JPH0857033A - X-ray contrasting medical molding - Google Patents
X-ray contrasting medical moldingInfo
- Publication number
- JPH0857033A JPH0857033A JP6200819A JP20081994A JPH0857033A JP H0857033 A JPH0857033 A JP H0857033A JP 6200819 A JP6200819 A JP 6200819A JP 20081994 A JP20081994 A JP 20081994A JP H0857033 A JPH0857033 A JP H0857033A
- Authority
- JP
- Japan
- Prior art keywords
- ray contrast
- ray
- contrast
- halogenated
- property
- 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
Links
- 238000000465 moulding Methods 0.000 title abstract description 8
- 229920000642 polymer Polymers 0.000 claims abstract description 35
- 239000003822 epoxy resin Substances 0.000 claims abstract description 13
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 13
- 229920000728 polyester Polymers 0.000 claims abstract description 12
- 229920002635 polyurethane Polymers 0.000 claims abstract description 11
- 239000004814 polyurethane Substances 0.000 claims abstract description 11
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 10
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical class OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000004952 Polyamide Substances 0.000 claims abstract description 9
- 229920002647 polyamide Polymers 0.000 claims abstract description 9
- 229920005989 resin Polymers 0.000 claims abstract description 9
- 239000011347 resin Substances 0.000 claims abstract description 9
- 150000002367 halogens Chemical class 0.000 claims abstract description 8
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 8
- 239000004417 polycarbonate Substances 0.000 claims abstract description 8
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 7
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 13
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 10
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 6
- 125000001246 bromo group Chemical group Br* 0.000 claims description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 4
- 229910052740 iodine Inorganic materials 0.000 claims description 4
- 239000011630 iodine Substances 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 abstract description 5
- 230000003287 optical effect Effects 0.000 abstract description 2
- 150000004820 halides Chemical class 0.000 abstract 5
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 abstract 1
- 239000000178 monomer Substances 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 239000002872 contrast media Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 239000000806 elastomer Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- MQCPOLNSJCWPGT-UHFFFAOYSA-N 2,2'-Bisphenol F Chemical compound OC1=CC=CC=C1CC1=CC=CC=C1O MQCPOLNSJCWPGT-UHFFFAOYSA-N 0.000 description 2
- KKJUPNGICOCCDW-UHFFFAOYSA-N 7-N,N-Dimethylamino-1,2,3,4,5-pentathiocyclooctane Chemical compound CN(C)C1CSSSSSC1 KKJUPNGICOCCDW-UHFFFAOYSA-N 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- -1 poly (trimethylhexamethylene) tetrabromoterephthalamide Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- FUQAGKYWAUZSEJ-UHFFFAOYSA-N 2,3,4,5-tetrabromo-6-(2-hydroxyphenyl)phenol Chemical compound OC1=CC=CC=C1C1=C(O)C(Br)=C(Br)C(Br)=C1Br FUQAGKYWAUZSEJ-UHFFFAOYSA-N 0.000 description 1
- OIVGHSVTPGSCSB-UHFFFAOYSA-N 2,3-dibromo-4-(2,3-dibromo-4-hydroxyphenoxy)phenol Chemical compound BrC1=C(Br)C(O)=CC=C1OC1=CC=C(O)C(Br)=C1Br OIVGHSVTPGSCSB-UHFFFAOYSA-N 0.000 description 1
- HAZQOBXSUKWCIZ-UHFFFAOYSA-N 2,3-dibromo-4-[(2,3-dibromo-4-hydroxyphenyl)methyl]phenol Chemical compound BrC1=C(Br)C(O)=CC=C1CC1=CC=C(O)C(Br)=C1Br HAZQOBXSUKWCIZ-UHFFFAOYSA-N 0.000 description 1
- VXHYVVAUHMGCEX-UHFFFAOYSA-N 2-(2-hydroxyphenoxy)phenol Chemical compound OC1=CC=CC=C1OC1=CC=CC=C1O VXHYVVAUHMGCEX-UHFFFAOYSA-N 0.000 description 1
- ZVAKZVDJIUFFFP-UHFFFAOYSA-N 2-chlorooxolane Chemical compound ClC1CCCO1 ZVAKZVDJIUFFFP-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- PXKLMJQFEQBVLD-UHFFFAOYSA-N Bisphenol F Natural products C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- 229920000305 Nylon 6,10 Polymers 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004959 Rilsan Substances 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- XAEZALCLBRUCLR-UHFFFAOYSA-K bismuth;hydrogen carbonate Chemical compound [Bi+3].OC([O-])=O.OC([O-])=O.OC([O-])=O XAEZALCLBRUCLR-UHFFFAOYSA-K 0.000 description 1
- 229940106691 bisphenol a Drugs 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229940127554 medical product Drugs 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- ZETYUTMSJWMKNQ-UHFFFAOYSA-N n,n',n'-trimethylhexane-1,6-diamine Chemical compound CNCCCCCCN(C)C ZETYUTMSJWMKNQ-UHFFFAOYSA-N 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical class C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 125000003011 styrenyl group Chemical class [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- WPZJSWWEEJJSIZ-UHFFFAOYSA-N tetrabromobisphenol-F Natural products C1=C(Br)C(O)=C(Br)C=C1CC1=CC(Br)=C(O)C(Br)=C1 WPZJSWWEEJJSIZ-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Materials For Medical Uses (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明はＸ線造影性を有し、かつ
光透明性を有する医療用成型品に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a medical molded article having X-ray contrast and light transparency.
【０００２】[0002]
【従来の技術とその課題】カテーテルをはじめとした体
内へ留置或は挿入する医療用具に於いてはその用途上Ｘ
線造影性を有する事が不可欠である。医療用具にはプラ
スティックス（高分子材料）が多用されているが、高分
子材料は基本的には光透明性と同時にＸ線透明性であ
り、何らかの手段により前記目的を達成する必要があ
る。従来、プラスティックスにＸ線造影性を付与する方
法としては硫酸バリウム、重炭酸ビスマスなどの重金属
塩、金属タングステン粉末などの無機（化合）物をプラ
スティックに混合する事が行われてきた。2. Description of the Related Art In medical devices such as catheters that are placed or inserted in the body, they are used for X purposes.
It is indispensable to have line contrast. Although plastics (polymer materials) are often used in medical devices, the polymer materials are basically light-transparent and X-ray transparent at the same time, and it is necessary to achieve the above-mentioned object by some means. Heretofore, as a method for imparting X-ray contrast property to plastics, it has been carried out to mix plastics with a heavy metal salt such as barium sulfate or bismuth bicarbonate, or an inorganic compound such as metal tungsten powder.
【０００３】これらの材料を使用した場合、該材料の本
質的な問題のため医療用具は光学的に不透明になり、
又、黄色や黒色に着色する場合があり望ましくない場合
が多々あった。その具体的な問題点としては特にカテー
テルとしたときに顕著になる。即ち管内に存在する流体
の状況が確認できない事である。この問題点を改善する
次善の策として造影材を含有した樹脂をストライプ状に
入れたカテーテルが使われている。しかし、充分な造影
性を確保するにはこれら造影剤が占めるストライプ幅を
大きくする必要があり、従って内容を容易に確認する事
は難しいのが現状であった。When these materials are used, the medical device becomes optically opaque due to the inherent problems of the materials,
In addition, there are many cases in which it is not desirable because it may be colored yellow or black. The specific problem becomes remarkable especially when a catheter is used. That is, the condition of the fluid existing in the pipe cannot be confirmed. As a suboptimal measure for solving this problem, a catheter in which a resin containing a contrast material is put in a stripe shape is used. However, in order to secure a sufficient contrast property, it is necessary to increase the stripe width occupied by these contrast agents, and thus it has been difficult to easily confirm the contents.
【０００４】一方、透明性を有する造影性付与材の検討
がなされている。具体的には、臭素やヨウ素がＸ線吸収
性があることを利用しハロゲン化低分子化合物をプラス
ティックに混合した例が米国特許４,２８２,８７６号公
報に開示されている。しかしながら、本方法では造影剤
の溶出が避けられず安全性において問題である。On the other hand, studies have been conducted on a contrast-imparting material having transparency. Specifically, US Pat. No. 4,282,876 discloses an example in which a halogenated low molecular weight compound is plastically mixed by utilizing the fact that bromine and iodine have X-ray absorbing properties. However, this method cannot avoid the elution of the contrast agent, which is a problem in safety.
【０００５】また、特許公報特開平６−２３０３４に
は、ハロゲン化されたポリウレタンを用い造影性ととも
に光透過性を確保した材料及びこれを用いたカテーテル
が開示されている。しかし、該発明においてはハロゲン
化ポリウレタンを新たに合成する必要があり、要求され
る物性が大きく異なる各医療用具ごとに一つ一つ合成し
ていたのでは実用的ではない。又、ポリウレタンは鎖延
長剤やソフトセグメントとしてポリエーテル等を使用す
る為ポリマー中に占めるハロゲンの含有量が高くならず
Ｘ線造影性の面で不十分になりやすい欠点を有してい
る。Further, Japanese Patent Laid-Open Publication No. 6-23034 discloses a material using halogenated polyurethane, which has a contrast property and a light transmission property, and a catheter using the same. However, in the present invention, it is necessary to newly synthesize a halogenated polyurethane, and it is not practical to synthesize one by one for each medical device having greatly different required physical properties. Further, since polyurethane uses a chain extender or a polyether as a soft segment, the content of halogen in the polymer does not become high, and the polyurethane tends to be insufficient in terms of X-ray contrast.
【０００６】[0006]
【課題を解決する為の手段】本発明者らは上記の課題を
鋭意検討した結果、本発明に到達した。上記の課題を解
決する本発明とは以下の通りである。The present inventors have arrived at the present invention as a result of extensive studies on the above problems. The present invention that solves the above problems is as follows.
【０００７】（１） Ｘ線造影性を有するハロゲン化ポ
リマーが、前記Ｘ線造影性を有するハロゲン化ポリマー
以外の樹脂中に線状或いは層状に含まれることを特徴と
するＸ線造影性医療用成型品。(1) X-ray contrasting medical use characterized in that the halogenated polymer having X-ray contrasting property is contained in a resin other than the halogenated polymer having X-ray contrasting property in a linear or layered form. Molded product.
【０００８】（２） 前記Ｘ線造影性を有するハロゲン
化ポリマーが、ポリアミド、エポキシ樹脂、ポリウレタ
ン、ポリエステル、ポリカーボネート、ビニル系重合体
のうちの少なくとも一つからなる上記（１）に記載のＸ
線造影性医療用成型品。(2) The X according to (1) above, wherein the halogenated polymer having X-ray contrast property is at least one of polyamide, epoxy resin, polyurethane, polyester, polycarbonate, and vinyl polymer.
Line-contrast medical molded products.
【０００９】（３） 前記Ｘ線造影性を有するハロゲン
化ポリマーのハロゲンが、臭素及び／又はヨウ素である
上記（１）及び（２）に記載のＸ線造影性医療用成型
品。(3) The X-ray contrast-imparting medical molded article according to the above (1) or (2), wherein the halogen of the halogenated polymer having X-ray contrast is bromine and / or iodine.
【００１０】（４） 前記Ｘ線造影性を有するハロゲン
化ポリマーが、臭素化ジフェノールから誘導されるエポ
キシ樹脂又はポリカーボネートである上記（１）乃至
（３）に記載のＸ線造影性医療用成型品。(4) The X-ray contrast-imparting medical molding according to any of (1) to (3) above, wherein the halogenated polymer having X-ray contrast is an epoxy resin or a polycarbonate derived from brominated diphenol. Goods.
【００１１】（５） 前記臭素化ジフェノールが、テト
ラブロムビスフェノール−Ａである上記（１）乃至
（４）に記載のＸ線造影性医療用成型品。(5) The X-ray contrast-enhanced medical molded article according to any one of (1) to (4) above, wherein the brominated diphenol is tetrabromobisphenol-A.
【００１２】（６） 前記Ｘ線造影性を有するハロゲン
化ポリマーが下記の式１で示されるエポキシ樹脂である
上記（１）乃至（５）に記載のＸ線造影性医療用成型
品。(6) The X-ray contrast-imparting medical molded article according to any one of (1) to (5), wherein the halogenated polymer having X-ray contrast is an epoxy resin represented by the following formula 1.
【００１３】[0013]
【化２】 Embedded image
【００１４】（式中、Ｂｒは臭素、Ｍｅはメチル基、Ｐ
ｈはフェニル基、ｎは任意の整数を示す。）(In the formula, Br is bromine, Me is a methyl group, and P is
h represents a phenyl group, and n represents an arbitrary integer. )
【００１５】（７） 前記Ｘ線造影性を有するハロゲン
化ポリマーが、臭素化ジカルボン酸から誘導されるポリ
アミド及び／又はポリエステルである上記（１）乃至
（３）に記載のＸ線造影性医療用成型品。(7) The X-ray contrast-imaging medical product according to any one of (1) to (3) above, wherein the halogenated polymer having X-ray contrast property is a polyamide and / or polyester derived from brominated dicarboxylic acid. Molded product.
【００１６】（８） 前記臭素化ジカルボン酸が、テト
ラブロムテレ（イソ）フタル酸である上記（１）乃至
（３）及び（７）に記載のＸ線造影性医療用成型品。(8) The X-ray contrast-enhanced medical molded article according to any of (1) to (3) and (7) above, wherein the brominated dicarboxylic acid is tetrabromobutele (iso) phthalic acid.
【００１７】（９） チューブ状の形状を有する上記
（１）乃至（８）のＸ線造影性医療用成型品。(9) The X-ray contrast-enhanced medical molded article according to the above (1) to (8), which has a tubular shape.
【００１８】以下、本発明をさらに詳しく説明する。本
発明に用いるＸ線造影性を有するハロゲン化ポリマーと
は、原子団として臭素、ヨウ素等のハロゲン置換基を有
するものである。この中で置換基は特に光や熱に対する
安定性の点で臭素が好適である。The present invention will be described in more detail below. The halogenated polymer having an X-ray contrast property used in the present invention has a halogen substituent such as bromine or iodine as an atomic group. Of these, bromine is particularly preferable as the substituent in terms of stability to light and heat.
【００１９】具体的にはハロゲンを含有したポリマーと
してはハロゲン化スチレン、ハロゲン化フェニル（メ
タ）アクリレート等から合成されるラジカル重合物、ハ
ロゲン化（イソ、テレ）フタル酸、ハロゲン化ジフェノ
ール類等から誘導されるポリアミド、ポリエステル、ポ
リカーボネート、ポリウレタン、エポキシ樹脂等が挙げ
られる。Specifically, the halogen-containing polymer is a radical polymer synthesized from halogenated styrene, halogenated phenyl (meth) acrylate, etc., halogenated (iso, tere) phthalic acid, halogenated diphenols, etc. Examples thereof include polyamides, polyesters, polycarbonates, polyurethanes, epoxy resins and the like.
【００２０】これらの中でも、原料モノマー或いはポリ
マーの入手の容易さ、価格、ハロゲン含量等の点で、特
にハロゲン化ジフェノール、ハロゲン化ジカルボン酸を
原料モノマーとしたエポキシ樹脂、ポリエステル、ポリ
アミドが望ましい。Among these, epoxy resins, polyesters and polyamides using halogenated diphenols or halogenated dicarboxylic acids as raw material monomers are particularly preferable in view of availability of raw material monomers or polymers, price, halogen content and the like.
【００２１】本発明に於けるエポキシ樹脂とはハロゲン
化ジフェノールとクロルプロピレンオキシド、クロルブ
チレンオキシド等のハロゲン化エポキシドとの反応等に
よって得られる重合体を示す。又、ポリカーボネートと
してはハロゲン化ジフェノールとホスゲン等の反応によ
り合成される。The epoxy resin in the present invention means a polymer obtained by a reaction of a halogenated diphenol with a halogenated epoxide such as chloropropylene oxide and chlorobutylene oxide. The polycarbonate is synthesized by reacting a halogenated diphenol with phosgene or the like.
【００２２】本発明に於けるハロゲン化ジフェノールの
好適な具体例としては、テトラブロモビスフェノール−
Ａ、テトラブロモビスフェノール−Ｆ、テトラブロモビ
フェノール、ジ（ヒドロキシジブロモフェニル）エーテ
ル、ジ（ヒドロキシジブロモフェニル）メタン等が挙げ
られる。中でも経済的な面でテトラブロモビスフェノー
ル−Ａが望ましい。本発明に於いてテトラブロモビスフ
ェノール−Ａとともにビスフェノール−Ａ、ビスフェノ
ール−Ｆ、ジ（ヒドロキシフェニル）エーテル、ジ（ヒ
ドロキシフェニル）メタンを造影性を低下させない範囲
で共重合させる事は自由である。A preferred specific example of the halogenated diphenol in the present invention is tetrabromobisphenol-
A, tetrabromobisphenol-F, tetrabromobiphenol, di (hydroxydibromophenyl) ether, di (hydroxydibromophenyl) methane and the like can be mentioned. Among them, tetrabromobisphenol-A is preferable from the economical aspect. In the present invention, it is free to copolymerize bisphenol-A, bisphenol-F, di (hydroxyphenyl) ether and di (hydroxyphenyl) methane together with tetrabromobisphenol-A within a range that does not reduce the contrast property.
【００２３】本発明のポリアミド、ポリエステルとはジ
カルボン酸とジアミン又はジオールの縮重合によって合
成されるが、ハロゲン化モノマーとしては以下のものが
例えば使用される。ハロゲン化ジカルボン酸としてはテ
トラブロムテレ（イソ）フタル酸、トリブロムテレ（イ
ソ）フタル酸、臭素化ナフタリンジカルボン酸等が、ハ
ロゲン化ジアミンとしてはテトラブロムジアミノベンゼ
ン、テトラブロムジアミノナフタリン、ブロム化キシリ
レンジアミン等の芳香族系ジアミン等、ハロゲン化ジオ
ールとしては上記ハロゲン化ジフェノールが使用でき
る。尚、上記モノマー群は一例であり、これに限定され
るものではなく、又、例えばテトラブロムテレフタル酸
とエチレングリコールの組み合わせからなるポリエステ
ル、テトラブロムテレフタル酸とトリメチルヘキサメチ
レンジアミンの組み合わせからなるポリアミドの様にハ
ロゲン化モノマーと非ハロゲン化モノマーを組み合わせ
て使用する事は自由である。The polyamide and polyester of the present invention are synthesized by polycondensation of a dicarboxylic acid and a diamine or a diol, and the following halogenated monomers are used, for example. Examples of the halogenated dicarboxylic acid include tetrabromtere (iso) phthalic acid, tribromutere (iso) phthalic acid, brominated naphthalene dicarboxylic acid, etc. The above halogenated diphenols can be used as the halogenated diol such as aromatic diamine. The above monomer group is an example, and the present invention is not limited to this. For example, a polyester composed of a combination of tetrabromterephthalic acid and ethylene glycol, a polyamide composed of a combination of tetrabromterephthalic acid and trimethylhexamethylenediamine is used. Similarly, it is free to use the halogenated monomer and the non-halogenated monomer in combination.
【００２４】本発明に於いてＸ線造影性を有するハロゲ
ン化ポリマー以外の樹脂としては、特に限定されること
なく、またＸ線造影性でもＸ線透過性であっても良い。
具体的には、各種ナイロン、ポリウレタン、ポリエステ
ル、エラストマー、シリコーン等が挙げられる。In the present invention, the resin other than the halogenated polymer having X-ray contrast property is not particularly limited, and may be X-ray contrast property or X-ray transmissive property.
Specific examples include various nylons, polyurethanes, polyesters, elastomers and silicones.
【００２５】本発明に於いてＸ線造影性を有するハロゲ
ン化ポリマーを医療用成型品に導入する方法としては、
公知の方法をはじめ種々の方法が使用できる。例えば、
チューブ状成型物の場合、Ｘ線造影性を有するハロゲン
化ポリマーをチューブ軸方向に対し平行に一本或いは数
本、線状（ストライプ状等）に入れる方法、溶融多層成
形法を利用した方法、該Ｘ線造影性を有するハロゲン化
ポリマーを有機溶媒に溶解しコーティングする方法が挙
げられる。In the present invention, a method for introducing a halogenated polymer having an X-ray contrast property into a medical molded article is as follows:
Various methods including known methods can be used. For example,
In the case of a tubular molded article, a method in which one or several halogenated polymers having X-ray contrast properties are placed in parallel with the axial direction of the tube in a linear shape (stripe shape, etc.), a method utilizing a melt multilayer molding method, Examples thereof include a method in which the halogenated polymer having X-ray contrast property is dissolved in an organic solvent and coated.
【００２６】また、３次元成型物の場合は線状を含めた
多層射出成形、及びコーティング法が挙げられる。Ｘ線
造影性を有するハロゲン化ポリマーは基本的に光透明性
である事から上記方法により作製された成型品は光学的
に透明なものとなる。Further, in the case of a three-dimensional molded product, a multilayer injection molding including a linear shape and a coating method can be mentioned. Since the halogenated polymer having the X-ray contrast property is basically light-transparent, the molded product produced by the above method becomes optically transparent.
【００２７】上述のストライプ成形、多層成形等により
造影性を付与された成型品はＸ線造影性を有するハロゲ
ン化ポリマー単味で成形されているのではないので、成
型品の物性コントロールが極めて容易である。即ち、Ｘ
線造影性を有するハロゲン化ポリマー以外の造影性の付
与対象となる成型品を主に構成する樹脂の物性（例え
ば、各種ナイロン、ポリウレタンなど）とＸ線造影性を
有するハロゲン化ポリマーの物性を組み合わせる事によ
り成型品の物性を任意に制御する事ができる。Since the molded product having the contrast property imparted by the above-mentioned stripe molding, multi-layer molding, etc. is not molded with the halogenated polymer having the X-ray contrast property, it is extremely easy to control the physical properties of the molded product. Is. That is, X
Combining the physical properties of resins (for example, various nylons, polyurethanes, etc.) that mainly make up molded articles other than halogenated polymers having X-ray contrast properties and the properties of halogenated polymers having X-ray contrast properties By doing so, the physical properties of the molded product can be controlled arbitrarily.
【００２８】本発明のＸ線造影性医療用成型品の具体例
としては、チューブ状の物として、留置針カテーテル、
ガイディングカテーテル、ＰＴＣＡカテーテル、経腸栄
養チューブなどのカテーテル類など、３次元成型物とし
て、シャント、ステントなどが挙げられる。Specific examples of the X-ray contrast-enhanced medical molded article of the present invention include a tubular article, an indwelling needle catheter,
Three-dimensional molded products such as guiding catheters, PTCA catheters, and catheters such as enteral feeding tubes include shunts and stents.
【００２９】[0029]
【実施例】以下に具体的に実施例を用い本発明を説明す
るが、これに限定されるものではない。EXAMPLES The present invention will be described below in greater detail by giving Examples, but the invention is not limited thereto.
【００３０】（実施例１）テトラブロモビスフェノール
−Ａとエピクロルヒドリンから誘導されるエポキシ樹脂
（東都化成（株）、ＹＰＢ、ブロム含有量５３ｗｔ％）
を中間層（厚さ６０μｍ）に、ナイロン１２（東レ
（株）、リルサンＡＥＳＮ ＯＴＬ）を外層にした３層
構造を有する外径１.２ｍｍ、内径０.９ｍｍのチューブ
を成型機から多層押出し成形した。このチューブは光学
的には透明であった。本チューブのＸ線不透過性をＡＡ
ＭＩ基準、IV、カテーテル基準記載の方法に従い試験し
たところ、アルミニウム板厚が７ｍｍまでチューブの存
在が確認され十分な造影性が付与されている事が示され
た。(Example 1) Epoxy resin derived from tetrabromobisphenol-A and epichlorohydrin (Toto Kasei Co., Ltd., YPB, bromine content 53 wt%)
A tube with an outer diameter of 1.2 mm and an inner diameter of 0.9 mm, which has a three-layer structure in which nylon 12 (Toray Industries, Inc., Rilsan AESN OTL) was used as the outer layer in the middle layer (thickness 60 μm), was multilayer extruded from the molding machine. did. The tube was optically transparent. X-ray opacity of this tube is AA
When tested according to the methods described in MI standard, IV standard and catheter standard, the presence of a tube was confirmed up to an aluminum plate thickness of 7 mm, and it was shown that sufficient contrast was imparted.
【００３１】（実施例２）実施例１と同じブロム含有エ
ポキシ樹脂がストライプ状に４本入ったポリエステルエ
ラストマー（東レ・デュポン（株）製ハイトレル５５５
７）製チューブを押出成形した。本チューブは光学的に
透明であり、Ｘ線不透過性を実施例１と同様に検討した
ところ、アルミニウム板厚８ｍｍまでチューブの存在が
確認され十分な造影性が確認された。Example 2 A polyester elastomer (Hytrel 555 manufactured by Toray-Dupont Co., Ltd.) containing four stripes of the same bromine-containing epoxy resin as in Example 1
7) The tube made from was extruded. This tube was optically transparent, and when the X-ray opacity was examined in the same manner as in Example 1, the presence of the tube was confirmed up to an aluminum plate thickness of 8 mm, and sufficient contrast was confirmed.
【００３２】（実施例３）ポリ（トリメチルヘキサメチ
レン）テトラブロムテレフタルアミドがストライプ状に
４本入ったポリプロピレンオキサイドセグメント化ナイ
ロン６１０製チューブを作製した（外径１.２ｍｍ、内
径０.９ｍｍ）。本チューブのＸ線不透過性を検討した
ところアルミニウム厚が７ｍｍまでチューブの存在が確
認され、十分な造影性が付与されている事が確認され
た。Example 3 A tube made of polypropylene oxide segmented nylon 610 containing four strips of poly (trimethylhexamethylene) tetrabromoterephthalamide was prepared (outer diameter 1.2 mm, inner diameter 0.9 mm). When the X-ray opacity of this tube was examined, the presence of the tube was confirmed up to an aluminum thickness of 7 mm, and it was confirmed that sufficient contrast was imparted.
【００３３】（実施例４）ポリエチレンテトラブロムテ
レフタレートを中間層（厚さ７５μm）に、ポリエステ
ルエラストマー（東レ・デュポン（株）製ハイトレル５
５５７）を外層にした３層構造を有する外径１.５５ｍ
ｍ、内径０.９ｍｍのチューブを成型機から多層押し出
し成形した。このチューブは光学的には透明であった。
本チューブのＸ線造影性を検討したところアルミニウム
板厚８ｍｍまでチューブの存在が確認され、十分な造影
性が付与されている事が示された。Example 4 Polyethylene tetrabrom terephthalate was used as an intermediate layer (thickness: 75 μm) and a polyester elastomer (Hytrel 5 manufactured by Toray DuPont Co., Ltd.).
The outer diameter is 1.55 m with a three-layer structure with 557) as the outer layer.
A tube having a diameter of m and an inner diameter of 0.9 mm was extrusion-molded from a molding machine in multiple layers. The tube was optically transparent.
When the X-ray contrast property of this tube was examined, the existence of the tube was confirmed up to an aluminum plate thickness of 8 mm, and it was shown that sufficient contrast property was imparted.
【００３４】（比較例）特開平６−２３０３４に開示さ
れた方法に従って、Ｘ線造影性を有するポリウレタン
（ハロゲン含量２０ｗｔ％）を合成し、外径１.２ｍ
ｍ、内径０.９ｍｍの単のチューブを作製した。本チュ
ーブのＸ線造影性はアルミニウム板厚１０ｍｍまでチュ
ーブの存在が確認された。Comparative Example A polyurethane having an X-ray contrast property (halogen content 20 wt%) was synthesized according to the method disclosed in JP-A-6-23034, and the outer diameter was 1.2 m.
A single tube having a diameter of m and an inner diameter of 0.9 mm was prepared. Regarding the X-ray contrast property of this tube, the existence of the tube was confirmed up to an aluminum plate thickness of 10 mm.
【００３５】[0035]
【発明の効果】上述した通り、本発明のＸ線造影性を有
する医療用成型品は、Ｘ線造影性を有するハロゲン化ポ
リマーを、前記Ｘ線造影性を有するハロゲン化ポリマー
以外の造影性の付与対象となる成型品を主に構成する樹
脂中に線状或いは層状に設けることにより、造影性を有
しながらも光学的な透明性を維持できる。As described above, in the medical molded article having X-ray contrast property of the present invention, the halogenated polymer having X-ray contrast property is used as the contrast agent other than the halogenated polymer having X-ray contrast property. By providing the molded product to be applied in the resin that mainly constitutes the resin in a linear or layered form, it is possible to maintain optical transparency while having contrast properties.
【００３６】本発明のＸ線造影性医療用成型品は、留置
針カテーテル、ガイディングカテーテル、ＰＴＣＡカテ
ーテル、経腸栄養チューブなどのカテーテル類等の医療
用具に有効に使用できる。The X-ray contrast-enhanced medical molded article of the present invention can be effectively used for medical devices such as indwelling needle catheters, guiding catheters, PTCA catheters, enteral feeding tubes and other catheters.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 鬼頭 秀彰 神奈川県足柄上郡中井町井ノ口1500番地 テルモ株式会社内 (72)発明者 石川 健次 神奈川県足柄上郡中井町井ノ口1500番地 テルモ株式会社内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hideaki Kito 1500 Inoguchi, Nakai-cho, Ashigarashami-gun, Kanagawa Terumo Corporation (72) Inventor Kenji Ishikawa 1500, Inoguchi, Nakai-cho, Ashigagami-gun, Kanagawa Terumo Corporation
Claims (9)
が、前記Ｘ線造影性を有するハロゲン化ポリマー以外の
樹脂中に線状或いは層状に含まれることを特徴とするＸ
線造影性医療用成型品。1. A X-ray contrast-enhancing halogenated polymer is contained in a resin other than the X-ray contrast-enhancing halogenated polymer in a linear or layered form.
Line-contrast medical molded products.
ーが、ポリアミド、エポキシ樹脂、ポリウレタン、ポリ
エステル、ポリカーボネート、ビニル系重合体のうちの
少なくとも一つからなる請求項１に記載のＸ線造影性医
療用成型品。2. The X-ray contrast property according to claim 1, wherein the halogenated polymer having the X-ray contrast property is at least one of polyamide, epoxy resin, polyurethane, polyester, polycarbonate and vinyl polymer. Medical molded products.
ーのハロゲンが、臭素及び／又はヨウ素である請求項１
及び請求項２に記載のＸ線造影性医療用成型品。3. The halogen of the halogenated polymer having an X-ray contrast property is bromine and / or iodine.
And the X-ray contrast-enhanced medical molded article according to claim 2.
ーが、臭素化ジフェノールから誘導されるエポキシ樹脂
又はポリカーボネートである請求項１乃至３に記載のＸ
線造影性医療用成型品。4. The X according to claim 1, wherein the halogenated polymer having X-ray contrast property is an epoxy resin or a polycarbonate derived from brominated diphenol.
Line-contrast medical molded products.
ビスフェノール−Ａである請求項１乃至４に記載のＸ線
造影性医療用成型品。5. The X-ray contrast-enhanced medical molded article according to claim 1, wherein the brominated diphenol is tetrabromobisphenol-A.
ーが下記の式１で示されるエポキシ樹脂である請求項１
乃至５に記載のＸ線造影性医療用成型品。 【化１】 （式中、Ｂｒは臭素、Ｍｅはメチル基、Ｐｈはフェニル
基、ｎは任意の整数を示す。）6. The halogenated polymer having an X-ray contrast property is an epoxy resin represented by the following formula 1.
6. An X-ray contrast-enhanced medical molded article according to any one of 5 to 6. Embedded image (In the formula, Br represents bromine, Me represents a methyl group, Ph represents a phenyl group, and n represents an arbitrary integer.)
ーが、臭素化ジカルボン酸から誘導されるポリアミド及
び／又はポリエステルである請求項１乃至３に記載のＸ
線造影性医療用成型品。7. The X according to claim 1, wherein the halogenated polymer having X-ray contrast property is a polyamide and / or polyester derived from brominated dicarboxylic acid.
Line-contrast medical molded products.
テレ（イソ）フタル酸である請求項１乃至３及び請求項
７に記載のＸ線造影性医療用成型品。8. The X-ray contrast-enhanced medical molded article according to any one of claims 1 to 3 and 7, wherein the brominated dicarboxylic acid is tetrabromtere (iso) phthalic acid.
のＸ線造影性医療用成型品。9. The method according to claim 1, which has a tubular shape.
X-ray contrastable medical molded product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6200819A JPH0857033A (en) | 1994-08-25 | 1994-08-25 | X-ray contrasting medical molding |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6200819A JPH0857033A (en) | 1994-08-25 | 1994-08-25 | X-ray contrasting medical molding |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0857033A true JPH0857033A (en) | 1996-03-05 |
Family
ID=16430735
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6200819A Pending JPH0857033A (en) | 1994-08-25 | 1994-08-25 | X-ray contrasting medical molding |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0857033A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000037562A1 (en) * | 1998-12-18 | 2000-06-29 | Bayer Aktiengesellschaft | Use of polycarbonates containing iodine and/or bromine for moulded parts with high x-ray contrast and moulded parts produced with same |
| JP2008509722A (en) * | 2004-08-13 | 2008-04-03 | ラトガース，ザ ステート ユニバーシティ | Radiopaque polymeric stent |
-
1994
- 1994-08-25 JP JP6200819A patent/JPH0857033A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000037562A1 (en) * | 1998-12-18 | 2000-06-29 | Bayer Aktiengesellschaft | Use of polycarbonates containing iodine and/or bromine for moulded parts with high x-ray contrast and moulded parts produced with same |
| JP2008509722A (en) * | 2004-08-13 | 2008-04-03 | ラトガース，ザ ステート ユニバーシティ | Radiopaque polymeric stent |
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