JP2021192742A - Indwelling device with film for digestive organ, method for manufacturing indwelling device with film for digestive organ - Google Patents
Indwelling device with film for digestive organ, method for manufacturing indwelling device with film for digestive organ Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- 210000004798 organs belonging to the digestive system Anatomy 0.000 title claims abstract description 17
- 229920002050 silicone resin Polymers 0.000 claims abstract description 27
- 229910052709 silver Inorganic materials 0.000 claims abstract description 16
- 239000004332 silver Substances 0.000 claims abstract description 16
- 230000002496 gastric effect Effects 0.000 claims description 42
- 238000000576 coating method Methods 0.000 claims description 38
- 239000011248 coating agent Substances 0.000 claims description 37
- 229920001296 polysiloxane Polymers 0.000 claims description 37
- 239000000126 substance Substances 0.000 claims description 29
- 239000000203 mixture Substances 0.000 claims description 27
- 125000003342 alkenyl group Chemical group 0.000 claims description 15
- 210000001035 gastrointestinal tract Anatomy 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 210000000013 bile duct Anatomy 0.000 claims description 7
- 239000002775 capsule Substances 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- 210000002429 large intestine Anatomy 0.000 claims description 7
- 239000002243 precursor Substances 0.000 claims description 7
- 229910019142 PO4 Inorganic materials 0.000 claims description 5
- 230000002183 duodenal effect Effects 0.000 claims description 4
- 230000002093 peripheral effect Effects 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 claims description 2
- 230000003214 anti-biofilm Effects 0.000 abstract description 19
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 14
- 230000014759 maintenance of location Effects 0.000 abstract 1
- 125000001424 substituent group Chemical group 0.000 description 25
- 230000000694 effects Effects 0.000 description 20
- 241000894006 Bacteria Species 0.000 description 17
- 125000003118 aryl group Chemical group 0.000 description 15
- 125000000217 alkyl group Chemical group 0.000 description 14
- 238000011156 evaluation Methods 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 9
- 230000000844 anti-bacterial effect Effects 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 238000007259 addition reaction Methods 0.000 description 7
- 239000011256 inorganic filler Substances 0.000 description 7
- 229910003475 inorganic filler Inorganic materials 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 230000001580 bacterial effect Effects 0.000 description 6
- 229910010272 inorganic material Inorganic materials 0.000 description 6
- 239000011147 inorganic material Substances 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 235000021317 phosphate Nutrition 0.000 description 4
- 239000008055 phosphate buffer solution Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 235000010469 Glycine max Nutrition 0.000 description 3
- 244000068988 Glycine max Species 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 3
- 239000005018 casein Substances 0.000 description 3
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 3
- 235000021240 caseins Nutrition 0.000 description 3
- 238000006482 condensation reaction Methods 0.000 description 3
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- 229910000166 zirconium phosphate Inorganic materials 0.000 description 3
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 description 3
- 229920001817 Agar Polymers 0.000 description 2
- 241000588724 Escherichia coli Species 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000008272 agar Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000001506 calcium phosphate Substances 0.000 description 2
- 229910000389 calcium phosphate Inorganic materials 0.000 description 2
- 235000011010 calcium phosphates Nutrition 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
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- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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- 206010028980 Neoplasm Diseases 0.000 description 1
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- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
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- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000005161 aryl oxy carbonyl group Chemical group 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 210000003445 biliary tract Anatomy 0.000 description 1
- 230000032770 biofilm formation Effects 0.000 description 1
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- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
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- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000004663 dialkyl amino group Chemical group 0.000 description 1
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- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 230000001079 digestive effect Effects 0.000 description 1
- 210000002249 digestive system Anatomy 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
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- 150000004676 glycans Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
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- 125000005386 organosiloxy group Chemical group 0.000 description 1
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 1
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
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- 150000003378 silver Chemical class 0.000 description 1
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Abstract
Description
本発明は、被膜付き消化器用留置デバイス、および、被膜付き消化器用留置デバイスの製造方法に関する。 The present invention relates to a coated gastrointestinal indwelling device and a method for manufacturing a coated gastrointestinal indwelling device.
胆管、食道、十二指腸、および、大腸などの消化器系体内管腔が、がん細胞などにより狭窄または閉塞した場合に、体内管腔を確保する目的で、ステントおよびカテーテルなどの留置デバイスが使用されている。
一方で、消化器においては種々の細菌が存在し、これらの細菌が留置デバイスの表面に付着して増殖し、菌体外物質（ポリサッカライド）を産生しながら複雑な立体構造を構築することで、いわゆるバイオフィルムが形成される場合がある。このようなバイオフィルムが形成されると、体内管腔の閉塞につながるおそれがある。本明細書においては、バイオフィルムの形成の抑制に優れることを、抗バイオフィルム性に優れるともいう。
Indwelling devices such as stents and catheters are used to secure internal lumens such as the bile duct, esophagus, duodenum, and large intestine when the internal lumen of the digestive system is narrowed or occluded by cancer cells or the like. ing.
On the other hand, various bacteria exist in the digestive tract, and these bacteria adhere to the surface of the indwelling device and proliferate, producing extracellular substances (polysaccharides) and constructing a complex three-dimensional structure. , So-called biofilms may be formed. The formation of such biofilms can lead to obstruction of internal lumens. In the present specification, excellent suppression of biofilm formation is also referred to as excellent anti-biofilm property.
一方で、特許文献１においては、菌に対する耐性を持った抗菌性医療デバイスが開示されている。この抗菌性医療デバイスにおいては、Ａｇ（銀）ナノ粒子を用いることが開示されている。 On the other hand, Patent Document 1 discloses an antibacterial medical device having resistance to bacteria. It is disclosed that Ag (silver) nanoparticles are used in this antibacterial medical device.
消化器においてはバイオフィルムが形成されやすいため、消化器に適用される留置デバイスに関しては、抗バイオフィルム性のより一層の向上が望まれている。
本発明者らは、特許文献１の記載を参照して銀粒子を含む被膜を有する留置デバイスについて検討を行ったところ、留置デバイス上にバイオフィルムが形成されやすく、抗バイオフィルム性に関して改善の余地があることを知見した。
Since biofilms are likely to be formed in the digestive tract, further improvement in antibiofilm properties is desired for indwelling devices applied to the digestive tract.
The present inventors examined an indwelling device having a coating film containing silver particles with reference to the description in Patent Document 1, and found that a biofilm is likely to be formed on the indwelling device, and there is room for improvement in antibiofilm properties. It was found that there is.
また、留置デバイスは長時間体内に留置される場合があるため、長時間経過した後においても抗バイオフィルム性に優れることが求められる。本発明では、長時間経過した後においても抗バイオフィルム性が維持されることを、抗バイオフィルム性の持続性に優れるともいう。 Further, since the indwelling device may be indwelled in the body for a long time, it is required to have excellent anti-biofilm properties even after a long period of time. In the present invention, maintaining the anti-biofilm property even after a long period of time is also referred to as being excellent in sustainability of the anti-biofilm property.
本発明は、上記実情に鑑みて、抗バイオフィルム性に優れると共に、抗バイオフィルム性の持続性に優れる、被膜付き消化器用留置デバイスを提供することを課題とする。
また、本発明は、被膜付き消化器用留置デバイスの製造方法も提供することも課題とする。
In view of the above circumstances, it is an object of the present invention to provide a film-coated gastrointestinal indwelling device having excellent anti-biofilm properties and excellent durability of anti-biofilm properties.
It is also an object of the present invention to provide a method for manufacturing a capsule-coated gastrointestinal indwelling device.
本発明者は、上記課題を解決すべく鋭意検討した結果、以下の構成により課題を解決できることを見出した。 As a result of diligent studies to solve the above problems, the present inventor has found that the problems can be solved by the following configurations.
（１） 消化器用留置デバイスと、
消化器用留置デバイス上に配置された被膜と、を有する、被膜付き消化器用留置デバイスであって、
被膜は、銀担持無機物と、シリコーン樹脂とを含み、
銀担持無機物は、無機担体と、無機担体上に配置された銀とを含み、
銀担持無機物の含有量が、被膜全質量に対して、１．０〜３３．０質量％である、被膜付き消化器用留置デバイス。
（２） 銀担持無機物の含有量が、被膜全質量に対して、９．０〜２９．０質量％である、（１）に記載の被膜付き消化器用留置デバイス。
（３） 無機担体が、リン酸塩である、（１）または（２）に記載の被膜付き消化器用留置デバイス。
（４） シリコーン樹脂が、ケイ素原子に結合したアルケニル基を有する第１オルガノポリシロキサンと、ケイ素原子に結合した水素原子を有する第２オルガノポリシロキサンとを反応させて得られる、（１）〜（３）のいずれかに記載の被膜付き消化器用留置デバイス。
（５） 胆管ステント、十二指腸ステント、および、大腸ステントからなる群から選択される少なくとも１つに用いられる、（１）〜（４）のいずれかに記載の被膜付き消化器用留置デバイス。
（６） （１）〜（５）のいずれかに記載の被膜付き消化器用留置デバイスの製造方法であって、
銀担持無機物、シリコーン樹脂またはその前駆体、および、溶媒を含む被膜形成用組成物と留置デバイスとを接触させて、消化器用留置デバイス上に被膜を形成する工程を有し、
銀担持無機物の含有量が、被膜形成用組成物の全固形分に対して、１．０〜３３．０質量％である、被膜付き消化器用留置デバイスの製造方法。
（７） 消化器用留置デバイスがステントであり、
ステントの少なくとも内周面に被膜が形成される、（６）に記載の被膜付き消化器用留置デバイスの製造方法。
(1) Indwelling device for digestive organs and
A coated gastrointestinal indwelling device having a capsule placed on a gastrointestinal indwelling device.
The coating contains silver-supported inorganic material and silicone resin.
The silver-supported inorganic material comprises an inorganic carrier and silver placed on the inorganic carrier.
A coated indwelling device for gastrointestinal tracts, wherein the content of the silver-supported inorganic substance is 1.0 to 33.0% by mass with respect to the total mass of the coating.
(2) The film-coated gastrointestinal indwelling device according to (1), wherein the content of the silver-supported inorganic substance is 9.0 to 29.0% by mass with respect to the total mass of the film.
(3) The coated gastrointestinal indwelling device according to (1) or (2), wherein the inorganic carrier is phosphate.
(4) The silicone resin is obtained by reacting a first organopolysiloxane having an alkenyl group bonded to a silicon atom with a second organopolysiloxane having a hydrogen atom bonded to a silicon atom, (1) to (1). The coated indwelling device for digestive organs according to any one of 3).
(5) The capsule-coated gastrointestinal indwelling device according to any one of (1) to (4), which is used for at least one selected from the group consisting of a bile duct stent, a duodenal stent, and a large intestine stent.
(6) The method for manufacturing a capsule-coated gastrointestinal indwelling device according to any one of (1) to (5).
It comprises a step of contacting a film-forming composition containing a silver-supported inorganic substance, a silicone resin or a precursor thereof, and a solvent with an indwelling device to form a film on a gastrointestinal indwelling device.
A method for producing a film-coated gastrointestinal indwelling device, wherein the content of the silver-supported inorganic substance is 1.0 to 33.0% by mass with respect to the total solid content of the film-forming composition.
(7) The indwelling device for digestive organs is a stent.
The method for manufacturing a coated gastrointestinal indwelling device according to (6), wherein a coating is formed on at least the inner peripheral surface of the stent.
本発明によれば、抗バイオフィルム性に優れると共に、抗バイオフィルム性の持続性に優れる、被膜付き消化器用留置デバイスを提供できる。
また、本発明によれば、被膜付き消化器用留置デバイスの製造方法も提供できる。
According to the present invention, it is possible to provide a film-coated gastrointestinal indwelling device having excellent anti-biofilm properties and excellent durability of anti-biofilm properties.
Further, according to the present invention, it is also possible to provide a method for manufacturing a capsule-coated gastrointestinal indwelling device.
以下、本発明について詳細に説明する。
本明細書において、「〜」を用いて表される数値範囲は、「〜」の前後に記載される数値を下限値、および、上限値として含む範囲を意味する。
Hereinafter, the present invention will be described in detail.
In the present specification, the numerical range represented by using "~" means a range including the numerical values before and after "~" as the lower limit value and the upper limit value.
本発明の消化器用留置デバイスの特徴点としては、銀担持無機物およびシリコーン樹脂を用いる点が挙げられる。
特に、銀担持無機物を使用することにより、抗バイオフィルム性に優れると共に、抗バイオフィルム性の持続性にも優れる。
A feature of the indwelling device for digestive organs of the present invention is that a silver-supported inorganic substance and a silicone resin are used.
In particular, by using a silver-supported inorganic substance, the anti-biofilm property is excellent and the durability of the anti-biofilm property is also excellent.
本発明の消化器用留置デバイスは、消化器用留置デバイスと、消化器用留置デバイス上に配置された被膜と、を有する。
以下、本発明の消化器用留置デバイスに含まれる各部材について詳述する。
The gastrointestinal indwelling device of the present invention has a gastrointestinal indwelling device and a coating film placed on the gastrointestinal indwelling device.
Hereinafter, each member included in the indwelling device for digestive organs of the present invention will be described in detail.
＜消化器用留置デバイス＞
消化器用留置デバイスとは、消化器に適用される留置デバイスである。留置デバイスとしては、ステント（消化器用ステント）、および、カテーテルが挙げられ、ステントが好ましい。
<Digestive indwelling device>
A gastrointestinal indwelling device is an indwelling device applied to the gastrointestinal tract. Examples of the indwelling device include a stent (stent for digestive organs) and a catheter, and a stent is preferable.
ステントとは、人体の管状の部分（食道、十二指腸、大腸、および、胆道など）を管腔内部から広げる医療機器である。ステントは、通常、中空の機器である。
ステントの種類は特に制限されず、公知のステントが挙げられる。例えば、ステントの好適態様の一つとしては、メッシュ状の管状体である。ステントとしては、例えば、１本の線状の金属または高分子材料からなるコイル状のタイプ、金属チューブをレーザーなどによって切り抜き加工したタイプ、線状の部材をレーザーなどで溶接して組み立てたタイプ、および、複数の線状金属を織って作ったタイプがある。
ステントを構成する材料は特に制限されず、金属であっても、樹脂であってもよい。
ステント上に配置される被膜の位置は特に制限されないが、中空のステントの少なくとも内周面に被膜が配置されることが好ましい。
A stent is a medical device that expands the tubular parts of the human body (esophagus, duodenum, large intestine, and biliary tract, etc.) from inside the lumen. A stent is usually a hollow device.
The type of stent is not particularly limited, and examples thereof include known stents. For example, one preferred embodiment of the stent is a mesh-like tubular body. Examples of the stent include a coil type made of a single linear metal or polymer material, a type in which a metal tube is cut out by a laser or the like, and a type in which a linear member is welded by a laser or the like and assembled. And there is a type made by weaving multiple linear metals.
The material constituting the stent is not particularly limited, and may be a metal or a resin.
The position of the coating placed on the stent is not particularly limited, but it is preferable that the coating is placed on at least the inner peripheral surface of the hollow stent.
＜被膜＞
被膜は、上記消化器用留置デバイス上に配置される膜である。
被膜は、銀担持無機物およびシリコーン樹脂を含む。
<Coating>
The membrane is a membrane placed on the gastrointestinal indwelling device.
The coating contains a silver-supported inorganic material and a silicone resin.
（銀担持無機物）
銀担持無機物は、無機担体と、無機担体上に配置された銀とを含む。
無機担体は特に制限されず、公知の無機担体が挙げられる。例えば、リン酸塩（例えば、リン酸亜鉛カルシウム、リン酸カルシウム、リン酸ジルコニウム、リン酸アルミニウム）、ケイ酸塩（例えば、ケイ酸カルシウム）、アルミノケイ酸塩（例えば、ゼオライト）、活性炭、活性アルミナ、シリカゲル、水ガラス、アパタイト、および、ヒドロキシアパタイトが挙げられる。
なかでも、本発明の効果が優れる点で、リン酸塩が好ましく、リン酸ジルコニウムがより好ましい。
(Silver-supported inorganic substance)
The silver-supported inorganic material includes an inorganic carrier and silver placed on the inorganic carrier.
The inorganic carrier is not particularly limited, and examples thereof include known inorganic carriers. For example, phosphates (eg calcium phosphate, calcium phosphate, zirconium phosphate, aluminum phosphate), silicates (eg calcium silicate), aluminosilicates (eg zeolite), activated charcoal, activated alumina, silica gel. , Water glass, apatite, and hydroxyapatite.
Among them, phosphate is preferable, and zirconium phosphate is more preferable, because the effect of the present invention is excellent.
銀担持無機物中に含まれる銀の形態は特に制限されず、例えば、金属銀、銀イオン、および、銀塩の形態が挙げられる。
銀は、共有結合、イオン結合、および、配位結合などの種々の相互作用により無機担体上に担持されていてもよい。
なお、銀担持無機物には、銀以外の金属が担持されていてもよい。
The form of silver contained in the silver-supported inorganic substance is not particularly limited, and examples thereof include metallic silver, silver ions, and silver salts.
Silver may be supported on an inorganic carrier by various interactions such as covalent bonds, ionic bonds, and coordination bonds.
A metal other than silver may be supported on the silver-supported inorganic substance.
銀担持無機物の平均粒径は特に制限されないが、０．０１〜１００μｍが好ましく、０．１〜１０μｍがより好ましい。 The average particle size of the silver-supported inorganic substance is not particularly limited, but is preferably 0.01 to 100 μm, more preferably 0.1 to 10 μm.
被膜中における銀担持無機物の含有量は、被膜全質量に対して、１．０〜３３．０質量％である。なかでも、抗バイオフィルム性がより優れる点、および、抗バイオフィルム性の持続性がより優れる点の少なくとも一方が得られる点（以下、単に「本発明の効果がより優れる点」ともいう。）で、９．０〜２９．０質量％が好ましい。 The content of the silver-supported inorganic substance in the coating film is 1.0 to 33.0% by mass with respect to the total mass of the coating film. Among them, at least one of a point where the anti-biofilm property is more excellent and a point where the anti-biofilm property is more excellent in sustainability can be obtained (hereinafter, also simply referred to as “the point where the effect of the present invention is more excellent”). Therefore, 9.0 to 29.0% by mass is preferable.
（シリコーン樹脂）
被膜は、シリコーン樹脂を含む。
シリコーン樹脂とは、所定のオルガノシロキシ単位を含む樹脂であり、通常、硬化性シリコーンを硬化させて得られる。硬化性シリコーンとしては、その硬化機構により付加反応型シリコーン、縮合反応型シリコーン、紫外線硬化型シリコーン、および、電子線硬化型シリコーンが挙げられる。なかでも、本発明の効果がより優れる点で、付加反応型シリコーンまたは縮合反応型シリコーンが好ましく、付加反応型シリコーンがより好ましい。つまり、シリコーン樹脂は、付加反応型シリコーンを硬化させて得られる樹脂であることが好ましい。
(Silicone resin)
The coating contains a silicone resin.
The silicone resin is a resin containing a predetermined organosiloxy unit, and is usually obtained by curing a curable silicone. Examples of the curable silicone include addition reaction type silicone, condensation reaction type silicone, ultraviolet curable silicone, and electron beam curable silicone depending on the curing mechanism. Among them, addition reaction type silicone or condensation reaction type silicone is preferable, and addition reaction type silicone is more preferable, because the effect of the present invention is more excellent. That is, the silicone resin is preferably a resin obtained by curing the addition reaction type silicone.
シリコーン樹脂としては、本発明の効果がより優れる点で、ケイ素原子に結合したアルケニル基を有する第１オルガノポリシロキサンと、ケイ素原子に結合した水素原子を有する第２オルガノポリシロキサンとを反応させて得られるシリコーン樹脂が好ましい。
第１オルガノポリシロキサンおよび第２オルガノポリシロキサンは、直鎖状であっても、分岐鎖状であってもよい。
As the silicone resin, the first organopolysiloxane having an alkenyl group bonded to a silicon atom is reacted with a second organopolysiloxane having a hydrogen atom bonded to a silicon atom in that the effect of the present invention is more excellent. The resulting silicone resin is preferred.
The first organopolysiloxane and the second organopolysiloxane may be linear or branched.
第１オルガノポリシロキサンとしては、本発明の効果がより優れる点で、式（１）で表されるオルガノポリシロキサンが好ましい。 As the first organopolysiloxane, the organopolysiloxane represented by the formula (1) is preferable because the effect of the present invention is more excellent.
Ｒａ１〜Ｒａ８は、それぞれ独立に、置換基を有していてもよいアルキル基、置換基を有していてもよいアリール基、または、アルケニル基を表し、Ｒａ１〜Ｒａ８の少なくとも１つはアルケニル基を表す。 R a1 to R a8 each independently represent an alkyl group which may have a substituent, an aryl group which may have a substituent, or an alkenyl group, and at least 1 of R a1 to R a8. Represents an alkenyl group.
Ｒａ１〜Ｒａ８の少なくとも１つは、アルケニル基を表す。なかでも、本発明の効果がより優れる点で、Ｒａ１〜Ｒａ８のうちの２つ以上がアルケニル基を表すことが好ましく、Ｒａ１〜Ｒａ８のうちの２〜３つがアルケニル基を表すことがより好ましく、Ｒａ１〜Ｒａ８のうちの２つがアルケニル基を表すことがさらに好ましい。 At least one of R a1 to R a8 represents an alkenyl group. Among them, in terms of the effect of the present invention is more excellent, it is preferable to represent two or more alkenyl groups of R a1 to R a8, represent a two to three but alkenyl groups of R a1 to R a8 still more preferably, it is more preferably represents two are alkenyl groups of R a1 to R a8.
なかでも、本発明の効果がより優れる点で、Ｒａ１〜Ｒａ２は、それぞれ独立に、置換基を有していてもよいアルキル、または、置換基を有していてもよいアリール基を表し、Ｒａ３〜Ｒａ８は、それぞれ独立に、置換基を有していてもよいアルキル、置換基を有していてもよいアリール基、または、アルケニル基を表し、Ｒａ３〜Ｒａ８の少なくとも１つはアルケニル基を表すことが好ましく、Ｒａ１〜Ｒａ２は、それぞれ独立に、置換基を有していてもよいアルキル、または、置換基を有していてもよいアリール基を表し、Ｒａ３〜Ｒａ８は、それぞれ独立に、置換基を有していてもよいアルキル、置換基を有していてもよいアリール基、または、アルケニル基を表し、Ｒａ３〜Ｒａ５の少なくとも１つはアルケニル基を表し、Ｒａ６〜Ｒａ８の少なくとも１つはアルケニル基を表すことがより好ましい。 Among them, in terms of the effect of the present invention is more excellent, R a1 to R a2 represent each independently an alkyl which may have a substituent, or an aryl group which may have a substituent , R a3 to R a8 each independently represent an alkyl which may have a substituent, an aryl group which may have a substituent, or an alkenyl group, and at least one of R a3 to R a8. It is preferable that one represents an alkenyl group, and R a1 to R a2 each independently represent an alkyl which may have a substituent or an aryl group which may have a substituent, and represent R a3. ~ R a8 each independently represents an alkyl which may have a substituent, an aryl group which may have a substituent, or an alkenyl group, and at least one of R a3 to R a5 is alkenyl. It represents a group, and it is more preferable that at least one of R a6 to R a8 represents an alkenyl group.
Ｒａ１〜Ｒａ８で表される置換基を有していてもよいアルキル基のアルキル基部分の炭素数は特に制限されず、１〜１０が好ましく、１〜５がより好ましく、１〜３がさらに好ましい。
Ｒａ１〜Ｒａ８で表される置換基を有していてもよいアリール基のアリール基部分の炭素数は特に制限されず、６〜１２が好ましい。
上記アルキル基および上記アリール基が有していてもよい置換基は特に制限されず、例えば、ハロゲン原子、ヒドロキシル基、カルボキシル基、アミノ基、シアノ基、アリール基、アルコキシ基、アリールオキシ基、アシル基、アルコキシカルボニル基、アリールオキシカルボニル基、アシルオキシ基、モノアルキルアミノ基、ジアルキルアミノ基、モノアリールアミノ基、および、ジアリールアミノ基が挙げられる。
The number of carbon atoms of the alkyl group portion of the alkyl group which may have a substituent represented by R a1 to R a8 is not particularly limited, and is preferably 1 to 10, more preferably 1 to 5, and 1 to 3 More preferred.
The number of carbon atoms of the aryl group portion of the aryl group which may have a substituent represented by R a1 to R a8 is not particularly limited, and 6 to 12 is preferable.
The alkyl group and the substituent which the aryl group may have are not particularly limited, and for example, a halogen atom, a hydroxyl group, a carboxyl group, an amino group, a cyano group, an aryl group, an alkoxy group, an aryloxy group and an acyl group are used. Examples thereof include a group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, a monoalkylamino group, a dialkylamino group, a monoarylamino group, and a diarylamino group.
ｎ１は、１〜２０００を表す。なかでも、本発明の効果がより優れる点で、４〜２０００が好ましく、９〜１７００がより好ましく、５０〜８００がさらに好ましい。 n1 represents 1 to 2000. Among them, 4 to 2000 is preferable, 9 to 1700 is more preferable, and 50 to 800 is further preferable, because the effect of the present invention is more excellent.
第２オルガノポリシロキサンとしては、本発明の効果がより優れる点で、式（２）で表されるオルガノポリシロキサンが好ましい。 As the second organopolysiloxane, the organopolysiloxane represented by the formula (2) is preferable because the effect of the present invention is more excellent.
Ｒｂ１〜Ｒｂ８は、それぞれ独立に、水素原子、置換基を有していてもよいアルキル基、置換基を有していてもよいアリール基を表し、Ｒｂ１〜Ｒｂ８の少なくとも１つは水素原子を表す。 R b1 to R b8 each independently represent a hydrogen atom, an alkyl group which may have a substituent, and an aryl group which may have a substituent, and at least one of R b1 to R b8 is Represents a hydrogen atom.
Ｒｂ１〜Ｒｂ８で表される置換基を有していてもよいアルキル基の好適態様は、Ｒａ１〜Ｒａ８で表される置換基を有していてもよいアルキル基の好適態様と同じである。
Ｒｂ１〜Ｒｂ８で表される置換基を有していてもよいアリール基の好適態様は、Ｒａ１〜Ｒａ８で表される置換基を有していてもよいアリール基の好適態様と同じである。
The preferred embodiment of the alkyl group which may have a substituent represented by R b1 to R b8 is the same as the preferred embodiment of the alkyl group which may have a substituent represented by R a1 to R a8. Is.
The preferred embodiment of the aryl group which may have a substituent represented by R b1 to R b8 is the same as the preferred embodiment of the aryl group which may have a substituent represented by R a1 to R a8. Is.
ｎ２は、１〜２０００を表す。なかでも、本発明の効果がより優れる点で、５〜１５００が好ましく、１０〜１０００がより好ましく、１０〜１００がさらに好ましい。 n2 represents 1 to 2000. Among them, 5 to 1500 is preferable, 10 to 1000 is more preferable, and 10 to 100 is further preferable, because the effect of the present invention is more excellent.
式（２）で表されるオルガノポリシロキサンとしては、式（３）で表されるオルガノポリシロキサンが好ましい。 As the organopolysiloxane represented by the formula (2), the organopolysiloxane represented by the formula (3) is preferable.
Ｒｃ１は、水素原子を表し、Ｒｃ２〜Ｒｃ１０は、それぞれ独立に、置換基を有していてもよいアルキル基、または、置換基を有していてもよいアリール基を表す。 R c1 represents a hydrogen atom, and R c2 to R c10 each independently represent an alkyl group which may have a substituent or an aryl group which may have a substituent.
Ｒｃ２〜Ｒｃ１０で表される置換基を有していてもよいアルキル基の好適態様は、Ｒａ１〜Ｒａ８で表される置換基を有していてもよいアルキル基の好適態様と同じである。
Ｒｃ２〜Ｒｃ１０で表される置換基を有していてもよいアリール基の好適態様は、Ｒａ１〜Ｒａ８で表される置換基を有していてもよいアリール基の好適態様と同じである。
The preferred embodiment of the alkyl group which may have a substituent represented by R c2 to R c10 is the same as the preferred embodiment of the alkyl group which may have a substituent represented by R a1 to R a8. Is.
The preferred embodiment of the aryl group which may have a substituent represented by R c2 to R c10 is the same as the preferred embodiment of the aryl group which may have a substituent represented by R a1 to R a8. Is.
ｎ３は、１〜１０００を表す。なかでも、本発明の効果がより優れる点で、１〜７５０が好ましく、２〜５００がより好ましく、２〜１００がさらに好ましい。
ｎ４は、１〜１０００を表す。なかでも、本発明の効果がより優れる点で、５〜１５００が好ましく、１０〜１０００がより好ましく、１０〜１００がさらに好ましい。
n3 represents 1 to 1000. Among them, 1 to 750 is preferable, 2 to 500 is more preferable, and 2 to 100 is further preferable, because the effect of the present invention is more excellent.
n4 represents 1 to 1000. Among them, 5 to 1500 is preferable, 10 to 1000 is more preferable, and 10 to 100 is further preferable, because the effect of the present invention is more excellent.
被膜中におけるシリコーン樹脂の含有量は特に制限されないが、本発明の効果がより優れる点で、被膜全質量に対して、６７．０〜９９．０質量％が好ましく、６７．０〜９６．０質量％がより好ましく、７１．０〜９１．０質量％がさらに好ましい。 The content of the silicone resin in the coating film is not particularly limited, but is preferably 67.0 to 99.0% by mass, preferably 67.0 to 96.0% by mass, based on the total mass of the coating film, in that the effect of the present invention is more excellent. The mass% is more preferable, and 71.0 to 91.0 mass% is further preferable.
＜他の成分＞
被膜は、銀担持無機物およびシリコーン樹脂以外の他の成分を含んでいてもよい。
他の成分としては、例えば、無銀担持無機物以外の無機フィラーを含んでいてもよい。 無機フィラーの種類は特に制限されず、公知の無機フィラーが挙げられる。例えば、シリカ、アルミナ、および、酸化チタンが挙げられる。
無機フィラーは、その表面が表面修飾されていてもよい。
被膜が上記無機フィラーを含む場合、無機フィラーの含有量は、被膜全質量に対して、５〜５０質量％が好ましく、１５〜４５質量％がより好ましい。
<Other ingredients>
The coating may contain other components other than the silver-supported inorganic material and the silicone resin.
As other components, for example, an inorganic filler other than the silver-free-supported inorganic substance may be contained. The type of the inorganic filler is not particularly limited, and examples thereof include known inorganic fillers. For example, silica, alumina, and titanium oxide can be mentioned.
The surface of the inorganic filler may be surface-modified.
When the coating film contains the above-mentioned inorganic filler, the content of the inorganic filler is preferably 5 to 50% by mass, more preferably 15 to 45% by mass, based on the total mass of the coating film.
他の成分としては、硬化性シリコーンの硬化に使用される触媒（例えば、金属触媒）が挙げられる。硬化性シリコーンが付加反応型シリコーンである場合、触媒としては白金触媒が挙げられ、硬化性シリコーンが縮合反応型シリコーンである場合、触媒としてはアルミニウム触媒およびジルコニウム触媒が挙げられる。 Other components include catalysts (eg, metal catalysts) used to cure curable silicones. When the curable silicone is an addition reaction type silicone, the catalyst may be a platinum catalyst, and when the curable silicone is a condensation reaction type silicone, the catalyst may be an aluminum catalyst or a zirconium catalyst.
上記以外の他の成分としては、シリコーン樹脂以外の樹脂、帯電防止剤、難燃剤、接着性付与剤、レベリング剤、艶消し剤、光安定剤、染料、顔料、香料、および、分散安定剤が挙げられる。 Other components other than the above include resins other than silicone resin, antistatic agents, flame retardants, adhesive-imparting agents, leveling agents, matting agents, light stabilizers, dyes, pigments, fragrances, and dispersion stabilizers. Can be mentioned.
被膜の厚みは特に制限されず、本発明の効果がより優れる点で、０．１〜１０００μｍが好ましく、１〜１００μｍがより好ましい。 The thickness of the coating film is not particularly limited, and is preferably 0.1 to 1000 μm, more preferably 1 to 100 μm, in that the effect of the present invention is more excellent.
＜被膜付き消化器用留置デバイスの製造方法＞
上述した被膜付き消化器用留置デバイスの製造方法は特に制限されず、公知の方法を組み合わせて実施できる。
なかでも、生産性が優れる点から、銀担持無機物、シリコーン樹脂またはその前駆体、および、溶媒を含む被膜形成用組成物と消化器用留置デバイスとを接触させて、消化器用留置デバイス上に被膜を形成する工程を有し、銀担持無機物の含有量が、被膜形成用組成物の全固形分に対して、１．０〜３３．０質量％である、被膜付き消化器用留置デバイスの製造方法が好ましい。
以下、上記製造方法について詳述する。
<Manufacturing method of indwelling device for gastrointestinal tract with coating>
The method for producing the above-mentioned film-coated gastrointestinal indwelling device is not particularly limited, and known methods can be combined and carried out.
Among them, from the viewpoint of excellent productivity, a film-forming composition containing a silver-supported inorganic substance, a silicone resin or a precursor thereof, and a solvent is brought into contact with the gastrointestinal indwelling device to form a film on the gastrointestinal indwelling device. A method for producing a film-coated gastrointestinal indwelling device, which comprises a step of forming and has a silver-supported inorganic substance content of 1.0 to 33.0% by mass based on the total solid content of the film-forming composition. preferable.
Hereinafter, the above manufacturing method will be described in detail.
上記被膜形成用組成物は、銀担持無機物、シリコーン樹脂またはその前駆体、および、溶媒を含む。
銀担持無機物の態様は、上述した通りである。
シリコーン樹脂の態様は、上述した通りである。
シリコーン樹脂の前駆体とは、被膜形成時にシリコーン樹脂となる化合物であり、例えば、上述した硬化性シリコーンが挙げられる。硬化性シリコーンとしては、上述したように、付加反応型シリコーンが好ましく、ケイ素原子に結合したアルケニル基を有する第１オルガノポリシロキサンおよびケイ素原子に結合した水素原子を有する第２オルガノポリシロキサンの組み合わせがより好ましい。
The film-forming composition contains a silver-supported inorganic substance, a silicone resin or a precursor thereof, and a solvent.
The aspects of the silver-supported inorganic material are as described above.
The aspect of the silicone resin is as described above.
The precursor of the silicone resin is a compound that becomes a silicone resin when the film is formed, and examples thereof include the above-mentioned curable silicone. As the curable silicone, as described above, addition reaction type silicone is preferable, and a combination of a first organopolysiloxane having an alkenyl group bonded to a silicon atom and a second organopolysiloxane having a hydrogen atom bonded to a silicon atom is preferable. More preferred.
溶媒の種類は特に制限されず、水、および、有機溶媒が挙げられる。
有機溶媒としては、アルコール系溶媒、グリコールエーテル系溶媒、芳香族炭化水素系溶媒、脂環族炭化水素系溶媒、エーテル系溶媒、および、ケトン系溶媒が挙げられる。
The type of solvent is not particularly limited, and examples thereof include water and organic solvents.
Examples of the organic solvent include alcohol-based solvents, glycol ether-based solvents, aromatic hydrocarbon-based solvents, alicyclic hydrocarbon-based solvents, ether-based solvents, and ketone-based solvents.
被膜形成用組成物は、上述した、銀担持無機物、シリコーン樹脂またはその前駆体、および、溶媒以外の他の成分を含んでいてもよい。
他の成分としては、上述した被膜に含まれていてもよい他の成分（例えば、銀担持無機物以外の無機フィラー、触媒）が挙げられる。
The film-forming composition may contain the above-mentioned silver-supported inorganic substance, silicone resin or precursor thereof, and other components other than the solvent.
Examples of other components include other components that may be contained in the above-mentioned coating film (for example, inorganic fillers other than silver-supported inorganic substances, catalysts).
被膜形成用組成物中における銀担持無機物の含有量は、被膜形成用組成物の全固形分に対して、１．０〜３３．０質量％である。なかでも、本発明の効果がより優れる点で、９．０〜２９．０質量％が好ましい。
なお、固形分とは、溶媒以外の成分（膜を形成し得る成分）を意図する。その成分の性状が液状であっても、溶媒以外の膜を形成し得る成分に該当する場合、固形分として扱う。
The content of the silver-supported inorganic substance in the film-forming composition is 1.0 to 33.0% by mass with respect to the total solid content of the film-forming composition. Among them, 9.0 to 29.0% by mass is preferable because the effect of the present invention is more excellent.
The solid content is intended to be a component other than the solvent (a component capable of forming a film). Even if the properties of the component are liquid, if it corresponds to a component other than the solvent that can form a film, it is treated as a solid content.
被膜形成用組成物中におけるシリコーン樹脂またはその前駆体の含有量は特に制限されないが、被膜形成用組成物の全固形分に対して、６７．０〜９９．０質量％が好ましく、６７．０〜９６．０質量％がより好ましく、７１．０〜９１．０質量％がさらに好ましい。 The content of the silicone resin or its precursor in the film-forming composition is not particularly limited, but is preferably 67.0 to 99.0% by mass, preferably 67.0, based on the total solid content of the film-forming composition. ~ 96.0% by mass is more preferable, and 71.0 to 91.0% by mass is further preferable.
被膜形成用組成物は、上述した必須成分および任意成分を、適宜混合することによって調製できる。なお、上記成分の混合の順番は特に制限されない。 The film-forming composition can be prepared by appropriately mixing the above-mentioned essential components and optional components. The order of mixing the above components is not particularly limited.
被膜形成用組成物を消化器用留置デバイスと接触させる方法特に制限されず、消化器用留置デバイス上に被膜形成用組成物を塗布する方法、および、被膜形成用組成物中に消化器用留置デバイスを浸漬させる方法が挙げられる。
なお、上記被膜形成用組成物を塗布する方法としては、スプレー塗布法、ロールコータ法、および、スピンコータ法などの公知の塗布方法が挙げられる。
The method of contacting the film-forming composition with the gastrointestinal indwelling device is not particularly limited, and the method of applying the film-forming composition on the gastrointestinal indwelling device and the method of immersing the gastrointestinal indwelling device in the film-forming composition. There is a way to make it.
Examples of the method for applying the film-forming composition include known coating methods such as a spray coating method, a roll coater method, and a spin coater method.
消化器用留置デバイスの被膜形成用組成物と接触させる部分は特に制限されず、消化器用留置デバイスの全面であってもよいし、一部であってもよい。例えば、消化器用留置デバイスがステントである場合、ステントの内周面だけであってもよいし、ステントの全面であってもよい。 The portion of the gastrointestinal indwelling device that comes into contact with the film-forming composition is not particularly limited, and may be the entire surface or a part of the gastrointestinal indwelling device. For example, when the indwelling device for gastrointestinal tract is a stent, it may be only the inner peripheral surface of the stent or the entire surface of the stent.
消化器用留置デバイスと被膜形成用組成物とを接触させた後、必要に応じて、形成された塗膜から溶媒を除去するための乾燥処理を実施してもよい。
また、必要に応じて、形成された塗膜に対して硬化処理を施してもよい。硬化処理としては、加熱処理および光照射処理が挙げられ、加熱処理が好ましい。
After contacting the indwelling device for digestive organs with the composition for forming a film, a drying treatment for removing the solvent from the formed coating film may be carried out, if necessary.
Further, if necessary, the formed coating film may be subjected to a curing treatment. Examples of the curing treatment include heat treatment and light irradiation treatment, and heat treatment is preferable.
加熱処理の条件は特に制限されず、加熱温度は、５０〜２５０℃が好ましく、７０〜２００℃がより好ましい。
加熱時間は、０．１〜１０時間が好ましく、０．５〜５時間がより好ましい。
The conditions of the heat treatment are not particularly limited, and the heating temperature is preferably 50 to 250 ° C, more preferably 70 to 200 ° C.
The heating time is preferably 0.1 to 10 hours, more preferably 0.5 to 5 hours.
＜用途＞
本発明の消化器用留置デバイスは、消化器に好適に適用できる。上述したように、消化器においてはバイオフィルムが形成されやすいため、胆管、十二指腸、および、大腸などの消化器に従来の留置デバイスを置くと、留置デバイス上にバイオフィルムが形成されやすいが、本発明の被膜付き消化器用留置デバイス上にはバイオフィルムが形成されにくい。
<Use>
The indwelling device for digestive organs of the present invention can be suitably applied to the digestive organs. As mentioned above, since biofilms are likely to form in the digestive tract, placing conventional indwelling devices in the digestive tracts such as the bile duct, duodenum, and large intestine tends to form biofilms on the indwelling devices. Biofilms are less likely to form on the coated gastrointestinal indwelling device of the invention.
本発明の消化器用留置デバイスは、胆管ステント、十二指腸ステント、または、大腸ステントに好適適用でき、胆管ステントにより好適に適用できる。つまり、本発明の消化器用留置デバイスは、胆管ステント用、十二指腸ステント用、および、大腸ステント用に好適に適用できる。 The indwelling device for gastrointestinal tract of the present invention can be suitably applied to a bile duct stent, a duodenal stent, or a large intestine stent, and can be more preferably applied to a bile duct stent. That is, the indwelling device for gastrointestinal tract of the present invention can be suitably applied to a bile duct stent, a duodenal stent, and a large intestine stent.
以下に実施例に基づいて本発明をさらに詳細に説明する。以下の実施例に示す材料、使用量、割合、処理内容、および、処理手順は、本発明の趣旨を逸脱しない限り適宜変更することができる。したがって、本発明の範囲は以下に示す実施例により制限的に解釈されるべきものではない。 Hereinafter, the present invention will be described in more detail based on examples. The materials, amounts, ratios, treatment contents, and treatment procedures shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention should not be construed as limiting by the examples shown below.
＜被膜形成用組成物の調製＞
後述する表１に記載した樹脂組成物を溶媒に混合した後に、抗菌性化合物を添加して、被膜形成用組成物を調製した。なお、表１中の「−」は、その成分を用いなかったことを表す。
表中の各数値は、被膜形成用組成物全質量に対する、各成分の含有量（質量％）を表す。
<Preparation of film-forming composition>
After mixing the resin composition shown in Table 1 described later with a solvent, an antibacterial compound was added to prepare a film-forming composition. In addition, "-" in Table 1 indicates that the component was not used.
Each numerical value in the table represents the content (mass%) of each component with respect to the total mass of the film-forming composition.
上記表１中に使用された成分は以下のとおりである。
「ＤＭＳ−Ｖ３１」：ビニル末端ポリジメチルシロキサン（ゲレスト社製）（以下、構造式参照。分子量２８０００（式中、ｎ：約３７６））
The components used in Table 1 above are as follows.
"DMS-V31": Vinyl-terminated polydimethylsiloxane (manufactured by Gerest) (Refer to the structural formula below. Molecular weight 28000 (in the formula, n: about 376))
「ＨＭＳ−３０１」：メチルヒドロシロキサン−メチルシロキサンコポリマー（ゲレスト社製）（以下、構造式参照。分子量１９００〜２０００（式中、ｍ：約７、ｎ：約１９）） "HMS-301": Methylhydrosiloxane-methylsiloxane copolymer (manufactured by Gerest) (Refer to the structural formula below. Molecular weight 1900 to 2000 (in the formula, m: about 7, n: about 19))
「ＭＳ５１」：ＭＫＣシリケートＭＳ５１（テトラメトキシシランの部分加水分解オリゴマー、三菱ケミカル社製）
「シリカ」：ＨＭＤＳ処理シリカ（ＳＩＳ６９６２．０、三菱ケミカル社製）
「白金触媒」：ＳＩＰ６８２９．２（ゲレスト社製）
「Ａｌ触媒」：アルミニウム触媒（３２９−２２４４２、和光純薬製）
"MS51": MKC silicate MS51 (partially hydrolyzed oligomer of tetramethoxysilane, manufactured by Mitsubishi Chemical Corporation)
"Silica": HMDS-treated silica (SIS6962.0, manufactured by Mitsubishi Chemical Corporation)
"Platinum catalyst": SIP6829.2 (manufactured by Gerest)
"Al catalyst": Aluminum catalyst (329-22442, manufactured by Wako Pure Chemical Industries, Ltd.)
「抗菌性化合物」欄の「Ｘ」〜「Ｚ」は以下を表す。
「Ｘ」：ノバロンＡＧ３００（銀担持リン酸ジルコニウム、東亞合成社製）
「Ｙ」：バクテキラーＢＭ−１０３ＣＩ−Ｚ（銀担持水ガラス、富士ケミカル社製）
「Ｚ」：銀粒子（型番：４８４０５９、Ａｌｄｒｉｃｈ社製）
「溶媒」欄の「Ｓ１」はキシレンを、「Ｓ２」はトルエンを表す。
「比率」欄は、被膜全質量に対する、抗菌性化合物の含有量を表す。なお、上記「比率」欄の数値は、被膜形成用組成物中の全固形分に対する、抗菌性化合物の含有量にも該当する。
"X" to "Z" in the "antibacterial compound" column represent the following.
"X": Novalon AG300 (silver-supported zirconium phosphate, manufactured by Toagosei Co., Ltd.)
"Y": Bactekiller BM-103CI-Z (silver-supported water glass, manufactured by Fuji Chemical Co., Ltd.)
"Z": Silver particles (model number: 484059, manufactured by Aldrich)
In the "solvent" column, "S1" represents xylene and "S2" represents toluene.
The "ratio" column represents the content of the antibacterial compound with respect to the total mass of the coating film. The numerical value in the "ratio" column also corresponds to the content of the antibacterial compound with respect to the total solid content in the film-forming composition.
＜被膜付き消化器用留置デバイスの製造１＞
筒状の金属メッシュチューブからなるステントを、棒状の治具に固定して、高さ方向を回転軸として回転させながら上記で製造した被膜形成用組成物を滴下して、ステント上に塗膜を作製した。
その後、塗膜付きステントに対して、７５℃で１時間、１５０℃で２時間の加熱処理を施して、ステント上に被膜を形成した。表１のいずれの被膜形成用組成物を使用した場合も、ステント上に被膜（厚み：２０μｍ）が形成された。
<Manufacturing of indwelling device for gastrointestinal tract with coating 1>
A stent made of a tubular metal mesh tube is fixed to a rod-shaped jig, and the film-forming composition produced above is dropped while rotating with the height direction as a rotation axis to form a coating film on the stent. Made.
Then, the coated stent was heat-treated at 75 ° C. for 1 hour and at 150 ° C. for 2 hours to form a film on the stent. When any of the coating composition for forming a coating in Table 1 was used, a coating (thickness: 20 μm) was formed on the stent.
＜被膜付き消化器用留置デバイスの製造２＞
シリコーン製の樹脂チューブからなるステントを、上記で製造した被膜形成用組成物に５分間浸漬させた。その後、ステントを上記で製造した被膜形成用組成物から引き揚げて、過剰量の塗布液を滴らせて除き、その後、得られた塗膜付きステントに対して、７５℃で１時間、１５０℃で２時間の加熱処理を施して、ステント上に被膜を形成した。表１のいずれの被膜形成用組成物を使用した場合も、ステント上に被膜（厚み：２０μｍ）が形成された。
<Manufacturing of indwelling device for gastrointestinal tract with coating 2>
A stent made of a silicone resin tube was immersed in the film-forming composition produced above for 5 minutes. Then, the stent is withdrawn from the film-forming composition produced above, and an excess amount of the coating liquid is dropped and removed. Then, the obtained coated stent is subjected to 150 ° C. for 1 hour at 75 ° C. The stent was heat-treated for 2 hours to form a film on the stent. When any of the coating composition for forming a coating in Table 1 was used, a coating (thickness: 20 μm) was formed on the stent.
＜評価＞
被膜の特性を評価するために以下の実験を行った。
<Evaluation>
The following experiments were performed to evaluate the properties of the coating.
（評価用サンプルの作製）
ガラス基板上に各被膜形成用組成物をキャストして、得られた塗膜付きガラスに対して、７５℃で１時間、１５０℃で２時間の加熱処理を施して、ガラス基板上に被膜（厚み：２０μｍ）を形成して、評価用サンプルを得た。
(Preparation of sample for evaluation)
Each coating film-forming composition was cast on a glass substrate, and the obtained coated glass was heat-treated at 75 ° C. for 1 hour and at 150 ° C. for 2 hours to form a film on the glass substrate. A sample for evaluation was obtained by forming a thickness (thickness: 20 μm).
（殺菌性評価）
大腸菌をソイビーン・カゼイン・ダイジェスト寒天培地（ＳＣＤＡ）に接種し、３７℃で２４時間培養後、ＰＢＳ（リン酸緩衝液）を用いて、菌数が１０４ＣＦＵ／ｍＬになるよう調液したものを、試験菌液とした。
この試験菌液を評価用サンプルに接種し、温度３７℃、湿度９０％以上の環境下にて４時間培養した。培養後、ソイビーン・カゼイン・ダイジェスト液体培地をサンプルに流しかけ、この洗い出し液中の生菌数をＣＦＵアッセイにてカウントした。
試験菌液中の菌数（初期菌数）を基準とし、培養後の生菌数との差（菌数の減少率）を求め、以下の基準により評価した。
Ａ：生菌がいない（初期菌数との差が９９．９％以上）
Ｂ：生菌がほぼいない（初期菌数との差が９９％以上９９．９％未満）
Ｃ：生菌があまりいない（初期菌数との差が５０％以上９０％未満）
Ｄ：生菌がいる（初期菌数との差が５０％未満）
(Evaluation of bactericidal properties)
E. coli was inoculated into soybean casein digest agar (SCDA), after 24 hours incubation at 37 ° C., with PBS (phosphate buffer solution), which was adjusted solution to the number of bacteria becomes 10 4 CFU / mL Was used as the test bacterial solution.
This test bacterial solution was inoculated into an evaluation sample and cultured for 4 hours in an environment of a temperature of 37 ° C. and a humidity of 90% or more. After culturing, a soybean casein digest liquid medium was poured onto the sample, and the viable cell count in the washout solution was counted by the CFU assay.
Based on the number of bacteria in the test bacterial solution (initial number of bacteria), the difference from the number of viable bacteria after culturing (rate of decrease in the number of bacteria) was determined and evaluated according to the following criteria.
A: No live bacteria (difference from the initial number of bacteria is 99.9% or more)
B: Almost no viable bacteria (difference from the initial number of bacteria is 99% or more and less than 99.9%)
C: There are not many live bacteria (the difference from the initial number is 50% or more and less than 90%).
D: There are live bacteria (difference from the initial number of bacteria is less than 50%)
（抗バイオフィルム性の評価）
大腸菌をソイビーン・カゼイン・ダイジェスト寒天培地（ＳＣＤＡ）に接種し３７℃で２４時間培養後、ブレイン・ハート・インフュージョン液体培地を用いて、菌数が１０３ＣＦＵ／ｍＬになるよう調液したものを試験菌液とした。
この試験菌液を評価用サンプルに接種し、温度３７℃、相対湿度９０％以上で４８時間培養した。培養後、余分な菌液を洗い流して、０．１質量％のクリスタルバイオレット溶液で５分間染色した。染色後、余分な染色液を洗い流して、エタノールで染色箇所を溶出させ、この溶出液の吸光度（波長５７０ｎｍ）を測定した。
被膜を備えないガラス基板を用いて上記手順を行った結果を基準とし、各サンプルとの吸光度の差（吸光度の減少率）を求め、以下の基準により評価した。
Ａ：バイオフィルムが付着しない（基準との差が９０％以上）
Ｂ：バイオフィルムがほぼ付着しない（基準との差が５０％以上９０％未満）
Ｃ：バイオフィルムがあまり付着しない（基準との差が１０％以上５０％未満）
Ｄ：バイオフィルムが付着する（基準との差が１０％未満）
(Evaluation of anti-biofilm properties)
After 24 hours of culture of E. coli in inoculated 37 ° C. to soybean casein digest agar (SCDA), using Brain Heart Infusion broth, those as liquid preparation to the number of bacteria is 10 3 CFU / mL Was used as the test bacterial solution.
This test bacterial solution was inoculated into an evaluation sample and cultured at a temperature of 37 ° C. and a relative humidity of 90% or more for 48 hours. After culturing, excess bacterial solution was washed away and stained with 0.1% by mass crystal violet solution for 5 minutes. After staining, the excess staining solution was washed away, the stained area was eluted with ethanol, and the absorbance (wavelength 570 nm) of this eluate was measured.
Based on the result of performing the above procedure using a glass substrate without a coating film, the difference in absorbance (rate of decrease in absorbance) from each sample was determined and evaluated according to the following criteria.
A: Biofilm does not adhere (difference from standard is 90% or more)
B: Biofilm hardly adheres (difference from the standard is 50% or more and less than 90%)
C: Biofilm does not adhere much (difference from the standard is 10% or more and less than 50%)
D: Biofilm adheres (difference from standard is less than 10%)
（持続性の評価）
ＰＢＳへ１０日間浸漬した後の評価用サンプルを用いて、上記（抗バイオフィルム性の評価）を実施した。
評価用サンプルをＰＢＳへ１０日間浸漬する手順において、評価用サンプルから銀が長時間にわたって流出している。この浸漬処理は、被膜付き消化器用留置デバイスを体内に長時間留置した場合のモデル実験に該当する。
(Evaluation of sustainability)
The above (evaluation of anti-biofilm property) was carried out using the evaluation sample after soaking in PBS for 10 days.
In the procedure of immersing the evaluation sample in PBS for 10 days, silver is discharged from the evaluation sample for a long time. This immersion treatment corresponds to a model experiment in which a coated gastrointestinal indwelling device is indwelled in the body for a long time.
表１に示すように、本発明の被膜付き消化器用留置デバイスは、所望の効果を示した。抗バイオフィルム性に優れる実施例においては、殺菌性にも優れており、被膜に付着した菌に対して影響を与えていることが知見された。
なかでも、実施例１と６との比較より、シリコーン樹脂が付加反応型シリコーン（特に、式（１）で表される第１オルガノポリシロキサンおよび式（２）で表される第２オルガノポリシロキサンの組み合わせ）を用いて形成された樹脂である場合、より優れた効果が得られることが確認された。
また、実施例１と４との比較より、無機担体としてリン酸塩を用いた場合、より優れた効果が得られることが確認された。
また、実施例１〜３および５の比較より、被膜全質量に対する銀担持無機物の含有量が９．０〜２９．０質量％である場合、より優れた効果が得られることが確認された。
As shown in Table 1, the coated gastrointestinal indwelling device of the present invention showed the desired effect. It was found that in the examples having excellent anti-biofilm properties, they were also excellent in bactericidal properties and had an effect on bacteria adhering to the film.
Among them, from the comparison between Examples 1 and 6, the silicone resin is an addition reaction type silicone (particularly, the first organopolysiloxane represented by the formula (1) and the second organopolysiloxane represented by the formula (2). It was confirmed that a more excellent effect can be obtained in the case of the resin formed by using (combination of).
Further, from the comparison between Examples 1 and 4, it was confirmed that a more excellent effect can be obtained when phosphate is used as the inorganic carrier.
Further, from the comparison of Examples 1 to 3 and 5, it was confirmed that a more excellent effect can be obtained when the content of the silver-supported inorganic substance with respect to the total mass of the coating film is 9.0 to 29.0% by mass.
Claims (7)
前記消化器用留置デバイス上に配置された被膜と、を有する、被膜付き消化器用留置デバイスであって、
前記被膜は、銀担持無機物と、シリコーン樹脂とを含み、
前記銀担持無機物は、無機担体と、前記無機担体上に配置された銀とを含み、
前記銀担持無機物の含有量が、前記被膜全質量に対して、１．０〜３３．０質量％である、被膜付き消化器用留置デバイス。 Indwelling device for gastrointestinal tract and
A coated gastrointestinal indwelling device comprising a capsule placed on the gastrointestinal indwelling device.
The coating contains a silver-supported inorganic substance and a silicone resin.
The silver-supported inorganic substance contains an inorganic carrier and silver placed on the inorganic carrier.
A film-coated gastrointestinal indwelling device in which the content of the silver-supported inorganic substance is 1.0 to 33.0% by mass with respect to the total mass of the film.
前記銀担持無機物、前記シリコーン樹脂またはその前駆体、および、溶媒を含む被膜形成用組成物と留置デバイスとを接触させて、前記消化器用留置デバイス上に被膜を形成する工程を有し、
前記銀担持無機物の含有量が、前記被膜形成用組成物の全固形分に対して、１．０〜３３．０質量％である、被膜付き消化器用留置デバイスの製造方法。 The method for manufacturing a capsule-coated gastrointestinal indwelling device according to any one of claims 1 to 5.
It comprises a step of contacting a film-forming composition containing the silver-supported inorganic substance, the silicone resin or its precursor, and a solvent with the indwelling device to form a film on the gastrointestinal indwelling device.
A method for producing a film-coated gastrointestinal indwelling device, wherein the content of the silver-supported inorganic substance is 1.0 to 33.0% by mass with respect to the total solid content of the film-forming composition.
前記ステントの少なくとも内周面に前記被膜が形成される、請求項６に記載の被膜付き消化器用留置デバイスの製造方法。
The indwelling device for gastrointestinal tract is a stent.
The method for manufacturing a coated gastrointestinal indwelling device according to claim 6, wherein the coating is formed on at least the inner peripheral surface of the stent.
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