーを沈殿させた後、メタノールおよび水で洗浄して
乾燥した。次に、このブロモアシル化フェノキシ樹脂5g
をジメチルホルムアミド50mlに溶解後、N,N-ジメチルオ
クチルアミン 6.0mlを加えて80℃で 8時間反応させた。
飽和食塩水中に投じて沈殿させた後、水とエタノールで
洗浄・乾燥してアルキル基(炭素数 8)を含む4級アン
モニウム基を有する抗菌性材料を得た。4級アンモニウ
ム基の導入量はフェノキシ樹脂の繰り返し単位 1モルあ
たり0.36モルであった。
Example 1 Commercially available phenoxy resin (manufactured by Uniencarbite, P
10 g of henoxy) was dissolved in 70 ml of dimethylformamide, 4 ml of 11 bromoundecanoyl chloride was added, and the mixture was heated to 80 ° C.
And reacted for 3 hours. The solution was poured into methanol to precipitate a polymer, which was washed with methanol and water and dried. Next, 5 g of this bromoacylated phenoxy resin
Was dissolved in 50 ml of dimethylformamide, 6.0 ml of N, N-dimethyloctylamine was added, and the mixture was reacted at 80 ° C. for 8 hours.
The mixture was poured into saturated saline for precipitation, washed with water and ethanol and dried to obtain an antibacterial material having a quaternary ammonium group containing an alkyl group (having 8 carbon atoms). The amount of quaternary ammonium group introduced was 0.36 mol per mol of repeating units of the phenoxy resin.

【0016】実施例2 実施例1に示した抗菌性材料の10wt%クロロホルム溶
液にポリウレタンのチューブを軸方向に浸漬してチュー
ブに抗菌性材料を塗布して乾燥した。材料を塗布したチ
ューブをアルコールで消毒した後、黄色ブドウ球菌(FR
I1169 株)を菌濃度106 個/mlになるように懸濁し
た生理食塩水に浸漬し、24時間静置した。24時間後にチ
ューブに付着した菌数を測定した。対照として抗菌性材
料を塗布していないポリウレタンチューブについても同
様に操作した。その結果、付着菌数は、抗菌性材料を塗
布していないポリウレタンチューブの場合は2909個、抗
菌性材料を塗布したチューブでは 128個であった。
Example 2 A polyurethane tube was axially dipped in a 10 wt% chloroform solution of the antibacterial material shown in Example 1 to apply the antibacterial material to the tube and dried. After sterilizing the coated tube with alcohol, Staphylococcus aureus (FR
I1169 strain) was immersed in a physiological saline solution having a bacterial concentration of 10 6 cells / ml, and allowed to stand for 24 hours. After 24 hours, the number of bacteria attached to the tube was measured. As a control, the same operation was performed for a polyurethane tube not coated with the antibacterial material. As a result, the number of adhered bacteria was 2909 in the case of the polyurethane tube not coated with the antibacterial material and 128 in the case of the tube coated with the antibacterial material.

【0017】実施例3 実施例1に示したブロモアシル化フェノキシ樹脂5gをジ
メチルホルムアミド50mlに溶解後、N,N-ジメチルドデシ
ルアミン 8.0mlを加えて80℃で16時間反応させた。飽和
食塩水中に投じて沈殿させた後、水とエタノールで洗浄
・乾燥して長鎖のアルキル基(炭素数12)を含む4級ア
ンモニウム基を有する抗菌性材料を得た。4級アンモニ
ウム基の導入量はフェノキシ樹脂の繰り返し単位 1モル
あたり0.31モルであった。
Example 3 After dissolving 5 g of the bromoacylated phenoxy resin shown in Example 1 in 50 ml of dimethylformamide, 8.0 ml of N, N-dimethyldodecylamine was added and reacted at 80 ° C. for 16 hours. The mixture was poured into a saturated saline solution to be precipitated, washed with water and ethanol and dried to obtain an antibacterial material having a quaternary ammonium group containing a long-chain alkyl group (having 12 carbon atoms). The amount of the quaternary ammonium group introduced was 0.31 mol per mol of the repeating unit of the phenoxy resin.

【0018】実施例4 実施例3に示した抗菌性材料の10wt%クロロホルム溶
液にポリウレタンのチューブを軸方向に浸漬してチュー
ブに抗菌性材料を塗布して乾燥した。実施例2と同様に
実験した結果、付着菌数は、抗菌性材料を塗布していな
いポリウレタンチューブの場合は2909個、抗菌性材料を
塗布したチューブでは32個であった。
Example 4 A polyurethane tube was axially immersed in a 10 wt% chloroform solution of the antibacterial material shown in Example 3 to apply the antibacterial material to the tube and dried. As a result of the same experiment as in Example 2, the number of adherent bacteria was 2909 in the case of the polyurethane tube to which the antibacterial material was not applied, and 32 in the case of the tube to which the antibacterial material was applied.

【0019】実施例5 実施例1に示したブロモアシル化フェノキシ樹脂5gをジ
メチルホルムアミド50mlに溶解後、N,N-ジメチルヘキサ
デシルアミン12.0mlを加えて80℃で16時間反応させた。
飽和食塩水中に投じて沈殿させた後、水とエタノールで
洗浄・乾燥して長鎖のアルキル基(炭素数16)を含む4
級アンモニウム基を有する抗菌性材料を得た。4級アン
モニウム基の導入量はフェノキシ樹脂の繰り返し単位 1
モルあたり0.42モルであった。
Example 5 After dissolving 5 g of the bromoacylated phenoxy resin shown in Example 1 in 50 ml of dimethylformamide, 12.0 ml of N, N-dimethylhexadecylamine was added and reacted at 80 ° C. for 16 hours.
After being poured into a saturated saline solution to precipitate, washed with water and ethanol and dried to contain a long-chain alkyl group (16 carbon atoms) 4
An antibacterial material having a quaternary ammonium group was obtained. The amount of quaternary ammonium group introduced depends on the repeating unit of the phenoxy resin.
It was 0.42 mol per mol.

【0020】実施例6 実施例5に示した抗菌性材料の10wt%クロロホルム溶
液にポリウレタンのチューブを軸方向に浸漬して、チュ
ーブに抗菌性材料を塗布して乾燥した。実施例2と同様
に実験した結果、付着菌数は、抗菌性材料を塗布してい
ないポリウレタンチューブの場合は2909個、抗菌性材料
を塗布したチューブでは32個であった。 実施例7 実施例1と同様の市販のフェノキシレジン 10gをジメチ
ルホルムアミド70mlに溶解後、4-ブロモブチリルクロリ
ド 4mlを加えて80℃で 3時間反応させた。この溶液をメ
タノール中に投じポリマーを沈殿させた後、メタノール
および水で洗浄して乾燥した。次に、このブロモアシル
化フェノキシ樹脂5gをジメチルホルムアミド50mlに溶解
後、N,N-ジメチルブチルアミン 5.0mlを加えて80℃で 4
時間反応させた。飽和食塩水中に投じて沈殿させた後、
水とエタノールで洗浄・乾燥してアルキル基(炭素数
4)を含む4級アンモニウム基を有する抗菌性材料を得
た。4級アンモニウム基の導入量はフェノキシ樹脂の繰
り返し単位 1モルあたり0.45モルであった。
Example 6 A polyurethane tube was axially immersed in a 10 wt% chloroform solution of the antibacterial material shown in Example 5, the tube was coated with the antibacterial material, and the tube was dried. As a result of the same experiment as in Example 2, the number of adherent bacteria was 2909 in the case of the polyurethane tube to which the antibacterial material was not applied, and 32 in the case of the tube to which the antibacterial material was applied. Example 7 10 g of a commercially available phenoxy resin similar to that used in Example 1 was dissolved in 70 ml of dimethylformamide, 4 ml of 4-bromobutyryl chloride was added, and the mixture was reacted at 80 ° C. for 3 hours. The solution was poured into methanol to precipitate a polymer, which was washed with methanol and water and dried. Next, after dissolving 5 g of this bromoacylated phenoxy resin in 50 ml of dimethylformamide, add 5.0 ml of N, N-dimethylbutylamine and
Reacted for hours. After being poured into saturated saline to precipitate,
Wash with water and ethanol and dry to remove alkyl groups (carbon number
An antibacterial material having a quaternary ammonium group containing 4) was obtained. The amount of the quaternary ammonium group introduced was 0.45 mol per mol of the repeating unit of the phenoxy resin.

【0021】実施例8 実施例7に示した抗菌性材料の10wt%クロロホルム溶
液にポリウレタンのチューブを軸方向に浸漬して、チュ
ーブに抗菌性材料を塗布して乾燥した。材料を塗布した
チューブをアルコールで消毒した後、大腸菌(MC1061
株)あるいは黄色ブドウ球菌(FRI1169 株)を菌濃度が
それぞれれ106 個/mlになるように懸濁した生理食塩
水に浸漬し、24時間静置した。24時間後にチューブに付
着した菌数を測定した。対照として抗菌性材料を塗布し
ていないポリウレタンチューブについても同様に操作し
た。その結果、大腸菌では抗菌性材料を塗布していない
ポリウレタンチューブの場合は3868個、抗菌性材料を塗
布したチューブでは 144個であった。黄色ブドウ球菌で
は、抗菌性材料を塗布していないポリウレタンチューブ
の場合は2909個、抗菌性材料を塗布したチューブでは24
個であった。
Example 8 A polyurethane tube was axially dipped in a 10 wt% chloroform solution of the antibacterial material shown in Example 7, the antibacterial material was applied to the tube and dried. After sterilizing the tube coated with the material with alcohol, E. coli (MC1061
Strain) or Staphylococcus aureus (FRI1169 strain) were immersed in a physiological saline solution in which the bacterial concentration was 10 6 cells / ml, and the mixture was allowed to stand for 24 hours. After 24 hours, the number of bacteria attached to the tube was measured. As a control, the same operation was performed for a polyurethane tube not coated with the antibacterial material. As a result, for E. coli, the number was 3868 for polyurethane tubes not coated with antibacterial material and 144 for tubes coated with antibacterial material. For Staphylococcus aureus, 2909 pieces for polyurethane tubes not coated with antibacterial material, and 24 for tubes coated with antibacterial material.
It was an individual.

【0022】実施例9 実施例7に示したブロモアシル化フェノキシ樹脂5gをジ
メチルホルムアミド50mlに溶解後、N,N-ジメチルオクチ
ルアミン 7.5mlを加えて80℃で 6時間反応させた。飽和
食塩水中に投じて沈殿させた後、水とエタノールで洗浄
・乾燥してアルキル基(炭素数 8)を含む4級アンモニ
ウム基を有する抗菌性材料を得た。4級アンモニウム基
の導入量はフェノキシ樹脂の繰り返し単位 1モルあたり
0.52モルであった。
Example 9 After dissolving 5 g of the bromoacylated phenoxy resin shown in Example 7 in 50 ml of dimethylformamide, 7.5 ml of N, N-dimethyloctylamine was added and reacted at 80 ° C. for 6 hours. The mixture was poured into saturated saline for precipitation, washed with water and ethanol and dried to obtain an antibacterial material having a quaternary ammonium group containing an alkyl group (having 8 carbon atoms). The amount of quaternary ammonium group introduced is per 1 mol of the repeating unit of the phenoxy resin.
It was 0.52 mol.

【0023】実施例10 実施例9に示した抗菌性材料の10wt%クロロホルム溶
液にポリウレタンのチューブを軸方向に浸漬して、チュ
ーブに抗菌性材料を塗布して乾燥した。材料を塗布した
チューブをアルコールで消毒した後、黄色ブドウ球菌
(FRI1169 株)を菌濃度106 個/mlになるように懸濁
した生理食塩水に浸漬し、24時間静置した。24時間後に
チューブに付着した菌数を測定した。対照として抗菌性
材料を塗布していないポリウレタンチューブについても
同様に操作した。その結果、抗菌性材料を塗布していな
いポリウレタンチューブの場合は2909個、抗菌性材料を
塗布したチューブでは 8個であった。
Example 10 A polyurethane tube was axially dipped in a 10 wt% chloroform solution of the antibacterial material shown in Example 9, the antibacterial material was applied to the tube and dried. After the tube coated with the material was disinfected with alcohol, Staphylococcus aureus (FRI1169 strain) was immersed in a physiological saline solution having a bacterial concentration of 10 6 cells / ml, and allowed to stand for 24 hours. After 24 hours, the number of bacteria attached to the tube was measured. As a control, the same operation was performed for a polyurethane tube not coated with the antibacterial material. As a result, the number of polyurethane tubes not coated with antibacterial material was 2909, and the number of tubes coated with antibacterial material was 8.

【0024】実施例11 実施例7に示したブロモアシル化フェノキシ樹脂5gをジ
メチルホルムアミド50mlに溶解後、N,N-ジメチルドデシ
ルアミン10.0mlを加えて80℃で 7時間反応させた。飽和
食塩水中に投じて沈殿させた後、水とエタノールで洗浄
・乾燥してアルキル基(炭素数12)を含む4級アンモニ
ウム基を有する抗菌性材料を得た。4級アンモニウム基
の導入量はフェノキシ樹脂の繰り返し単位 1モルあたり
0.51モルであった。
Example 11 After dissolving 5 g of the bromoacylated phenoxy resin shown in Example 7 in 50 ml of dimethylformamide, 10.0 ml of N, N-dimethyldodecylamine was added and reacted at 80 ° C. for 7 hours. After being poured into a saturated saline solution to precipitate, washed with water and ethanol and dried to obtain an antibacterial material having a quaternary ammonium group containing an alkyl group (having 12 carbon atoms). The amount of quaternary ammonium group introduced is per 1 mol of the repeating unit of the phenoxy resin.
It was 0.51 mol.

【0025】実施例12 実施例11に示した抗菌性材料の10wt%クロロホルム
溶液にポリウレタンのチューブを軸方向に浸漬して、チ
ューブに抗菌性材料を塗布して乾燥した。実施例10と
同様に実験した結果、抗菌性材料を塗布していないポリ
ウレタンチューブの場合は2909個、抗菌性材料を塗布し
たチューブでは 3個であった。
Example 12 A polyurethane tube was axially dipped in a 10 wt% chloroform solution of the antibacterial material shown in Example 11, the tube was coated with the antibacterial material and dried. As a result of the same experiment as in Example 10, the number of polyurethane tubes to which the antibacterial material was not applied was 2909, and the number of tubes to which the antibacterial material was applied was 3.

【0026】実施例13 実施例7に示したブロモアシル化フェノキシ樹脂5gをジ
メチルホルムアミド50mlに溶解後、N,N-ジメチルヘキサ
デシルアミン12.5mlを加えて80℃で10時間反応させた。
飽和食塩水中に投じて沈殿させた後、水とエタノールで
洗浄・乾燥してアルキル基(炭素数16)を含む4級アン
モニウム基を有する抗菌性材料を得た4級アンモニウム
基の導入量はフェノキシ樹脂の繰り返し単位 1モルあた
り0.62モルであった。
Example 13 After dissolving 5 g of the bromoacylated phenoxy resin shown in Example 7 in 50 ml of dimethylformamide, 12.5 ml of N, N-dimethylhexadecylamine was added and reacted at 80 ° C. for 10 hours.
An antibacterial material having a quaternary ammonium group containing an alkyl group (having 16 carbon atoms) was obtained by throwing it into saturated saline for precipitation, washing with water and ethanol, and then drying it. The amount of the quaternary ammonium group introduced was phenoxy. It was 0.62 mol per mol of the repeating unit of the resin.

【0027】実施例14 実施例13に示した抗菌性材料の10wt%クロロホルム
溶液にポリウレタンのチューブを軸方向に浸漬して、チ
ューブに抗菌性材料を塗布して乾燥した。実施例10と
同様の実験をした結果、抗菌性材料を塗布していないポ
リウレタンチューブの場合は2909個、抗菌性材料を塗布
したチューブでは 0個であった。
Example 14 A polyurethane tube was axially dipped in a 10 wt% chloroform solution of the antibacterial material shown in Example 13, the antibacterial material was applied to the tube and dried. As a result of the same experiment as in Example 10, the number of polyurethane tubes not coated with the antibacterial material was 2909, and the number of tubes coated with the antibacterial material was 0.

【0028】実施例15 実施例1と同様の市販のフェノキシレジン 50gをジメチ
ルホルムアミド 300mlに溶解後、6-ブロモヘキサノイル
クロリド27mlを加えて80℃で 3.5時間反応させた。この
溶液をメタノール中に投じポリマーを沈殿させた後、メ
タノールおよび水で洗浄して乾燥した。次に、このブロ
モアシル化フェノキシ樹脂5gをジメチルホルムアミド50
mlに溶解後、N,N-ジメチルオクチルアミン 6.7mlを加え
て80℃で5時間反応させた。飽和食塩水中に投じて沈殿
させた後、水とエタノールで洗浄・乾燥してアルキル基
(炭素数 8)を含む4級アンモニウム基を有する抗菌性
材料を得た。
Example 15 50 g of the commercially available phenoxy resin similar to that used in Example 1 was dissolved in 300 ml of dimethylformamide, 27 ml of 6-bromohexanoyl chloride was added, and the mixture was reacted at 80 ° C. for 3.5 hours. The solution was poured into methanol to precipitate a polymer, which was washed with methanol and water and dried. Next, 5 g of this bromoacylated phenoxy resin was added to 50 g of dimethylformamide.
After dissolving in ml, 6.7 ml of N, N-dimethyloctylamine was added, and the mixture was reacted at 80 ° C for 5 hours. The mixture was poured into saturated saline for precipitation, washed with water and ethanol and dried to obtain an antibacterial material having a quaternary ammonium group containing an alkyl group (having 8 carbon atoms).

【0029】実施例16 実施例15に示した抗菌性材料の10wt%クロロホルム
溶液にポリウレタンのチューブを軸方向に浸漬してチュ
ーブに抗菌性材料を塗布して乾燥した。材料を塗布した
チューブをアルコールで消毒した後、黄色ブドウ球菌
(FRI1169 株)を菌濃度106 個/mlになるように懸濁
した生理食塩水に浸漬し、24時間静置した。24時間後に
チューブに付着した菌数を測定した。対照として抗菌性
材料を塗布していないポリウレタンチューブについても
同様に操作した。その結果、抗菌性材料を塗布していな
いポリウレタンチューブの場合は2968個抗菌性材料を塗
布したチューブでは 300個であった。
Example 16 A polyurethane tube was axially immersed in a 10 wt% chloroform solution of the antibacterial material shown in Example 15 to apply the antibacterial material to the tube and dried. After the tube coated with the material was disinfected with alcohol, Staphylococcus aureus (FRI1169 strain) was immersed in a physiological saline solution having a bacterial concentration of 10 6 cells / ml, and allowed to stand for 24 hours. After 24 hours, the number of bacteria attached to the tube was measured. As a control, the same operation was performed for a polyurethane tube not coated with the antibacterial material. As a result, the number of polyurethane tubes to which the antibacterial material was not applied was 2968, and the number of tubes to which the antibacterial material was applied was 300.

【0030】実施例17 実施例15に示したブロモアシル化フェノキシ樹脂5gを
ジメチルホルムアミド50mlに溶解後、N,N-ジメチルドデ
シルアミン 8.8mlを加えて80℃で 6時間反応させた。飽
和食塩水中に投じて沈殿させた後、水とエタノールで洗
浄・乾燥してアルキル基(炭素数12)を含む4級アンモ
ニウム基を有する抗菌性材料を得た。
Example 17 5 g of the bromoacylated phenoxy resin shown in Example 15 was dissolved in 50 ml of dimethylformamide, 8.8 ml of N, N-dimethyldodecylamine was added, and the mixture was reacted at 80 ° C. for 6 hours. After being poured into a saturated saline solution to precipitate, washed with water and ethanol and dried to obtain an antibacterial material having a quaternary ammonium group containing an alkyl group (having 12 carbon atoms).

【0031】実施例18 実施例17に示した抗菌性材料の10wt%クロロホルム
溶液にポリウレタンのチューブを軸方向に浸漬してチュ
ーブに抗菌性材料を塗布して乾燥した。実施例16と同
様に実験した結果、抗菌性材料を塗布していないポリウ
レタンチューブの場合は2968個、抗菌性材料を塗布した
チューブでは13個であった。
Example 18 A polyurethane tube was axially dipped in a 10 wt% chloroform solution of the antibacterial material shown in Example 17, the tube was coated with the antibacterial material, and the tube was dried. As a result of the same experiment as in Example 16, the number of polyurethane tubes to which the antibacterial material was not applied was 2968, and the number of tubes to which the antibacterial material was applied was 13.

【0032】実施例19 実施例15に示したブロモアシル化フェノキシ樹脂5gを
ジメチルホルムアミド50mlに溶解後、N,N-ジメチルヘキ
サデシルアミン11.0mlを加えて80℃で 7時間反応させ
た。飽和食塩水中に投じて沈殿させた後、水とエタノー
ルで洗浄・乾燥してアルキル基(炭素数16)を含む4級
アンモニウム基を有する抗菌性材料を得た。
Example 19 5 g of the bromoacylated phenoxy resin shown in Example 15 was dissolved in 50 ml of dimethylformamide, 11.0 ml of N, N-dimethylhexadecylamine was added, and the mixture was reacted at 80 ° C. for 7 hours. The mixture was poured into saturated saline for precipitation, washed with water and ethanol and dried to obtain an antibacterial material having a quaternary ammonium group containing an alkyl group (having 16 carbon atoms).

【0033】実施例20 実施例19に示した抗菌性材料の10wt%クロロホルム
溶液にポリウレタンのチューブを軸方向に浸漬して、チ
ューブに抗菌性材料を塗布して乾燥した。実施例16と
同様に実験した結果、抗菌性材料を塗布していないポリ
ウレタンチューブの場合は2968個、抗菌性材料を塗布し
たチューブでは 7個であった。
Example 20 A polyurethane tube was axially dipped in a 10 wt% chloroform solution of the antibacterial material shown in Example 19, the antibacterial material was applied to the tube and dried. As a result of the same experiment as in Example 16, the number of polyurethane tubes to which the antibacterial material was not applied was 2968, and the number of tubes to which the antibacterial material was applied was 7.

【0034】[0034]

【発明の効果】本発明の抗菌性能を有する材料は、プラ
スチック製品、特に医療用具には容易に塗布でき、細菌
が高濃度であっても良好な抗菌能を示し、その効果は長
期間持続する。本発明品には抗菌官能基が共有結合され
ており、抗菌官能基が溶離することがないため、抗菌性
能が長期間持続し人体にも無害である。
Industrial Applicability The material having antibacterial properties of the present invention can be easily applied to plastic products, especially medical devices, and exhibits good antibacterial activity even at a high concentration of bacteria, and its effect lasts for a long period of time. . Since the antibacterial functional group is covalently bonded to the product of the present invention and the antibacterial functional group does not elute, the antibacterial performance continues for a long time and is harmless to the human body.

───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.7,DB名) A61L 15/00 - 33/18 CA/MEDLINE/BIOSIS/E MBASE(STN) JICSTファイル(JOIS)─────────────────────────────────────────────────── ─── Continuation of front page (58) Fields surveyed (Int.Cl. 7 , DB name) A61L 15/00-33/18 CA / MEDLINE / BIOSIS / E MBASE (STN) JISST file (JOIS)

Claims (5)

(57)【特許請求の範囲】(57) [Claims] 【請求項1】水酸基の一部が下記一般式(1)(但し、
式中、Aは、エーテル基又はエステル基を含む結合基を
示し、R1 はメチレン基を、R2 、R3 は炭素数1〜4
のアルキル基を、R4 はアルキル基を示す。Xはハロゲ
ンイオン、硫酸イオンおよびカルボン酸イオンから選ば
れる。)で表される官能基で置換されているフェノキシ
樹脂からなることを特徴とする抗菌性材料。 【化1】
1. A part of the hydroxyl group is represented by the following general formula (1) (provided that
In the formula, A represents a linking group containing an ether group or an ester group, R 1 represents a methylene group, and R 2 and R 3 each have 1 to 4 carbon atoms.
Is an alkyl group, and R 4 is an alkyl group. X is selected from halogen ion, sulfate ion and carboxylate ion. ) An antibacterial material comprising a phenoxy resin substituted with a functional group represented by [Chemical 1]
【請求項2】該基材に、請求項1記載の抗菌性材料を主
成分としてなる組成物を被覆してなることを特徴とする
抗菌性成型品。
2. An antibacterial molded article, characterized in that the base material is coated with the composition comprising the antibacterial material according to claim 1 as a main component.
【請求項3】該基材が、医療用体内挿入用成型品である
ことを特徴とする請求項2記載の抗菌性成型品。
3. The antibacterial molded article according to claim 2, wherein the base material is a molded article for insertion into a medical body.
【請求項4】該基材が、ポリウレタン、天然ゴム、シリ
コン樹脂、ポリ塩化ビニルおよびポリアミドから選ばれ
ることを特徴とする請求項2または3記載の抗菌性成型
品。
4. The antibacterial molded article according to claim 2, wherein the base material is selected from polyurethane, natural rubber, silicone resin, polyvinyl chloride and polyamide.
【請求項5】該基材が、カテーテル、チューブ、チュー
ブコネクター、アクセスポート、排液バックおよび血液
回路から選ばれることを特徴とする請求項2記載の抗菌
性成型品。
5. The antibacterial molded article according to claim 2, wherein the base material is selected from a catheter, a tube, a tube connector, an access port, a drain bag and a blood circuit.
JP30011995A 1995-11-17 1995-11-17 Antibacterial material and antibacterial molded product using the same Expired - Fee Related JP3422151B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
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Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP30011995A JP3422151B2 (en) 1995-11-17 1995-11-17 Antibacterial material and antibacterial molded product using the same

Publications (2)

Publication Number Publication Date
JPH09135894A JPH09135894A (en) 1997-05-27
JP3422151B2 true JP3422151B2 (en) 2003-06-30

Family

ID=17880958

Family Applications (1)

Application Number Title Priority Date Filing Date
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Country Status (1)

Country Link
JP (1) JP3422151B2 (en)

Also Published As

Publication number Publication date
JPH09135894A (en) 1997-05-27

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